JP2932767B2 - Coating method for ceramic products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coating a surface of a ceramic product, and more particularly to a method for applying a curable composition to the surface of a ceramic product and curing the composition by heating or high-energy radiation. The present invention relates to a method for forming a coating film having high gloss, excellent hardness, surface damage resistance, water resistance, and durability.

[0002]

2. Description of the Related Art It is a common practice to coat the surface of building materials of ceramic products with various paints for the purpose of design, waterproofing, and durability. At that time, it is considered that it is desirable to apply a glaze used for obtaining a tile-like luster to the surface of the ceramic product and to integrate it by baking in all aspects of aesthetics, gloss, hardness, water resistance and weather resistance.

[0003]

On the other hand, organic polymer-based paints are excellent in appearance, but have defects in durability and are insufficient in hardness. In addition, since organic polymer-based paints usually have poor durability, they need to be repainted every certain months, and the maintenance costs are large.

It is known that organic pigments for coloring paints and cured products themselves are inferior in durability and easily discolored. However, inorganic pigments having excellent durability, on the other hand, have drawbacks in that the coloring is not clear and only a dull color tone can be exhibited.

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving these problems in organic polymer paints and pigments that can replace inorganic paints such as glazes, and provides glaze-like gloss to the surface of ceramic products. An object of the present invention is to provide a method for forming a coating film having improved hardness, abrasion resistance, water resistance, weather resistance, and the like.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, they have identified a polyorganosilsesquioxane having a specific acrylic functional group in a part of a side chain. After applying a composition comprising a poly (meth) acrylate and / or a polymerization initiator to the surface of a ceramic product, by heating or irradiating with high-energy radiation, the composition is cured to have high gloss, hardness, It has been found that a coating film having excellent surface damage resistance, water resistance and durability is formed.

That is, the present invention relates to (A) a (meth) acryl-functional polyorganosilsesquioxane represented by the following general formula (I):

Embedded image (Wherein R ₁ and R ₂ represent an alkyl group having 1 to 3 carbon atoms, a phenyl group, an acryl represented by the following general formula (II) and / or
Or, it contains a methacryl functional group, and each of the m structural units is the same or different. R ₃ , R ₄ , R ₅ , and R ₆ are each composed of two or more selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group, and the hydrogen atom is always included. m indicates the degree of polymerization. The general formula (II) is Wherein R ₇ represents a hydrogen atom or a methyl group, R ₈ is a substituted or unsubstituted divalent hydrocarbon having 1 to 12 carbon atoms, R _7,
R ₈ may be different among m structural units. (B) a poly (meth) acrylate represented by the following general formula (III)

Embedded image (Wherein R ₉ is a hydrogen atom or a methyl group, and one R
₉ may all not be the same. R ₁₀ is a polyvalent hydrocarbon residue having a (meth) acrylic acid residue bonded to a different carbon atom, a polyvalent hydrocarbon residue having oxygen in the main chain, or a polyhydric alcohol and a polybasic acid Represents a residue of an ester, and 1 is an integer of 2 or more. ) And (C) a method of coating a ceramic product, wherein the composition comprising a polymerization initiator is applied to the surface of the ceramic product and cured by heating or irradiating with high-energy radiation, and the curability described above. The present invention relates to a method for coating a ceramic product, comprising coating and curing the surface of a ceramic product containing the composition after polishing.

Hereinafter, the present invention will be described in detail. The (meth) acryl-functional polyorganosilsesquioxane used as the component (A) in the present invention is represented by the following general formula (I) and comprises m repeating structural units of silsesquioxane units. It is.

Embedded image R ₁ and R ₂ in the repeating structural unit have 1 to 3 carbon atoms.
Alkyl group, phenyl group and general formula (II) And containing acrylic and / or methacrylic functional groups.

The acrylic and / or methacrylic functional groups referred to herein include those containing an acrylic and / or methacrylic group as a part of the functional groups. In addition, carbon number 1
The alkyl group 3 is any one of a methyl group, an ethyl group, a propyl group, and an isopropyl group, and does not include these alkyl groups. If the alkyl group has 4 or more carbon atoms, the hardness and abrasion resistance of the cured film become insufficient. Not preferred. Further, if it does not contain a phenyl group, it is inferior in toughness, crack resistance and impact resistance. In the acrylic and / or methacrylic functional group represented by the general formula (II), R ₇ is a hydrogen atom or a methyl group, and R ₈ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms. is there. Examples of unsubstituted divalent hydrocarbon group R ₈ include methylene, ethylene, trimethylene, include alkylene groups such as tetramethylene, and the alkyl group and examples of the substituent of the substituted divalent hydrocarbon group R ₈ , An alkenyl group, an aryl group, a cycloalkyl group, or a group in which a part of a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, a cyano group, or the like.

The respective silsesquioxane units forming the repeating unit of the formula (I) are determined by the choice of R ₁ and R ₂ , but may be the same or different. R ₁ and R ₂ of the m repeating units of the general formula (I) are an alkyl group having 1 to 3 carbon atoms, a phenyl group and the general formula (I)
The acrylic and / or methacrylic functional groups represented by I), and the molar ratio between the functional substituents, the alkyl groups and the phenyl groups is preferably 5 to 50:95 to 50. When the acrylic and / or methacrylic functional substituent is less than 5 mol%, the curing speed is slow, and when it exceeds 50 mol%, the curability is good, but the hardness, abrasion resistance, heat resistance, water resistance, etc. It will be chipped. The molar ratio between the alkyl group of R ₁ and R ₂ and the phenyl group is preferably from 99: 1 to 70:30. When the alkyl group exceeds 99%, the adhesion, water resistance, and solvent resistance are poor, and the phenyl group is inferior. If it exceeds 30%, hardness and curability are inferior.

Next, in the general formula (I), R ₃ , R ₄ ,
R ₅ and R ₆ are composed of two or more selected from a hydrogen atom, a methyl group and an ethyl group, but always include a hydrogen atom. That is, the terminal groups OR ₃ , OR ₄ , OR ₅ , OR _{6 of} the polymer
At least one is a hydroxyl group, and the other is a methoxy group and / or an ethoxy group.

The contents of R ₃ , R ₄ , R ₅ and R ₆ are influenced by the types and ratios of a plurality of trialkoxys used as raw materials, and the reaction conditions such as reactivity to hydrolysis and condensation reaction, reaction temperature and time. Is done. For example, when trimethoxysilane and triethoxysilane are used together in a certain ratio as a raw material, the reactivity to hydrolysis and condensation reaction is higher for methoxysilane, and the reaction is stopped in a state where the condensation reaction has progressed to a certain stage, Of the terminal groups of the general formula (I) used as the component (A) of the present invention, when hydroxyl groups are excluded, the residual ratio of ethoxy groups is higher than the residual ratio of methoxy groups.
The ratio of ethoxy groups is higher than the ratio in the raw material stage. As described herein, the alkoxy group is hydrolyzed into a hydroxyl group, and the subsequent condensation reaction proceeds while taking the form of a dehydration reaction between the hydroxyl groups or a dealcoholation reaction between the hydroxyl group and the alkoxy group. Obviously, it is essential that is always contained in the oligomer of (I).

The number average molecular weight of the component (A) is determined by gel permeation chromatography (hereinafter abbreviated as GPC).
Is easily measured by a measuring method such as
A range of 100,000 is preferred. Molecular weight 1,000
If the molecular weight is less than 100,000, the viscosity of the composition becomes too high, and the viscosity of the composition becomes too high. It becomes difficult to coat the thin film. By making the component (A) a polymer having such a molecular weight range, shrinkage of the cured film is reduced, and it is possible to avoid adverse effects such as cracks.

As a method for synthesizing the component (A), there is the following method. If necessary, a trialkoxysilane having an acryl and / or methacryl functional group, an alkyltrialkoxysilane having an alkyl group having 1 to 3 carbon atoms, and a phenyltrialkoxysilane having a phenyl group are added in the presence of water and an acid or a base, if necessary. After heating and condensing, it is produced by removing coexisting water and by-product alcohol. Here, the component (A) can be synthesized by performing hydrolysis and condensation using trichlorosilane instead of trialkoxysilane.

The component (B) is a polyacrylate or polymethacrylate represented by the following general formula:

Embedded image (III) In the formula, R ₉ is a hydrogen atom or a methyl group, and all 1 R ₉ may not be the same. R ₁₀ is a polyvalent hydrocarbon residue having a (meth) acrylic acid residue bonded to a different carbon atom, a polyvalent hydrocarbon residue having oxygen in the main chain, or a polyhydric alcohol and a polybasic acid Represents a residue of an ester, and 1 is an integer of 2 or more.

In this case, a polyvalent hydrocarbon residue in which a (meth) acrylic acid residue is bonded to different carbon atoms of R ₁₀ , or
Polyacrylate or polymethacrylate which is a polyvalent hydrocarbon residue having oxygen in the main chain can be produced by reacting an esterification reaction between an organic polyhydric alcohol and acrylic acid or methacrylic acid under known conditions. it can.

The organic polyhydric alcohol includes ethylene glycol, diethylene glycol, 2,2,4-
Trimethyl-1,3-pentanediol, dipropylene glycol, propylene glycol, average molecular weight of about 15
Polypropylene glycol having from 0 to about 600, triethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2,2-dimethyl-3
-Hydroxypropyl, 2,2-dimethyl-3-hydroxypropanate, polyethylene glycol having an average molecular weight of about 150 to about 600, 2,2-bis [4- (2
-Hydroxyethoxy) phenyl] propane, 2,2-
Bis [4- (2-hydroxypropoxy) phenyl] propane, triethanolamine, 2,3-butanediol, tetraethylene glycol, 2,2-bis (4-hydroxyphenyl) propane, glycerin, trimethylolpropane, 1, 4-butanediol, a polycaprolactone ester of trimethylolpropane containing about 1.5 equivalents of caprolactone, a polycaprolactone ester of trimethylolpropane containing about 3.6 equivalents of caprolactone, 2-ethyl-1,3-hexanediol,
1,5-pentanediol, tripropylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,6-hexanetriol, 1,3-propanediol, 1,6-hexanediol, and the like. , One or more of these may be used.

The polyacrylate or polymethacrylate is not particularly limited, but
Examples thereof include diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and trimethylolpropane trimethacrylate.

[0019] In the case of obtaining a polyacrylate or polymethacrylate having a residue of an ester composed of a polyhydric alcohol and a polybasic acid as R _10, polyhydric alcohols, such as ethylene glycol, 1,2-propylene Glycol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, sorbitol, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol and the like.

On the other hand, polybasic acids include, for example, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, hymic acid, succinic acid,
Examples include polybasic acids such as adipic acid, dodecanoic acid, sebacic acid, maleic acid, itaconic acid, fumaric acid, pyromellitic acid and trimellitic acid or anhydrides thereof. Incidentally, ester residue R ₁₀ does not need to be a one polyhydric alcohol and one polybasic acid, it may be composed of two or more polybasic acids, respectively.

Specific examples of such a polyester acrylate include:

Embedded image

Embedded image

Embedded image And the like.

The preferred blending amounts of the components (A) and (B) (totaling 100 parts by weight) are as follows:
For 95 parts by weight, more preferably 40 to 90 parts by weight, 70 to 5 parts by weight, more preferably 60 parts by weight of the component (B).
To 10 parts by weight. If the amount of the component (A) is less than 30 parts by weight, characteristics such as hardness, water resistance, and gloss based on the component (A) are insufficient. Poor solvent resistance. When the component (B) exceeds 70 parts by weight, the water resistance, hardness,
The adverse effects of poor abrasion resistance and large curing shrinkage appear. On the other hand, when the component (B) is less than 5 parts by weight, the curing rate is low, and the cured film is brittle and easily cracks, which is not preferable.

In addition to the components (A) and (B), a compound having a polymerizable monofunctional unsaturated group is used in combination to adjust the viscosity by dilution, adhesion to a substrate, antistatic properties, and other properties. It is also possible to improve. A wide selection of monomers of this type is possible, but methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl-acid phosphate, methacrylic acid, N-vinyl-
Examples thereof include 2-pyrrolidone and styrene.

As the polymerization initiator which is the component (C), various conventionally known polymerization initiators can be used. That is, when cured by heating, benzoyl peroxide, peroxides such as lauroyl peroxide, hydroperoxides such as butyl hydroperoxide, azo compounds such as azobisisobutyronitrile alone or It is used as a polymerization initiator in combination with a curing accelerator such as an amine or a metal soap. When curing with high energy radiation, acetophenone, propiophenone, benzophenone, benzoin,
Examples thereof include benzoin alkyl ether, xanthol, fluorenone, benzaldehyde, fluorene, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, and 4,4'dimethoxybenzophenone. However, when curing is performed using an electron beam, the above-mentioned initiator may not be added.

These polymerization initiators can be used alone or as a mixture of two or more. or,
In the present invention, when the above polymerization initiator is used,
It is also possible to further enhance the ultraviolet curability by using a so-called accelerator such as a graded amine. As the tertiary amine, various aliphatic and aromatic tertiary amines can be used, and examples thereof include N-dimethanolamine, triethanolamine, N-methyldiethanolamine, triethylamine, and ethyl P-dimethylaminobenzoate. .

When these polymerization initiators and accelerating aids are used except in the case of electron beam irradiation, 0.1 to 10 parts by weight based on 100 parts by weight of the total of both components (A) and (B) And more preferably in the range of 1 to 4 parts by weight.
If the amount of the component (C) is less than 0.1 part by weight, the curing speed is slow and impractical. If the amount exceeds 10 parts by weight, the strength and weather resistance are adversely affected.

The composition composed of the components (A), (B) and (C) is generally used after preliminarily mixing and preserving it. Even in some places, polymerization, gelation, etc. may occur, so keep the three components separately and mix them before use, or store them in a mixture of both (A) and (B). Before use, a method such as adding the component (C) and mixing the components is used. There is no particular problem when only the components (A) and (B) are used. When mixing the three components, a solvent such as butanol, methyl cellosolve, or butyl cellosolve may be added as necessary.

The composition can be cured by blending various substances or compounds for the purpose of improving the physical properties of the cured product or depending on the use of the cured product. These additives include hydroquinone and P as heat stabilizers.
-Methoxy phenol, phthalocyanine blue, phthalocyanine green, titanium white, etc. as coloring pigments; silica, calcium carbonate, kaolin, clay, colloidal silica, etc. as a thickener; various ultraviolet absorbers, antioxidants, etc. A normal diorganopolysiloxane or the like may be added according to the purpose of use as long as the characteristics of the composition are not impaired.

The ceramic product according to the present invention is clay,
Sintered body of inorganic powder such as silicon oxide, aluminum oxide, silicon nitride, etc., building materials, crafts, tableware, automobile parts,
It is used for electric parts and the like. By coating and curing the composition adjusted as described above on this surface, a beautiful ceramic product having excellent hardness, gloss, etc., and durability can be obtained.

Further, various aggregates, fillers, and extenders, for example, sand, natural and artificial lightweight aggregates, fly ash, slag, cinder, perlite, and the like may be added. It may be used and reinforced. The shape of ceramic products is plate-like, cylindrical, irregular, etc., and these molding methods include slurry casting,
Various molding methods such as press, roll, extrusion, and papermaking can be adopted.

The ceramic product may be colored by adding a pigment to the ceramic material or by applying a coloring paint containing the pigment on the surface. By further applying the composition of the present invention to the surface of the glazed ceramic product, hardness, abrasion resistance,
A cured film having excellent water resistance and weather resistance can be provided. Examples of inorganic pigments used for coloring ceramic products include titanium oxide, carbon black, iron oxide, cadmium compounds, cobalt compounds, graphite, zinc chromate, cyanamide lead, and white Portland cement.

When the above pigment is added to a ceramic product, only a pale and dull color has been obtained conventionally.
By applying and curing the composition consisting of the components (A), (B), and (C) or the components (A) and (B) on the surface of the ceramic product, it is possible to realize a dark and vivid original color. It became.

Here, as a pre-coating step of the composition, the surface of a ceramic product containing an inorganic pigment may be polished.
This is to remove substances that impair the original coloring. Polishing can be performed by a generally known method such as a belt sander and a sand blast. As a method of applying the composition to a ceramic product, any method such as spray coating, brush coating, dip coating, flow coating, and spin coating is used.

The thickness of the composition when it is applied to a ceramic product is preferably 3 to 100 μm.
In the case of a thick film having a thickness of m or more, the content of uncured monomer increases during curing, and moreover, adverse effects such as cracks tend to occur in the cured film. In curing the composition, in the case of thermal curing, it is performed by heating in a furnace using steam, electric heat, infrared rays, etc., and in the case of ultraviolet curing, as an ultraviolet light source, an ultraviolet fluorescent lamp, a high pressure mercury lamp, a carbon arc lamp. The irradiation is performed using a metal halide lamp or the like, and the irradiation amount can be appropriately selected. In the case of electron beam irradiation, it is performed using various accelerators.

[0035]

The coating agent for a ceramic product of the present invention is a composition comprising a (meth) acryl-functional polyorganosilsesquioxane, a poly (meth) acrylate and a polymerization initiator, which is applied to the surface of the ceramic product. However, a cured film can be formed by various curing methods. When the composition is cured with energy rays, the reaction can be performed at room temperature, and when cured by heating, the composition is cured at a low temperature of 40 to 90 ° C., so that the problem of breakage due to high-temperature heating has been solved. In addition, when an inorganic pigment was added to a ceramic product, it became possible to form a deep and vivid color because the surface of the ceramic product was polished in advance to remove substances that hinder the coloring of the surface layer. This is considered to be because the product penetrates deeply into the porous portion on the surface of the product and forms a transparent and flat cured film after curing.

The cured film thus obtained not only retains the gloss, water resistance, hardness, abrasion resistance and the like characteristic of the ladder type polysiloxane as shown by the formula (I),
Poly (meth) acrylate has characteristics such as easy curability and easy compatibility with various functions.

[0037]

The present invention will be described below in detail with reference to examples. “Parts” in the examples indicate “parts by weight” unless otherwise specified. In addition, each physical property value in an Example was measured according to the following method.

(Abrasion resistance) A bundle of steel wool having a thickness of # 0000 was rubbed 15 times with the cured coating while applying a load of 500 g, and then the degree of scratches on the coating was examined and evaluated according to the following four ranks. did. A: No scratches B: No more than 10 scratches C: 10 or more scratches but still retains gloss D: Loss of gloss with countless scratches (Surface hardness) Pencil for paint JIS using a scratch tester
It was measured according to K5401. (Water resistance) The film was immersed in warm water at 800 ° C., and the time during which abnormalities such as cracks occurred in the cured film was measured. (Weather resistance) A carbon arc sunshine weather meter test was performed in accordance with the provisions of JIS B7753. The judgment was made by comparing and observing the surface of the test specimen after 500 hours with that of the test specimen.

(Synthesis Example 1 of Component (A)) A 1-liter flask equipped with a thermometer, a stirrer, and a reflux condenser was placed in a flask.
γ-methacryloxypropyltrimethoxysilane 149
g (0.6 mol), 356 g of methyltriethoxysilane
(2.0 mol), 96 g of phenyltriethoxysilane
(0.4 mol), 0.002 mol of hydrochloric acid, 108 g of water (6
Mol), 0.01 g of P-methoxyphenol,
The temperature in the flask is raised to 60 ° C., and
Hold for 0 minutes. Subsequently, the temperature was raised to 70 ° C., and the mixture was reacted for 1 hour. Then, 0.6 g (0.0082 mol) of n-butylamine was added dropwise, and the mixture was further reacted for 45 minutes.
4 g (0.0087 mol) was added dropwise and kept at 70 ° C. for 30 minutes. After washing with water, dehydrated with anhydrous sodium sulfate,
When the solvent was removed using a rotary evaporator, 2
Viscous (A) -1 component 320 having a viscosity of 450 cps at 5 ° C.
g was obtained. The molecular weight of this component (A) -1 was determined by GPC and found to be a number average molecular weight of 5,700 and a weight average molecular weight of 13,800. In the component (A) -1 of this synthesis example, the molar ratio of the methyl group, phenyl group, and methacryl group in the side chain was about 67:13:20.

(Synthesis Example 2 of Component (A)) A 1-liter flask equipped with a thermometer, a stirrer, and a reflux condenser was placed in a 1-liter flask.
γ-methacryloxypropyltrichlorosilane 128 g
(0.5 mol), 450 g of methyltrichlorosilane
(3.0 mol), 42 g of phenyltrichlorosilane
(0.2 mol), 80 g (5 mol) of water, and 0.01 g of P-methoxyphenol.
C. and kept for 60 minutes with stirring. Then gradually raise the temperature, keep at 90 ℃ for 15 minutes,
It was returned to room temperature and neutralized with sodium hydroxide. The reaction solution was filtered, washed with water, dehydrated with anhydrous sodium sulfate, and desolvated using a rotary evaporator. The viscosity was 600 cps at 25 ° C (A) -2.
The components were obtained. The number average molecular weight of the component (A) -2 determined by GPC was 4,800, and the weight average molecular weight was 11,000.
Met. The molar ratio of the side chain methyl group, phenyl group and methacryl group was about 88: 4: 8.

Example 1 20 parts of (A) -1 component, 27 parts of pentaerythritol tetraacrylate, 4 parts of N-vinyl-2-pyrrolidone, 6 parts of caprolactone-modified pentaerythritol hexaacrylate, 1.5 parts of benzoyl peroxide , Methylcellosolve 35 parts and butyl cellosolve 5 parts were mixed to obtain a curable composition. This solution was applied to a ceramic style (100 × 100 cm) whose surface was not glazed by sandblasting, and dried thickness (30 μm)
Was spray coated. After drying at 60 ° C. for 10 minutes to evaporate the solvent, the mixture was heated at 120 ° C. for 30 minutes to be completely cured. The appearance of the resulting ceramic style was colorful and had a glaze-like luster. Table 1 shows the physical properties of the cured film.

Example 2 42 parts of (A) -2 component, 28 parts of trimethylolpropane triacrylate, 10 parts of isobornyl acrylate, 12 parts of methyl isobutyl ketone
The parts were mixed to obtain a curable composition. 10mm thick, 3 length
The composition was flow-coated on the surface of a ceramic style having a color pattern having a width of 300 mm and a width of 300 mm and a slightly uneven pattern, to a film thickness of 20 g / m ² . After drying at 50 ° C for 30 minutes, low energy accelerator Electrocurtain CB2
Using 0d50 / 30 (Energy Science Industry Co., Ltd.), an electron beam of 0.6 Mrad was irradiated to completely cure. The resulting ceramic style had a glaze-like deep luster. Table 1 shows the physical properties of the cured film.

Example 3 The coating solution of Example 1 was glazed with a ceramic style (100 × 100 c).
m). First, the surface of the ceramic style was washed with water and then dried. A 1% methanol solution of a coupling agent (gamma aminopropyltriethoxysilane) was sprayed at a rate of 10 g / m ² and dried at 100 ° C. for 10 minutes. The coating solution was then dried to thickness (1
0 μm). 1 at 60 ° C
After drying for 0 minutes to evaporate the solvent, it was completely cured by heating at 120 ° C. for 30 minutes. The resulting ceramic style had a deep luster. Table 1 shows the physical properties of the cured film.

Example 4 A round rod of alumina sintered body having a radius of 10 mm and a length of 100 mm was impregnated with the composition of Example 2 (provided that 2 parts of benzoin methyl ether was added as a polymerization initiator). It was pulled up and coated to a thickness of 15 μm. While rotating the round bar, ultraviolet rays were irradiated from a high-pressure mercury lamp to complete the curing. The cured coating had a uniform, glaze-like luster. Table 1 shows the physical properties of the cured film.

[0045]

[Table 1]

[0046]

According to the method for coating a ceramic product of the present invention, a hardened film excellent in glaze, hardness, abrasion resistance, water resistance, and weather resistance can be applied to the surface of the ceramic product, and it can be used for construction and decoration. Can be widely used in fields including related.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takuhiko Motoyama 1-13-9 Shiba-Daimon, Minato-ku, Tokyo Inside Showa Denko KK (56) References JP-A-62-197423 (JP, A) JP-A-Hei JP-A-3-296515 (JP, A) JP-A-4-76059 (JP, A) JP-A-4-28722 (JP, A) JP-A-3-281616 (JP, A) JP-A-4-182371 (JP, A A) JP-A-4-50243 (JP, A) JP-A-4-33936 (JP, A) JP-A-4-178411 (JP, A) JP-A-4-31806 (JP, A) JP-A-4 JP-A-271306 (JP, A) JP-A-62-275132 (JP, A) JP-A-56-151731 (JP, A) JP-A-63-117024 (JP, A) JP-A-4-353521 (JP, A) JP-A-4-372614 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C04B 41/00-41/91 C09D 1/00 -201/10 C08F 290/00-290/14 C08F 299/00-299/08

Claims (3)

(57) [Claims] 1. A ceramic product characterized in that a composition comprising the following components (A), (B) and (C) is applied to the surface of a ceramic product and cured by heating or irradiation with high-energy radiation. Coating method. (A) a (meth) acryl-functional polyorganosilsesquioxane represented by the following general formula (I): (Wherein R ₁ and R ₂ represent an alkyl group having 1 to 3 carbon atoms, a phenyl group, an acryl represented by the following general formula (II) and / or
Or, it contains a methacryl functional group, and each of the m structural units is the same or different. R ₃ , R ₄ , R ₅ , and R ₆ are each composed of two or more selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group, and the hydrogen atom is always included. m indicates the degree of polymerization. The general formula (II) is Wherein R ₇ represents a hydrogen atom or a methyl group, R ₈ is a substituted or unsubstituted divalent hydrocarbon having 1 to 12 carbon atoms, R _7,
R ₈ may be different among m structural units. (B) a poly (meth) acrylate represented by the following general formula (III): (Wherein R ₉ is a hydrogen atom or a methyl group, and one R
₉ may all not be the same. R ₁₀ is a polyvalent hydrocarbon residue having a (meth) acrylic acid residue bonded to a different carbon atom, a polyvalent hydrocarbon residue having oxygen in the main chain, or a polyhydric alcohol and a polybasic acid Represents a residue of an ester, and 1 is an integer of 2 or more. (C) Polymerization initiator 2. A coating of a ceramic product, comprising applying a composition comprising the components (A) and (B) according to claim 1 to a surface of the ceramic product and irradiating the composition with an electron beam. Method. 3. The method for coating a ceramic product according to claim 1, wherein the surface of the ceramic product containing an inorganic pigment is polished and then coated on the surface.