JPS6314752B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating composition for improving surface conditions such as surface hardness, weather resistance, and chemical resistance of plastic, wood products, metal products, and the like. Plastic moldings such as polycarbonate, polymethyl methacrylate, polystyrene,
Polyvinyl chloride and other materials have excellent transparency, lightness, ease of processing, and impact resistance, but they have poor abrasion resistance and solvent resistance, and their surfaces are easily scratched and easily attacked by organic solvents. There is a drawback. Although methods of coating with various curable resins have been proposed as a method to improve these drawbacks, at present no fully satisfactory method has been obtained. Trialkoxysilanes such as methyltrialkoxysilane and phenyltrialkoxysilane. Combinations of this with tetraalkoxysilanes such as ethyl silicate and butyl silicate, or mixtures with other resin paints, etc., are known. A product with all good physical properties has not been obtained. Also, JP-A-51-42752,
Japanese Patent Publications No. 52-13818 and No. 53-15743 describe the use of epoxy group-containing alkoxysilanes with Lewis acids such as BF ₃ and BF ₃ etherate, or their complexes, HClHBr, Hl,
Prensted acids such as HNO ₃ , HClO ₄ , H ₃ PO ₄ ,
The use of metal salts of organic acids such as cobalt naphthenate and zinc naphthenate as curing catalysts has been disclosed, but these are not practical because the pot life of the paint is short or curing takes a long time. JP-A-49-117529 discloses a composition containing an epoxy group-containing alkoxysilane and a zinc borofluoride, tin borofluoride, or boron trifluoride amine complex, but these compositions are not applicable to the methods taught in the disclosure. In this case, sufficient hardness cannot be obtained and the hardness decreases after the hot water test. Japanese Patent Publication No. 52-39691 discloses a coating composition containing a hydrolyzate of colloidal silica and methyltrimethoxysilane as main components, and this cured coating film has sufficient hardness but is not flexible. Furthermore, it is extremely difficult to obtain good adhesion to plastic substrates. JP-A-53-111336 describes one or more compounds selected from compounds containing epoxy groups and/or silanol and/or siloxane groups, silica fine particles of 1 to 100 millimicrons, and aluminum chelate compounds. However, the hardness of these cured coatings is insufficient and the hardness decreases when immersed in boiling water. 39) and bisphenol type polycarbonate. Based on the above, the inventors of the present invention have repeatedly researched a coating composition that eliminates these drawbacks, has good abrasion resistance, hot water resistance, adhesion, weather resistance, etc., and has a long paint pot life. We have arrived at the present invention. The present invention is a coating composition containing the following (A), (B), (C) and (D). That is, the present invention provides (A) general formula (1)

[Formula] (In the formula, R ¹ is an organic group having an epoxy group, R ²
is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, ^R3 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a is 1 to 3, b is 0 to 2 and a+b≦3
It is. ) 100 parts by weight of one or more hydrolysates selected from silicon compounds having epoxy groups (calculated on solid content,

Calculate as [Formula]. ) (B) General formula (2) R ⁴ _c ―S _i ―(OR ⁵ ) _4-c (2) (In the formula, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, an amino group , a mercapto group, an organic group having fluorine or chlorine,
R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, C
is 0-3. ) 56 to 550 parts by weight of hydrolyzed organosilicon compound (calculated based on solid content)

Calculate as [Formula]. ] (C) 4 to 334 parts by weight of colloidal silica, [calculated based on solid content and calculated as SiO ₂ ] However, (B)
and (C) not exceeding 567 parts by weight, and (D) a coating composition containing a curing catalyst. Component (A) represented by general formula (1) used in the present invention
Examples of the silicon compound having an epoxy group include the following. Specific examples of silicon compounds having one glycidoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri(methoxyethoxy)silane, γ-glycidoxypropyltriacetoxysilane, δ-glycidoxybutyltri Methoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyl(methyl)dimethoxysilane, glycidoxymethyl(ethyl)dimethoxysilane, glycidoxymethyl(phenyl)dimethoxysilane, Glycidoxymethyl (vinyl) dimethoxysilane, glycidoxymethyl (dimethyl) methoxysilane, β-glycidoxyethyl (methyl) dimethoxysilane, β-
Glycidoxyethyl (ethyl) dimethoxysilane, β-glycidoxyethyl (dimethyl) methoxysilane, γ-glycidoxypropyl (methyl)
Dimethoxysilane, γ-glycidoxypropyl (ethyl) dimethoxysilane, γ-glycidoxypropyl (dimethyl) methoxysilane, δ-glycidoxybutyl (methyl) dimethoxysilane, δ
-Glycidoxybutyl(ethyl)dimethoxysilane, δ-glycidoxybutyl(dimethyl)methoxysilane, Specific examples of silicon compounds having two or three glycidoxy groups include bis(glycidoxymethyl)dimethoxysilane, Bis(glycidoxymethyl)diethoxysilane, Bis(glycidoxyethyl)dimethoxysilane, Bis(glycidoxypropyl)diethoxysilane, Tris(glycidoxymethyl)methoxysilane, Tris(glycidoxymethyl)ethoxy Silane, Tris(glycidoxyethyl)methoxysilane, Tris(glycidoxyethyl)ethoxysilane, Tris(glycidoxypropyl)methoxysilane, Tris(glycidoxypropyl)ethoxysilane, Specifications of silicon compounds with glycidyl groups Examples include glycidylmethyltrimethoxysilane, glycidylmethyltriethoxysilane, β-glycidylethyltrimethoxysilane, β-glycidylethyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, γ- Glycidylpropyltri(methoxyethoxy)silane, γ-glycidylpropyltriacetoxysilane. Specific examples of silicon compounds having an alicyclic epoxy group include 3,4-epoxycyclohexylmethyltrimethoxysilane, 3,4-epoxycyclohexylmethyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3, Examples include 4-epoxycyclohexylpropyltrimethoxysilane and 3,4-epoxycyclohexylbutyltrimethoxysilane. The above general formula (2) which is the component (B) used in the present invention
Examples of the organosilicon compound represented by the above include the following. That is, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, vinyltriacetoxy Silane, γ
-methacryloxypropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β
-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane,
N-β-(aminoethyl)-γ-aminopropyl(methyl)dimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. . These may be used alone or in combination of two or more. Component (C) colloidal silica is an acidic or basic colloidal solution in which ultrafine particles of silicic anhydride, preferably with a particle size of 1 to 100 millimicrons, are dispersed in a dispersion solvent such as water or alcohol. , manufactured by a well-known method and commercially available. By using component (B) and component (C) in combination with component (A), the weather resistance of the coating film is improved, and the appearance and hardness after a weather resistance test are improved. In the present invention, one or more hydrolysates selected from the silicon compounds having an epoxy group represented by the general formula (1) used as the component (A) and the general formula ( The hydrolyzate of one or more selected from the organosilicon compounds shown in 2) is one in which a part or all of the alkoxy group, alkoxyalkoxy group, or acyloxy group in the silicon compound is substituted with a hydroxyl group. and some naturally condensed substituted hydroxyl groups. These hydrolysates can be obtained by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid, as is known in the art. When the silicon compounds represented by the general formulas (1) and (2) are used without being hydrolyzed, the cured coating film becomes white and the abrasion resistance is insufficient. When using the silicon compounds represented by the general formulas (1) and (2) as a hydrolyzate, better results are often obtained by mixing them and simultaneously co-hydrolyzing them than by hydrolyzing them separately. In the present invention, the mixing amount of components (A), (B), and (C) is 100 parts by weight in total of component (A) (calculated based on solid content).

Calculate as [Formula]. ), a total of 56 to 550 parts by weight of component (B) (calculated on solid content,

Calculate as [Formula]. ] and component (C) 4 to 334 parts by weight [calculated on solid content]
Calculated as _SiO2 . ] and the total of component (B) and component (C) is 60 to 567 parts by weight. More preferably, based on 100 parts by weight of component (A),
(B) is 105 to 430 parts by weight, component (C) is 16 to 200 parts by weight, and the total of component (B) and component (C) is 121 to 473 parts by weight. If the total of component (B) and component (C) is less than 60 parts by weight, the effect of using them together will be small, and if it exceeds 567 parts by weight, the adhesion to the substrate will be extremely poor and cracks may occur. It becomes easier. Next, the curing catalyst which is component (D) of the present invention will be explained in detail. That is, the following catalysts are well known as curing catalysts for silicon compounds having epoxy groups. Namely, perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its complex with an electron donor. SnCl ₄ , ZnCl ₃ , FeCl ₃ , AlCl ₃ , SbCl ₅ , TiCl ₄
Lewis acids such as and their complexes. sodium acetate,
Organic acid metal salts such as zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate. Boufurated metal salts such as zinc borofluoride and tin borofluoride. Boric acid organic esters such as ethyl borate and methyl borate. Alkali such as sodium hydroxide and potassium hydroxide. Titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium. Metal acetylacetonates such as chromium acetylacetonate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate. Examples include amines such as n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, biguanide, and imidazole.
However, since perchloric acid is an overt catalyst, the pot life of the coating liquid is extremely short. Further, the coloring of the cured coating film is also significant. Hydrochloric acid, para-toluenesulfonic acid, 3
Brønsted acid or its complex with an electron donor, such as a boron fluoride monoethylamine complex. Lewis acids such as SnCl ₄ and ZnCl ₃ . Metal salts of organic acids such as zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate. Alkali such as sodium hydroxide and potassium hydroxide. Titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium. Chromium acetylacetonate. Amines such as n-butylamine, di-n-butylamine, tri-n-butylamine, and imidazole require heating at high temperatures for a long period of time in order to cause sufficient curing, which is not practical. Coating films using zinc borofutide, tin borofutide, etc.
It has insufficient water resistance and hardness decreases when immersed in hot water, and aluminum acetylacetonate has insufficient hardness and adhesion to substrates. Curing catalysts that have a long pot life for coating liquids, cure sufficiently in a short time even at relatively low temperatures, and have good adhesion are latent catalysts such as ammonium perchlorate, ammonium chloride, ammonium sulfate, ammonium nitrate, and sodium acetate. These are salts of inorganic acids or carboxylic acids, highly fluorinated aliphatic sulfonates, and highly fluorinated aliphatic sulfonylates. The choice of preferred catalyst will depend on the particular composition for which the catalyst is to be used and the application for which the composition is to be used, but the most preferred catalyst is ammonium perchlorate. The amount of the curing catalyst added is 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on the solid content of the composition [component (A) + component (B) + component (C)].
It is 5 parts by weight. Examples of solvents that may be included in the coating composition include alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, and one or two of these. It can be used as a mixed solvent of the above. Especially methanol, ethanol,
Lower alcohols such as propanol, isopropanol, butanol. Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve.
Lower alkyl carboxylic acids such as formic acid, acetic acid, and propionic acid. Aromatic compounds such as toluene and xylene. It is preferable to use esters such as ethyl acetate and butyl acetate alone or as a mixed solvent. Furthermore, if necessary, a flow control agent made of a block copolymer of alkylene oxide and dimethylsiloxane, such as NUC Silicone Y-7006 (trade name) manufactured by Nippon Unicar Co., Ltd., can be added to obtain a smooth coating film. The amount of these flow control agents added is sufficient in a small amount, and is 0.01 to 55 parts by weight, more preferably 0.03 to 3 parts by weight, based on the entire coating composition. Further, small amounts of antioxidants, ultraviolet absorbers, etc. can also be added. After coating with the composition of the present invention by a commonly used coating method such as dipping, spraying, roller coating, or flow coating, By baking and curing for 20 minutes to 5 hours, a coating film with good abrasion resistance, hot water resistance, adhesion and weather resistance can be obtained. The preferred thickness of this coating is 1 to 30 microns.
More preferably, it is 3 to 15 microns. If it is less than 1 micron, the wear resistance will not be sufficient;
When the thickness exceeds microns, cracks are more likely to occur. The compositions of the invention can be applied to plastic substrates such as polycarbonate, polymethyl methacrylate, polystyrene and polyvinyl chloride. If adhesion is a particular problem, a primer treatment can provide a coating film with sufficiently effective adhesion. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited by these Examples. Note that parts and % in the examples indicate parts by weight and % by weight, respectively. The performance of the coating film was evaluated using the following method. That is, abrasion resistance: The resistance to scratching was examined by rubbing with #0000 steel wool and judged as follows. A: No scratches even if rubbed strongly. B: Slight damage occurs when rubbed strongly. C: Even weak friction causes scratches. Adhesion: In the so-called cross-cut tape test, 11 parallel lines were placed vertically and horizontally at 1 mm intervals on the surface of the coating film, and 100 squares were cross-cut.
After adhering a cellophane adhesive tape thereon, the tape was peeled off, and the number of squares that did not peel off among 100 squares was indicated. Hot water resistance: The state of the coating film was examined after being immersed in boiling water for 1 hour. Heat resistance: The state of the coating film was examined after being stored in a hot air drying oven at 120°C for 100 hours. Chemical resistance: The state of the coating film was examined after being immersed in the following chemicals at room temperature for 100 hours. 3% sulfuric acid, 1% sodium hydroxide, 95% ethanol, acetone, ethyl acetate, carbon tetrachloride,
Toluene, n-heptane, 10% saline. Example 1 γ-glycidoxypropyltrimethoxysilane
80 parts, 144 parts of methyltrimethoxysilane, colloidal silica (Snowtex manufactured by Nissan Chemical Industries, Ltd.)
C, solid content 20%) 71 parts and 170 parts of 0.1N hydrochloric acid aqueous solution
The mixture was mixed and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 12.2%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 15.3
Colloidal silica calculated as % and _SiO2
It contained 3.1%. The ternary cohydrolyzate solvent obtained in this way
A paint was prepared by adding 73 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to 410 parts. Pre-washed diethylene glycol bisallyl carbonate polymer (trade name
CR-39) Apply the above paint to a flat plate and dry it in a hot air drying oven.
It was dried and cured by heating at 130°C for 60 minutes. The coating film thus obtained was transparent, had abrasion resistance of A, adhesion of 100/100, good hot water resistance and heat resistance, and had abrasion resistance and adhesion of A and 100, respectively, after the hot water resistance test. /100, which was good. Furthermore, the appearance, hardness and adhesion after 500 hours of Sunshine Weathermeter test were extremely good. Example 2 γ-glycidoxypropyltrimethoxysilane
60 parts methyltrimethoxysilane 173 parts Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex)
C, solid content 20%) 71 parts and 01N hydrochloric acid aqueous solution 190
The two parts were mixed and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

8.6% of γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula], 17.3% of methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5
and colloidal silica 2.9 calculated as _SiO2
It contained %. To 436 parts of the ternary cohydrolyzate solution thus obtained were added 47 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to prepare a paint. pre-washed
Apply the above paint to a CR-39 flat plate and dry it in a hot air drying oven for 130 minutes.
It was cured by heating and drying at -60 minutes. The coating film obtained in this way was transparent, with no abnormalities observed in its appearance after a chemical resistance test, and a good appearance after a 500-hour Sunshine Weather Meter test, with good hardness and adhesion. Each was A, 100/100, which was extremely good. Example 3 γ-glycidoxypropyltrimethoxysilane
40 parts, 202 parts of methyltrimethoxysilane, 71 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
211 parts were mixed and refluxed at 80-85°C for 1 hour to perform hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 5.4%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 19.0%
and colloidal silica 2.7 calculated as _SiO2
It contained %. To 463 parts of the ternary cohydrolyzate solution thus obtained were added 20 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to prepare a paint. The above paint was applied to a CR-39 flat plate that had been cleaned in advance, and cured by heating and drying in a hot air drying oven at 120°C for 60 minutes. The coating film obtained in this way had a good appearance after 500 hours of sunshine weather meter testing, and its hardness and adhesion were A and 100/100, respectively.
It was extremely good. Example 4 γ-glycidoxypropyltrimethoxysilane
60 parts, 144 parts of methyltrimethoxysilane, 142 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
98 parts were mixed and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 9.6%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 16.0%
and colloidal silica calculated as SiO ₂ 6.4
It contained %. To 417 parts of the ternary cohydrolyzate solution thus obtained were added 66 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to prepare a paint. pre-washed
Apply the above paint to a CR-39 flat plate and dry it in a hot air drying oven for 120 minutes.
It was cured by heating and drying at -60 minutes. The coating film thus obtained had a good appearance after 500 hours of Sunshine Weather Meter testing, and its hardness and adhesion were both A and 100/100, which were extremely good. Example 5 77 parts of isopropyl alcohol, 60 parts of γ-glycidoxypropyltrimethoxysilane, 115 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20)
%) 213 parts and 5 parts of 1N hydrochloric acid were added and heated to 80-85℃.
Hydrolysis was carried out by refluxing for 2 hours. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 9.1% calculated as [Formula], methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5
12.1% and 9.1% colloidal silica calculated as _SiO2 . 3 obtained in this way
Ethyl cellosolve 66 to 417 parts of original cohydrolyzate solution
1.3 parts of ammonium perchlorate and a small amount of flow control agent were added to prepare a paint. The above paint was applied to a CR-39 flat plate that had been cleaned in advance, and cured by heating and drying in a hot air drying oven at 120°C for 60 minutes. The coating film obtained in this way has good weather resistance, has a good appearance after 500 hours of sunshine weather meter testing, and has good hardness and adhesion of A and 100/100, respectively. Ta. Example 6 γ-glycidoxypropyltrimethoxysilane
39 parts, 3,3,3-trifluoropropyltrimethoxysilane 2.9 parts, methyltrimethoxysilane
110 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd.)
Snowtex-C, solid content 20%) 75 parts and 0.1
100 parts of a normal aqueous hydrochloric acid solution was added and refluxed at 80 to 85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 8.5% calculated as [Formula], 3,3,3-trifluoropropyltrimethoxysilane hydrolyzate 0.6 calculated as CF ₃ C ₂ H ₄ SiO _1.5 %, 16.7% methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 and 4.6% colloidal silica calculated as SiO ₂ . Ethyl cellosolve was added to 310 parts of the quaternary cohydrolyzate solution obtained in this manner.
49 parts of ammonium perchlorate, 0.9 parts of ammonium perchlorate, and a small amount of flow control agent were added to prepare a paint. The above paint was applied to a CR-39 flat plate that had been cleaned in advance, and cured by heating and drying in a hot air drying oven at 120°C for 60 minutes.
The coating film obtained in this way is transparent and has good weather resistance, and it was tested in the Sunshine Weather Meter test.
The appearance after 500 hours was good, and the hardness and adhesion were both A and 100/100. Example 7 γ-glycidoxypropyltrimethoxysilane
150 parts, 72 parts of methyltrimethoxysilane, 179 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
52 parts were added and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 23.5%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 7.8
Colloidal silica calculated as % and _SiO2
It contained 7.9%. Add 164 parts of ethyl cellosolve to 319 parts of the ternary cohydrolyzate solution thus obtained.
1.3 parts of ammonium perchlorate and a small amount of flow control agent were added to make a paint. The above coating material was applied to a CR-39 flat plate that had been cleaned in advance, and cured by heating and drying in a hot air drying oven at 120°C for 60 minutes. The coating film thus obtained was transparent, had abrasion resistance of A, adhesion of 100/100, and good hot water and heat resistance.
Furthermore, the abrasion resistance and adhesion after the hot water resistance test were good, being A and 100/100, respectively. Further, no abnormality was observed in the appearance after the chemical resistance test. Example 8 γ-glycidoxypropyltrimethoxysilane
60 parts, methyltrimethoxysilane 58 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex)
C, solid content 20%) 355 parts and 0.1N hydrochloric acid aqueous solution 21
1 part was added and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 8.6% calculated as [Formula], methyltrimethoxysilane hydrolyzate 5.7% calculated as CH ₃ SiO _1.5 and colloidal silica 14.4% calculated as SiO ₂
It contained. To 434 parts of the ternary cohydrolyzate solution thus obtained were added 49 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to prepare a paint. pre-washed
Apply the above paint to a CR-39 flat plate and dry it in a hot air drying oven.
It was cured by heating and drying at 130°C for 60 minutes. The coating film thus obtained was transparent and had good abrasion resistance of A and adhesion of 100/100, or good abrasion resistance and adhesion of A and 100/100 after the hot water resistance test. . Example 9 γ-glycidoxypropyltrimethoxysilane
80 parts, methyltrimethoxysilane 86 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex)
C, 213 parts of solid content 20%), 90 parts of isopropyl alcohol and 35 parts of 0.1N hydrochloric acid aqueous solution were added to 80~
Hydrolysis was carried out by refluxing at 85°C for 2 hours. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 11.3%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 8.5%
and colloidal silica calculated as SiO ₂ 8.5
It contained %. To 417 parts of the ternary cohydrolyzate solution thus obtained were added 66 parts of ethyl cellosolve, 1.0 part of ammonium perchlorate, and a small amount of a flow control agent to prepare a paint. The above paint was applied to a pre-cleaned CR-39 flat plate and dried in a hot air drying oven.
It was cured by heating at 130°C for 60 minutes. The coating film thus obtained was transparent and had good abrasion resistance and adhesion after a hot water resistance test of A and 100/100, respectively. Example 10 The paint prepared in Example 2 was allowed to stand at room temperature for one month, and then applied to a CR-39 plate that had been cleaned in advance in the same manner as in Example 2, and cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The various properties of the coating film thus obtained were similar to those of Example 2 and were good. Comparative example 1 γ-glycidoxypropyltrimethoxysilane
10 parts of methyltrimethoxysilane, 144 parts of methyltrimethoxysilane, 320 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%) and 6 parts of 0.1N hydrochloric acid aqueous solution were mixed and heated at 80 to 85°C for 2 hours. Hydrolysis was carried out under reflux. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 1.5% calculated as [Formula], methyltrimethoxysilane hydrolyzate 14.8% calculated as CH ₃ SiO _1.5 and colloidal silica 13.3% calculated as SiO ₂
It contained. To 400 parts of the ternary cohydrolyzate solution obtained in this way, 82 parts of ethyl cellosolve, a small amount of flow control agent, and 1.3 parts of ammonium perchlorate or 0.8 parts of sodium acetate as a curing catalyst were added, and two types of paints were prepared. Prepared. Apply each of the above paints to a pre-cleaned CR-39 flat plate,
It was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes.
All of the coating films thus obtained had good hardness, but had poor adhesion and peeled off after 500 hours of Sunshine Weathermeter test.

Claims (1)

[Claims] 1 The following (A), (B), (C) and (D) (A) General formula (1) [Formula] (In the formula, R ¹ is an organic group having an epoxy group, R ²
is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, ^R3 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a is 1 to 3, b is 0 to 2 and a+b≦3
It is. ) 100 parts by weight of one or more hydrolysates selected from silicon compounds having epoxy groups (calculated based on solid content and as [formula]) (B) General formula (2) ) R ⁴ _c ―S _i ―(OR ⁵ ) _4-c (2) (In the formula, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a mercapto group, fluorine, or chlorine. an organic group having
R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, C
is 0-3. ) 56 to 550 parts by weight of the hydrolyzate of the organosilicon compound shown in [Formula] based on solid content. ] (C) 4 to 334 parts by weight of colloidal silica, [calculated based on solid content and calculated as SiO ₂ ] However, (B)
and (C) the sum of which does not exceed 567 parts by weight, and (D) a curing catalyst. 2 The content of the hydrolyzate (B) is 105 to 430 parts by weight, and the content of the colloidal silica (C) is 16 to 430 parts by weight.
200 parts by weight, and the total of (B) and (C) does not exceed 473 parts by weight. 3. Claims in which the curing catalyst is a curing catalyst selected from perchlorates, hydrochlorides, sulfates, nitrates, carboxylates, highly fluorinated aliphatic sulfonates, and highly fluorinated aliphatic sulfonylates. Coating composition according to item 1 or 2. 4. The coating composition according to claim 1 or 2, wherein the curing catalyst is ammonium perchlorate, ammonium chloride, ammonium sulfate, or ammonium nitrate.