JPH01172473A - Coating composition - Google Patents

Abstract

PURPOSE:To make it possible to give a cured film having excellent nonglaringness, weather resistance, heat resistance and abrasion resistance, by mixing two specified organoalkoxysilane hydrolyzates or condensates thereof and a polymethylsilsesquioxane powder. CONSTITUTION:This coating composition comprises a hydrolyzate of an organoalkoxysilane of formula I (wherein R<1> is a monovalent group selected from among a 1-3C alkyl, vinyl, phenyl, gamma-chloropropyl, gamma-methacryloxypropyl, gamma-glycidyloxypropyl, 3,4-epoxycyclohexylethyl and gamma-mercaptopropyl, R<2> is a 1-3C alkyl, and m is 0 or 1) and/or its condensate, a hydrolyzate of an organoalkoxysilane of formula II (wherein R<1> and R<2> are as defined above) and/or its condensate, and a polymethylsilsesquioxane powder of a mean particle diameter of 0.1-100mu. When this composition is applied to the surface of a substrate such as plastic, wood or metal and cured by heating, it can form a cured film having excellent surface hardness, chemical resistance and glare- inhibiting effect.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a coating composition, and more particularly to a coating composition that is applied to the surface of various substrates made of plastic, wood, metal, etc. and cured by heating. The present invention relates to a coating composition in which the film has excellent surface hardness and chemical resistance, and exhibits an excellent anti-glare effect.

[Technical background of the invention and its problems] In recent years, molded bodies made of transparent plastic have been used in place of transparent glass for glasses and other products due to their light weight, easy moldability, easy coloring, and excellent impact resistance. optical lenses, building window glass,
It is widely used in window glass of transportation vehicles such as trains and automobiles.

Among such transparent plastic materials, polycarbonate resin is one of the most widely used materials.

Molded objects made of this material have excellent impact resistance, can withstand high heat deflection temperatures, and have excellent dimensional stability, workability, and self-extinguishing properties, but due to their low surface hardness, they may be prone to abrasions and scratches. The problem is that the transparency, which is most important for lenses and glass, is easily lost.

In addition, other plastic materials such as polymethyl methacrylate, polystyrene, and polyvinyl chloride are used for various purposes due to their excellent transparency, lightness, processability, and impact resistance. There is. However, molded bodies made of these materials also have problems in that they have low abrasion resistance, chemical resistance, and solvent resistance, and their surfaces are easily scratched.

In order to solve these problems, various attempts have been made to improve surface properties, particularly surface hardness and solvent resistance. For example, the surface of polycarbonate resin is protected by applying a coating agent to the surface. These coatings not only provide scratch resistance and chemical resistance to transparent plastics, but also provide weather resistance, antistatic properties, etc.
It increases light transmittance and improves transparency. As surface hardening coating compositions used for this purpose, melamine resins, curable acrylic resins, polyester resins, polyurethane resins, silicone resins, and the like have been studied. In particular, coating materials using silicone resin are being studied in various ways because they have excellent weather resistance. For example, JP-A-48-26822 discloses a composition comprising a hydrolyzate of 4-alkoxy silicon, a hydrolyzed condensate of trialkoxysilane, and a curing agent.
No. 32 discloses a composition comprising a hydrolyzate of trialkoxysilane and an alkali metal salt. Also,
JP-A-51-2736, JP-A-53-13073
No. 2, JP-A-54-87736, and JP-A-55-94971 disclose the use of silica such as colloidal silica or silica gel and hydrolyzable organosilane for the purpose of improving wear resistance and film hardness. Coating compositions are disclosed in which a compound is dissolved or dispersed in a hydrolysis medium such as alcohol or water.

All of these coating compositions can form a transparent film on the surface of a substrate, but while the resulting film surface has excellent light transmittance, it has a specular gloss and can be difficult to see depending on the viewing angle. Since the coating composition is reflected, for example, when these coating compositions are applied to a cathode ray tube display or a display panel, it becomes difficult to read characters and figures. Also,
When working while looking at such a cathode ray tube display, display panel, etc. for a long time, problems such as a decrease in the visual acuity of the worker and an increase in fatigue level arise. For these reasons, there is an increasing demand for a composition that can form a matte type film. Applications of this matte type coating composition include, for example, anti-reflection filters for cathode ray tube displays, light transmitting plates in front of display panels, etc. that require anti-glare effects; light bulbs or fluorescent lights for indoor/outdoor lighting equipment. Items that require a high-class appearance such as light protection boards, advertising lights, and billboards; Items that require a concealing or shielding effect such as bathroom window glass; and other items or points that require an anti-reflection effect. It is possible to change the light source into a surface light source.

In order to obtain a so-called non-glare type film, processing methods such as sandblasting, surface scratching, and adding inorganic fine powder such as silica to the coating composition have been known. It is being Also 1
As a processing method for obtaining an antireflection film, a method of vacuum vapor deposition of a metal oxide or the like is known. However, among these methods, the sandblasting method and the surface scratching method destroy the film formed on the surface of the plastic etc., so they lose the purpose of protecting the substrate.
The method of blending inorganic fine powder such as silica into the coating composition requires complicated work to uniformly disperse the fine powder, and the powder settles after dispersion, which makes redispersion difficult. It is not easy to do so, and furthermore, there are problems such as a decrease in the transparency of the film. Furthermore, the method of vacuum evaporating metal oxides requires a large amount of equipment and is not yet suitable for general use, and metal oxide films that have sufficient adhesion to plastic substrates, etc. The problem is that it is difficult to form.

[Object of the Invention] The present invention solves the above-mentioned problems, and provides a coating composition that provides an excellent anti-glare effect to the resulting cured film without reducing its transparency, and is easy to redisperse. The purpose is to provide something.

[Structure of the Invention] In order to achieve the above-mentioned object, the present inventors have conducted intensive research to obtain a song glare film, and as a result, by using finely powdered polymethylsilsesquioxane as a constituent component, the present inventors have found that by using finely powdered polymethyl silsesquioxane as a constituent component, various substrates The present invention was completed based on the discovery that an excellent coating composition can be obtained for surface protection.

The present invention is based on the formula (A)-maximum%% () (wherein R1 is an alkyl group having 1 to 3 carbon atoms, a vinyl group,
Phenyl group, γ-chloropropyl group, γ-methacryloxypropyl group, γ-glycidyloxypropyl group, 3
．． Represents a monovalent group selected from the group consisting of 4-epoxycyclohexylethyl group and γ-mercaptopropyl group; R2 represents an alkyl group having 1 to 3 carbon atoms; m represents 0 or 1) Hydrolyzate of organoalkoxysilane and/or condensate thereof; and (B)-maximum % formula % (in the formula, the definitions of R1 and R2 are the same as in formula (I)) a hydrolyzate and/or a condensate thereof; and (C) a polymethylsilsesquioxane powder having an average particle size of 0.1 to 100;
The present invention relates to a coating composition comprising components A), (B), and (C), and further contains colloidal silica as component CD).

What is the hydrolyzate of flukoxysilane and/or its condensate as component (A) used in the present invention?

It is a hydrolyzate of the organoalkoxysilane represented by the above formula (I), a condensate thereof, or a mixture thereof. As the organoalkoxysilane used in this case, for example, CH3S i (OCH3) s
, CH3Si (OC2Is) s, CH3Si
(OC387)3. C2R5Si (OCH3
)3, CH2=CH3i (OCH3)s, CH2
=CH5i (OC2H5)3, C6Hs S i (
OCH3) s, CI CH2CH2CH2S i (
OCH3)! , CH2=C(CH3) -Coo-(
CH2)s -3i (OCH3)s.

CH2-CH-CH2-0-(CH2)s-5i
(OCH3)s.

\ 1 R5CH2CH2CH2S i (OCH3) 3, S
i(OCH3)*.

Examples include Si(OC2H5)4.5i(OC3H7)4, and one or more selected from the group consisting of these may be used. Among these, CH3S i (OCHx )s or CH3S i
It is preferable to use (OC2R5)3 from the viewpoint of reducing the product price and the hardness and wear resistance of the film formed, but of course there is no problem in mixing other organoalkoxysilanes.

Examples of organohydroxysilanes and partial condensates thereof as component (A) of the present invention obtained by hydrolyzing the above-mentioned organoalkoxysilanes include CHx Si (OH) s , C2R5S 1 (
OH) s, CH2=CH3i (OH) s, C
s Hs S i (OH) s, CJICH2CH2
CH2S i (OH) s .

CH2=C(CH3) COO-(CH2)s Si
(OH) 3°. αKari CH2CH2S i (OH)
3. Organohydroxysilanes represented by R3CH2CH2CH2S i (OH) s and the like and partial condensates thereof can be mentioned, and one or more kinds selected from the group consisting of these can be used.

The organoalkoxysilane hydrolyzate and/or its condensate as component (B) used in the present invention is represented by the above formula (n).

The definitions of R1 and R2 in formula (II) are as above. As the organoalkoxysilane of component (B), for example, (CH3) 2 Si (
OCHa ) 2, (CHx)2si (OCzHs)
z.

(CH3)2 Si (OC3H?)2. CH3Si
(C2H5) (OCH3)2゜CH2=CH5i (C
H3) C0CHs ) 2, CH2=CH3i (
CH3) (OC2H%) 2, Cs Hs S
i CCHs ) (OCHx ) 2 .

CI CH2C) (2CH2S i (CH3) (
OCH3) 2, CH2-C(CH3)-Coo-(C
H2)3-5t (CH3)(OCH3)2, CH2-
CH-CH2-0-(CH2)3-5i (CH3)
(OCI (3) 2, \ 1. [Existence] -CH2CH2S i (CH3) (OCH
3) 2,) ISCH2CH2CH25E CCHs
) C0CHs ) s.

etc., and one or more types selected from the group consisting of these can be used.

Among these, (CH3)2 Si (OC
H3)2 or (CH3)2 Si (OC2H5)2
The use of is preferred from the viewpoint of reducing the product price and the hardness and abrasion resistance of the film formed, and is particularly effective in preventing the occurrence of cracks in the film.

Of course, there is no problem in mixing other organoalkoxysilanes.

Examples of organohydroxysilanes and partial condensates thereof as component (B) of the present invention obtained by hydrolyzing the above-mentioned organoalkoxysilanes.

(CH3)2Si(OH)2, C2H5(CH
3) Si(OH)2.

CH2=CH(CH3)Si(OH)2,C
m Hs Si (CH3) (OH) 2, CI C
H2CH2CH2S i (CH3) (OH) 2,
CH2=C(CH3) -Coo -(CH2) s
Si (CH3) (OH) 2, CH2-CH-CH
2-0-(CH2), -3i (CH,)(OH)2,
\1. αxcu2c)I2S i (CH3) (OH)
2゜H5CH2CH2CH2Si (CH,)(OH)
Organohydroxysilanes represented by 2 and the like and partial condensates thereof can be mentioned, and one or more types selected from the group consisting of these can be used.

The amount of component (B) can be changed as appropriate depending on the properties required of the film obtained by curing the coating composition, but since it gives the cured film appropriate hardness, (
It is preferably 30 parts by weight or less per 100 parts by weight of component A), and from the viewpoint of the balance between film hardness and crack prevention, it is 1 to 1.
Parts by weight of O are more preferred.

The polymethylsilsesquioxane powder, component (C) of the present invention, is used as a filler, and by adding it, a certain level of matting is achieved regardless of the coating method or coating thickness, and , it is possible to obtain a cured film that maintains appropriate transparency. Furthermore, it provides good lubricity to the composition, and even if the composition is kept for a long time and the powder settles, it can be easily redispersed. this(
Component C) has a lower specific gravity than other silica-based fillers such as crushed quartz and diatomaceous earth powders that have similar average particle diameters, so even if it is filled in a large amount, the specific gravity of the composition will not increase very much. Furthermore, a composition with a small increase in viscosity and excellent fluidity can be obtained.

The polymethylsilsesquioxane powder used in the present invention is disclosed in Japanese Unexamined Patent Publication No. 13813/1983 and Japanese Patent Application No. 1983/1983.
No. 247345, and the powder is made by hydrolyzing methyltrialkoxysilane or a condensate obtained by hydrolyzing it and condensing it in an aqueous solution of ammonia or amines, and then condensing it. The resulting product is almost free of impurities such as chlorine atoms, alkaline earth metals, and alkali metals, and is also spherical and has excellent free-flowing properties. preferable.

The particle size of polymethylsilsesquioxane powder is 0.1N
100. , preferably 0.1 to 20 μm, 0.1
In the case of terminal vortices, it is difficult to manufacture, difficult to handle, and difficult to disperse uniformly, and if it exceeds 100, the toughness and flexibility of the film will be lost, making it difficult to achieve the purpose of the present invention. Not enough for.

The amount of component (C) in the composition of the present invention is not particularly limited, but the total amount of components (A) and (B) is 1
The amount is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight. If the amount is too small, the matting effect and anti-glare effect of the cured film will be small, and if it is too large, it will be difficult to blend and the transparency of the film will be impaired.

By including the above components (A), (B) and (C) as essential components, a cured film having an excellent anti-glare effect can be formed, and a coating composition having good lubricity can be obtained. However, by blending colloidal silica as component (D) in addition to components (A), (B), and (C), the formed cured film has even better hardness and wear resistance. It is possible to obtain a coating composition having properties. The colloidal silica used here preferably has an average particle diameter of 5 to 150IiII, more preferably 5 to 30μ. Also,
This colloidal silica is used as an aqueous dispersion, but for the purpose of increasing wear resistance, the pH of the dispersion is 8.
The content of silica in the dispersion is preferably 15 to 40% by weight.

The blending amount of component (D) is preferably 5 to 200 parts by weight, including solid content, based on 100 parts by weight of the total amount of components (A) and (B). If the blending amount is less than 5 parts by weight, The hardness of the formed film is low, and if the amount exceeds 200 parts by weight, silica aggregates or precipitates in the composition, making it impossible to obtain a stable dispersion.

The coating composition of the present invention can be produced, for example, by the following method, but of course it is not limited to this method.

First, the organoalkoxysilanes (A) and (B) are either hydrolyzed in an aqueous solution of a hydrophilic organic solvent such as methanol or ethanol, or in the case of a composition containing colloidal silica as an essential component, the organoalkoxysilane is Organohydroxysilanes are obtained by hydrolyzing alkoxysilanes in an aqueous dispersion of colloidal silica.

Hydrolysis is carried out by maintaining the liquid temperature at 10 to 70°C and under normal pressure.
It is preferably carried out with stirring for ~30 hours, and more preferably carried out with stirring at a liquid temperature of 25 to 35°C for 12 to 24 hours.

Furthermore, in any case, a hydrolysis catalyst such as various inorganic acids, organic acids, or aluminum chelate can be used as required during the hydrolysis. Such hydrolysis catalysts include, for example, hydrochloric acid, formic acid, acetic acid,
Acids such as glacial acetic acid, chloroacetic acid, propionic acid, oxalic acid, malonic acid, dimethylmalonic acid, maleic acid, glycolic acid, glutaric acid, citric acid, benzoic acid, and toluenesulfonic acid, and aluminum acetylacetonate and aluminum acetylacetonate. Examples include aluminum chelates such as acetate bisacetylacetonate, aluminum bisethylacetoacetate acetylacetonate, aluminum lamb di-n-butoxymonoethyl acetoacetate, and aluminum diisopropoxide monomethylacetoacetonate. Among these, it is particularly preferable to use acetic acid or glacial acetic acid.

The amount of the hydrolysis catalyst used is preferably 0.05 to 15 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). be.

Then such components (A) and (B) or (A
), (B) and (D) components is blended with polymethylsilsesquioxane powder (C). It is preferable to dissolve it in a solvent or to use a hydrophilic organic solvent together when blending component (C).

This adjusts the solid content in the final composition to a desired ratio, improves the workability of coating onto the substrate, improves the dispersion stability of the composition, and facilitates the blending of component (C). It's for a reason. Examples of the wood-loving organic solvent used in this case include lower aliphatic alcohols such as methanol, ethanol, propatool, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol. Examples include ethylene glycol acetate derivatives such as monoethyl ether and diacetone alcohol, and one or more selected from the group consisting of these can be used.

Among these, it is particularly preferable to use at least one selected from the group consisting of ethanol, impropatol, n-butanol, imbutanol, acetic ester of ethylene glycol monoethyl ether, and diacetone alcohol. When blending component (C), a predetermined amount thereof is added and then stirred using a high-speed stirrer or a homomixer until the mixture becomes uniform, thereby obtaining the coating composition of the present invention.

The coating composition of the present invention thus obtained may further contain a leveling agent, a thickener, a pigment, a dye,
There is no problem in using additives such as ultraviolet absorbers and antioxidants, or modifiers.

In order to apply the coating composition of the present invention onto a substrate and obtain a cured film, it is possible to employ, for example, the following method.

That is, the composition of the present invention is coated onto a substrate by a commonly known method such as flow coating, spray coating, or dip coating, preferably in a coating of about 0.5 to 20, more preferably about 2 to 2.
Apply to a thickness of 10-.

Then, by heating at about 120°C for 60 minutes,
A film having good adhesion to the base material can be obtained.

Note that if it is desired to cure under milder conditions, a silanol condensation catalyst is added to the composition. Such silanol condensation catalysts include, for example, alkali metal carboxylates such as sodium acetate and potassium formate; amine carboxylates such as dimethylamine acetate, ethanolamine acetate, and dimethylaniline formate; transition metal salts of carboxylic acids such as tin naphthenate; amines such as triethanolamine and pyridine; hydroxides of alkali metals such as sodium hydroxide and ammonium hydroxide; Examples include amine-based silane coupling agents such as ethoxysilane and γ-ethylenediaminepropyltrimethoxysilane; and aluminum chelate compounds; one or more selected from the group consisting of these may be used. Can be done. The amount of these condensation catalysts can be selected depending on the curing conditions, but (
0.05 to 0.0% based on the total amount of components A) and (B).
By incorporating the above-mentioned condensation catalyst, preferably 5% by weight, the composition of the present invention has a concentration of about 7% by weight on the substrate.
It is cured in a relatively short time at a temperature of 5 to 180°C, and an excellent non-glare film can be obtained.

Substrate materials to which the coating composition of the present invention can be applied include, for example, transparent or opaque plastics,
Examples include metal, wood, leather, glass and ceramics. Among these, examples of plastic materials include acrylic resin, polyester resin, polyimide resin, polyamide resin, acrylonitrile-butadiene copolymer resin, polyvinyl chloride resin, polyethylene resin, polycarbonate resin, etc. Examples of the material include aluminum, sputtered chromium alloy, and the like. At this time, if the adhesion between the composition of the present invention and the substrate becomes a problem, it is possible to improve the adhesion by subjecting the surface of the substrate to a primer treatment in advance. Therefore, the compositions of the present invention can be applied to the surface of almost any solid material. The compositions of the present invention are useful as coatings for polycarbonate resins and acrylic resins, among others.

[Effects of the Invention] By using the coating composition of the present invention, a non-glare type film can be formed on the surface of various base materials such as plastics, and the reduction in transparency due to this film is extremely small. The polymethylsilsesquioxane in the composition of the present invention can easily redisperse the settled powder even if the composition is stored for a long time. By using the composition of the present invention, excellent non-glare properties, An antireflection coating having weather resistance, heat resistance, and abrasion resistance can be obtained.

[Examples of the Invention] The present invention will be described in more detail below with reference to Examples. In addition, all "parts" below represent "parts by weight."

First, polymethylsilsesquioxane was synthesized by the method shown below.

Synthesis Example A 4-tubular flask equipped with a thermometer, a reflux device, and a stirrer was charged with aqueous ammonia in the amount and concentration shown in Table 1.
Into this ammonia aqueous solution, methyltrimethoxysilane shown in Table 1 was gradually added dropwise over 60 to 120 minutes with stirring. The mixture was heated with a mantle heater to reflux at 84°C, and stirring was continued at this temperature for about 1 hour. After cooling, the product precipitated in the flask is collected, washed with water, dried, and crushed to form powdered polymethylsilsesquioxane (F-
1-F-4) was obtained.

Examples 1-3 and Comparative Examples 1-3 500 parts of water and 0.0 parts of water were placed in a flask. IN acetic acid aqueous solution 50
After adding 0 parts, 250 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane were added while stirring.
Then, hydrolysis and condensation were carried out while holding at a temperature of 25 to 35 ° C. for 24 hours to obtain a methanol solution A1 of a mixture consisting of a hydrolyzate and a condensate of methyltrimethoxysilane and dimethyldimethoxysilane. Ta.

After blending each component shown in Table 2 with this A, the mixture was mixed for 5 minutes using a homomixer to obtain a coating composition. In Table 2, Aerosil 200 (trade name: manufactured by Nippon Aerosil Co., Ltd.) is atomized silica, and Manchuria talc with an average particle diameter of 7 was used.

The composition thus obtained was applied to the surface of a polycarbonate plate (product name: NILEXAN SHEET 9030, manufactured by General Electric Company) with a pretreatment solution (product name: PH
91 (manufactured by Toshiba Silicone Co., Ltd.) by a flow coating method, and heated at 120° C. for 1 hour to obtain a cured film. Table 2 shows the results of measuring the appearance, adhesion, transparency, abrasion resistance, and 60 degree specular gloss of these cured films using the methods described below.

Appearance: The smoothness and irregularities of the cured film were visually observed.

Adhesion: Evaluated by base tape peel test. In addition,
The denominator is the number of substrates, and one numerator is the number of substrates that did not peel off.

Transparency: Evaluated by total light transmittance (%).

A scratch test was conducted using abrasion-resistant steel wool #0000.

A: It won't get damaged even if you rub it hard.

B: If rubbed too hard, it will be slightly damaged.

C: It just hurts.

60 degree specular gloss: Tested according to JIS K 5400. The glossiness was measured using a gloss meter model GM-26 (manufactured by Murakami Shikizai Kenkyushin). However, the test piece was prepared using the following method.

First, 91,200 parts of pH, 8 parts of carbon black, and 150 parts of glass peas with a diameter of 2 parts as a dispersion medium for carbon black were put into a vessel of a sand grinder (manufactured by Igarashi Kikai) and stirred at high speed for about 3 hours. Thereafter, the glass beads were removed to obtain a black paint containing PH91 as a vehicle.

After diluting the obtained black paint with thinner, it was applied uniformly to one surface of a polycarbonate board (LOOX100X 3 layers) by a spray method to the extent that transmitted light was eliminated to form a black paint film. The composition obtained in the example was applied onto the black coating film by a spray method, and then
It was heated at ℃ for 60 minutes to form a cured film, which was used as a test piece.

As is clear from Table 2, the cured film obtained from the composition of the present invention has excellent appearance (surface smoothness and matte surface), adhesion to the substrate, transparency (light transmittance) and It had excellent abrasion resistance, and its specular gloss was low and satisfactory.

Examples 4 to 6 and Comparative Examples 4 to 5 In a flask, 500 parts of water, 0. After adding 50 parts of IN hydrochloric acid aqueous solution, 200 parts of methyltriethoxysilane, 710 parts of dimethyljethoxysilane and 30 parts of tetraethoxysilane were added while stirring.
By maintaining the temperature at 35° C. for 24 hours, an ethanol solution A2 of a mixture consisting of a hydrolyzate of the silane compound and a condensate thereof was obtained.

Each component shown in Table 3 was added to this A2 in the same manner as in Example 1 to obtain a coating composition. The same tests as in Example 1 were conducted using these compositions. The results are shown in Table 3.

As is clear from Table 3, the cured film obtained from the composition of the present invention has excellent appearance (surface smoothness and matte surface), adhesion to the substrate, transparency (light transmittance), It had excellent abrasion resistance, and its specular gloss was low and satisfactory.

Examples 7 to 9 and Comparative Examples 6 to 7 Ludox (colloidal silica aqueous solution with an average particle size of 12-, solid content concentration 30%) was placed in a flask.

After adding 250 parts of pH 8.2 (trade name, manufactured by DuPont) and 1 part of glacial acetic acid, 2 parts of methyltrimethoxysilane
80 parts and 20 parts of dimethyldimethoxysilane were added.Then, the reaction solution was kept at a temperature of 25-30°C for 24 hours with stirring to obtain a reaction solution with a solid content concentration of 40%.Then, isobutanol was added to this solution. After adjusting the solid content concentration to 20%, 1 part of 2,4-dihydroxybenzophenone was added as a weather resistance improver, stirred until uniform, and filtered to obtain the composition of the present invention. Mixture A containing components (A) and (D) of
Got 3.

Each component shown in Table 4 was added to this mixture in the same manner as in Example 1 to obtain a coating composition.

The same tests as in Example 1 were conducted using these compositions. In addition, the appearance and adhesion when immersed in warm water at 60° C. for 200 hours were also tested. The results are shown in Table 4.

As is clear from Table 4, the cured film obtained from the composition of the present invention has excellent appearance (surface smoothness and matte surface), adhesion to the substrate, and hot water resistance (improvement of appearance in hot water). It was excellent in change state and adhesion to the substrate), transparency (light transmittance), and abrasion resistance, and its specular gloss was low and satisfactory. In addition, Examples 7 to 9
By incorporating colloidal silica into the composition, it was possible to improve the wear resistance among the above-mentioned properties. Furthermore, after exposing the cured films obtained from the compositions of Examples 7 to 9 for 2,000 hours using a Sunshine Weather-Ometer weather resistance acceleration tester, the appearance and adhesion were examined, and the results were good with no abnormalities. Met.

Claims (1)

[Claims] 1. (A) General formula (R^1)_mSi(OR^2)_4_-_m(I)
(In the formula, R^1 is an alkyl group having 1 to 3 carbon atoms, a vinyl group, a phenyl group, a γ-chloropropyl group, a γ-methacryloxypropyl group, a γ-glycidyloxypropyl group,
Represents a monovalent group selected from the group consisting of 3,4-epoxycyclohexylethyl group and γ-mercaptopropyl group; R^2 represents an alkyl group having 1 to 3 carbon atoms; m represents 0 or 1 ) A hydrolyzate of organoalkoxysilane and/or a condensate thereof; (B) General formula (R^1)_2Si(OR^2)_2(II) (wherein R
The definitions of ^1 and R^2 are the same as in formula (I)) A hydrolyzate of organoalkoxysilane and/or a condensate thereof; and (C) polymethyl having an average particle size of 0.1 to 100 μm. A coating composition comprising: silsesquioxane powder. 2. The coating composition according to claim 1, wherein the amount of component (B) blended is 1 to 30 parts by weight based on 100 parts by weight of component (A). 3. The coating composition according to claim 1, wherein the amount of component (C) blended is 1 to 200 parts by weight based on 100 parts by weight of the total amount of components (A) and (B). 4. The polymethylsilsesquioxane powder of component (C) is a finely powdered polymethyl obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolysis/condensation product in an aqueous solution of ammonia or amines. The coating composition according to any one of claims 1 to 3, which is a silsesquioxane. 5. The coating composition according to claim 1 or 4, wherein the polymethylsilsesquioxane powder as component (C) has an average particle diameter of 0.1 to 20 μm. 6, (A) General formula (R^1)mSi(OR^2)_4_-_m(I)(
In the formula, R^1 is an alkyl group having 1 to 3 carbon atoms, a vinyl group,
Phenyl group, γ-chloropropyl group, γ-methacryloxypropyl group, γ-glycidyloxypropyl group, 3
, 4-epoxycyclohexylethyl group and γ-mercaptopropyl group; R^2 represents an alkyl group having 1 to 3 carbon atoms; m is 0
or 1); (B) General formula (R^1)_2Si(OR^2)_2 (wherein R^1 and R^2 (definition is the same as formula (I)) A hydrolyzate of organoalkoxysilane and/or a condensate thereof; (C) polymethylsilsesquioxane powder with an average particle size of 0.1 to 100 μm; and (D) Colloidal silica; A coating composition comprising: (D) Colloidal silica. 7. The coating composition according to claim 6, wherein the amount of component (B) blended is 1 to 30 parts by weight based on 100 parts by weight of component (A). 8. The coating composition according to claim 6, wherein the amount of component (C) blended is 1 to 200 parts by weight based on 100 parts by weight of the total amount of components (A) and (B). 9. The polymethylsilsesquioxane powder of component (C) is a finely powdered polymethyl obtained by hydrolyzing and condensing methyltrialkoxysilane or its hydrolysis/condensation product in an aqueous solution of ammonia or amines. The coating composition according to claim 6, which is silsesquioxane. 10. The coating composition according to claim 6 or 9, wherein the polymethylsilsesquioxane powder as component (C) has an average particle diameter of 0.1 to 20 μm. 11. The coating composition according to claim 6, wherein the amount of component (D) blended is 5 to 200 parts by weight based on 100 parts by weight of the total amount of components (A) and (B).