JPS60135465A - Coating composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives a coating film having excellent wear resistance, adhesion, etc., by adding a silicone-modified acrylic rein in a specified ratio to a dispersion contg. an organotrihydroxysilane (partial condensate) and colloidal silica. CONSTITUTION:A disperson contg. an organotrihydroxysilane (partial condensate) of formula I (wherein R<1> is a monovalent hydrocarbon group) and colloidal silica, is prepd. 0.1-50wt% (based on the quantity, on a solid basis, of the dispersion) silicone-modified acrylic resin is added to the dispersion to obtain the desired coating compsn. As the silicone-modified acrylic resin, copolymers of a radical- polymerizable acrylate monomer of formula II (wherein R<2> is H, an n-valent aliph. hydrocarbon group, etc.; R<3> is H, lower alkyl; n is 1-4) with an acryloxy- functional silane of formula III (wherein R<4>, R<5> are each a hydrocarbon group; R<6> is H, a hydrocarbon group) are preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a coating composition, and more particularly,
For plastic molded products, especially acrylic resin molded products,
By coating without an undercoat and then heating and curing, it has excellent adhesion to the coated object, and also has excellent surface hardness, abrasion resistance, flexibility, chemical resistance, stain resistance, stainability, and surface properties. The present invention relates to a coating composition useful for protecting substrates, which provides a coating that is excellent in properties such as slipperiness, water repellency, and weather resistance, and has a transparent to anti-glare effect.

[Technical Background of the Invention and Problems Therein] Plastic molded products, by taking advantage of their advantages such as lightness, ease of processing, and excellent impact resistance, can be used for lens closures for eyeglasses and optical equipment, window glasses for buildings, A wide range of applications are being considered, including window glass for transportation vehicles such as trains and cars.

However, plastic molded products have drawbacks such as being easily scratched and easily eroded by solvents, so they have serious problems in that their transparency and appearance are easily impaired, and their use is limited to a certain extent. Limited.

In order to solve these problems, several proposals have been made regarding coating compositions for forming a film with high hardness and excellent solvent resistance on the surface of plastic molded products. There is.

However, conventional coating compositions have problems such as insufficient scratch resistance or poor workability because an undercoat must be used in advance to improve adhesion. .

Such coating compositions include, for example, tetrafunctional silanes such as ethyl silicate; trifunctional silanes such as methyltrimethoxysilane and vinyltrialkoxysilane and their hydrolyzed condensates; Silicone resin coating compositions containing various combinations of silane coupling agents such as trimethoxysilane and γ-aminopropyltrimethoxysilane; colloidal silica and organic compound components such as methylolated melamine and polyvinyl alcohol have already been commercialized. It is used in plastic sunglass lenses, etc. However, these coating compositions require a heat curing temperature of 80 to 100°C or higher in order to obtain practically sufficient hardness and adhesion to the object being coated, and depending on the type of plastic substrate, thermal deformation may occur. The problem is that the temperature cannot be fully utilized because the temperature exceeds the temperature.

As a solution to these problems, a primer liquid is used to improve adhesion to the substrate, and a curing catalyst is added to the coating composition to ensure sufficient hardness even when heated and cured at relatively low temperatures. methods have been adopted. However, in this method, the number of coating treatments is large, resulting in poor workability, and addition of a curing catalyst shortens the pot life of the coating composition. Furthermore, although the resulting film has sufficient hardness, it does not have sufficient adhesion to the substrate, and due to the influence of the catalyst remaining in the film, heat resistance and weather resistance decrease, and there are problems such as easy cracking. It has points.

On the other hand, recently there has been an increasing demand for matte type coating compositions in addition to transparent type coating compositions. The matte type coating composition is used in applications that require anti-glare effects, such as anti-reflection filters for cathode ray tube displays and light transmitting plates in front of display panels; light bulbs or fluorescent lights for indoor and outdoor lighting equipment. to soften the light of protective boards, advertising lights, billboards, etc.
Items that are used for the purpose of giving a high-class appearance; items that require a concealing or shielding effect such as bathroom window glass; and items that require an anti-reflection effect or that can convert a point light source to a surface light source. In terms of what is required.

Conventionally used transparent coating compositions have a mirror-like gloss on the film surface and have excellent light transmittance. When applied to a panel or the like, there is a problem in that the sharpness of characters and figures deteriorates.

On the other hand, when a plastic molded body or film, etc. that is not coated with a coating composition is used as an antireflection filter for a cathode ray tube display, there is a problem that the surface is easily scratched when a light pen or the like is used. ing. In addition, when applied to reflective plates or protective plates of lighting equipment, they may be discolored or deformed by spray insecticides, etc., and when applied to advertising protective plates or signboards used outdoors, Due to insufficient weather resistance,
It has problems such as yellowing and spoiling the appearance. Furthermore, when ground glass is used for windows in bathrooms, etc., it generally has the problem that when the surface of ground glass becomes wet, its light scattering ability decreases, its concealing or shielding effect is impaired, and its shatter resistance is poor. ing.

Furthermore, conventionally known processing methods for obtaining a non-glare effect include, for example, a sandblasting method, a surface scratching method, and a method of blending inorganic powder such as silicon dioxide into a coating composition. Furthermore, as a processing method to obtain an antireflection film, for example, a base film of silicon dioxide is provided on the plastic surface, and thin films of two or more metal oxides with different refractive indexes are laminated to a constant thickness on top of the base film. A method of forming a multiple interference film by, for example, a vacuum evaporation method, a sputtering method, or a high frequency ion blating method is known. However, among the above methods, sandblasting and surface scratching only roughen the surface precision of materials such as glass and plastic, and do not solve the above-mentioned problems. further required. In addition, the method of blending inorganic powder such as silicon dioxide into a coating composition has problems such as poor stability of the composition due to agglomeration and sedimentation of the powder, and difficulty in obtaining a uniform or fixed appearance with good reproducibility. There are problems in handling and work, such as difficulty in handling. Furthermore, the method of forming a thin film of metal oxide requires a large amount of equipment and is not yet suitable for general use. The problem is that it is difficult to form.

[Object of the Invention] The object of the present invention is to solve the above-mentioned problems, and to provide a material that has excellent adhesion to the substrate when applied to a substrate such as a plastic molded article, especially an acrylic resin molded article, and which can be obtained. The film has transparency and anti-glare effect, and has excellent abrasion resistance.
An object of the present invention is to provide a coating composition having flexibility, chemical resistance, water repellency, and weather resistance.

[Summary of the invention] The coating composition of the present invention is:

General formula [11: RS+(OH)3 [wherein R represents a substituted or unsubstituted monovalent hydrocarbon group]. ] A dispersion of organotrihydroxysilane and its partial condensate represented by colloidal silica, and a silicone-modified acrylic resin, and the silicone-modified acrylic resin is added in a proportion of 0.1 to 0.1% to the total solid content of the dispersion. 50
It is characterized by containing % by weight.

In the following, the invention will be explained in more detail.

The organotrihydroxysilane represented by the general formula [11] used in the present invention has the following formula: % formula %) (wherein R' represents a monovalent alkyl group, and R1 has the same meaning as above. ) It can be obtained by hydrolyzing the organotrialkoxysilane shown below. Such organotrialkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxyprobyltrimethoxysilane, γ-7minoprobyltrimethoxysilane, γ- Aminopropyltriethoxysilane, 3,3.
Examples include 3-tripleopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the organotrihydroxysilane used in the present invention include those in which the alkoxy group of the above-mentioned organoalkoxysilane is substituted with a hydroxy group.

The dispersion of organotrihydroxysilane and its partial condensate and colloidal silica used in the present invention is prepared by stirring and suspending at least one of these organotrialkoxysilanes in colloidal silica, for example,
Using acid or aluminum chelate etc. as a catalyst, 2
It can be prepared by mild hydrolysis in the temperature range of 0 to 40°C. Since this dispersion has poor stability as it is, for example, after diluting with an alcohol and/or glycol ether solvent, water in the system and hydrolyzed by-products can be removed by azeotrope of water-alcohol solvent under reduced pressure. It is preferable to remove biological low-boiling alcohols such as methanol and ethanol from the system, and then dilute the dispersion again so that the solid content of the dispersion becomes 10 to 40% by weight and store it. In order to obtain the surface hardness necessary for the coating composition, the dispersion liquid contains 10 to 80% by weight of silica derived from colloidal silica based on the total amount of solids, and the remainder is composed of organometallic silica. Trihydroxysilane and its partial condensates are preferred. Further, it is more preferable that at least 60 mol% of the organotrihydroxysilane is methyltrihydroxysilane. Preferred solvents used for diluting the dispersion include isopropyl alcohol, isobutyl alcohol, arsenic acid ethylene glycol 7-ethyl ether, and the like.

The silicone-modified acrylic resin that forms another component of the coating composition of the present invention is not particularly limited as long as it is one in which a part of the acrylic resin is replaced with silane or silicone, but it must be easily available and Since good adhesion is obtained, [wherein R2 is a hydrogen atom, a substituted or unsubstituted n-valent aliphatic hydrocarbon residue, and a substituted n-valent aliphatic hydrocarbon having at least one ether bond] It represents a group selected from the group consisting of hydrocarbon residues, R3 represents a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 4. At least one radically polymerizable acrylate monomer represented by [wherein R is a monovalent hydrocarbon group, R5 is a divalent hydrocarbon group, and R6 is a hydrogen atom or a -valent hydrocarbon group] Represents a hydrogen group. ] Preferably, the copolymer is a copolymer with at least one acryloxy-functional silane represented by the following.

Further, in the present invention, the above monomers may be copolymerized with, for example, acrylonitrile, methacrylate trile, and the like.

Examples of the radically polymerizable acrylate monomer represented by the general formula [11] include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, and 2-hydroxyethyl acrylate. , 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate,
Monoacrylate monomers such as methoxytetraethylene methacrylate and allyl methacrylate: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,! , 3-butylene gelicoldimethacrylate.

Neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, 2,2-bis(4-methacryloxyjethoxyphenyl)propane polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate and 2°2°-bis(4- Diacrylate monomers such as acryloxy-propoxyphenyl)propane: triacrylate monomers such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, and tetramethylol Examples include tetraacrylate monomers such as methane tetraacrylate, and one or more monomers selected from the group consisting of these monomers are used.

Further, examples of the acryloxy-functional silane represented by the general formula [ml include γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxysilane. Examples include propyltriisoproboxysilane, and one or more selected from the group consisting of these are used. Among these, it is preferable to use γ-methacryloxypropyltrimethoxysilane because it is easily available.

The silicone-modified acrylic resin of the present invention can be obtained by copolymerizing at least one of the above acrylate monomers and at least one acryloxy-functional silane in a suitable solvent using a radical polymerization initiator. It is possible. Copolymerization is preferably carried out by solution polymerization in a solvent such as alcohol and/or ester for the purpose of suppressing the degree of polymerization, and the polymer obtained in this way can be easily blended with a dispersion. .

Examples of the radical polymerization initiator include organic peroxides; benzoyl peroxide, diglorbenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-di(peroxybenzoate) hexine-3
,1,3-bis(t-butylperoxyisopropyl)
Benzene, lauroyl peroxide, t-butyl peracetate, t-butyl perbenzoate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-
perester compounds such as 3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane; and azo compounds such as azobisisobutyronitrile (hereinafter referred to as AIBN) and dimethylazobutyrate. Examples include compounds.

The amount of radical polymerization initiator is 0.01 per 1,000 units.
It is preferable to add up to 0.5% by weight, more preferably 0.05 to 0.2% by weight. When the amount of the radical polymerization initiator added is less than 0.01% by weight, the molecular weight of the copolymer becomes high, and mixing with the dispersion liquid may become difficult. On the other hand, even if it is added in an amount exceeding 0.5% by weight, the degree of polymerization of the copolymer does not decrease, and when the obtained silicone-modified acrylic resin and dispersion are mixed and coated, the cured film and the plastic substrate, In particular, the adhesion to acrylic resin molded products does not improve beyond a certain level.

The composition of the silicone-modified acrylic resin is preferably 70 to 88 mol % of the radically polymerizable acrylate monomer, and the remainder is an acryloxy-functional silane.

If the amount of the acryloxy-functional silane is less than 2 mol %, the copolymerization product may have poor compatibility with the solid content of the dispersion, making it difficult to obtain a transparent film. Moreover, if it exceeds 30 mol%, scratch resistance will decrease.

Moreover, it is preferable that at least 80 mol% of the radically polymerizable acrylate monomers is a monoacrylate monomer, and furthermore, at least 50 mol% of the 1,000-no-acrylate monomers is a methacrylic ester and/or a monoacrylate monomer.
Or acrylic ester is preferable. If the monoacrylate monomer content of the radically polymerizable acrylate monomer is less than 80 mol %, the resulting copolymer may have poor compatibility with the dispersion and may separate and precipitate. Furthermore, among the monoacrylates, the amount of methacrylic ester and/or acrylic ester is 50
If the amount is less than mol%, the copolymer tends to gel.
Control of the reaction may be difficult. As such methacrylic ester and/or acrylic ester, it is particularly preferable to use methyl methacrylate from the viewpoint of improving the adhesion of the film.

The silicone-modified acrylic resin obtained as described above can be stored in a stable state by diluting it with an appropriate solvent and adding a polymerization inhibitor or the like as necessary.

The coating composition of the present invention includes a dispersion of the organotrihydroxysilane and its partial condensate and colloidal silica, and a silicone-modified acrylic resin in proportion to the total solid content of the dispersion. If the purpose is to form a transparent film, the amount of 0.
It is blended in an amount of 1% by weight or more and less than 10% by weight. If the solid content of the silicone-modified acrylic resin is less than 0.1% by weight, good adhesion to the object to be coated cannot be obtained.On the other hand, when the purpose is to form a film with anti-glare effect, It is blended in an amount of 10 to 50% by weight, more preferably 10 to 40% by weight. Within this range, various degrees of anti-glare effect can be selected. When it exceeds 50% by weight, the dispersibility of the solid content
This is not preferable because the hardness of the cured product becomes low.

In addition, the coating composition of the present invention has a solid content of 15 to 3 to ensure workability and film thickness during application.
It is preferable to adjust the amount to 0% by weight.

Furthermore, an ultraviolet absorber, a leveling agent, a curing catalyst, etc. may be added to the coating composition of the present invention, if necessary.

When the coating composition of the present invention is applied to an object made of acrylic resin or the like, it is coated without a special undercoat, air-dried, and then heated at 70 to 80"C for 2 to 3 hours. It is possible to obtain a film that has excellent adhesion to the object to be coated.

In addition, when the coating composition of the present invention is used in applications that require anti-glare effects, it can be applied to polycarbonate resin molded products without a special undercoat, and 100%
It is also possible to obtain a film having excellent adhesion to the object to be coated by heating at -120"0 for 1 to 2 hours.

[Effects of the Invention] According to the coating composition of the present invention, excellent adhesion to the object to be coated can be achieved by coating a plastic molded article, especially an acrylic resin molded article, without an undercoat and then heating and curing it. It also has surface hardness, wear resistance,
It provides a film that is useful for protecting substrates and has excellent properties such as flexibility, chemical resistance, stain resistance, dyeability, surface slipperiness, water repellency, and weather resistance, as well as transparency and anti-glare effects. Ru.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but these are not intended to limit the present invention in any way. In the examples, 1 part represents part by weight.

[Examples of the Invention] Preparation Example 1 "LlLJll Methyltriethoxysilane 32@, colloidal silica (
40 parts of Nisnortex (trade name; manufactured by Nissan Chemical Co., Ltd.) and 0.2 parts of acetic anhydride were placed in a flask, and the mixture was stirred for 24 hours while controlling the temperature at 25 to 30°C to hydrolyze the alkoxysilane. To this reaction solution, 30 parts of isobutyl alcohol was added, and azeotropic stripping was performed under reduced pressure of 20 to 70 layers at a temperature of 20 to 40 inches to remove the ethanol and colloidal silica contained in the hydrolysis by-products. Then, a mixed solvent of inpropyl alcohol, isobutyl alcohol, and acetic acid ethylene glycol ethyl ether in a weight ratio of 1:5:1 was added so that the solid content was 30% by weight. It was diluted to obtain a dispersion.

Preparation Example 2 Silicone Acrylic Acid Various methacrylic esters and optionally methacrylic acid or acrylonitrile are combined with γ-methacryloxypropyltrimethoxysilane (trade name: A-174; Nippon Unicar) according to the formulation shown in Table 1. Co., Ltd.) was copolymerized in a mixed solution of inpropyl alcohol and ethyl acetate in a weight ratio of 1:1 using AIBN as a polymerization initiator. This reaction solution was diluted with ethylene glycol 7-ethyl ether acetate, and 7 types (sample numbers A-1 to A
-7) Silicone-modified acrylic resin was obtained.

In the table, sample number A-8 is a comparative sample that does not contain silicone.

Below is a margin Example 1 Using the dispersion obtained in Preparation Examples 1 and 2 and a silicone-modified acrylic resin, the solid content of the silicone-modified acrylic resin was determined in the amount shown in Table 2 based on 100 parts of the solid content of the dispersion. parts) and diluted with a mixed solvent of isobutyl alcohol and ethylene glycol monoethyl ether acetate in a weight ratio of 9:1 so that the total solid content was 23% by weight. Furthermore, 1.0% by weight of 2,4-dihydroxybenzophenone as an ultraviolet absorber and 0.1% of polyoxyalkylene-modified silicone oil as a leveling agent.
% by weight were added and mixed to obtain coating compositions 1 to 9 according to the present invention. These formulations are shown in Table 2. Comparative Example 1 The same procedure as Example 3 was carried out except that the dispersion obtained in Preparation Example 1 and the comparative acrylic resin (Sample No. A-8) obtained in Example 2 were used. Comparative coating composition 10 was obtained.

Comparative Example 2 Comparative coating composition 11 was obtained in the same manner as in Example 1 except that the silicone-modified acrylic resin was not used.

Table 2 Example 2 The coating compositions obtained in Example 1 and Comparative Examples 1 and 2 were placed on an acrylic resin molded plate (trade name: Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd.) that had been degreased and washed with isopropyl alcohol. Flow coating, 23-25°C 135-4
After air drying for 30 to 40 minutes in clean air with temperature and humidity controlled to 5% R)I, a cured film was obtained by heat treatment at 80° C. for 12 hours in a hot air circulation constant temperature bath. Using this coated plate as a test plate, the following coating film performance test was conducted. The results are shown in Table 3. However, the heat resistance is determined by using a primer (product name: PH91) on a polycarbonate plate (product name: NILEXAN SHEET; manufactured by General Electric Co., Ltd.).
, manufactured by Toshiba Silicone Co., Ltd.), then flow-coated, +
A test plate obtained by heating and curing at 20°O for 1 hour was used.

ti> Appearance of film...Visual test. A smooth, transparent film with no cracks, cloudiness, or discoloration is considered good.

+2) Adhesion of the film to the object to be coated... Base tape peel test, JIS D-0202゜(n) Abrasion resistance of the film...#! Semi-wearing wheel O8
-10 was used, and the haze value was measured after 200 rotations with a load of 500 g using a Rotary Abure 7 Sur (manufactured by Toyo Seiki Co., Ltd.).

) Pencil hardness...JIS K-5400゜■
Total light transmittance...The total light transmittance of the test plate was measured.

■Chemical resistance: Good if there is no abnormality in the coating film after immersion in 0.1 mol nitric acid and o and i mol sodium hydroxide at room temperature for 24 hours.

■Poor solvent property: The coating film is rated as good if there is no abnormality after immersion in acetone, ethanol, benzine, thinner, or toluene at room temperature for 24 hours.

(α Heat resistance: Good if there is no abnormality in the coating after being left at 120'C for 240 hours.

■Water resistance: Good if there is no abnormality in the coating after immersion in 70°C warm water for 240 hours.

dφChochu resistance・・・・・・Conducted accelerated weathering test in carbon arc sunshine weather meter, 1500
A case where there is no abnormality on the coating film after a certain period of time is considered good.

As is clear from Table 3, the cured film obtained from the coating composition of the present invention has superior adhesion to the acrylic ballast molded plate and has improved abrasion resistance and weather resistance compared to conventional products. It was confirmed that It was also confirmed that other coating film performances were comparable to those of conventional coating compositions.

Furthermore, the cured film of the coating composition according to the present invention has improved flexibility and dyeability with polyester disperse dyes and the like. Furthermore, by adding a silicone-modified acrylic resin to the coating composition of the present invention, the aging process for developing coating film performance, which was conventionally required in silicone coating agents used for this purpose, can be omitted. It is possible to do so. The coating composition of the present invention can be applied to plastic molded products other than acrylic resin, wood products, metal products (including plated products), and others.

Example 3 Using the dispersion obtained in Preparation Example 1 and the silicone-modified acrylic resin A-1-A-3 obtained in Preparation Example 2, the solid content of the silicone-modified acrylic resin was adjusted to 100 parts of the solid content of the dispersion. , and diluted with a mixed solvent of diacetone alcohol and ethylene glycol monoethyl ether acetate in a weight ratio of 9:1 so that the total solid content was 23% by weight. Furthermore, 1.0% of 2,4-dihydroxypenzophenone was used as an ultraviolet absorber.
% by weight and 0.1% by weight of polyoxyalkylene-modified silicone oil as a leveling agent were added and mixed to obtain coating compositions 12 to 16 according to the present invention. Using these coating compositions, the coating film performance was evaluated in the same manner as in Example 2. The results are shown in Table 4. Note that instead of the abrasion resistance and total light transmittance in Example 2, scratch resistance, transparency, and resolution were measured under the following conditions.

Scratch resistance: Scratch test with steel wool #0000.

(Evaluation method) A: No scratches even when rubbed strongly 6B = Slight scratches when rubbed strongly.

C: Easily scratched by rubbing.

Transparency: Transmittance is measured using a spectrophotometer.

The average value of the transmittance in the range of 400 to 700 nm (visible region) was defined as the transparency.

Resolution: The readability of characters when a painted board is placed on a cathode ray tube display.

Table 4 Example 4 Using the dispersion obtained in Preparation Examples 1 and 2 and the silicone-modified acrylic resin, the solid content of the silicone-modified acrylic resin is shown in Table 5 based on 100 parts of the solid content of the dispersion. The mixture was diluted with a mixed solvent of isobutyl alcohol and ethylene glycol monoethyl ether acetate in a weight ratio of 9:1 so that the total solid content was 23% by weight. Furthermore, 1.0% by weight of 2,4-dihydroxybenzophenone as an ultraviolet absorber and 0.1% of polyoxyalkylene-modified silicone oil as a leveling agent.
% by weight were added and mixed to obtain coating compositions 14 and 17 to 23 according to the present invention. These formulations are shown in Table 5.

Table 5 Example 5 γ-glycidoxypropylene trichloride was deposited on a cast polymer plate of allyl diglycol carbonate (monomer trade name: CR-39, manufactured by Pittsburgh Platoglass Co., Ltd.) which had been degreased and washed with isopropyl alcohol. Methoxysilane and γ-ureidopropyltriethoxysilane (2:1
), then flow-coated the coating compositions obtained in Examples 1 and 4 and Comparative Example 2, and
'C! A cured film was obtained by heat treatment for 2 hours. Using these coated plates as test plates, the following dyeability test was conducted. The results are shown in Table 6.

Dyeability test: One cup of hot water at 92 to 83° C. was placed in a curved beaker, and 90 cc of a staining agent (trade name Nibrown H; manufactured by Nippon Kogaku Kogyo Co., Ltd.) was dissolved therein to prepare a staining solution. After immersing the test plate in this staining solution for 5 to 30 minutes while maintaining it at 82 to 83°C on a hot plate,
The degree of staining density was visually inspected.

Table 6 Example 6 Using the dispersion obtained in Preparation Example 1 and the silicone-modified acrylic resins A-1-A-3 obtained in Preparation Example 2, the solid content of the silicone-modified acrylic resin was 100% of the solid content of the dispersion. parts, and diluted with a mixed solvent of diacetone alcohol and ethylene glycol monoethyl ether acetate in a weight ratio of 9:l so that the total solid content was 20% by weight. did. Furthermore, 0.8 2,4-dihydroxybenzophenone was added as a UV absorber.
% by weight and 1.0% by weight of polyoxyalkylene-modified silicone oil as a leveling agent were added and mixed to obtain coating compositions 24 to 29 according to the present invention.

The coating composition obtained as described above was applied to a polycarbonate plate (
Product name: Nirexan Sheet (manufactured by General Electric Company), flow coated without undercoating, 23-25℃,
After air drying for 30 minutes in clean air with temperature and humidity controlled at 35 to 45% RH, a cured film was obtained by heat treatment at 120"C for 11 hours in a hot air circulation constant temperature bath.

Using this coated plate as a test plate, the coating film performance test described below was conducted.

The results are also listed in Table 7.

All tests except for the boiling water resistance test were carried out under the same conditions as in Example 2 or 3.

Boiling water resistance test for film: The test plate is immersed in boiling water for 2 hours, taken out and washed with water, then wiped of water and left to stand for 1 hour to examine the appearance and adhesion to the object to be coated. The test was carried out in the same manner as in Example 2, and the case where there was no abnormality was evaluated as 117.

As is clear from the results shown in the margin below, the coating composition of the present invention has excellent adhesion to the object to be coated, and also has excellent surface hardness, abrasion resistance, flexibility, chemical resistance, and It was confirmed that the film had excellent properties in terms of stain resistance, dyeability, surface slipperiness, water repellency, weather resistance, etc., and was furthermore capable of providing a film having a transparent or anti-glare effect.

Claims (1)

[Claims] 1. - General formula: R51(OH)3 [wherein R1 represents a substituted or unsubstituted monovalent hydrocarbon group]. ] A dispersion of organotrihydroxysilane and its partial condensate represented by colloidal silica, and a silicone-modified acrylic resin, and the silicone-modified acrylic resin is added in a proportion of 0.1 to 0.1% to the total solid content of the dispersion. 50
A coating composition characterized in that it contains % by weight. 2. The silicone-modified acrylic resin is [wherein R2 is a hydrogen atom or a substituted n-valent aliphatic hydrocarbon having a substituted or unsubstituted n-valent aliphatic hydrocarbon residue and at least one ether bond] R3 represents a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 4. ] At least one radically polymerizable acrylate monomer represented by
With seeds. [In the formula, R4 is a monovalent hydrocarbon group, R5 is a divalent hydrocarbon group, and R6 represents a hydrogen atom or a -valent hydrocarbon group. The coating composition according to claim 1, which comprises a copolymer with at least one acryloxy-functional silane represented by the following. 3. The coating composition according to claim 2, wherein at least 50 mol% of (A) is a methacrylic ester and/or an acrylic ester. 4. The coating composition according to claim 3, wherein (A) is methyl methacrylate. 5. The coating according to claim 2, which contains 2 to 30 mol% of the acryloxy-functional silane (B) of the silicone-modified acrylic resin based on the combined amount of (A) and (B). Composition. 6. Containing silicone-modified acrylic resin at 0.1% by weight or more and less than 10% by weight based on the total solid content of the dispersion,
A coating composition according to claim 1, which provides a transparent film. 7. The coating composition according to claim 1, which contains a silicone-modified acrylic resin in an amount of 10 to 50% by weight based on the total solid content of the dispersion, and provides a film having an anti-glare effect and dyeability.