JPH1025451A - Ultraviolet-absorbing coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ultraviolet-absorbing coating composition which gives a film excellent in ultraviolet absorptivity, abrasion resistance, transparency, heat resistance, water resistance, hardness, etc., by using specified (partially condensed) silanol compound(s) and a specified ultraviolet-absorbing component as the constituents. SOLUTION: This composition contains preferably 100 pts.wt. of at least one of silanol compounds represented by the formula R<2> n Si(OR<1> )4-n [wherein R<1> is H or lower alkyl; R<2> is lower alkyl, vinyl, fluoropropyl, γ-glycidoxypropyl or γ-(meth)acryloxypropyl; and n is 0 to 2] or partial condensates thereof and preferably 1-1,000 pts.wt. ultraviolet-absorbing components containing zinc oxide and ceric oxide at a weight ratio of (1:0.1) to (1:10), preferably used in the form of sol(s) dispersed in water or an organic solvent (e.g. n-butanol) alone or a mixture thereof, and comprising sols respectively containing the oxides or a sol mixture containing these two oxides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition capable of forming a colorless and transparent inorganic film having excellent ultraviolet absorption.

[0002]

2. Description of the Related Art Plastics molded articles are lighter in weight than metals, glass and the like, and have recently been widely used in automobiles, aircraft, buildings and the like. However, plastics have the drawback that they are easily degraded and decomposed by ultraviolet rays, causing surface deterioration and cracks.

In order to prevent such deterioration due to ultraviolet rays, a method of preliminarily blending an ultraviolet absorber into raw materials of plastics, and an organic resin coating composition containing an ultraviolet absorber is applied to the surface of a plastics substrate. A method of forming a protective film by coating has been attempted. However, these methods cannot prevent deterioration due to ultraviolet rays for a long period of time because the effect of absorbing ultraviolet rays decreases with time.
Even if a protective film is formed with an organic resin paint, properties such as abrasion resistance are not satisfactory.

As an inorganic coating film formed on plastics, an abrasion-resistant film composed of colloidal silica and polysiloxane, an ultraviolet absorbing film composed of colloidal titania and polysiloxane, and the like are known. When used outdoors, there is a disadvantage that the plastics of the base material is deteriorated by the ultraviolet rays of the sun.The latter absorbs the ultraviolet rays to some extent but has a limited absorption wavelength and is satisfactory in the effect of blocking the ultraviolet rays. It doesn't work.

[0005] As an inorganic coating film having an excellent ultraviolet absorbing property, a composition in which a specific silanol compound is mixed with fine-grained seria is known (JP-A-5-22233).
No. 8). However, the film formed by this composition becomes yellowish and changes the color tone of the substrate, which is not practically satisfactory.

[0006]

SUMMARY OF THE INVENTION The main object of the present invention is to:
An object of the present invention is to provide a coating composition which is excellent in ultraviolet absorption and abrasion resistance and can form an inorganic film having excellent transparency.

[0007]

Means for Solving the Problems In view of the above-mentioned problems, the present inventors have conducted intensive studies and found that an inorganic coating composition containing a silanol compound or a partial condensate thereof as a film forming component was oxidized. When zinc and ceric oxide are combined in a certain ratio, a bluish film is formed when zinc oxide is used alone.
Despite the formation of a yellowish film when ceric oxide alone is blended, it is quite unexpectedly possible to form a film that is substantially colorless and excellent in transparency. In addition to having good UV absorption, it also exhibits excellent properties such as abrasion resistance and stain resistance, and also has good low-temperature curability due to the presence of zinc oxide, enabling film formation even at room temperature. It has been found that a good film can be easily formed even on a material having low heat resistance such as plastic, and the present invention has been completed.

That is, the present invention relates to (i) a compound represented by the general formula R ² _n S
i (OR ¹ ) _4-n (wherein, R ¹ represents hydrogen or a lower alkyl group, and R ² represents a lower alkyl group, a vinyl group, a fluoropropyl group, a γ-glycidoxypropyl group, or a γ-
It represents a (meth) acryloxypropyl group, and n is 0, 1 or 2. ), And (ii) zinc oxide and ceric oxide in the former: latter (weight ratio) = 1: 0.
The present invention relates to an ultraviolet-absorbing coating composition containing an ultraviolet-absorbing component contained in a ratio of 1 to 1:10.

[0009]

Coating composition of the present invention DETAILED DESCRIPTION OF THE INVENTION, represented by the general formula _{^{R 2 n Si (OR 1)}} ( wherein, R ^1, R ^2, and n are as defined above.) _4-n A ceramic film-forming substance comprising at least one of a silanol compound and a partial condensate thereof is contained as a film-forming component.

In the above formula, examples of the lower alkyl group represented by R ¹ or R ² include an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and isopropyl. Further, as the fluoropropyl group, a 3,3,3-trifluoropropyl group can be preferably exemplified.

[0011] Specific examples of the formula R ² _n Si (OR ¹⁾ silanol compounds represented by _4-n may be exemplified the following compounds.

Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ ,
Si (OC ₃ H ₇ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ , CH ₃ S
i (OC ₂ H ₅ ) ₃ , CH ₃ Si (OC ₃ H ₇ ) ₃ , (CH ₃ )
₂ Si (OCH ₃ ) ₂ , (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ ,
(CH ₃ ) ₂ Si (OC ₃ H ₇ ) ₂ C ₂ H ₅ Si (OCH ₃ ) ₃ , C ₂ H ₅ Si (OC ₂ H ₅ ) ₃ ,
C ₂ H ₅ Si (OC ₃ H ₇ ) ₃ , (C ₂ H ₅ ) ₂ Si (OC
_{H 3) 2, (C 2} H 5) 2 Si (OC 2 H 5) 2, (C 2 H 5) 2
Si (OC ₃ H ₇ ) ₂ , C ₃ H ₇ Si (OCH ₃ ) ₃ , C ₃ H ₇
Si (OC ₂ H ₅ ) ₃ , C ₃ H ₇ Si (OC ₃ H ₇ ) ₃ , C ₆ H
_{5 Si (OCH 3) 3,} C 6 H 5 Si (OC 2 H 5) 3, C 6 H 5
Si (OC ₃ H ₇ ) ₃ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , C
H ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHSi (OC _{3
H 7) 3, CF 3 CH} 2 CH 2 Si (OCH 3) 3, CF 3 CH
₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ CH ₂ CH ₂ Si (OC
₃ H _{7) 3,}

[0013]

Embedded image

The partial condensate of the silanol compound is not particularly limited, and condensates of the same or different types of compounds among the silanol compounds represented by the above general formula can be used. Can be freely changed. The degree of condensation is not particularly limited, but is preferably about 2 to 10 mer. Specific examples of the condensate include the following.

[0015]

Embedded image

(R ¹ and R ² are the same as above, and n is about 1 to 5.) In the composition of the present invention, it is necessary to use a combination of zinc oxide and ceric oxide as an ultraviolet absorbing component. It is. It is suitable to use zinc oxide and ceric oxide each having a particle size in the range of about 5 to 150 millimicrons. The mixing ratio of zinc oxide and ceric oxide is as follows: zinc oxide: ceric oxide (weight ratio) =
1: about 0.1 to 1:10, preferably zinc oxide:
Cerium oxide (weight ratio) = 1: 0.2 to 1: 5, more preferably zinc oxide: ceric oxide (weight ratio) = 1: 0.5 to 1: 2. By mixing and using the specific two components in such a mixing ratio, an excellent ultraviolet blocking effect can be exhibited, and a colorless and highly transparent film can be formed.

In the present invention, in particular, zinc oxide and ceric oxide are preferably used as a sol dispersed in water or an organic solvent alone or in a mixed solvent. In the liquid, zinc oxide and ceric oxide are mixed very well with a ceramic film-forming substance comprising at least one of a silanol compound and a partial condensate thereof, and are substantially colorless and extremely excellent in transparency. In addition, it is possible to form an inorganic film having a good ultraviolet blocking effect. The sol of zinc oxide and ceric oxide may be used in any form of a sol containing a single component or a mixed sol containing these two components.

The organic solvent used for obtaining the sol is usually methanol, ethanol, propanol,
Lower alcohols such as isopropanol, n-butanol, isobutanol, etc .; alkyl groups such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and cypropylene glycol monoalkyl ether; methyl, ethyl, propyl, butyl, etc. Acetic acid esters of the above hydrocarbon ether alcohols, such as hydrocarbon ether alcohols having ethylene glycol monoalkyl ether acetate, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate; Acetates of alcohols such as ethyl acetate, methyl acetate, ethyl acetate , Propyl acetate, acetic acid esters of butyl acetate, acetone, xylene, benzene, n-hexane or the like is used. The solid content concentration in the sol may be about 1 to 50% by weight, and preferably about 5 to 30% by weight, for both the sol containing a single component and the mixed sol containing these two components. .

The composition of the present invention uses a combination of a ceramic film-forming substance comprising at least one of the above silanol compounds and partial condensates thereof, and zinc oxide and ceric oxide as ultraviolet absorbing components. , A film formed by polymerization and gelation of a silanol compound or a partial condensate thereof becomes a ceramic film excellent in heat resistance, abrasion resistance, water resistance, non-staining property, etc., and zinc oxide and ceric oxide UV-absorbing component consisting of 190 to 380 n without coloring the film
m can be sufficiently absorbed in a wide range of ultraviolet rays. Therefore, according to the composition of the present invention, it is possible to form a protective film that effectively absorbs ultraviolet light without changing the color tone of the substrate at all, and by forming such a film, the ultraviolet light can reach the substrate. In addition, deterioration of the base material due to ultraviolet rays can be prevented. The absorbed ultraviolet light is thermally converted, but is hardly deteriorated by heat because the film is a ceramic film mainly composed of silica, zinc oxide and ceric oxide. In addition, since the bond of SiO ₂ , which is the skeleton of the ceramic film, is not cut by ultraviolet rays, it is possible to prevent long-term deterioration of organic base materials, such as organic resins, fibers, and wood, which are easily degraded by ultraviolet rays, The transparency of the film is maintained for a long time.

The coating composition of the present invention comprises the above-mentioned ceramic film-forming substance, zinc oxide and ceric oxide.
Water, an organic solvent or a mixed solvent thereof is dissolved or dispersed in the ceramic film-forming substance itself without using a solvent, and as it is, zinc oxide and ceric oxide are dispersed therein. be able to. As the organic solvent, the same type of organic solvent that can be used when preparing the sol containing zinc oxide and ceric oxide described above can be used.

In the composition of the present invention, the mixing ratio of the ceramic film-forming substance and the ultraviolet absorbing component composed of zinc oxide and ceric oxide is 10%.
The total solid content of zinc oxide and ceric oxide may be in the range of about 1 to 1000 parts by weight, preferably in the range of about 5 to 100 parts by weight with respect to 0 parts by weight.

In the composition of the present invention, the total amount of the ceramic film-forming substance and zinc oxide and ceric oxide as ultraviolet absorbing components is about 5% by weight or more as a solid concentration in the composition. Preferably, 10 to 50
It is more preferable that the amount is about% by weight. In this specification, the solid content of the ceramic film-forming substance is based on the amount of a silanol compound or a partial condensate thereof used as the ceramic film-forming substance in terms of SiO ₂ .

In the present invention, if necessary, a colloidal substance can be added to the above-mentioned coating composition.
The colloidal substance used in the present invention is also referred to as a sol-like substance, and refers to a substance in which liquid or solid particles of about 10 to 10000 angstroms are dispersed in a dispersion medium. Can be used. As the dispersion medium, usually, the above-mentioned lower alcohols, hydrocarbon ether alcohols, organic solvents such as acetates thereof and water are used alone or in combination, and the concentration of the dispersed particles is 10 to 60% by weight. % Is common. In the present invention, any of these colloidal substances can be used. Specific examples of the colloidal substance include colloidal silica (silica sol), colloidal alumina (alumina sol), colloidal titanium oxide (titania sol), and colloidal zirconium oxide (zirconia sol). By adding the colloidal substance, the formed ceramic layer becomes denser and tougher, and is less likely to crack. Further, the film thickness can be increased. The amount of the colloidal substance is preferably about 3 to 230 parts by weight, and more preferably about 3 to 70 parts by weight, based on 100 parts by weight of the ceramic film-forming substance (equivalent to SiO ₂ ). Is more preferred.

The colloidal substance can be added to the composition of the present invention as it is. At the time of film formation, the colloidal substance condenses with a silanol compound which is a ceramic film-forming substance or a partial condensate thereof to form a film. Since it is a component, it is also possible to mix a colloidal substance and a ceramic film-forming substance in advance as a hydrolyzed condensate in the state of hydrolytic condensation. When compounding a colloidal substance as a hydrolysis condensate with a ceramic film forming substance,
The degree of condensation is not particularly limited as long as it is uniformly dissolved or dispersed in the composition of the present invention and does not cause precipitation. The method for obtaining the hydrolyzed condensate may be in accordance with a conventional method. For example, in the case of an aqueous colloidal substance, various organic solvents as described above are used for the ceramic film forming substance and the colloidal substance. In the case of a non-aqueous colloidal substance, water is added, and acids, which are known hydrolytic condensation catalysts, such as hydrochloric acid and acetic acid, are added thereto. The hydrolysis and condensation may be performed for about 5 hours.

In the present invention, a resin-modified silicone resin can be blended into the above composition for the purpose of imparting flexibility to the formed ceramic film or for enabling thick coating. By blending the resin-modified silicone resin, the flexibility of the ceramic film can be improved while maintaining good adhesion to the plastics material. As the resin-modified silicone resin, any resin-soluble silicone resin can be used without limitation as long as it is soluble in the coating composition of the present invention. Examples of the type of resin modification include epoxy modification, polyester modification, alkyd modification, phenol modification, and acrylic modification. And the like.
The compounding amount of the resin-modified silicone resin is preferably about 5 to 100 parts by weight, and more preferably about 5 to 70 parts by weight as a solid content based on 100 parts by weight of the ceramic film-forming substance (SiO ₂ equivalent). Is more preferable.

The composition of the present invention may be added by dissolving resins such as fluororesin, silicone resin, polyester resin, nylon resin and acrylic resin in the above-mentioned organic solvent. By adding these resins,
Properties such as flexibility and shock absorption can be imparted to the formed film. The compounding amount is 5 to 1 as a solid content based on 100 parts by weight of the ceramic film-forming substance (SiO ₂ equivalent).
It is preferably about 00 parts by weight, more preferably about 5 to 70 parts by weight.

Further, the composition further comprises a buffered latent catalyst, which does not cause gelation of the composition at room temperature but dissociates by heating to accelerate the polymerization of the composition. Acid metal salts, amine carboxylate, quaternary ammonium carboxylate, nitrate and the like can be added to the composition up to about 1.5% by weight. Examples of such a buffered latent catalyst include dimethylamine acetate, ethanolamine acetate, dimethylaniline formate, sodium acetate, sodium propionate, potassium formate, sodium formate, benzyltrimethylammonium acetate, sodium nitrate, ammonium nitrate, and ammonium acetate. Is exemplified.

The composition of the present invention is preferably adjusted to a pH of about 2.5 to 6.0 in order to prevent rapid gelation. For pH adjustment, for example, hydrochloric acid, acetic acid, chloroacetic acid, citric acid, maleic acid, oxalic acid, toluenesulfonic acid,
Organic acids and inorganic acids such as glutaric acid, dimethylmalonic acid, benzoic acid and hydrogen peroxide can be used.

In the present invention, the above-mentioned coating composition is applied onto a substrate by a spray method, a roll coating method, a dipping method, a curtain flow method, a printing method, or the like, and polymerized and gelled to form a ceramic coating layer. Can be formed. There is no particular limitation on the type of the substrate, and in addition to organic substrates such as plastics, organic coatings, paper, fibers, and wood, metals, glass, ceramics, and the like can be used as the substrate.

In the composition of the present invention, it is considered that zinc oxide blended as an ultraviolet absorbing component also acts as a polymerization catalyst. Due to the presence of zinc oxide, the composition has extremely excellent low-temperature curability. A good ceramic layer can be formed only by leaving the composition at room temperature for about 3 to 24 hours after application. Further, the composition of the present invention can be heated to shorten the gelation time, increase the polymerization density, and make the ceramic film more dense. The higher the heating temperature is, the more dense the ceramic layer can be.
It is appropriate to heat at about 200 ° C. for about 10 to 30 minutes. In order to completely prevent the occurrence of pinholes in the ceramic film, after coating and drying or heat curing of the coating composition of the present invention, one or more coating compositions of the same or different types are further applied. It is preferable to form two or more ceramic films by coating and curing more than one layer.

The thickness of the film formed by the composition of the present invention may be appropriately changed depending on the type of the base material, the use of the film, and the like. Usually, the total thickness is about 0.5 to 100 μm. do it.

[0032]

The film formed from the coating composition of the present invention is a substantially colorless and transparent ceramic film,
Since ultraviolet rays in a wide wavelength range of about 190 μm to 380 μm can be absorbed, it is possible to prevent the deterioration of the base material due to the ultraviolet rays by forming the film. In particular, by applying it to the surface of an organic base material such as plastics, organic paint, paper, wood, fiber, etc., deterioration of the organic material due to ultraviolet rays is prevented, and yellowing, cracks, peeling, whitening, etc. are prevented. it can. In addition, since the film itself is colorless and transparent, the color tone of the substrate does not change at all, and the film itself does not change color for a long time, so that the color tone of the substrate can be maintained for a long time. Further, the coating is excellent in heat resistance, water resistance, acid resistance, non-staining property, etc., and can improve scratch resistance, abrasion resistance, etc., for example, when the coating is formed on plastics. Has improved surface hardness, wear resistance, etc., and can be used as a substitute for glass.

Further, the film is non-staining and, when formed on an organic film or plastics, is effective as a contamination preventing coating to prevent the adhesion of dirt when used outdoors.

In addition, by coating the surface of the metal, corrosion resistance, abrasion resistance, scratch resistance, and the like can be improved. By coating the glass, it is possible to prevent the transmission of ultraviolet light and to use it as a window glass that is not permeable to ultraviolet light.

As described above, according to the coating composition of the present invention, a film that is colorless and transparent and has excellent ultraviolet absorption can be formed. Moreover, the formed film has corrosion resistance, heat resistance, weather resistance, UV resistance, abrasion resistance, heat insulation, insulation,
It has excellent properties such as optical properties, stain resistance, scratch resistance, solvent resistance, and chemical resistance. For example, houses (interior and exterior materials), vehicles (automobiles, bicycles, motorcycles, airplanes, trains), ships , Electrical appliances, civil engineering, space related, gas, oil,
It can be used in various fields such as electric power, glass, glasses, tanks, plants, and communications to provide new products with unprecedented performance.

An example of such a method of use is to form a film of the composition of the present invention on an organic coating film of a housing exterior material (panel, roofing material, etc.) to prevent damage.
At the same time as imparting non-staining properties, water resistance, water repellency, etc., the weather resistance can be improved. For example, the durability of about 7 to 8 years has been improved to about 20 to 30 years. Can be included. Similar effects can be obtained by forming a film of the composition of the present invention on an automobile film, a building exterior material, an article formed with an organic film used outdoors, and the like. Further, by forming a film on a transparent plastic, glass, or the like, it is possible to obtain a glass having an ultraviolet transmission preventing property, and a transparent plastic for a lighting device such as a headlight,
It can also be applied to glass and the like.

[0037]

The present invention will be described in more detail with reference to the following examples.

Example 1 Cerium oxide sol in which ceric oxide having a particle size of about 20 μm is dispersed in n-butanol (concentration: 20% by weight)
And zinc oxide having a particle size of about 30 μm with n-butanol and 2-
50 g of a mixed sol obtained by mixing a 1: 1 (weight ratio) zinc oxide sol (concentration: 20% by weight) in a 1: 1 (weight ratio) butoxyethanol mixed solvent, comprising methylmethoxysilane and a silica sol. Hydrolysis condensate (methylmethoxysilane 50 g, silica sol (isopropyl alcohol 20% dispersion) 10 g, isopropyl alcohol 30
g, 10 g of water and 1 g of acetic acid were reacted at 80 ° C. for 3 hours) (concentration: 20%), 200 g, and 2 g of ethanolamine acetate were mixed to prepare a stable one-part coating composition.

This composition was applied to the surface of each substrate shown in Table 1 below, and heated at 80 ° C. to 200 ° C. for 5 minutes to 20 minutes to form a 0.5-8 μm thick colorless and transparent ceramic film. .

[0040]

[Table 1]

The results of the physical properties tests on the obtained samples are shown in Table 2 below. In addition, acrylic paint board, acrylic urethane paint board, urethane paint board, epoxy paint board, melamine paint board, and alkyd paint board, respectively,
Samples were prepared using aluminum plate, ABS resin plate, slag-cement plate and wood as base materials. The test results were the same when the base materials were different.

Evaluation criteria for physical properties (1) Weather resistance: 3000 hours in QUV test (2) Weather resistance: Sunshine weatherometer 300
0 hours (3) Salt spray resistance: JIS-Z-2371 salt spray test 3000 hours (4) Water resistance: 25 ° C tap water immersion 240 hours (5) Gasoline resistance: 25 ° C gasoline immersion 240 hours (6) Adhesion Properties: Adhesion test of JIS-K-5400 coating film (7) Hardness: Pencil hardness (8) Stain resistance: Washing and removing test for mud stains (9) Stain resistance: Thinner washing test for magic ink (10) Chemical resistance: state after 24 hours after dropping 1 drop of 5% H ₂ SO ₄ (11) Chemical resistance: 24 drops after dropping 3% NaOH
State after time (12) Heat resistance: Temperature measurement at which the substrate changes.

(13) Scratch resistance: steel wool (N
o. Rubbing 10 times with a load of 100 g / cm ² at 000) (14) Boiling water resistance: 24 hours immersion in boiling water Evaluation result criteria (1) No change in base material and coating film. 〇 (2) No change in base material but slight abnormality in coating film △ (3) No change in coating film but slight abnormality in base material △ (4) Abnormality of base material or coating film × Evaluation result

[0044]

[Table 2]

As can be seen from the above results, the transparent film formed by the coating composition of the present invention has excellent weather resistance, chemical resistance, etc., and also has excellent water repellency, abrasion resistance, etc.
Rust prevention of metal and effects such as improvement of weather resistance, water resistance and water repellency of various materials such as resin, paper, wood, cement board, tile, and ceramics can be exhibited.

The above composition was applied to a quartz cell of a spectrophotometer and heated at 180 ° C. for 30 minutes to form a film having a thickness of 3 μm. Thereafter, ultraviolet light and visible light in the range of 200 to 500 nm were used using this cell. Was measured. The results are shown in FIG. FIG. 2 shows the measurement results of the transmittance of the quartz cell in a state where no film was formed. As is clear from the comparison between FIG. 1 and FIG. 2, it can be seen that the use of the composition of the present invention makes it possible to form a film having excellent ultraviolet light shielding properties. In addition, since this film has good transmittance of visible light, it can be understood that the film is excellent in transparency with almost no coloring.

Example 2 30 g of ceric oxide having a particle size of about 20 mμ and a particle size of about 3
10 g of zinc oxide of 0 μm is dispersed in a mixed solution containing water and isopropyl alcohol in a ratio of 1: 2 (weight ratio), and a mixed sol of ceric oxide and zinc oxide (concentration: 20%) is used.
%) 200 g were obtained. To this, 2 g of acetic acid was added and stirred, and 60 g of methyltrimethoxysilane was further added to prepare a transparent aqueous coating composition.

Using this composition, a physical property test of a film formed in the same manner as in Example 1 was performed.
It was the same result as.

Example 3 25 g of a sol (concentration: 20%) in which ceric oxide having a particle diameter of about 20 μm was dispersed in n-butanol, and a particle diameter of about 20 m
12.5 g of a sol (concentration 20%) in which 1 μm of zinc oxide was dispersed in a mixed solvent of 1: 1 (weight ratio) of n-butanol and 2-butoxyethanol, and a silica sol having a particle diameter of 20 μm (isopropyl alcohol 20% dispersion) Liquid) 12.5 g,
20 g of isopropyl alcohol, 25 g of a mixture of a hydrolysis condensate of tetramethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane (1: 3: 1 (weight ratio) of tetramethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane), 5 g of water,
And 0.5 g of acetic acid were added and mixed, and reacted at 80 ° C. for 3 hours (concentration: 20%), and 150 g was mixed to prepare a non-aqueous coating composition.

Using this composition, a physical property test was performed on a film formed in the same manner as in Example 1.
It was the same result as.

Example 4 A partially hydrolyzed condensate of methyltrimethoxysilane and silica sol (100 g of methylmethoxysilane, 20 g of silica sol (20% dispersion of isopropyl alcohol), 60 g of isopropyl alcohol, 20 g of water and 2 g of acetic acid were added in 8 parts).
(Reacted at 0 ° C. for 3 hours) (molecular weight 1500) 20
0 g, 35 g of a sol (concentration: 20%) in which ceric oxide having a particle diameter of about 20 m is dispersed in n-butanol, and zinc oxide having a particle diameter of about 20 m are 1: 1 (weight: n-butanol and 2-butoxyethanol). 15 g of a sol (concentration: 20%) dispersed in a mixed solvent having a ratio of 20% and 30 g of an acrylic silicone resin solution (50%) were mixed, and 2 g of ethanolamine was used as a polymerization catalyst, 20 g of ethylene glycol monoethyl ether was used as a solvent, and butyl acetate was used. 20 g of isopropyl alcohol and 20 g of isopropyl alcohol were mixed to prepare a transparent non-aqueous coating composition.

Using this composition, a physical property test was performed on a film formed in the same manner as in Example 1. The results are shown in Table 3 below.
Shown in

[0053]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a graph showing the results of measuring the transmittance of ultraviolet light and visible light using a quartz cell having a ceramic film formed from the composition of the present invention.

FIG. 2 is a graph showing the results of measuring the transmittance of ultraviolet light and visible light using a quartz cell on which a ceramic film is not formed.

Claims (3)

[Claims] (I) The general formula R ² _n Si (OR ¹ ) _4-n
(Wherein, R ¹ represents hydrogen or a lower alkyl group, R ² represents a lower alkyl group, a vinyl group, a fluoropropyl group, γ
A glycidoxypropyl group or a γ- (meth) acryloxypropyl group, and n is 0, 1 or 2. )), And (ii) ultraviolet absorption containing zinc oxide and ceric oxide in a ratio of the former to the latter (weight ratio) = 1: 0.1 to 1:10. An ultraviolet-absorbing coating composition comprising a component. 2. The coating composition according to claim 1, wherein zinc oxide and ceric oxide are blended as a sol or a mixed sol containing each alone. 3. An ultraviolet absorbing component is contained in an amount of 1 to 1000 parts by weight based on 100 parts by weight of at least one of the silanol compound and its partial condensate.
Or the coating composition according to 2.