JPH09100141A - Production of water repellent glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce water repellent glass excellent in transparency and having high water repellent effect. SOLUTION: This production of water repellent glass is to coat a hydrolyzed product of a metal alkoxide or a hydrolyzed product of a metal chelate and a coating solution for undercoating containing superfine particles of a metal oxide to form an irregular layer and form a water repellent layer by treating the coated glass with a water repellent agent having fluoroalkyl groups in a molecule. As metal oxide superfine particles, particles having 2-500nm diameter can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing water-repellent glass, and more particularly to a method for producing water-repellent glass suitable for vehicles or buildings, which can secure a comfortable visual field or which is not easily stained by a window glass. .

[0002]

2. Description of the Related Art As one of the methods for making a glass surface water repellent, Journal of Physical Chemistry, Ithaca,
1965, 69, 1507, it is known that the water-repellent effect is enhanced by making the surface of the substrate uneven and forming a water-repellent film on it. In JP-A-4-288349 and JP-A-4-239633, a silicate glass and fine particles are mixed to form a concavo-convex layer of submicron to micron order, and then a polymer film layer containing a fluorocarbon group and a siloxane group or a chemisorption single layer is formed. A water repellent treatment method of providing a molecular layer is described.

[0003]

However, in JP-A-4-288349 and JP-A-4-239633,
The height of the irregularities was 0.5 to 10 μm, and the water-repellent glass obtained scatters visible light and impaired transparency. An object of the present invention is to solve the above problems and produce a water-repellent glass having excellent transparency and a high water-repellent effect.

[0004]

That is, the present invention provides an undercoat coating liquid containing a hydrolyzate of a metal alkoxide or a hydrolyzate of a metal chelate and metal oxide fine particles on the surface of a glass substrate. In the method for producing a water-repellent glass, the water-repellent glass is formed by coating to form a concavo-convex layer, and then treated with a water-repellent agent having a fluoroalkyl group in the molecule to obtain 2 parts of the metal oxide fine particles.
A method for producing water-repellent glass, characterized in that a glass having a diameter of ˜500 nm is used.

In the present invention, a hydrolyzate of a metal alkoxide or a hydrolyzate of a metal chelate is used as a component of the undercoat coating liquid.

Examples of the metal species of the metal alkoxide or metal chelate include Si, Zr and Ti, examples of the alkoxide include ethoxide, isopropoxide and butoxide, and examples of the chelate include an acetylacetonate complex. Examples of metal alkoxides and chelates are tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, zirconium tetraisopropoxide, zirconium tetrabutoxide, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium diacetylacetonate, titanium diacetylacetate. Nate and the like. Further, a high molecular weight type alkyl silicate (for example, ethyl silicate 40 manufactured by Colcoat, MS manufactured by Mitsubishi Chemical)
56S, etc.) can also be used. A coating liquid is prepared by hydrolyzing these compounds, but instead of the preparation, a commercially available glass coating liquid, for example, "HAS-10" manufactured by Colcoat Co., Ltd., "Ceramica G-02 manufactured by Nitban Kenkyusho Co., Ltd." -6 ", Nippon Soda" Atron N "
A hydrolyzed solution of alkoxysilane such as "SI-500" may be used.

The metal alkoxide or the metal chelate is added with water for causing hydrolysis, a catalyst for hydrolysis, and a solvent typified by alcohols, stirred, and allowed to stand for a predetermined time, A hydrolyzate is formed. As a catalyst for the hydrolysis of metal alkoxide or metal chelate, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, as well as organic acids such as acetic acid, citric acid and sulfonic acid are used. As the amphipathic solvent for the hydrolyzate of metal alkoxide or metal chelate, water-soluble organic solvents such as alcohols and ketones are used.
Examples of alcohols include methanol, ethanol, propanol, butanol and the like. Examples of ketones include acetone and methyl ethyl ketone.

The metal oxide fine particles used as a component of the coating liquid for undercoating are one-component metal oxide fine particles such as colloidal silica fine particles, silicate glass fine particles, titania fine particles, zirconia fine particles, ceria fine particles, and alumina fine particles. And a mixture thereof, and fine particles of a composite metal oxide composed of two or more kinds of these components (for example, titania-silica, titania-ceria or silica-zirconia), which are in the form of a solvent-dispersed sol. It is preferably used in. As metal oxide sol, for example, Nissan Chemical
In addition to water-dispersed silica sols such as Snowtex OL, O, and OUP, Nissan Chemical's MIBK-ST, XBA-ST
Organic solvent-dispersed silica sol, such as Catalyst manufactured by Catalyst Kasei
loid SI-80P (silica sol) and the like can be mentioned. A water-repellent film formed using fine particles of titania, ceria, etc. can be expected to have a secondary function other than water repellency such as absorption of ultraviolet rays. Among these, colloidal silica is particularly preferable because it has many OH groups on the surface.

The metal oxide fine particles have a diameter of 2 nm.
~ 500 nm is preferable, and more preferably diameter is 4 nm.
~ 80 nm. When the diameter is less than 2 nm, there is no effect of unevenness, and when the diameter exceeds 500 nm, the unevenness is too large and the transparency is impaired, and the metal oxide fine particles are easily precipitated in the coating liquid, which is not preferable. Due to such unevenness, the durability, particularly the fastness, of the water-repellent film coated thereon is improved.

If the concentration of the metal oxide fine particles contained in the composition for water-repellent coating is too low, the metal oxide fine particles are sparsely arranged at the time of drying, so that the unevenness is not reduced.
On the contrary, if the concentration is too high, the metal oxide fine particles are piled up in the film too much in multiple layers, for example, 10 or more layers, and the hardness of the whole film is lowered during drying, which is not preferable. The preferable concentration of the metal oxide fine particles in the coating liquid for undercoating is, for example, 0.1 to 20% by weight, and more preferably 0.5 to 5% by weight, in the case of coating by using a dipping and lifting method. . Further, in the case of coating using a roll coater method, it is preferably 0.5 to 25% by weight, more preferably 1 to 10% by weight. Further, in the case of coating using a flow coating method, the content is preferably 0.05 to 10% by weight, more preferably 0.1 to 1.0% by weight.

These metal oxide fine particles are added to a hydrolyzing solution of a metal alkoxide or a metal chelate to prepare a coating solution.

In the coating liquid for undercoat used in the present invention, the ratio of the metal oxide fine particles to the metal alkoxide or the metal chelate is expressed by the molar ratio of metal atoms, and the metal oxide is mixed with the metal alkoxide or the metal chelate 100. The fine particles are preferably 10 to 200, and more preferably 20 to 150. In this range, the unevenness on the upper portion of the metal oxide fine particles is maintained after drying, and the metal oxide fine particles are firmly fixed to the film containing a metal oxide formed from a metal alkoxide or a metal chelate as a main component. If the metal oxide fine particles are smaller than this range, the metal oxide fine particles will sink into the film, making it difficult to form the desired unevenness on the film surface, and conversely larger than this range. In this case, it becomes difficult for the metal oxide fine particles to be firmly fixed to the film.

The preferred amount of the coating material for the uneven undercoat used is as follows based on the metal alkoxide or metal chelate. Metal alkoxide or metal chelate 100 parts by weight Metal oxide fine particles 10 to 200 parts by weight Water 4 to 100 parts by weight Catalyst 10 ^-5 to 10 parts by weight Solvent 500 to 10000 parts by weight

The above metal alkoxide or metal chelate is dissolved in a water-soluble organic solvent, a catalyst and water are added, and the mixture is hydrolyzed at a predetermined reaction temperature between room temperature and the boiling point of the solution for 2 hours to 2 days, and then metal oxidation is carried out. A metal oxide fine particle such as a substance sol is added and, if necessary, further reacted at a predetermined reaction temperature between room temperature and the boiling point of the solution for 2 hours to 2 days to obtain a coating solution for uneven undercoat. The metal oxide fine particles may be added before the hydrolysis treatment, or may be added before or simultaneously with dissolving the metal alkoxide or metal chelate in the water-soluble organic solvent. The obtained coating liquid may be subsequently diluted with an appropriate solvent depending on the coating method. As the water-soluble organic solvent, alcohols, ketones and the like are used. Examples of alcohols include methanol, ethanol, propanol, butanol and the like.
Examples of ketones include acetone and methyl ethyl ketone.

When the water repellent coating composition cannot be uniformly applied to the surface of the base material depending on the base material, it can be improved by washing or modifying the surface of the base material. As a cleaning method, degreasing cleaning with a solvent such as alcohol or acetone,
Examples include cleaning with an alkali or acid solution, polishing the surface with an abrasive, and surface modification such as plasma treatment and UV ozone treatment.

The undercoat layer coating method may be a coating method using an apparatus such as a spin coater, a roll coater, a spray coater or a curtain coater, as well as a dipping / pulling method, a flow coating method, or a screen printing method.
Printing methods such as gravure printing and curved surface printing may be used.

The coated glass has room temperature to 2
After drying at a temperature of 00 ° C., firing is performed at a temperature of 400 ° C. to the softening point of the glass for several seconds to several hours. The metal alkoxide hydrolyzate or metal chelate hydrolyzate thus applied forms a metal oxide, and the metal oxide fine particles are embedded or deposited in the metal oxide film. The thickness of the undercoat layer is preferably 2 to 500 nm, more preferably 4 to 80 nm.

Further, the critical inclination angle of the water-repellent film, that is, the inclination angle of the glass plate on which the water-repellent film-covered glass plate placed horizontally is started to roll, is reduced to reduce the water drop. In order to facilitate the falling, it is more preferable that the particle diameter of the metal oxide fine particles is small and 4 to 80 nm.

The water repellent having a fluoroalkyl group in the molecule of the present invention is represented by the following formula (1), (2) or (3).
A fluoroalkylsilyl compound represented by is preferably used.

Embedded image CF ₃ — (CF ₂ ) _n —R—SiX _p Y _3−p (1) (where n is an integer of 3 to 12 and R is a carbon number of 2 to 2).
10 divalent organic groups (for example, methylene group, ethylene group) or groups containing a silicon atom and an oxygen atom, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms (for example, alkyl group,
A cycloalkyl group, an allyl group) or a substituent selected from these derivatives, or hydrogen, p is 0, 1 or 2, and Y is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group).

Embedded image CF ₃ — (CF ₂ ) _n —R—SiX _p Cl _3−p (2) (where n is an integer of 3 to 12, R is a methylene group, an ethylene group, or a silicon atom and an oxygen atom). A group containing
Is H or a substituent selected from an alkyl group, a cycloalkyl group, an allyl group or derivatives thereof, and p is 0, 1
Or 2)

Embedded image CF ₃ — (CF ₂ ) _n —R—Si— (NH—Si—R— (CF ₂ ) _n —R—Si) _r —NH—Si—R— (CF ₂ ) _n —CF ₃ (3) (where n is an integer of 3 to 12, R is a methylene group, an ethylene group, or a group containing a silicon atom and an oxygen atom, r
Is 0 or an integer of 1 or more)

Further, in order to reduce the critical inclination angle of the water repellent film so that water drops can easily fall off, the chemicals represented by the following formulas 4 to 6 may be added to the water repellent and used. . The amount used is represented by solid content and is usually 20 to 80% by weight based on the total amount of the water repellent.

Embedded image A- (Si (CH ₃ ) ₂ —O) _n —Si (CH ₃ ) ₂ B (4) (wherein A and B are independently a hydroxyl group, a methyl group, a methoxy group or an ethoxy group, (n is an integer from 5 to 10)

Embedded image (CH ₃ ) ₃ SiY (5) (wherein Y is chlorine or an alkoxy group having 1 to 3 carbon atoms)

Embedded image ((CH ₃ ) ₃ Si) ₂ NH (6)

The water repellent is hydrolyzed as necessary, and then
Used for coating the water repellent layer. Among the water repellents, those represented by the chemical formula (1) are dissolved in a water-soluble organic solvent,
An acid catalyst and water are added, and the mixture is hydrolyzed at a certain temperature for a certain period of time, diluted if necessary, and used for coating. When used without being hydrolyzed, the water repellent treatment agent has low reactivity with the glass surface and low abrasion resistance.

As the hydrolysis catalyst for hydrolyzing the water repellent, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, as well as organic acids such as acetic acid, citric acid and sulfonic acid are used.

As the water-soluble organic solvent for the water repellent, alcohols, ketones, etc. are used. Examples of alcohols include methanol, ethanol, propanol, butanol and the like. As ketones,
Acetone, methyl ethyl ketone, etc. can be illustrated.

Among the water repellents, those represented by the above chemical formulas (2) and (3) are water-insoluble organic solvents having a sufficiently reduced dissolved water content, such as xylene, n-hexane, cyclohexane, and hexafluorometaxylene. Dissolved in
Provide for coating. Even if a catalyst for hydrolysis, water, etc. is not added, it is hydrolyzed by the amount of water contained in the atmosphere, so that the reactivity with the glass surface is sufficiently high.

The polysiloxane compound (4) is subjected to a hydrolysis treatment and surface treatment in the same manner as the water repellent (1).
You may mix and co-hydrolyze with the water repellent of (1)-(3), and may use it.

The one represented by the above chemical formula (2) is
The water repellent treatment may be carried out by the method shown in the low pressure CVD method (Japanese Patent Laid-Open No. 6-279062).

As the water repellent having a fluoroalkyl group in the molecule of the present invention, a cohydrolysis of a perfluoroalkyl group-containing organosilicon compound and a hydrolyzable group-containing methylpolysiloxane compound in a hydrophilic solvent is further used. A water repellent prepared by blending a compound, an organopolysiloxane, and a strong acid is preferably used. This water repellent is used in a hydrophilic solvent of a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (7) and a hydrolyzable group-containing methylpolysiloxane compound represented by the following general formula (8). Is a mixture of the co-hydrolyzate of (1), an organopolysiloxane represented by the following general formula (9), and a strong acid.

Embedded image (However, in the formula, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is an alkoxy group or acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. Is a group, a is 0 or 1, and p is an integer of 1 to 12.)

Embedded image (However, in the formula, R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ is an alkoxy group or acyloxy group having 1 to 4 carbon atoms, A is a methyl group or —Z—Si (R ³ _b ) R
⁴ _3-b (b is 0, 1 or 2), Z is an oxygen atom or a divalent organic group having 2 to 10 carbon atoms. Further, m is an integer of 3 to 100, n is an integer of 0 to 50, and 5 ≦ m + n ≦ 100. When n = 0, at least one of A at both ends is -Z-Si.
(R ³ _b ) is a group represented by R ⁴ _3-b . In addition, -Z-Si
When there are two or more (R ³ _b ) R ⁴ _3-b , these may be the same or different from each other. )

Embedded image (However, in the formula, R ⁵ is the same or different from each other and has 1 carbon atom.
To 20 monovalent hydrocarbon groups, B is the same or different from each other, and is a hydroxy group or a monovalent hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group or an acyloxy group. r is an integer of 1 to 100. )

In the co-hydrolyzate, the perfluoroalkyl group-containing organosilicon compound of the formula (7) is effective for imparting water repellency, and the hydrolyzable group-containing methylpolysiloxane compound of the formula (8) is a water repellent film. Contributes to the effect of reducing the critical tilt angle of the above, and the silanol groups produced by the cohydrolysis of these two components are highly reactive with the inorganic surface. Further, the organopolysiloxane of the formula (9) further improves the effect of reducing the critical tilt angle of the water-repellent film, and the strong acid contains the above-mentioned perfluoroalkyl group-containing organosilicon compound and hydrolyzable group-containing methylpolysiloxane compound. It further improves the reactivity with the inorganic surface, imparts excellent durability, and exerts the effect of maintaining the effect for a long period of time.
Furthermore, since all of these components are soluble in a hydrophilic solvent, it is not necessary to use a special fluorine-based solvent.

Specific examples of the perfluoroalkyl group-containing organosilicon compound of the above formula (7) include C ₄ F ₉ CH ₂ C
_{H 2 Si (CH 3) (} OCH 3) 2, C 8 F 17 CH 2 CH 2 Si (O
CH _{3) 3,} etc. can be exemplified.

Specific examples of the hydrolyzable group-containing polysiloxane compound of the above formula (8) include those of the following formulas 10 to 12.

Embedded image

Embedded image

Embedded image (M is an integer of 3 to 100, n is an integer of 0 to 50, and 5 ≦ m + n ≦ 100, preferably 10 ≦ m + n ≦ 50.)

The perfluoroalkyl group-containing organosilicon compound of the above formula (7) and the hydrolyzable group-containing methylpolysiloxane compound of the above formula (8) are mixed in a weight ratio of (7) / (8). 10/90 to 90/10, especially 20 /
It is preferably 80 to 80/20. If the compounding ratio of the compound of the formula (7) is less than 10% by weight, sufficient water repellency may not be obtained, and if it exceeds 90% by weight, the water-repellent film has a large critical inclination angle and sufficient water repellency is obtained. Disappear.

Specific examples of the organopolysiloxane of the above formula (9) include those of the following formulas 13 to 16.

Embedded image

Embedded image

Embedded image

Embedded image (R is an integer of 1 to 100, and s + t = r.)

In the present invention, the blending amount of the organopolysiloxane of the above formula (9) is such that the perfluoroalkyl group-containing organosilicon compound of the above formula (7) and the hydrolyzable group-containing methylpolysiloxane of the above formula (8). The mixing ratio of the effective component amount of the cohydrolyzate with the compound (the amount obtained by removing the hydrophilic solvent from the cohydrolyzate) and the organopolysiloxane of the above formula (9) is 10/90 to 99 / by weight. 1, especially 40
The range of / 60 to 90/10 is preferable. If the amount of the active ingredient of the co-hydrolyzate is less than 10% by weight, sufficient durability may not be obtained in some cases, and if it exceeds 99% by weight, the critical inclination angle of the water-repellent film becomes large and sufficient water repellency is obtained. You may not be able to.

Further, the strong acid as the third component includes, for example, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, trichloroacetic acid, phosphoric acid, etc., but is not limited thereto. Not something.

The amount of the strong acid compounded is 0.01 to 100 parts by weight, particularly 0.1 to 50 parts by weight, based on 100 parts by weight of the total amount of the effective components of the cohydrolyzate and the amount of the organopolysiloxane. Parts by weight are desirable. If it is less than 0.01 part by weight, sufficient durability may not be obtained, and if it exceeds 100 parts by weight, the stability of the water repellent agent may deteriorate.

After baking and cooling the undercoat, the glass substrate is washed and then treated with a water repellent. This treatment is coating by a spray method, a flow coating method, a spin coating method, a dipping and pulling method or the like, and a surface adsorption by a liquid phase adsorption method, a low pressure CVD method or the like. After the glass treated with the water repellent is dried, the temperature is 300 ° C or lower, preferably 100 ° C to 250 ° C.
Heat treatment is performed at 10 ° C. for 10 minutes to 1 hour. If the water-repellent agent forms a monomolecular layer on the undercoat layer, it exhibits water-repellent performance, and even if the thickness of the water-repellent agent exceeds 10 nm, the effect is not further enhanced. Preferred thickness is 1
-10 nm.

Compounds (5) and (6) are applied to the surface of the glass after water repellent treatment in a vapor phase or dissolved in a solvent and applied in addition to the addition to the water repellent agent to give a critical water-repellent film. The tilt angle can be further reduced.

The uneven water-repellent film obtained by the present invention has not only higher water repellency (contact angle of water) but also extremely high fastness as compared with the flat water-repellent film similarly treated to be water-repellent. I understood. The term “fastness” as used herein means mechanical durability, which is mainly represented by abrasion resistance, and remarkably good durability was exhibited in a dry cloth reciprocating abrasion test or a wiper abrasion test described later. The reason why the uneven water-repellent film is stronger than the flat water-repellent film is that the uneven water-repellent film has apparently high water repellency (contact angle of water), so that even if it deteriorates due to abrasion, the water repellency is not so low. Are concentrated in the vicinity of the apex of the convex portion, no deterioration occurs in other parts, and the water repellency is maintained by the non-deteriorated parts. There are two points.

Further, the uneven water-repellent film obtained by the present invention is
Similarly, it was found that the weather resistance was remarkably higher than that of the flat water-repellent film which was treated to be water-repellent. That is, it showed remarkably high weather resistance in the super UV test described later. The reason why the uneven water-repellent film has higher weather resistance than the flat water-repellent film is that the uneven surface film has a large true surface area, so that the density of the water-repellent groups present per apparent unit area is higher than that of the flat film. It is thought that this is due to the fact that

A water-repellent layer is provided on the uneven layer. In the water repellent layer, a perfluoroalkyl group is chemically bonded or chemically adsorbed to the surface of the uneven undercoat layer (the surface of the metal oxide from the metal alkoxide or the metal chelate). As the perfluoroalkyl group, a heptadecafluorodecyl group, a nonadecafluorododecyl group, a pentadecafluorooctyl group, a tridecafluorohexyl group, or a mixture of two or more thereof. By making a dimethylpolysiloxane component or a trimethylsilyl component coexist with the fluorocarbon component in addition to these fluorocarbons, the critical inclination angle of the water repellent film can be further reduced.

The uneven undercoat layer of the present invention comprises the particle size of the metal oxide fine particles in the undercoat liquid, the compounding ratio of the metal alkoxide hydrolyzate or the metal chelate hydrolyzate to the metal oxide fine particles, and the solid content. By adjusting the concentration and the like, the height of the protrusions is 1.0 to 200 nm, the thickness of the uneven undercoat layer is about 2 to 300 nm, and the surface roughness of the undercoat layer is Ra value of 1.5 to 80 nm. Preferably. The thickness of the water repellent layer is smaller than the height of the unevenness of the undercoat layer, and the water repellent layer is formed with a substantially uniform thickness along the unevenness of the surface of the undercoat layer. The surface shape can be considered to be almost the same as that of the undercoat layer. If the height of the convex portion is less than 1.0 nm, the unevenness is too small and the effect of improving water repellency is insufficient and the effect of improving fastness is also insufficient. If it exceeds 200 nm, the water-repellent layer is clouded, which is a problem. If the thickness of the uneven undercoat layer exceeds 300 nm, interference color may occur, which is a problem. R
The surface roughness indicated by a reflects the height of the unevenness and the existing density. When the Ra value is smaller than 1.5 nm, the water repellency improving effect is small and the fastness improving effect is also small. Ra
If the value is larger than 80 nm, the water-repellent layer is clouded, which is a problem. Here, the surface roughness Ra value is JIS B
0601.

[0042]

Embodiments of the present invention will be described below. Example 1 Preparation of Coating Solution for Concavo-convex Undercoat Tetraethoxysilane (manufactured by Katayama Chemical Co., Ltd.) 31 parts by weight was added to 380 parts by weight of isopropanol, and further 1.6 parts by weight of 1N hydrochloric acid and 6.5 parts by weight of water were added. , At 0 ° C 3
After stirring for an hour, the mixture was stirred at room temperature for 1 day for hydrolysis. To this hydrolyzed solution, 30 parts by weight of colloidal silica (“Snowtex OL”, manufactured by Nissan Kagaku Co., Ltd., solid content 20% by weight) having a particle diameter of 50 nm was added, and the mixture was further stirred at room temperature for 5 hours. About 450 parts by weight to 180 parts by weight of the obtained liquid was collected, and isopropanol was added to adjust the solid content to 8% to obtain an uneven undercoat liquid.

Preparation of coating solution for water repellent layer 1 part by weight of heptadecafluorodecyltrichlorosilane was dissolved in 1000 parts by weight of hexafluoromethaxylene and used as a coating solution for the water repellent layer.

Formation of water-repellent film on glass Soda lime silicate glass plate (150 mm × 70 mm × 3.5 mm)
Is surface-polished and washed with a cerium oxide-based abrasive,
After drying, the uneven undercoat liquid was coated by a dipping and lifting method. After drying for 30 minutes in a 150 ° C. dryer, it was heated in a suspension strengthening furnace (electric furnace) until the plate temperature reached 650 ° C., immediately taken out, and rapidly cooled by air blow. After cooling to 50 ° C., ultraviolet irradiation is applied to remove organic deposits on the surface (dry cleaning), and the product is immersed in the above water-repellent layer coating solution for 1 day at room temperature to chemically adsorb and pull up, and then hexafluorometa-xylene. It was immersed in a solvent and ultrasonically washed to obtain a water-repellent tempered glass having a water-repellent surface.

The contact angle of water of the obtained water-repellent film was 120.8 degrees when the contact angle of a water droplet having a diameter of about 2 mm was measured using a contact angle meter manufactured by Kyowa Interface Science.

The surface shape of the water-repellent layer of the present glass was such that the height of the convex portions was about 30 nm, the silica film thickness excluding the convex portions was about 80 nm, and the surface roughness was Ra value of 10.6 nm. However, the height of the convex portions and the silica film thickness were measured by an electron microscope manufactured by Hitachi Ltd., and the surface roughness was measured by an atomic force microscope manufactured by Seiko Denshi. It was confirmed by electron microscope observation that the above-mentioned convex portions were derived from silica fine particles in colloidal silica.

Abrasion resistance test Regarding the abrasion durability of the water-repellent film, a dry cloth was attached to a reciprocating abrasion tester manufactured by Shinto Kagaku Co., Ltd. Robustness by measurement
Then, the wiper abrasion resistance was evaluated by the contact angle after reciprocating 50,000 times by the wiper abrasion tester.
The wiper abrasion test was carried out by applying a load of 20 g / cm to a commercially available rubber wiper blade having a length of 50 mm and supplying water of 20 g / min.
It was made to rub back and forth at a speed of mm / sec. As for the results of evaluation of wear resistance, as shown in Table 1, both the fastness (contact angle after dry cloth wear) and the wiper wear resistance (contact angle after wiper wear) were very excellent.

Weather resistance test The weather resistance of the water-repellent film was measured by using a weather resistance tester (Iwasaki Denki: "Eye Super UV Tester W13") at an illuminance of 76 mW / cm ² and a black panel temperature of 63 ° C. It was evaluated by the value of the contact angle after UV irradiation for 250 hours under the condition that water was showered for about 30 seconds every hour. The weather resistance evaluation result was very excellent as shown in Table 1.

Example 2 Preparation of coating solution for uneven undercoat 31 parts by weight of tetraethoxysilane (Katayama Chemical Co., Ltd.) was added to 380 parts by weight of isopropanol, 1.6 parts by weight of 1N hydrochloric acid and 6.5 parts by weight of water. Parts were added, and the mixture was stirred at 50 ° C. for 3 hours and then stirred at room temperature for 1 day to cause hydrolysis.
To this hydrolyzed solution, 30 parts by weight of colloidal silica (“Snowtex OL”, manufactured by Nissan Kagaku Co., Ltd., solid content 20% by weight) having a particle diameter of 50 nm was added, and the mixture was further stirred at room temperature for 5 hours. About 450 parts by weight of the obtained liquid was collected from 180 parts by weight, and ethyl acetoacetate was added to adjust the solid content to 8% to obtain an uneven undercoat liquid.

Formation of water-repellent film on glass Soda lime silicate glass plate (300 mm × 300 mm × 5 mm)
Was surface-polished and washed with a cerium oxide-based abrasive, dried, and then coated with the uneven undercoat liquid using a roll coater. After drying for 30 minutes in a 150 ° C. dryer, it was heated in a suspension strengthening furnace (electric furnace) until the plate temperature reached 600 ° C., immediately taken out, and rapidly cooled by air blow. After cooling to 50 ° C., ultraviolet rays are irradiated to remove organic deposits on the surface (dry cleaning), and then this glass plate and about 2 g of heptadecafluorodecyltrichlorosilane (H
FTCS) was put in a petri dish and set in the chamber. Vacuum for 2 minutes with a vacuum pump to bring the degree of vacuum to 5
After turning to Torr, the system was closed and heated to 80 ° C. 1
After reacting for a period of time, the temperature was raised to 99 ° C. while drawing a vacuum, excess HFTCS was removed by a cold trap, and the coated substrate glass was taken out to obtain a water repellent tempered glass.

As shown in Table 1, the initial water contact angle and the wiper abrasion resistance (contact angle after wiper abrasion) were very excellent.

Example 3 Preparation of water-repellent layer coating solution 3 parts by weight of heptadecafluorodecyltrimethoxysilane (TSL-8733 manufactured by Toshiba Silicone) and 3 parts by weight of dimethylpolysiloxane modified with silanols at both ends (produced by Petraque Co., Ltd.). Isopropanol 90
It was dissolved in 1 part by weight, 2 parts by weight of 0.1 N hydrochloric acid was added, the mixture was stirred at room temperature for 8 hours for hydrolysis, and 5000 parts by weight of cyclohexane was further added to prepare a coating solution for the water repellent layer.

In the formation of the water-repellent layer of Example 1, the unevenness undercoat similar to that of Example 1 was used except that the immersion time was changed to 7 days and cyclohexane was used as the washing solvent instead of hexafluorometaxylene. Water-repellent glass was produced by the operations of coating for water and coating of water-repellent layer.

As shown in Table 1, the results of evaluation of wear resistance were very excellent. Comparing the water-repellent glass of this example and the water-repellent glass prepared in Example 1 with each other, the glass inclination angle (critical inclination angle) at which a water drop having a diameter of 5 mm on the horizontally placed glass surface starts rolling is compared. The angle was about 30 degrees, while it was about 25 degrees in this example, and the critical angle of inclination was smaller and the water repellency was more excellent in this example.

Example 4 In the preparation of the coating solution for uneven undercoat of Example 1, instead of adding colloidal silica after the hydrolysis of tetraethoxysilane, the zirconium tetrachloride was hydrolyzed at about 5 ° C. after the hydrolysis of tetraethoxysilane. The same operation as in Example 1 was carried out except that butoxide was added to tetraethoxysilane in a molar ratio of 1/5 to further hydrolyze, and then colloidal silica was added. As shown in Table 1, the evaluation results of the initial water contact angle and the wiper wear resistance (contact angle after wiper wear) were very excellent.

Example 5 In the preparation of the coating solution for uneven undercoat of Example 1, the same amount of particle diameter 70 was used in place of Snowtex OL.
nm zirconium sol (Nissan Chemical Co., Ltd., “NZS-30
The procedure was as in Example 1, except that "A" solid content 30% by weight) was used. Table 1 shows the evaluation results of initial water contact angle and wiper wear resistance (contact angle after wiper wear).
It was very good as shown in.

Example 6 Preparation of Coating Solution for Concavo-convex Undercoat 9.6 parts by weight of alkoxysilane hydrolysis solution "HAS-10" (manufactured by Colcoat Co.) and diameter of 10 to 20 nm.
-Shaped rod-shaped colloidal silica with a length of 40 to 100 nm ("Snowtex OUP", Nissan Chemical Co., Ltd., solid content 15
% By weight) was added to 63.6 parts by weight of isopropanol, and the mixture was stirred at room temperature for 3 hours to obtain an uneven undercoat liquid.

Preparation of coating liquid for water repellent layer 2 parts by weight of heptadecafluorodecyltrimethoxysilane was dissolved in 32 parts by weight of t-butanol. 0.1
0.46 g of normal hydrochloric acid was added, the mixture was stirred at 20 ° C. for 24 hours for hydrolysis, and 64 parts by weight of n-hexane was further added to obtain a water repellent treatment stock solution. This stock solution of water repellent treatment was diluted with cyclohexane 100 times by weight and used as a coating solution for the water repellent layer.

Formation of water-repellent film on glass Soda lime silicate glass plate (150 mm × 70 mm × 3.5 mm)
Is surface-polished and washed with a cerium oxide-based abrasive,
After drying, the uneven undercoat liquid was coated by a dipping and lifting method. After drying in a dryer at 150 ° C for 30 minutes, baking at 500 ° C for 1 hour, immersing in the above water-repellent layer coating solution for 1 hour at room temperature to cause chemical adsorption, and then dipping in a cyclohexane solvent for ultrafiltration. After sonication, a water-repellent glass whose surface was made water-repellent was obtained.

As shown in Table 1, the initial water contact angle, wiper wear resistance (contact angle after wiper wear), and weather resistance were very excellent.

Example 7 Preparation of Coating Solution for Concavo-convex Undercoat Hydrolysis solution of alkoxysilane ("HAS-10" Colcoat) 46.9 parts by weight and diameter 10-20 nm.
-Shaped rod-shaped colloidal silica with a length of 40 to 100 nm ("Snowtex OUP", Nissan Chemical Co., Ltd., solid content 15
% By weight) 19.7 parts by weight of isopropanol 333.4
In addition to the parts by weight, this was further diluted 8 times with isopropanol and stirred at room temperature for 3 hours to obtain an uneven undercoat liquid.

Preparation of water-repellent layer coating liquid A perfluoro group-containing organosilicon represented by the formula C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was added to a 1 liter glass reactor equipped with a thermometer, a stirrer and a cooler. Compound 10.0 g, the following formula 1
10.0 g of a hydrolyzable group-containing methylpolysiloxane compound represented by 7 and isopropanol 4 as a hydrophilic solvent
Charge 80.0 g and 1.94 g of 0.1N hydrochloric acid water, and
A cohydrolysis reaction was carried out at 0 ° C. for 5 hours to obtain an isopropanol solution of the cohydrolyzate.

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Next, 10.0 g of the organopolysiloxane represented by the following formula 18 and 5.0 g of methanesulfonic acid were added thereto and stirred for 10 minutes to obtain a water repellent treatment solution.

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Formation of water-repellent film on glass Soda lime silicate glass plate (150 mm × 70 mm × 3.5 mm)
Is surface-polished and washed with a cerium oxide-based abrasive,
After drying, the uneven undercoat liquid was applied by a flow coating method. After drying in a dryer at 150 ° C for 30 minutes and baking at 500 ° C for 1 hour, 0.1 ml of the above water-repellent layer coating solution is spread 30 times with a cotton cloth, and the excess coating solution is wiped off with a dry cloth, and then 100 ° C. And heat-treated for 10 minutes to obtain a water-repellent glass having a water-repellent surface. As shown in Table 1, the initial water contact angle, wiper wear resistance (contact angle after wiper wear), and weather resistance were very excellent.

Example 8 Preparation of Coating Solution for Concavo-convex Undercoat In preparation of coating solution for concavo-convex undercoat of Example 7, the particle diameter was changed from 10 to 2 instead of Snowtex OUP.
The same operation as in Example 7 was performed except that 14.9 parts by weight of 0 nm colloidal silica (“Snowtex O”, manufactured by Nissan Chemical Industries, solid content 20% by weight) was used.

Preparation of water-repellent layer coating liquid and formation of water-repellent film on glass In the preparation of the water-repellent layer coating liquid of Example 7, t-butanol 36 was used instead of isopropanol as the hydrophilic solvent.
Using 0.0 g, to the resulting t-butanol solution,
Add 160.0 g of N-hexane as a hydrophobic solvent and add 10
After stirring for a minute, a water-repellent layer coating liquid was obtained. Using this solution, a water-repellent glass whose surface was made water-repellent was obtained in the same manner as in Example 7.

As shown in Table 1, the initial water contact angle, wiper wear resistance (contact angle after wiper wear), and weather resistance were very excellent.

Example 9 In the preparation of the coating liquid for uneven undercoat of Example 7, the particle diameter was changed from Snowtex OUP to 8-11n.
The same operation as in Example 7 was carried out except that m colloidal silica (“Snowtex OS”, manufactured by Nissan Chemical Co., Ltd., solid content: 20% by weight) was used. As shown in Table 1, the evaluation results of the initial water contact angle and the wiper wear resistance (contact angle after wiper wear) were very excellent.

Example 10 In the preparation of the coating solution for uneven undercoat of Example 8, instead of Snowtex O, colloidal silica having a particle diameter of 4 to 6 nm (“Snowtex OXS”, manufactured by Nissan Kagaku Co., Ltd., solid content 10% by weight) ) Was used, and the same operation as in Example 8 was carried out. As shown in Table 1, the evaluation results of the initial water contact angle and the wiper wear resistance (contact angle after wiper wear) were very excellent.

Example 11 Preparation of Coating Solution for Concavo-convex Undercoat 28.4 parts by weight of titanium isopropoxide was added to 20 parts by weight of acetylacetone and stirred for 2 hours to obtain a titanium raw material solution. Next, 166.9 parts by weight of isopropanol was added to 14.9 parts by weight of tetraethoxysilane, and 0.89 parts by weight of 1N hydrochloric acid, 3.42 parts by weight of water, 3.82 parts by weight of the titanium raw material solution, and particle diameter. Colloidal silica of 10 to 20 nm (“Snowtex IPA-ST”, manufactured by Nissan Kagaku Co., Ltd., solid content 30% by weight) was added, and the mixture was stirred at 50 ° C. for 3 hours and then stirred at room temperature for 1 day for hydrolysis. The obtained liquid was diluted 16 times with isopropanol to obtain a concave-convex undercoat liquid.

Preparation of water-repellent layer coating solution and formation of water-repellent film on glass In the same manner as in Example 7, a water-repellent glass having a water-repellent surface was obtained. The evaluation results of initial water contact angle and wiper wear resistance (contact angle after wiper wear) are as shown in Table 1.
Was very good.

Example 12 Preparation of Coating Solution for Concavo-convex Undercoat To 38.4 parts by weight of zirconium butoxide, 26.0 parts by weight of ethyl acetoacetate were added and stirred for 2 hours to obtain a zirconia raw material solution. Next, 164.6 parts by weight of ethanol was added to 11.3 parts by weight of tetraethoxysilane, and 0.89 parts by weight of 1N hydrochloric acid, 3.42 parts by weight of water, 9.71 parts by weight of the zirconia raw material liquid, and particle diameter. 10-20 nm colloidal silica (“Snowtex IPA-ST”,
Nissan Chemical Co., Ltd., solid content 30% by weight) is added and the mixture is heated at 50 ° C for 3
After stirring for an hour, it was hydrolyzed by stirring at room temperature for 1 day. The obtained liquid was diluted 16 times with ethanol to obtain a concave-convex undercoat liquid.

Preparation of Water-Repellent Layer Coating Liquid and Formation of Water-Repellent Film on Glass Water-repellent glass having a water-repellent surface was obtained in the same manner as in Example 7. As shown in Table 1, the initial water contact angle, wiper wear resistance (contact angle after wiper wear), and weather resistance were very excellent.

Comparative Example 1 In the preparation of the coating liquid for uneven undercoat,
Except that Snowtex OL was not added,
A water-repellent glass was produced by the same operation as in Example 1.
The results of the abrasion resistance test are shown in Table 1. The wear resistance and weather resistance were lower than those in Example 1.

Comparative Example 2 In the preparation of the coating liquid for undercoat of Example 1, 50 parts by weight of tetraethoxysilane was used instead of 31 parts by weight.
A water-repellent glass was produced in the same manner as in Example 1 except that the weight part was used and Snowtex OL was not added. The results of the abrasion resistance test are shown in Table 1. The wear resistance was lower than that of Example 1.

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[Table 1] ------------------------------------------ Example --- Metal oxide Ra value Contact angle (Degree) Height Coating thickness (nm) −−−−−−−−−−−−−−−−−− (nm) (nm) Initial flannel cloth Wiper After weathering test After wear After wear −−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 30 80 10.6 120.8 97.2 102.5 94.8 2 Same as above Same as above Same as above 110.3 −− 98.5 − − 3 〃 〃 〃 117.1 − − 94.9 −− 4 〃 〃 8.2 114.8 − − 105.4 − − 5 〃 〃 15.4 115.4 − − 110.2 − − 6 〃 〃 − − 119.5 − − 92.0 93.1 7 20 60 −− 116.3 − − 93.2 91.2 8 15 50 7.5 112.0 99.0 103.5 92.1 9 10 40 4.2 109.2 −− 100.0 −− 10 6 40 −− 108.5 −− 101.2 −− 11 15 50 −− 111.5 −− 101.5 −− 12 15 50 7.2 112.1 −− 105.1 95.5 −−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−− Comparative Example 1 0 80 0.7 104.1 73.4 39.7 78.3 2 0 150 0.9 102.5 −− 56.7 −− ========= ==========================

Comparative Example 3 In the preparation of the coating liquid for undercoat of Example 1, colloidal silica having a particle diameter of 50 nm (“Snowtex OL”, manufactured by Nissan Chemical Co., Ltd., solid content 20% by weight) 30
Particle diameter 10 μm (10000 nm) instead of parts by weight
Silica fine particles (DF10-60 manufactured by Asahi Glass Co., Ltd.)
A ") A water-repellent glass was prepared in the same manner as in Example 1, except that 6 parts by weight was used. The surface of the undercoated glass substrate had irregularities of about 10 μm. The water-repellent treated glass obtained was cloudy and had poor transparency.

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According to the present invention, a water-repellent glass having excellent transparency, high water-repellent effect, fastness and weather resistance can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Sunada 3-5-11 Doshumachi, Chuo-ku, Osaka City Japan Sheet Glass Co., Ltd. (72) Inventor Toyoyuki Teranishi 3-5-11 Doshumachi, Chuo-ku, Osaka Within Nippon Sheet Glass Co., Ltd.

Claims (6)

[Claims] 1. An uneven coating layer is formed by applying an undercoat coating liquid containing a hydrolyzate of a metal alkoxide or a hydrolyzate of a metal chelate and fine particles of a metal oxide on the surface of a glass substrate, and thereafter forming an uneven layer. In addition, in the method for producing water-repellent glass in which a water-repellent layer is formed by treating with a water-repellent agent having a fluoroalkyl group in the molecule, it is preferable to use the metal oxide fine particles having a diameter of 2 to 500 nm. A method for producing a water-repellent glass, which is characterized. 2. The method for producing water-repellent glass according to claim 1, wherein the metal oxide fine particles have a diameter of 4 to 80 nm. 3. The water-repellent layer has a protrusion height of 1.0 to 2
The method for producing water-repellent glass according to claim 1, wherein the water-repellent glass has irregularities having a surface roughness of 00 nm and an Ra value of 1.5 to 80 nm. 4. The water-repellent layer has a protrusion height of 2 to 40 n.
The water-repellent glass manufacturing method according to claim 3, wherein the water-repellent glass has irregularities of m and a surface roughness of Ra value of 1.5 to 15 nm. 5. The method for producing water-repellent glass according to claim 1, wherein the water-repellent agent is a water-repellent agent containing a fluoroalkyl group-containing silane compound. 6. The water repellent compounded with a cohydrolyzate of a perfluoroalkyl group-containing organosilicon compound and a hydrolyzable group-containing methylpolysiloxane compound in a hydrophilic solvent, an organopolysiloxane, and a strong acid. The method for producing water-repellent glass according to claim 5, wherein