JPH10167763A - Water-repelling glass and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the improvement of abrasion resistance, light resistance, adhesion, hardness and durability by subjecting a glass base board having ground surfaces to an acid treatment, then applying a coating solution for a water repelling film on the treated surfaces to form a water-repelling film layer. SOLUTION: After completing the hydrolysis reaction of a fluoroalkyl group- containing silane compound, the water content and the degree of polycondensation of the hydrolysis produce is controlled to obtain a coating solution for a water repelling film in which a weight ratio (expressed in g) of fluoroalkoxysilane compound: a diluting solvent: water by an acid catalyst is 1:(5-40):(0.09-1.0). After surfaces of a glass are polished with an aqueous suspension containing 0.1-10wt.% polishing agent composed mainly of an inorganic metal oxide, the glass is dipped into an aqueous acid solution of <=4.1 in pH at 5-70 deg.C for 10-600sec to modify the surfaces. Subsequently, the above-mentioned coating solution for a water repelling film is applied on the treated surfaces of the glass base board, and the product is dried and cured by heating at 80-350 deg.C for 1-60min. Thus, the fluoroalkyl group is fixed on the glass base board through siloxane bond to form a water-repelling film layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful not only for window materials for architecture, but also for window materials for vehicles such as automobiles, window materials for ships and aircraft, and various glass articles in various fields such as industrial glass. Water-repellent glass and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, there has been a demand for a water-repellent glass having more excellent durability and water repellency, and having excellent water repellency for a long time.

In order to meet these needs, for example, it is necessary to provide a water-repellent glass having a water-repellent thin film having high traverse resistance (abrasion resistance) and high light resistance. Therefore, the invention described in Japanese Patent Application No. 7-294106 filed by the present applicant has controlled the glass surface with high hardness, high mechanical strength, and excellent durability, with a high specific surface area. Forming a base film having a peculiar and finely uneven surface layer surface and forming a water-repellent film covering the base film, thereby increasing the adhesion efficiency and adhesion of the water-repellent film; Improves light resistance performance and demonstrates its performance remarkably, has high transparency without impairing optical characteristics, and has excellent water repellency, abrasion resistance, durability, etc. in the long term with strong adhesion Can be maintained as things.

[0004] In addition, Japanese Patent Application No. 8-13 filed by the present applicant has
In the invention described in No. 1595, etc., when a water-repellent film is formed on the surface of a glass substrate, the temperature of the glass substrate is about 90 to 200 ° C. Fine uneven glass substrate surface with streak flaws)
A water-repellent film layer, which exhibits outstanding water-repellent performance in weather resistance, abrasion resistance, scratch resistance and durability, and maintains its effect over a long period of time. It can be simply and efficiently formed without defects.

Japanese Patent Application Laid-Open No. Hei 3-247537 discloses a method for producing water-repellent glass, which includes a pretreatment step of polishing and cleaning the surface of a glass substrate using a polishing powder, and a method of hydrogenating an alkyl group of polydialkylsiloxane. A silicon-based water repellent in which 5% or more has been replaced by fluorine atoms on a pre-treated glass substrate to form a coating film, and curing the coating film to make it adhere to the glass substrate and form a film. And a curing step of forming a water-repellent cured film having a thickness of 0.1 to 2 μm.
The water-repellent coating film first reacts with the silanol groups present on the glass surface to form an adhesion film, and then in the thickness direction of the surface by polishing and washing with fine abrasive powder such as It is described that the curing of the resin proceeds.

Further, Japanese Patent Application Laid-Open No. 58-122979 and
JP-A-129082 describes a water- and oil-repellent agent for a glass surface. A glass plate (soda-lime glass) which is washed and washed with acetone, dipped in a 1% hydrochloric acid solution and dried, is prepared. Apply the adjusted water / oil repellent solvent solution to the surface
Apply at 120 ° C or 160% in 100% relative humidity.
It describes that the curing was performed at 20 ° C. for 20 minutes.

JP-A-5-96679 describes an adsorbed monomolecular film and a method for producing the same. In order to impart water and oil repellency, active hydrogen such as a hydroxyl group, an amino group or an imino group is used. A non-aqueous solution of two or more types of halogenated silane-based surface adsorbents or alkoxysilane-based surface adsorbents containing fluorine groups and having different molecular chain lengths is brought into contact with the surface of the base material having or added to the surface, Wash unreacted monomers,
It is described that a water-repellent, oil-repellent, anti-fogging, anti-fouling, adsorbed monomolecular film is obtained by reacting with water or moisture in the air and then dehydrating between molecules.

[0008]

For example, the water-repellent glass described in Japanese Patent Application No. 7-294106 already filed by the present applicant can sufficiently respond to the above-mentioned needs. Despite this, a water-repellent glass having a unique base film and a water-repellent film, a simple and simple single-layer film which can be used in various places, and a higher performance. This is what is desired.

[0009] Further, Japanese Patent Application No. 8-13 filed by the present applicant has been filed.
Water-repellent glass described in No. 1595 etc. is a water-repellent glass whose performance is improved in a single-layer film and has a performance closer to the water-repellent glass, but the workability during production, particularly its handling is sufficient. It is difficult to say that the method is simple and efficient.

In the pretreatment for polishing the glass substrate surface in the method for producing water-repellent glass described in JP-A-3-247537, although abrasion resistance is improved, long-term It is hard to say that the stability is sufficiently satisfactory.

Further, Japanese Patent Application Laid-Open No. 58-122979 and
In the washing and pretreatment with hydrochloric acid disclosed in the water- and oil-repellent agent for glass surfaces described in JP-A-129082, it is hard to say that both abrasion resistance and light resistance are sufficiently satisfactory for long-term stability. It is.

Further, in the adsorption monomolecular film and the method for producing the same described in JP-A-5-96679, an active hydrogen group such as a hydroxyl group, an amino group or an imino group is added to the surface in order to impart water / oil repellency. In order to introduce a fluorine-containing group on the surface of the base material having or added to the surface, there is a use of a halogenated silane-based or alkoxysilane-based compound, for example, a hydrolyzate of fluoroalkylalkoxysilane and on the substrate There is no mention of improving the efficiency of the reaction with a silanol group (forming a siloxane bond).

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made by modifying the surface of a glass substrate so as to completely terminate the hydrolysis reaction of the water-repellent liquid. At least adjusting the water content using a dehydrating agent or the like to increase the degree of polycondensation and control the liquid repellent film coating liquid to be stabilized to form a film on the modified surface in a controlled film environment. As a result, the obtained water repellent film has remarkably excellent wear resistance (traverse resistance) performance and light resistance performance. This water-repellent thin film has high hardness and high adhesion, has both durability and abrasion resistance, and can maintain excellent water-repellent performance over a longer period of time.

That is, according to the present invention, in a water-repellent glass having a water-repellent film formed by applying a water-repellent liquid on the surface of a glass substrate to form a water-repellent film layer, the surface is polished and then subjected to an acid treatment to modify the surface. A water-repellent glass comprising: a glass substrate; and a water-repellent film layer in which a coating solution for a water-repellent film is applied and formed on the surface-modified glass surface.

Further, the above-mentioned water-repellent glass is characterized in that the coating liquid for a water-repellent film is prepared by hydrolyzing and polycondensing a silane compound containing a fluoroalkyl group. Further, the water-repellent glass layer is characterized in that the water-repellent film layer is a water-repellent film layer formed by fixing a fluoroalkyl group to the surface-modified glass surface by a siloxane bond and forming a film.

In a method for producing a water-repellent glass in which a water-repellent liquid is applied on the surface of a glass substrate to form a water-repellent film layer, the surface of the glass is polished and acid-treated to modify the surface. And a coating step of applying a coating solution for a water-repellent film prepared by hydrolyzing and condensation-polymerizing a fluoroalkyl group-containing silane compound, and then immobilizing the fluoroalkyl group on the glass surface by a siloxane bond and repelling. A method for producing water-repellent glass, comprising: a curing step of forming a water film layer.

Further, the polishing liquid in the polishing treatment is as follows:
Abrasives mainly composed of inorganic metal oxides
A method for producing a water-repellent glass as described above, which is a suspension containing not less than 10 wt% and not more than 10 wt%.

Further, the method for producing a water-repellent glass described above, wherein the treatment temperature in the aqueous solution as the acid treatment liquid is 5 ° C. to 70 ° C., and the treatment time is 10 seconds to 600 seconds.

Further, in preparing the coating solution for a water-repellent film,
After terminating the hydrolysis reaction of the fluoroalkyl group-containing silane compound, adjust the water content in the coating solution for the water-repellent film,
A coating solution for a water-repellent film having a controlled degree of polycondensation is prepared, and the prepared water-repellent film coating solution is applied on a surface-modified surface of a glass substrate while controlling the temperature and humidity. A method for producing a water-repellent glass as described above, wherein a water-repellent film layer is formed by drying and curing for 1 minute to 60 minutes at a temperature of not more than ° C.

Further, the above-mentioned method for producing water-repellent glass, wherein the fluoroalkyl group-containing silane compound is a fluoroalkylalkoxysilane-based compound. Furthermore, the coating liquid for a water-repellent film is characterized in that in terms of g, the amount of the fluoroalkylalkoxysilane-based compound: the amount of the diluting solvent: the amount of water by the acid catalyst = 1: 5 to 40: 0.09 to 1.0. The method for producing the water-repellent glass described above.

Further, the adjustment of the water content in the coating solution for water-repellent film is an adjustment for removing excess water content in the coating solution for water-repellent film by dehydration. The present invention provides a method for producing an aqueous glass.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The glass substrate is a glass substrate used for a building window glass, an automobile window glass or the like.
Glass, especially its top surface, or a plate glass having various inorganic transparency such as roll-out glass, which is colorless or colored, and its type or color tone, combined with another functional film on another surface There is no particular limitation on the shape, shape and the like, and furthermore, various types of tempered glass and strengthened glass as well as bent plate glass can be used as a flat plate or a single plate, and can also be used as a multi-layer glass or a laminated glass.

Here, a glass substrate whose surface has been modified by polishing and acid-treating the surface as described above;
A water-repellent glass comprising a water-repellent film layer formed by applying a coating liquid for a water-repellent film on the surface-modified glass surface is obtained as follows.

In the polishing treatment for modifying the surface of the glass substrate, the top surface of the float glass containing a small amount of tin,
Luted glass surface or a bent or / and tempered glass surface thereof is coated with fine powder (average) containing an inorganic metal oxide such as cerium oxide (ceria) or / and aluminum oxide (alumina) or / and silicon oxide as a main component. Using a surface abrasive having a particle size of about 5 μm or less, and preferably about 1 μm or less), the type and the particle size of the powder to be used, and the polishing surface on a polishing surface such as a brush, a sponge or a cloth in a wet or dry method. By appropriately changing the material of the glass substrate and the contact pressure with the glass substrate, the polishing is performed while controlling the surface flaw state and the polishing state of the glass substrate surface.

Preferred examples of the conditions are as follows: the polishing surface of the brush rotating at about 200 rpm is pressed to about 0.02 kg / cm ² , and the abrasive is Millek (A + B) manufactured by Mitsui Kinzoku Kogyo KK
[Cerium oxide (ceria), particle size is about 1.2 ± 0.2μm]
When the surface of the glass substrate is polished using a polishing liquid suspended in water at a concentration of about 1 wt%, no flaws are observed on the glass substrate surface under a normal environment. It is possible to completely remove attached dirt, scale, and so-called burns,
Furthermore, a very thin vitreous layer on the surface, for example bent or / and
In addition, the composition-modified layer (silica-rich layer) formed on the surface of the tempered glass can be removed, and the effect of the acid treatment in the subsequent step is assisted.

The concentration of the polishing liquid is a suspension concentration in which the above-mentioned abrasive is contained in an amount of 0.1% by weight or more and 10% by weight or less with respect to water. It is difficult to completely remove so-called burns, and at a high concentration of more than 10 wt%, flaws appear on the glass surface under a normal environment, which further leads to uneconomical use of the abrasive. Preferably
It is a suspension concentration of 0.5 wt% or more and 5 wt% or less.

Next, the polished glass surface is treated with an acid treatment solution comprising an aqueous solution prepared by adding an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid or an organic acid such as acetic acid, formic acid or oxalic acid to a pH of 4 or less. The acid treatment is performed under the condition that the temperature of the acid treatment solution is 5 ° C. or more and 70 ° C. or less and the treatment time is 10 seconds or more and 600 seconds or less, whereby sodium ions are extracted from the surface of the polished glass and siloxane bonds are cut. A silanol group is formed efficiently, and the silanol group is
It is assumed that the hydroxyl group contributes to the immobilization of the water-repellent fluoroalkyl (Rf) group in the water-repellent treatment in the subsequent step.

The reason why the temperature of the acid treatment solution is set to 5 ° C. or more and 70 ° C. or less is that at a temperature lower than 5 ° C., the rate of the reaction for forming the silanol group is greatly reduced, and the treatment time is increased. In practical cases, the actual mass production tact
At a temperature higher than ℃, although the rate of the silanol group formation reaction increases, the acid concentration in the processing solution decreases due to evaporation of volatile components (particularly, acid components such as hydrochloric acid) and the acid concentration decreases due to evaporation of water. Inconveniences such as fluctuations and corrosion of peripheral equipment due to evaporation of acid components occur.

The reason why the acid treatment time is set to 10 seconds or more and 600 seconds or less is that, when the treatment time is less than 10 seconds, it is necessary to efficiently generate silanol groups by extracting sodium ions on the glass surface and cutting siloxane bonds. However, if the processing time exceeds 600 seconds, the actual mass production tact will lose its effectiveness.

Preferably, the acid treatment solution has a pH of 3.5 or less,
The temperature of the liquid is 10 ° C or more and 60 ° C or less, and the processing time is 15 seconds or more 42
Treat with acid under the condition of 0 seconds or less. The acid treatment is performed by immersing in an acid solution, but other methods such as a spray method, a flow coat method, etc.
There is no particular limitation as long as an acid treatment effect equivalent or similar to that obtained by the immersion method can be obtained.

Next, in preparing the coating solution for a water-repellent film, a hydroalkyl group-containing silane compound is used to terminate the hydrolysis reaction of the fluoroalkyl group-containing silane compound. The water content was adjusted to prepare a coating solution for a water-repellent film in which the degree of polycondensation was controlled, and the prepared coating solution for a water-repellent film was applied on the surface of a glass substrate while controlling the temperature and humidity. Drying and curing are performed at a temperature of not less than 350 ° C. for 1 minute to 60 minutes to form a water-repellent film layer.

Examples of the fluoroalkyl group-containing silane compound include a fluoroalkylalkoxysilane-based compound (hereinafter referred to as FAS). It should be noted that a silanol group on the glass surface can be sufficiently formed without requiring hydrolysis, such as a fluoroisocyanate silane compound or a fluoroalkyl halide silane compound, which is generally classified as a fluoroalkyl group-containing silane compound. A compound capable of forming a siloxane bond by reacting with the above can be sufficiently used as a coating solution for a water-repellent film without controlling the hydrolysis and polycondensation reactions.

As the diluting solvent, isopropyl alcohol (hereinafter referred to as i-PA), methanol,
A lower alcohol solvent having 5 or less carbon atoms, such as ethanol, may be used. In addition to alcohol, ethers, esters, and hydrocarbons can be used. Is preferred as a diluting solvent in the preparation of the coating solution.

The acid catalyst may be an organic acid such as acetic acid, hydrochloric acid, sulfuric acid or the like, in addition to nitric acid having a concentration of 0.01N or more, preferably about 0.1N to 13N. What is important is the amount of water due to the acid catalyst, and the amount of water is determined by the acid concentration in the acid catalyst and the amount of the acid catalyst itself.

Further, the coating liquid for the water-repellent film is expressed in g, and the amount of FAS [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ]: the amount of the diluting solvent: the amount of water by the acid catalyst = 1: 5 to 40: 0.09 to 1.0.

That is, FAS as a starting material, a diluting solvent
As i-PA, 0.1N-HNO as acid catalyst _ThreeFor water-repellent film
The coating liquid is FAS: i-PA: 0.1N-HNO_ThreeOf moisture = 1: 5
~ 50: 0.3 (g = display), the molecular dehydrate is molecular sieve
4A (dehydration time: 2 to 24 h, dipping amount: 5 g), coating environment
Preparation and coating of coating solution at room temperature and humidity of 55% RH or less
After applying the film, traverse sliding test (see Example 1 described later)
The contact angle (°) at 3500 sliding times
Evaluate the resistance to traverse, and formulate a coating solution for water-repellent film.
The FAS concentration (dilution factor) to improve traverse resistance
Of water repellent dilution (amount of diluent solvent)
Is 5 to 45 or 50 g per 1 g of starting material,
Some have a contact angle of about 95 ° after 3500 bushings.
But for vehicles such as automobiles or as belonging thereto
Preferably, the dilution ratio (amount of diluting solvent) of the water repellent is the starting material.
5-40 g, preferably 5-35 g, optimal for 1 g
5 to 30 g.

Further, FAS was used as a starting material, i-PA was used as a diluting solvent, 0.1N-HNO ₃ was used as an acid catalyst, and the coating liquid for the water-repellent film was FAS: i-PA: water content based on 0.1N-HNO ₃ = 1: 25: 0.
03-1.0 (g = display), molecular dehydrate is molecular sieve 4
A (dehydration time: 24 hours), the coating environment was prepared at room temperature and humidity of 55% RH, the coating liquid was prepared and the coating was performed. And the water content (g) by the acid catalyst in the preparation of the coating solution for the water-repellent film.
And the effect on the anti-traverse performance was determined, the contact angle was 80 ° or more after 3500 traverse slides even if the amount of water (g) by the acid catalyst was 0.1 g per 1 g of the starting material. so
Some are about 106 °, 0.09 / g of starting material
g, and the dilution ratio (amount of diluting solvent) of the water repellent is preferably 0.1 g or more, more preferably 0.13 g or more, most preferably 0.2 g or more and 1.0 g or less per 1 g of the starting material.
The reason why the upper limit is set to 1.0 g or less is that although it may be 1.0 g or more, even if it increases, it becomes gradually less economical.

As for the termination of the hydrolysis reaction of the starting material, FAS is used as the starting material, i-PA is used as the diluting solvent, 0.01N and 13N HNO ₃ are used as the acid catalyst, and the coating solution for the water-repellent film is FAS: i-PA: acid catalyst = 1: 25: 1.0 (g = display)
Progress degree of relationship of the hydrolysis reaction time (min) hydrolysis by HNO ₃ in 0.01N and 13N as an acid catalyst, although the initial hydrolysis rate is relatively large differences, or about 60 minutes No difference in the hydrolysis reaction time of
The hydrolysis reaction is almost completed in about minutes, and it can be confirmed that the hydrolysis reaction is completely completed in about 120 minutes. In order to complete the hydrolysis reaction (stirring), it is about 90 minutes, preferably about 90 minutes. It takes about 120 minutes.

Further, regarding the adjustment of the water content in the coating liquid for the water-repellent film, FAS was used as a starting material, and
i-PA, 0.1N-HNO ₃ was used as an acid catalyst, and the coating solution for the water-repellent film was FAS: i-PA: water content by 0.1N-HNO ₃ = 1: 25: 0.3
(G = indicated), 5 g of molecular sieve 4A as a dehydrating agent, dehydration time (h) and water content (ppm) under the condition that the dehydration condition is immersion for about 16 hours at room temperature and then filtration through No. 7 filter paper. As a result of determining the change with time, those having a contact angle of about 95 ° or more after a traverse resistance test (traverse sliding number of 3,500 times) have a dehydration time of 1 to 2 hours or more and a water content of about 4000 ppm, Preferably the water content is about 3000 ppm, more preferably the water content is about 2000 pp
m. Examples of the dehydrating agent include, for example, molecular
Sieves (4A and 3A), calcium chloride, magnesium sulfate, sodium sulfate, etc., or water removal as an azeotrope.

The water content in the coating solution for the water-repellent film is as follows:
It was determined by using a Karl Fisher coulometric titration method. Further, the prepared coating solution for the water-repellent film was coated on the surface of the glass substrate while controlling the temperature and humidity. The starting material was FAS, the diluting solvent was i-PA, and the acid catalyst was 0.1N-. using a HNO _3, water-repellent film coating solution for FAS: iP
A: Water content by 0.1N-HNO ₃ = 1: 25: 0.3 (g = display), dehydrating agent is molecular sieve 4A (dehydration time: 16
h, dipping amount: 5 g) Preparation of the coating solution under the condition of 5 g), coating the coating solution under the condition of the humidity of 15% RH to> 90% RH at room temperature, The contact angle (°) was determined, the traverse resistance was evaluated, and the influence of the atmospheric humidity (% RH) and the traverse resistance when the coating liquid for the water-repellent film was coated was examined. Even at about 80% RH,
The contact angle after 3,500 times of sliding is 80 ° or more and about 101 °, and even at room temperature and an atmospheric humidity of 70 to 80% RH, it is often about 75% RH or less, preferably Atmospheric humidity is about 60% RH or less, more preferably about 60% RH
It is about 15% RH or less, preferably about 55% RH or less and about 15% RH or less.

Further, as a method of applying a film to a glass substrate, hand coating, a nozzle flow coating method, a dipping method, a spraying method, a reverse coating method, a flexo method, a printing method, a flow coating method or a spin coating method. Known coating means such as a coating method and a combination thereof, and various coating methods proposed by the present applicant and the like can be appropriately employed.

Further, at a temperature of 80 ° C. or more and 350 ° C. or less for 1 minute to 60 ° C.
After drying and curing for a minute, the film was formed by curing the S-UV irradiation time (h) and the contact angle (°) at the curing temperatures of about 80 ° C, about 140 ° C, and about 250 ° C. As a result of the evaluation, even when the S-UV irradiation time was about 600 hours (h), the contact angle was about 70 ° or more and about 70 to 80 °, and the light resistance was good. Therefore, drying and curing are carried out at 80 ° C. or more and 350 ° C. or less for 1 minute to 60 minutes. Preferably, it is about 100 ° C. or more and about 300 ° C. or less.

As described above, according to the present invention, the surface of the glass substrate is modified and polished by polishing and acid treatment to complete the hydrolysis reaction of the coating solution for the water-repellent film in advance, and thereafter the dehydrating agent is prepared. A coating solution with a coating solution for a water-repellent film controlled to increase the degree of polycondensation and to stabilize the content by adjusting the water content by using the method described above, and to form a film on the modified surface under a controlled film environment. Thus, a coating solution having excellent performance can be easily obtained, and the obtained water-repellent film has traverse resistance and light resistance, which are extremely excellent wear resistance. This water-repellent film has excellent water-repellent performance over a long term, for example, a contact angle of about 70 ° to 80 ° or more,
Preferably about 80-90 degrees or more, more preferably about 90
°° to ° 100 ° or more, high hardness, high adhesiveness, durability, extremely controllable and extremely stable. Moreover, it is safe and has no troublesome process.
It is possible to easily and efficiently form a film, and to reduce the variation width in a long time under mass production with better control and to obtain a more reliable and stable quality. The present invention is useful for various glass articles in various fields such as window materials for automobiles and the like, window materials for ships and aircrafts, and electronic devices, of course.

[0044]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.

Example 1 As a raw material of a water repellent solution composition for forming a water repellent film layer, a fluoroalkylalkoxysilane [FAS: CF ₃ (CF
₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , manufactured by Toshiba Silicone; TSL8233]
And isopropyl alcohol (iPA; manufactured by Kishida Chemical)
If, 0.1N-nitric acid is used [Kishida Chemical Ltd.], the proportion _{FAS: iPA: 0.1N-HNO 3} = 1: 25: 0.3 ( unit: g) of the, and stirred for about 2 hours at room temperature the hydrolysis reaction I let it.

Then, about 5 g of molecular sieve 4A (manufactured by Kishida Chemical Co., Ltd.) was added to the solution subjected to the hydrolysis reaction, immersed and allowed to stand for about 16 hours to complete the dehydration while performing the condensation polymerization reaction. No. 7) to separate and remove the molecular sieve 4A to obtain a coating solution.

A glass surface was previously polished with a brush hand polisher using a suspension composed of Mille (A + B) [manufactured by Mitsui Kinzoku Kogyo]: water = 1: 100 (wt%). The glass was rinsed with water, immersed in a 0.1N (about pH 1) hydrochloric acid aqueous solution at about 35 ° C. for about 1 minute, subjected to an acid treatment, and then washed again with about 200 mm × 300 mm and about 3.5 mm thick float glass. The coating solution was manually applied to the top surface of the substrate in an environment at room temperature and a humidity of about 55% RH.

Subsequently, after coating and air-cooling, about 140
The film was formed by curing at about ° C for about 5 minutes to obtain a glass with a fluoroalkyl group-containing coating. Note that the obtained film thickness was about 5 nm to 25 nm.

The fluoroalkyl group-containing coating of the obtained glass with a fluoroalkyl group-containing coating was evaluated as follows. [Resistant traverse - scan test] Test machine: traverse - scan type sliding tester (Fig. 2) Sample Size: about 200 mm × load to 300mm Friction cloth: 0.1 kg to the canvas cloth / cm ² (JIS L 3102-1961 -1206) Stroke: 100mm reciprocal sliding (the number of reciprocations is the number of reciprocations) Sliding speed: 30 reciprocations / minute Evaluation: Contact angle θ for the number of reciprocations under each condition, for example, about 3500 times ) Behavior. [Water repellency test] Measuring equipment: CA-A type manufactured by Kyowa Interface Science Measurement environment: In the air (about 25 ° C) Water: Drop of pure water (2 μl) Measurement value: Contact angle θ (°) [Before each test The initial contact angle θ ₀ ° and the contact angle θ ° after each test were determined. (The drop angle is 45 μl water droplets.) [Light resistance test] Measuring equipment: Super UV (S-UV) light resistance acceleration tester (Iwaki Electric, EYE SUPER UV TESTER, SVU-W11 type).

Conditions: A durability test was carried out at about 76 mW / cm ² , a distance between the lamp and the sample of about 24 mm, a temperature of about 35 ° C. and a humidity of about 50% RH for about 300 hours and about 600 hours of SUV irradiation time.

Measured value: Behavior of contact angle θ (°) with respect to each SUV irradiation time. [Chemical Resistance Test] object: engine oil, gear oil, 25% sulfuric acid, washer fluid, 50% CaCl ₂ aqueous solution (pH = 7), lime (pH = 11), sea water, antifreeze (LL C).

Conditions: The above object is dropped on the surface of the water-repellent film of the water-repellent glass, left at room temperature, in an environment of 65% RH, and at a temperature of 80 ° C. for about 24 hours, and then washed and dried.

Measurement value: The contact angle θ ° of the surface of the water-repellent film was measured. As a result, those having an initial contact angle θ ₀ of about 111 ° (the initial falling angle of about 30 °) were about 35 ° in the traverse resistance test.
The contact angle θ after 00 times sliding becomes about 104 ° to 105 ° or more, and in the light resistance test, the contact angle θ ₃₀₀ after about 300 hours of S-UV irradiation time (hr) Angle θ ₀ approx.
About 95 ° for about 111 °, contact angle θ after about 600 hours
₆₀₀ showed about 80 °, etc., showing remarkable traverse resistance (abrasion resistance) and light resistance, maintaining water repellency over a long period of time, and having high durability.

[0054] Further, also in the chemical resistance test, the contact angle after the test with respect to the initial contact angle theta ₀ about 111 ° theta of about 108
° to 104 °, and the contact angle θ could be sufficiently maintained at about 100 ° or more.

Therefore, it is a useful water-repellent glass having extremely excellent abrasion resistance and light resistance even for various window glasses for automobiles. Example 2 Mille (A + B) [manufactured by Mitsui Kinzoku Kogyo]: water =
Using a suspension of 1: 1000 (wt%), the glass surface was polished with a brush hand polisher, washed thoroughly with water, and acid-treated and washed with water in the same manner as in Example 1.
A film was formed in the same manner as in Example 1 except that a float glass substrate having a size of 200 mm × 300 mm and a thickness of about 3.5 mm was used.

The fluoroalkyl group-containing coating of the obtained glass with a fluoroalkyl group-containing coating was evaluated in the same manner as in Example 1 described above. As a result, for example, when the initial contact angle θ ₀ is about 110 ° (the initial falling angle is about 30 °), the contact angle θ after sliding about 3500 times in the traverse resistance test is obtained.
Is about 98 ° to 103 ° or more. Also, in the light resistance test, the contact angle θ ₃₀₀ after the S-UV irradiation time (hr) is about 300 hours, for example, is less than the initial contact angle θ ₀ about 110 °. About 89 °
Approximately 600 hours later, the contact angle θ ₆₀₀ is about 70 °, etc., showing excellent traverse resistance (abrasion resistance) and sufficient light resistance. The water repellency was maintained and the durability was high.

Further, in the chemical resistance test, as in Example 1, the contact angle θ could be maintained at about 100 ° or more. Therefore, it is a useful water-repellent glass having excellent wear resistance and light resistance even for various window glasses for automobiles.

Example 3 After polishing in advance in the same manner as in Example 1, it was thoroughly washed with water, immersed in a 0.001N (about pH 3.5) hydrochloric acid aqueous solution at about 35 ° C. for about 1 minute, and acid-treated. Thereafter, a film was formed in the same manner as in Example 1 except that a float glass substrate having a size of about 200 mm × 300 mm and a thickness of about 3.5 mm, which was washed again with water, was used.

Evaluation of the fluoroalkyl group-containing film of the obtained glass with a fluoroalkyl group-containing film was performed in the same manner as in Example 1 described above. As a result, for example, when the initial contact angle θ ₀ is about 109 ° (the initial falling angle is about 31 °), the contact angle θ after sliding about 3500 times in the traverse resistance test is obtained.
Is about 100 ° to 102 ° or more. Also, in the light resistance test, the contact angle θ ₃₀₀ after an S-UV irradiation time (hr) of about 300 hours, for example, is higher than the initial contact angle θ _{0 of} about 109 °. About 92
° C., such as about 600 hours contact angle theta ₆₀₀ after is about 75 ° or so, excellent traverse - scan resistance (wear resistance) and showed sufficient light resistance, long-term shall not extend to Example 1 The water repellency was maintained and the durability was high.

Further, in the chemical resistance test, as in Example 1, the contact angle θ could be maintained at about 100 ° or more. Therefore, it is a useful water-repellent glass having excellent wear resistance and light resistance even for various window glasses for automobiles.

COMPARATIVE EXAMPLE 1 After the polishing treatment was carried out in the same manner as in Example 1, washing was carried out sufficiently, and the glass was immersed in a 0.1N (about pH 3.5) aqueous hydrochloric acid solution at about 35 ° C. for about 5 seconds to carry out an acid treatment. After washing with water again
A film was formed in the same manner as in Example 1 except that a float glass substrate having a size of 200 mm x 300 mm and a thickness of about 3.5 mm was used.

The coating of the obtained glass with the coating was evaluated in the same manner as in Example 1 described above. As a result, for example, the initial contact angle θ ₀ is about 108 ° (the initial falling angle is about 35 °)
However, in the traverse resistance test, the contact angle θ after sliding about 3500 times is about 100 ° to 104 °, and also in the light resistance test, the S-UV irradiation time (hr) is about The contact angle θ ₃₀₀ after 300 hours is about the initial contact angle θ _{0 of} about 108 °.
Although it has excellent traverse resistance (abrasion resistance), such as about 82 ° and the contact angle θ ₆₀₀ after about 600 hours is about 64 °, it is hard to say that light resistance is always sufficient. It could not be said that the desired long-term water repellency was maintained and the durability was high.

Therefore, it is hard to say that the glass is useful water-repellent glass that can be used for a long period of time with respect to various window glasses for automobiles. Comparative Example 2 Approximately 200 m without polishing and acid treatment
A film was formed in the same manner as in Example 1 except that a float glass substrate having a size of m × 300 mm and a thickness of about 3.5 mm was used.

The evaluation of the obtained thin film of the glass with a thin film was performed in the same manner as in Example 1 described above. As a result, for example, the initial contact angle θ ₀ is about 106 ° (the initial fall angle is about 35 °)
In the traverse resistance test, the contact angle θ after sliding about 3500 times is about 83 ° to 95 °, and in the light resistance test, the S-UV irradiation time (hr) is, for example, about The contact angle θ ₃₀₀ after 300 hours is about 70 ° compared to the initial contact angle θ _{0 of} about 106 °.
Approximately 600 hours later, the contact angle θ ₆₀₀ is approximately 42 °, and the traverse resistance (wear resistance) and light resistance are not sufficient, and the intended long-term water repellency is maintained. However, the durability was far from high.

Therefore, it is not a useful water-repellent glass that can be used for a long period of time with respect to various window glasses for automobiles. In the above Examples and Comparative Examples
The light resistance status by the S-UV irradiation test was determined by the S-UV irradiation time / h
FIG. 1 collectively shows the contact angle / ° with respect to.

[0066]

As described above, according to the present invention,
Highly durable glass with excellent traverse resistance (abrasion resistance) and light resistance, stable and reliable water-repellent performance for a long time under mass production, and high durability can be obtained easily and efficiently. , Can control and improve the quality homogenization with good controllability,
Since it does not impair the optical characteristics, it can be supplied with extremely stable quality not only for architectural use but also for automotive window materials, and for various fields such as ship and aircraft window materials, industrial glass such as mirrors, and various glass articles. It is possible to provide a useful water-repellent glass that can be widely used and has high utility value.

[Brief description of the drawings]

FIG. 1 shows the light fastness of the water-repellent glass of the present invention and the comparative example, which were determined by the S-UV irradiation test, as follows.
It is explanatory drawing shown by the change of the contact angle / degree with respect to h.

FIG. 2 shows one example of evaluating the long-term water repellency of the water-repellent film layer in the water-repellent glass of the present invention.
FIG. 2 is a diagram showing a traverse type sliding test machine on which a wear test (abrasion resistance) is performed.

[Description of Signs] 1 Traverse type sliding tester 2 units 3 Motor 4 Reducer 5 Crank disk 6 Friction cloth 7 Load 8 Glass substrate 9 Water repellent film

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeo Hamaguchi 1510 Oguchicho, Matsusaka-shi, Mie Central Glass Inside Glass Laboratory Co., Ltd.

Claims (10)

[Claims] 1. A water-repellent glass having a water-repellent film layer formed by applying a water-repellent liquid on the surface of a glass substrate to form a water-repellent film layer. A water-repellent glass, comprising a water-repellent film layer formed by applying a coating solution for a water-repellent film on the surface-modified glass surface. 2. The water-repellent glass according to claim 1, wherein the coating liquid for a water-repellent film is prepared by hydrolyzing and polycondensing a silane compound containing a fluoroalkyl group. 3. The water-repellent film layer according to claim 1, wherein the water-repellent film layer is a film formed by fixing a fluoroalkyl group to the surface-modified glass surface by a siloxane bond and forming a film. Aqueous glass. 4. In a method for producing a water-repellent glass in which a water-repellent liquid is applied on the surface of a glass substrate to form a film by forming a water-repellent film layer, the surface of the glass is polished and acid-treated to modify the surface. And then applying a coating solution for a water-repellent film prepared by hydrolyzing and polycondensing a fluoroalkyl group-containing silane compound, and then immobilizing the fluoroalkyl group on the glass surface by a siloxane bond. A method for producing a water-repellent glass, comprising a curing step of forming a water-repellent film layer. 5. The polishing liquid in the polishing treatment is a suspension containing an abrasive containing an inorganic metal oxide as a main component in an amount of 0.1% by weight or more and 10% by weight or less based on water. Item 6. A method for producing a water-repellent glass according to Item 4. 6. The water-repellent glass according to claim 4, wherein the treatment temperature in the aqueous solution as the acid treatment liquid is 5 ° C. to 70 ° C., and the treatment time is 10 seconds to 600 seconds. Recipe. 7. When preparing the coating solution for a water-repellent film, after terminating the hydrolysis reaction of the silane compound containing a fluoroalkyl group, the amount of water contained in the coating solution for a water-repellent film is adjusted, and the degree of polycondensation is adjusted. A water-repellent film coating solution is prepared, and the prepared water-repellent film coating solution is applied on a surface-modified surface of a glass substrate while controlling the temperature and humidity. 7. The method for producing a water-repellent glass according to claim 4, wherein the water-repellent film layer is formed by performing drying and curing for 1 minute to 60 minutes. 8. The method for producing a water-repellent glass according to claim 4, wherein the fluoroalkyl group-containing silane compound is a fluoroalkylalkoxysilane-based compound. 9. The coating solution for a water-repellent film, which is expressed in terms of g, is such that fluoroalkylalkoxysilane-based compound amount: diluting solvent amount: acid catalyst water content = 1: 5 to 40: 0.09 to 1.0. The method for producing a water-repellent glass according to any one of claims 4 to 8. 10. The method according to claim 4, wherein the adjustment of the amount of water contained in the coating liquid for a water-repellent film is an adjustment for removing excess water contained in the coating liquid for a water-repellent film by dehydration. 9
The method for producing the water-repellent glass described in the above.