JP3426284B2 - Water repellent glass and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention not only has water repellent performance,
INDUSTRIAL APPLICABILITY The present invention relates to a water-repellent glass having excellent weather resistance and a method for producing the same, and is useful for window glasses and mirrors for vehicles, ships, aircrafts, constructions, and the like.

[0002]

2. Description of the Related Art In order to improve the water repellency of glass, it has been attempted to apply a compound such as a fluoroalkyl group-containing compound or dimethylsiloxane to the glass surface. However, if these compounds are simply applied, the bonding force with the glass surface is weak, and the weather resistance and abrasion resistance cannot be sufficiently provided, and it is difficult to maintain the water repellency for a long time.

Up to now, various applications have been filed for polyfluoroalkyl group (Rf group) -containing silane compounds for imparting water repellency on materials such as glass. Specifically, JP-A-58-122979, JP-A-58-129082, JP-A-58-142958, JP-A-58-144743, JP-A-58-1.
72242, JP-A-58-172243,
JP-A-58-172244, JP-A-58-172
245, JP-A-58-172246, JP-A-58-190840, and JP-A-58-22.
3634, etc.

Further, for example, Japanese Unexamined Patent Publication (Kokai) No. 58-167448 discloses low-reflectance glass. By forming on the glass surface, without impairing the transparency, etc.
Those having low reflectance and water and oil repellency are disclosed.

However, such a conventional water repellent treatment method has a problem that the water repellency is deteriorated in a relatively short time in the durability and weather resistance tests. Further, as a material excellent in weather resistance, there is a glass coated with Teflon, but there is a problem that the film is soft and easily scratched, and the transparency is immediately deteriorated.

Further, in JP-A-60-231442, a water repellent coating film comprising both a polymer of an organosilicon compound having a siloxane bond as an adhesive component and a polymer of a fluorine compound as a water repellent component on a glass substrate. Although a water-repellent treated glass having a water-repellent structure is described, it has a problem that it is easily scratched because the surface has a large proportion of water-repellent components.

Further, Japanese Patent Laid-Open No. 153859/1993 discloses that
A surface-modified plastic in which a metal oxide layer is formed on a plastic substrate and a composite layer of a metal oxide and a fluororesin is laminated on the metal oxide layer is described, but since the substrate is plastic, the adhesion is not always satisfactory. There are problems such as not things.

Further, JP-A-5-512238 describes a metal oxide phase on a glass substrate and a structure in which the metal oxide phase is dispersed in the glass substrate. However, the structure is apt to be damaged. There was a problem.

[0009]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the above-mentioned conventional problems, and an object thereof is to provide a water-repellent glass which is excellent in adhesion and weather resistance and is hard.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art, and has a unique micropit-like surface layer, uneven surface layer or convex surface layer on a glass substrate. In addition, a sol-gel film in which the shape and size of the micropits, unevenness and protrusions can be controlled is used as the intermediate layer, and the specified water repellent layer made of SiO ₂ and fluororesin is formed on the intermediate layer film. By using a water-repellent glass as a laminated thin film, its performance will be remarkably exhibited. Especially, the optical characteristics are not impaired for a long period of time, and the stubborn adhesion is excellent in abrasion resistance or durability. Thus, the present invention provides a water-repellent glass which is useful in window materials for construction or automobiles, and various glass articles with a film.

Further, in the present invention, a specific metal alkoxide compound or metal acetylacetonate compound is selected, and the compounds having different average molecular weights are combined to prepare a coating solution having a different mixing ratio to form a coating film. By controlling the relative humidity at the time, even if it is sufficiently baked, it has a unique and unique micropit shape or uneven or convex shape, and has a surface layer whose shape and size are variously controlled. The sol-gel film, which is an oxide thin film that is both adhesive and has durability and wear resistance, and is useful not only as a single layer but also as an intermediate layer or underlayer, is highly safe, has no troublesome steps, and is inexpensive and efficient. obtained. Moreover the well-specific micro-pit shape or the surface of the uneven shape or the like, until in the film uneven singular SiO ₂ and fluorine resin particle dispersion Applying Le solution as allowed to cover the impregnation, there is provided a method for producing a water-repellent glass forming the baked film forming laminated film.

That is, according to the present invention, in a water-repellent glass having a water-repellent layer composed of at least SiO ₂ and a fluororesin, the content of the fluororesin is 5 to 450% by weight based on the SiO ₂ , and the glass substrate and A water-repellent glass comprising a sol-gel film, which is a micropit-like surface layer, an uneven surface layer, or a convex surface layer, as an intermediate layer between water-repellent layers.

Further, the micropit-like surface layer, the uneven surface layer, or the convex surface layer is characterized by using an intermediate layer of a sol-gel film comprising the micropits, the unevenness or the projections having a diameter of 200 to 400 nm. The water-repellent glass described above.

On the glass substrate, at least one compound selected from metal alkoxide compounds and metal acetylacetonate compounds ,
Select two or more compounds with different average molecular weight,
Adjust the mixing ratio of the above compounds and mix with the solvent.
To form a coating solution, which is then coated and preferably
Coating the solution while controlling the relative humidity
Then, a sol-gel film formed by heating at a temperature of 100 ° C. or higher is formed, and a solution prepared by mixing at least a silica sol solution and fluororesin particles or a suspension of fluororesin particles is applied onto the sol-gel film. A method for producing water-repellent glass, characterized in that the water-repellent layer film is formed by baking to form a film.

And two or more compounds selected above
Is a compound of one of the low average molecular weight is a molecular weight from 800 to 80
00 A compound, method of manufacturing the above-described water-repellent glass which is characterized in that compounds of the other one or more high-average molecular weight was a sol-gel film and the intermediate layer consisting of a compound having a molecular weight of from 100,000 to 400,000 .

Furthermore, the mixing ratio of the two or more selected compounds is adjusted by adjusting the mixing ratio of the low average molecular weight compound to 0.1 to 30 mol relative to 1 mol of the high average molecular weight compound. The method for producing a water-repellent glass as described above, characterized in that the layer is a layer.

Furthermore, the coating solution is added to 1
The method for producing water-repellent glass as described above, characterized in that the sol-gel film is formed by adjusting the viscosity to 10 cP. Furthermore, the metal alkoxide system of the coating solution
The method for producing water-repellent glass as described above, wherein a sol-gel film is formed when the concentration of the compound or the metal acetylacetonate compound is 0.01 to 10 wt%.

Furthermore, the relative humidity is 70-80.
%, A sol-gel film is formed, and the above-mentioned water-repellent glass manufacturing method is provided.

Here, as described above, at least one compound is selected from the metal alkoxide compounds and the metal acetylacetonate compounds because both compounds are stable and are prepared in solution. At this time, for example, it is easy to control the average molecular weight, and the transparency and hardness of the oxide thin film having various surface shapes of the formed micropit-like surface layer, uneven surface layer or convex surface layer are high, and the durability is also high. This is because it is excellent, relatively inexpensive and easily available .

The metal alkoxide compound is a compound in which only an alkoxy group is bonded to the metal, that is, not only methoxide, ethoxide, isopropoxide, etc., but a part of the compound is substituted with a methyl group, an ethyl group, etc. , For example, monomethyl alkoxide, monoethyl alkoxide and the like. Further, the metal acetylacetonate-based compound includes not only the case where only the acetylacetone group is bonded to the metal but also the case where a part thereof is substituted with a methylalkoxy group, an ethylalkoxy group or the like.

Further, although the metal is not particularly specified, it is preferable to select Si, Ti or Zr. Specific examples thereof include tetramethoxysilane [Si (OMe) ₄ Me: CH ₃ ], Tetraethoxysilane [Si (OEt) ₄ Et: C ₂ H ₅ ],
Methyltriethoxysilane [MeSi (OEt) ₃ ],
Methyltrimethoxysilane [MeSi (OMe) ₃ ],
Titanium tetraisopropoxide [Ti (O-iso-P
r) ₄ Pr: C ₃ H ₇ ], titanium acetylacetonate [Ti (CH ₂ COCH ₂ COCH ₃ ) ₄ ], zirconium normal butoxide [Zr (On-Bu) ₄
Bu: C ₄ H ₉ ], zirconium acetylacetonate [Zr (CH ₂ COCH ₂ COCH ₃ ) ₄ ] and the like are preferable, and in addition, for example, dimethyldiethoxysilane, dimethyldimethoxysilane, titanium tetranormal butoxide,
Examples include zirconium tetraisopropoxide and zirconium tetraoctylate.

The above-mentioned micropit-like surface layer, uneven surface layer, or convex surface layer has a micropit, unevenness, or projection having a diameter of 200 to 400 nm. The fluororesin particles added to the water layer have a particle size distribution in the vicinity of 0.3 μ (300 nm). The reason why the intermediate layer is formed into micropits, irregularities, or convex shapes is to trap these particles in the pores and improve durability. If it is less than 200 nm, the number of fluororesin particles to be trapped is very small, and only those having a small particle size are trapped, which is difficult to lead to long-term improvement in weather resistance and water repellency.
When it exceeds 00 nm, the film appears cloudy. That is, it is a limit pore size that does not impair transparency. Therefore, it is necessary to make the pore diameter around 300 nm that is good in trapping efficiency.

Furthermore, the odor of the selected compound
And selected two or more compounds with different average molecular weight.
The reason is that the surface layer of the coated thin film has a micropit shape, an uneven shape or a convex shape, and the average molecular weight of the two or more kinds of compounds to be mixed is 800 to 8000 (preferably 200).
0-7000) and 10,000-70000 or 10
A combination of 0000 to 400000 is preferable.

[0024] Two or more compounds having different average molecular weight of said selected is a different average molecular weight, one compound is a compound of low average molecular weights of from 800 to 8000, the other one or more compounds the molecular weight 100000-40
Was assumed to be a compound of high average molecular weight of 0000, by the different molecular weights, the Si-O-Si speed to form a (siloxane bond) and hydrolysis and polycondensation reaction rate
This is because, as a result, the surface shape is not flat but micropits, irregularities, or convex shapes.

On the other hand, control of the average molecular weight of above, quotes
In preparing the ing solution, the type of catalyst (for example, hydrochloric acid, nitric acid, acetic acid, etc.), its addition amount, that is, PH value (for example, PH = 1 to 6, preferably 2 to 4) and reaction temperature (for example, 20 to 80 ° C.) , Preferably 25 to 70 ° C.) and the like to control the hydrolysis reaction process or the condensation polymerization process. However, depending on the compound, the reaction time and the like are different, and there is a possibility that the compounds are not necessarily common to all.

In order to control the micropits, unevenness or convexity of the micropit-like surface layer, the uneven surface layer or the convex surface layer, the average molecular weight of two or more kinds of compounds to be mixed is 80.
0-8000 (preferably 2000-7000) and 10
000 to 70,000 or 100,000 to 40,000
The mixing ratio of the compound that is 0 is about 0.1 to 30 in terms of the solute molar ratio of the coating solution (as oxide),
When it is less than 1 or more than 30, it has a flat planar shape. Especially, it is preferably about 1 to 20, more preferably about 2 to 5.5 on the micropit surface layer, about 5.5 to 7 on the uneven surface layer, and about 7 to 15 on the convex surface.

[0027] The mixing ratio of two or more compounds having the different average molecular weight, relative to the compound 1mol of high average molecular weight, compound of low average molecular weight was 0.1~30mol
This is because the relationship between the mixing ratio of compounds (two or more raw materials having different average molecular weights) and the surface shape of the formed film is intimate, and the surface shape can be controlled to be micropits, unevenness, or convexity by the mixing ratio. If the mixing ratio of the compound having a low average molecular weight is less than 0.1 mol, the shape is flat, and if it exceeds 30 mol, the shape is also flat. The shape can be arbitrarily controlled within the range of 0.1 to 30 mol.

The coating solution may be added in an amount of 1 to 10c.
The reason why the viscosity is adjusted to P is that the coating solution usually uses alcohols as the solvent, so that the viscosity is 1 to 2
It is cP. If it exceeds 10 cP, cracks may occur in the film or the transparency may be impaired in the baking step after coating.

Further, the relative humidity, and 70-80%
This is because it is necessary to control the hydrolysis rate of the film during coating in order to control the size of the pore size.
When the relative humidity is less than 70%, even if pores can be formed, the diameter thereof is about several tens of nm to 100 nm at about 65%. Further, when it exceeds 80%, when the diameter is, for example, about 85%, it becomes about 500 nm, and the obtained film is whitened. In other words, there is a correlation between the relative humidity and the size of the pore size,
70-80% to obtain the target diameter around 300 nm
RH is required. The size of each of the above-mentioned surface layers can be controlled by the relative humidity at the time of coating.
When it is 0%, it is about 200 nm, and when it is about 80%, it is about 400 nm.

The concentration of the metal alkoxide-based compound or metal acetylacetonate-based compound in the alcohol solution is preferably about 0.01 wt% or more. It becomes more difficult to form the coating film which has 10w
If it exceeds about t%, the solution becomes viscous and although there are the above-mentioned three types of surface layer shapes, cracks are expressed and the film attachment itself becomes difficult. Further, as the alcohol solvent in the present alcohol solution, methyl alcohol, isopropyl alcohol, 1-butanol or the like can be adopted.

Further, as a method for applying a film to a glass substrate, known coating means such as a dipping method, a spray method, a flow coating method or a spin coating method can be appropriately adopted. After coating the coating solution, 1
It is preferable that each time a thin film of a layer is formed, it is dried at an ambient temperature of about 100 ° C. for about 30 minutes or less to form a gel film having the above-mentioned three types of surface layer shapes.

Furthermore, the three kinds of surface shape surface layers of the present invention are formed by the difference in the degree of polycondensation, and may disappear even by baking (for example, about 500 ° C. or higher) for strengthening the film. In addition, independent pits, concavities and convexities were formed up to the surface and near the interface with the substrate, and it was clearly observed at 10,000 times with a scanning electron microscope. The three types of surface shape surface layers can be formed.

Generally, as a method for forming irregularities on the surface of a metal oxide coating, for example, a method of etching the metal oxide coating with hydrofluoric acid, hydrofluoric nitric acid or the like, or an organic polymer which is burned and decomposed by heat treatment is used. Methods such as addition to a metal alkoxide solution are known.

However, in the method of etching the metal oxide film with hydrofluoric acid, nitric acid, etc., the etching solution, hydrofluoric acid, hydrofluoric nitric acid, etc., is an extremely dangerous substance to the human body and its handling is troublesome. Inferior in properties, there is a decrease in productivity due to the addition of an etching step, and there are portions that are easily etched and portions that are not easily etched due to their structure, and the portions that are easily etched become pit-shaped. If anything, it is continuous, it is difficult to control the film thickness and pits, and it is difficult to observe the pits at the above magnification.

In addition, for example, in the method of adding an organic polymer, which is decomposed by combustion by heat treatment, to a metal alkoxide solution, in the case where the sol-gel film is made porous by firing of organic matter, solvent and water, the temperature is usually around 250 to 300 ° C. Although the entire film is once made porous by firing, the micropit-like surface once formed by heating and firing at 400 ° C. or more causes densification, so that there is a constraint that various conditions for the heat treatment must be controlled. At the same time, it is difficult to obtain a stubborn coating due to this restriction. For example, when the coating is baked at 500 ° C. or higher, the film becomes dense and hardened, and at the same time, it becomes non-porous. The surface shape becomes flat even when observed with a scanning electron microscope at a magnification of 30,000 to 50,000.

Therefore, the above conventional method was obviously different from the micropit-like surface layer, the uneven surface layer or the convex surface layer of the present invention, which maintains the state even at 600 ° C., for example.

The fluororesin may be, for example, polytetrafluoroethylene type (polyflon or rublon:
(Trade name, manufactured by Daikin Industries), copolymer system of tetrafluoroethylene and ethylene (NEOFLON: trade name, manufactured by Daikin Industries), copolymer system of tetrafluoroethylene and hexafluoropropylene, copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether Particles such as a polymer system can be adopted. The particle size of the fluororesin particles is 0.6 μm or less, preferably 0.1 to 0.6 μm.
m, more preferably 0.5 to 0.1 μm.

[0038] Further, the mixing ratio of the fluorine resin to SiO ₂ is 5～450Wt% relative SiO _2, can not impart water repellency performance is less than 5 wt%, less likely effect of water repellency is sufficiently exhibited, For example, the contact angle with water is 60
The water repellency is no longer improved even if it exceeds 450 wt% and the contact angle to water is 110 to 1
This is because the film stays at about 15 ° and does not improve further, the effect cannot be obtained, and the film becomes soft. The preferred ratio of the SiO ₂ and the fluororesin is 30 to 300% by weight of the fluororesin with respect to the SiO ₂ .

Furthermore, as a solution for forming a specified water repellent layer of at least SiO ₂ and a fluororesin,
It is composed of at least a solution of fluororesin particles or a suspension of fluororesin particles and a silica sol. As the silica sol solution, a solution obtained by hydrolyzing and polycondensing silicon alkoxide or monomethylalkoxide is used. , Alkoxides such as Ti or monomethyl alkoxides or acetylacetonate salts and their polycondensation products may be contained, and as the alkoxides or monomethyl alkoxides, (monomethyl) methoxide, (monomethyl) ethoxide,
(Monomethyl) isobropoxide, (Monomethyl) n-
Butoxide and the like, and preferable acetylacetonate salts are acetylzirconium and titanium acetylacetonate.

The film thickness formed by a solution containing at least SiO ₂ and fluororesin is about 10
The thickness is not less than 20 nm, preferably about 20 to 1000 nm.

Furthermore, the heating temperature for applying the solution in which at least the silica sol solution is mixed with the fluororesin particles or the suspension of the fluororesin particles and applying the baked film is about 100 to 500 ° C. Needless to say, as the coating method, the existing method described above can be used to adjust the viscosity according to various methods to form a film.

Further, the glass substrate is an inorganic transparent plate glass, and is not particularly limited to colorless or colored, and its type, color tone, shape, etc. Further, as a bent plate glass, various strengthening is possible. Needless to say, it can be used as glass, strength-up glass, flat plate or single plate, and can also be used as multi-layer glass or laminated glass.

[0043]

As described above, the sol-gel film having the micropit-like surface layer, the uneven surface layer or the convex surface layer of the present invention is used as the intermediate layer thin film, and the water-repellent thin film made of the specified SiO ₂ and the fluororesin is formed into a film-repellent film. repellent glasses aqueous oxide film and the laminated film, and the manufacturing method thereof, before
The intermediate thin film does not become densified even when fired at a high temperature and becomes a clear and firm micropit-like, uneven or convex surface layer that is more independent and has a deeper appearance than ever before. The shape and diameter of the surface layer can be controlled, adhesion can be improved and a stubborn thin film can be formed, and adhesion can be significantly improved not only at the interface with the glass substrate but also at the interface between films in a multilayer film. Then, by embedding the specified water-repellent thin film impregnated with the coating and combining the coating, it has excellent weather resistance and durability, is transparent and has high hardness, and also has long-term water-repellent performance as well as optical characteristics. Can be sufficiently satisfied, and even things that were difficult to use outdoors conventionally can be used, etc.,
It is a highly safe and inexpensive process that can be obtained efficiently.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 A clear float glass substrate having a size of about 100 mm × 100 mm and a thickness of about 2 mm was sequentially washed with a neutral detergent, water rinse, alcohol, dried and then wiped with acetone to obtain a glass substrate for coating.

Methyltrimethoxysilane (average molecular weight:
About 3,000, solid content concentration: about 30 wt%) About 20.0
g, silicon ethoxide (average molecular weight: about 50,000)
0, solid content concentration: about 6 wt%) Approximately 30 g was put in a beaker, and the low-average molecular weight solid content / high-average molecular weight solid content was set to a molar ratio of about 3.5, and isopropyl alcohol about 50
g and diluted with about 100 g of 1-butanol to about 15
The coating solution was obtained by stirring for a time.

Then, the solution is coated on the surface of the glass substrate by a dipping method in an environment of about 23 ° C. and relative humidity of about 80%, and heated at about 270 ° C. for about 10 minutes to have a thickness of about 1
A gel film with a thickness of 00 nm is formed, and a film thickness of about 1 is formed on the gel film.
A 50 nm SiO ₂ thin film was formed. When the surface shape of the thin film was observed with a scanning electron microscope at a magnification of about 20,000, it was found to be a micropit-like surface layer having a diameter of about 200 to 300 nm.

Then, a mixed solution (dispersion solution) was prepared in advance on the substrate having the micropit shape so that the fluororesin (Neoflon: manufactured by Daikin Industries, Ltd.) in the water repellent layer was 100% by weight with respect to silica. The coating liquid was applied by the dipping method, and baked for about 30 minutes in an electric furnace set at about 400 ° C. for water repellent treatment. The film thickness was about 150 nm.

The following tests were conducted on the obtained glass substrate with a laminated thin film. (Water repellency test) The contact angle with respect to water in the atmosphere (about 25 ° C) was measured using Kyowa Interface Science CA-A type.

(Durability Test) The durability was evaluated by the sliding durability with an automobile wiper blade. Conditions: While dripping clean water, a load of about 105 g is applied and sliding is performed about 100,000 times (reciprocating once),
It was evaluated by the amount of decrease in contact angle.

As a result, the initial contact angle was about 110 °, the contact angle was about 88 ° after sliding 100,000 times of tap water, and the desired performance was obtained. (Weather resistance test) Evaluation was performed by irradiation with xenon.

Conditions: about 180 w / m ² , one cycle about 1
Water was sprayed at a temperature of 20 ° C. for 80 hours and the last about 25 minutes. The surface temperature of the glass substrate during irradiation is about 53.
It was about 0 ° C, and the contact angle was evaluated by the change with time.

As a result, the initial contact angle of about 110 ° was maintained at about 110 ° even after the irradiation time of about 2000 hours, and the desired performance was obtained. Example 2 A glass substrate similar to that of Example 1 was charged with about 30 g of methyltrimethoxysilane of Example 1 and about 23.1 g of silicon ethoxide of Example 1 in a beaker, and a low average molecular weight solid content / high average molecular weight was added. And a solid content of about 6.5 mol ratio,
Others were the same as in Example 1. As a result, an uneven surface layer having the same diameter as in Example 1 was obtained. Then, water repellent treatment was performed in the same manner as in Example 1. The thickness of the gel was about 100 nm, and the thickness of the water repellent layer was about 150 nm.

The glass substrate with the laminated thin film thus obtained was evaluated in the same manner as in Example 1. The durability test showed that the initial contact angle was about 111 ° and the contact angle after sliding 100,000 times on tap water was about. In the weather resistance test, the initial contact angle was about 111 °, but it remained at about 110 ° even after the irradiation time of about 2000 hours, and had the desired performance.

Comparative Example 1 Silicon ethoxide (average molecular weight: about 100,000,
About 200 g of solid content concentration: about 6 wt% was weighed into a beaker and used as it was as a coating solution. Otherwise, the procedure was the same as in Example 1, and then the water repellent treatment was performed in the same manner as in Example 1.

The SiO ₂ film of the obtained film had a flat surface layer, and the durability test showed that the initial contact angle was about 110 °.
The contact angle after sliding 100,000 times with tap water was about 70 °, and the weather resistance test showed that the initial contact angle was about 110 °, but after irradiation time of about 2000 hours it was about 110 °. It was far from the term.

Comparative Example 2 In the same manner as in Comparative Example 1, the obtained sample was about 0.2 wt%.
The surface was treated with an HF aqueous solution for about 5 minutes. Then, water repellent treatment was performed in the same manner as in Example 1.

After the HF treatment, the surface layer of the film was uneven like the second embodiment. The obtained product had an initial contact angle of about 112 ° in a durability test and a contact angle of about 72 ° after sliding 100,000 times in tap water, and a weather resistance test showed an initial contact angle of about 11 °.
What is 1 ° is about 11 after irradiation time of about 2000 hours.
It was about 1 °, and like Comparative Example 1, it could not be said that it was an extremely desired one.

[0059]

As described above, according to the water-repellent glass and the method for producing the same of the present invention, a film can be obtained inexpensively and efficiently by a simple and easy film forming means, and the peculiar controlled by the film can be obtained. By obtaining a metal oxide thin film having a rugged micropit-shaped, uneven or convex surface layer having a shape and diameter as an intermediate layer, and impregnating and embedding and coating the specified water-repellent oxide thin film, To demonstrate its performance, and without impairing optical characteristics, water repellency,
It is excellent in adhesion, scratch resistance, durability, weather resistance, etc. Suitable for window materials for construction or automobiles, various glass articles, especially wiper sliding parts in window materials for automobiles etc. The present invention provides a useful water-repellent glass that can be employed and a method for producing the same.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Arai 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center (72) Inventor Shigeo Hamaguchi 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center (72) Inventor Ichiro Nakamura 2 Takaramachi, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Inventor Ryuzo Uemura 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (56) References JP-A-6-329442 (JP, A) JP-A-6-16455 (JP, A) JP-A-5-319869 (JP, A) JP-A-5-213633 (JP, A) JP-A-5-147976 (JP , A) JP-A 4-124047 (JP, A) JP-A 62-3046 (JP, A) JP-A 61-10043 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 15/00-23/00 C09K 3/18 B32B 1/00-35/00

Claims (8)

(57) [Claims] 1. A water-repellent glass whose water-repellent layer comprises at least SiO ₂ and a fluororesin, wherein the fluororesin accounts for 5 to 450% by weight relative to the SiO ₂ , and the glass substrate and the water-repellent layer are A water-repellent glass characterized in that a sol-gel film which is a micropit-like surface layer, an uneven surface layer, or a convex surface layer is formed as an intermediate layer therebetween. 2. The intermediate layer is a sol-gel film, wherein the micropit-like surface layer, the uneven surface layer, or the convex surface layer has a diameter of 200 to 400 nm for the micropits, unevenness or projections. The water-repellent glass according to claim 1. 3. At least one compound selected from the group consisting of metal alkoxide compounds and metal acetylacetonate compounds on a glass substrate , wherein
Select two or more compounds with different molecular weights
Adjust the mixing ratio of the compound and mix it with the solvent.
To form a sol-gel film formed by coating the solution with heating at a temperature of 100 ° C. or higher, and forming a sol-gel film on the sol-gel film and at least a silica sol solution and fluororesin particles or a suspension of fluororesin particles. A method for producing water-repellent glass, characterized in that a water-repellent layer film is formed by coating by coating a solution obtained by mixing and baking to form a film. 4. Relative humidity when coating the coating solution.
Characterized by controlling the degree in the range of 70-80%
The method for producing the water-repellent glass according to claim 3. 5. One of the selected two or more compounds having different average molecular weights has a molecular weight of 800 to 8000.
A low average molecular weight compound of
High average molecular weight of 100,000-400,000
The method for producing water-repellent glass according to claim 3 or 4 , characterized in that a sol-gel film made of the compound of (1 ) is used as an intermediate layer. 6. The mixing ratio of two or more compounds having different average molecular weights to be selected is adjusted such that the compound having a low average molecular weight is 0.1 to 3 with respect to 1 mol of the compound having a high average molecular weight.
The method for producing water-repellent glass according to any one of claims 3 to 5, wherein the sol-gel film consisting of 0 mol is used as an intermediate layer. 7. The coating solution is added in an amount of 1 to 10 cP.
Method for producing a water-repellent glass according to any one of claims 3 to 6, characterized in that to form a sol-gel film by a viscosity adjusted. 8. A metal alkoxy of the coating solution.
Serial to any one of claims 3 to 7 conc <br/> degree of de-based compound or a metal acetylacetonate based compound and forming a sol-gel film by a 0.01-10 wt% <br /> A method for producing the water-repellent glass described above.