JPH1036142A - Method for producing water-repellent glass coat film - Google Patents

Abstract

(57) [Summary] [Problem] A water-repellent glass coating liquid changes with time, so it is necessary to regenerate the coating liquid every time coating is performed. Therefore, it is not necessary to re-create a new coating solution. An object of the present invention is to provide a method for producing an aqueous glass coat film. SOLUTION: TEOS as a glass coating liquid, water,
After an ethanol solution 3 in which hydrochloric acid is dissolved is applied and formed on the glass plate 4, a fluorine coat solution containing FMOS is further applied and formed on the glass plate 4. At this time, by making the solvent of the glass coating solution dissolve the FMOS and making the solvent of the glass coating solution insoluble in the solvent of the fluorine coating solution, the polymerization reaction of the FMOS over time can be prevented. As a result, it is possible to prevent deterioration of the fluorine coating liquid over time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a water-repellent glass coat film.

[0002]

2. Description of the Related Art A water-repellent glass coat film refers to a coat film having hardness and transparency comparable to silicon oxide glass and water repellency comparable to fluororesin.

[0003] A conventional method for producing a water-repellent glass coat film will be described below. For example, tetraethoxysilane (Si (OCH3) 4; hereinafter abbreviated as TEOS) and perfluoroalkylmethoxysilane (CF3
Water and hydrochloric acid were added to an ethanol solution in which (CF2) 7C2H4Si (OCH3) 3 (hereinafter abbreviated as FMOS) was dissolved to prepare a coating solution in which these compounds were hydrolyzed and polymerized (see FIG. 5). After dipping the substrate in
This coating solution is applied to a glass substrate by pulling up at a speed of 2 mm / s or less (dipping method), and this is further baked at 400 ° C. to form a water-repellent glass coat (Takao Kamigami et al., Tokyo Metropolitan Government) Industrial Technology Center Research Report No. 22, 1993).

[0004]

The water-repellent glass coat film formed by the above-mentioned conventional method has excellent abrasion resistance,
It is a coat film with higher heat resistance than fluororesin.

However, the characteristics of the above-mentioned conventional coating liquid change from the initial coating liquid over time.
This is considered to be due to the fact that TEOS and FMOS are polymerized with time, and the viscosity and characteristics are different from those of the initial coating liquid. Therefore, in order to produce a water-repellent glass coat film with good reproducibility, it is necessary to make a new coating liquid every time coating is performed. on the one hand,
Since a methoxysilane or ethoxysilane compound having a fluorocarbon chain (FMOS in the above-described conventional technique) is expensive, there is a demand that at least this compound alone be used for a long period of time.

Accordingly, an object of the present invention is to provide a method for producing a water-repellent glass coat film which does not require a new coating solution every time a water-repellent glass coat is formed.

[0007]

In order to achieve the above object, a method for producing a water-repellent glass coat film according to the present invention comprises a methoxysilane compound or an ethoxysilane compound which is a precursor of glass containing silicon oxide as a main component. A step of applying a glass coating solution in which a fluorinated carbon chain is dissolved to a substrate, and applying a fluorine coating solution in which an ethoxysilane or a methoxysilane compound containing a fluorocarbon chain is dissolved to the substrate, and removing the fluorocarbon chains in the fluorine coating solution. Impregnating the ethoxysilane or methoxysilane compound containing ethoxysilane or methoxysilane compound into the glass coating liquid applied to the substrate, and dissolving the ethoxysilane or methoxysilane compound containing a fluorocarbon chain. The configuration is characterized in that the solvent of the glass coating liquid is insoluble in the solvent of the fluorine coating liquid.

Further, according to the present invention, in the above method, the glass coating solution and the fluorine coating solution are separated from each other, placed in the same container, and the substrate is immersed in the container, so that the glass coating solution is And a fluorine coating solution is applied to the substrate.

With the above-mentioned structure, it is possible to prevent the polymerization reaction of the components in the fluorine coating solution from being promoted with time.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a method for preparing a water-repellent material using the above two solutions after preparing separate solutions of, for example, TEOS, FMOS, hydrochloric acid, etc., which were conventionally contained in the same coating solution. It is characterized in that a coating treatment is performed, whereby deterioration of the formed water repellent coating solution over time can be prevented.

Therefore, the above contents will be described below. First, a glass coat solution is prepared as a first solution. A glass coating solution containing a glass precursor containing silicon oxide as a main component includes Si (0CH3) 4, Si
(0C2H4) 4 (hereinafter abbreviated as TEOS), (CH3
0) 3SiOSi (OCH3) 3 or (C2H50) 3
It can be prepared by dissolving SiOSi (OC2H5) 3 in a solvent and subjecting it to hydrolysis and polymerization. FIG. 4 is a schematic view showing a process in which TEOS is hydrolyzed and polymerized to form a glass coating solution. As a solvent used for the above glass coating solution, a solvent capable of simultaneously dissolving TEOS and FMOS is used.
Examples include polar solvents such as methanol, ethanol, and propanol.

Next, a fluorine coating solution is prepared as a second solution. The fluorine coating solution is a fluorocarbon chain (-(CF
2) n-; n is an integer of 1 or more) and a methoxysilyl group (-
OCH3) or a compound having an ethoxysilyl group (-OC2H5), for example, CF3 (CF2) 7C2H4Si (0CH3)
3 (hereinafter abbreviated as FMOS) in a solvent. As the solvent used for the above-mentioned fluorine coating solution, a solvent which does not mix with the above-mentioned glass coating solution and dissolves FMOS is used. Examples thereof include n-perfluorooctane which is a polar solvent. And a solvent comprising a molecule containing a fluorocarbon chain.

Hereinafter, specific examples of the method for producing a water-repellent glass coat film of the present invention will be described with reference to examples.

Example 1 First, 150 ml of a mixed solution of TEOS and ethanol (4:10 in molar ratio)
A mixed solution of ethanol, water and hydrochloric acid (at a molar ratio of 10: 5:
0.05) 150 ml were prepared, and these were mixed little by little to prepare a glass coating solution. Thereafter, the two mixed solutions were placed in a cylindrical glass container having a diameter of 10 cm and a height of 20 cm. TEOS in this glass coat liquid
Is shown in FIG.

On the other hand, 300 ml of a mixed solution (molar ratio: 1:10) of FMOS and n-perfluorooctane was prepared as a fluorine coating solution. Then, this coating solution was placed in a cylindrical glass container having a diameter of 10 cm and a height of 20 cm. Since this fluorine coating solution does not contain water and an acid catalyst, FMOS does not polymerize over time,
The usable state can be maintained for a long time.

Next, a glass plate 11 (fixed by a fixing rod 10) having a size of 5 cm × 5 cm and a thickness of 2 mm as a substrate on which a water-repellent glass coat film is formed is fixed to a size of 5 cm × 5 cm.
2mm / s so that the main surface of 5cm is perpendicular to the solution
The glass plate 11 was immersed in the above-mentioned glass coating solution 13 at the speed described above, and when the entire glass plate was immersed in the coating solution, the lowering of the glass plate 11 was stopped and left for 30 seconds. Thereafter, the glass plate 11 was pulled up at a speed of about 2 mm / s (FIG. 2).

Then, the glass plate 11 was immersed in the above-mentioned fluorine coating solution and pulled up at a constant speed, in exactly the same manner as described above.

FIG. 1 shows the reaction process of the substrate surface in the fluorine coating liquid of the glass plate 4 after the treatment with the glass coating liquid. Since ethanol, water, and hydrochloric acid on the surface of the substrate are insoluble in the solvent of the fluorine coating solution, they do not dissolve from the surface of the substrate into the fluorine coating solution. Further, since the TEOS polymer on the surface of the base material is also hydrophilic, it does not dissolve into the fluorine coating solution. Here, the FMOS 1 is dissolved in a solvent (ethanol solution 3 in which TEOS, water and hydrochloric acid are dissolved) on the surface of the base material, and is polymerized by the catalytic action of hydrochloric acid in this solvent to form a polymerized FMOS 2.

Next, the glass substrate was dried at room temperature for 1 hour, and then fired at 100 ° C. for 10 minutes and subsequently at 350 ° C. for a minute.

The static contact angle of the coated glass with pure water was 109 degrees. This indicates that the water-repellent glass coat film was formed on the glass substrate by the method of this example.

In this embodiment, since a coating solution of only TEOS and a coating solution of FMOS not polymerized are used, the pulling speed of the base material is 2 mm / s.
Thus, a clean coat film is formed on the substrate. This is higher than the conventional pulling speed, and when mass-producing a water-repellent glass coat film, it is possible to obtain the effect of increasing the daily production amount and suppressing the processing cost.

(Embodiment 2) As in Embodiment 1 described above, T
Mixed solution of EOS and ethanol (4:10 in molar ratio) 1
150 ml of a mixed solution of 50 ml, ethanol, water and hydrochloric acid (molar ratio: 10: 5: 0.05) was prepared, and these were mixed little by little to prepare a glass coating solution. Further, as in Example 1, a mixed solution of FMOS and n-perfluorooctane (1:10 in molar ratio) was used.
0 ml was prepared and used as a fluorine coating solution.

The two liquids are placed in a cylindrical glass container having a diameter of 10 cm and a length of 20 cm in the order of a fluorine coating liquid and a glass coating liquid. Because these two solutions do not mix with each other,
As shown in FIG. 3, the two liquids are separated. Glass coating liquid 21
Although changes with time, the fluorine coating solution 22 is stable even after a lapse of time because the solution does not contain water and an acid catalyst necessary for FMOS polymerization. Therefore, after a lapse of time, only the glass coating solution in the glass container may be changed.

Next, a glass plate 11 having a size of 5 cm × 5 cm and a thickness of 2 mm as a base material on which a water-repellent glass coat film is formed is placed at 2 mm / s so that the main surface of 5 cm × 5 cm is perpendicular to the solution. The glass plate was immersed in the glass coating solution and the fluorine coating solution at the speed described above, and was held for 30 seconds when the glass plate was completely immersed in the fluorine coating solution. In this state, the glass coating liquid has already been applied to the surface of the glass plate 11. Therefore, the reaction process on the surface of the glass plate 11 in the fluorine coating liquid 22 is basically the same as the process shown in the first embodiment. Next, this glass plate 11
At a speed of 2 mm / s. At this time, the glass plate 11
Again passes through the glass coating solution, but the glass surface is made water-repellent by FMOS, so that the glass surface is no longer coated with the glass coating solution (FIG. 3).

Next, the glass substrate was dried at room temperature for 1 hour, and then fired at 100 ° C. for 10 minutes and subsequently at 350 ° C. for a minute.

The static contact angle of the coated glass with pure water was 109 degrees. This indicates that the water-repellent glass coat film was formed on the glass substrate by the method of this example.

In this embodiment, since the glass coating liquid is on the fluorine coating liquid, the glass coating liquid can be easily exchanged.

[0028]

According to the present invention, the coating solution in which the methoxysilane or ethoxysilane compound containing a fluorocarbon chain is dissolved is stable and can be used many times. Therefore, a water-repellent glass coat film can be formed at low cost.

Further, since the glass coat and the fluorine coat are formed in different processes, if the characteristics of the coat film vary when mass-producing the water-repellent glass coat, it is easy to analyze the causes of the variations, and as a result, the production process Is easy to manage.

In the above embodiment, the molecule containing a fluorocarbon chain is CF3 (CF2) 7C2H4Si.
Although (OCH3) 3 was used, the present invention is not limited to this, and it is needless to say that a fluorocarbon chain having 9 or more or 7 or less carbon atoms can be used. Further, in the above example, a triethoxysilane compound was used, but the present invention is not limited thereto, and dimethoxysilane, monomethoxysilane, or diethoxysilane,
It goes without saying that monoethoxysilane may be used.

[Brief description of the drawings]

FIG. 1 is a diagram showing a reaction process on a glass plate surface in a fluorine coating solution according to an embodiment of the present invention.

FIG. 2 is a sectional view showing a step of forming a water-repellent glass coat film according to the embodiment of the present invention.

FIG. 3 is a sectional view showing a step of forming a water-repellent glass coat film according to the embodiment of the present invention.

FIG. 4 is a diagram showing a process in which TEOS is hydrolyzed and polymerized to form a glass coating solution.

FIG. 5 is a diagram showing a process in which TEOS and FMOS are hydrolyzed and polymerized to form a coating solution.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 FMOS 2 FMOS polymerized 3 TEOS, ethanol solution in which water and hydrochloric acid are dissolved 4 Glass plate 10 Rod for fixing glass plate 11 Glass plate 12 Glass container 13 Coating solution 20 Glass container 21 Glass coating solution 22 Fluorine coating solution 30 TEOS, FMOS hydrolysis / polymer 40 TEOS hydrolysis / polymer

Claims (2)

[Claims] 1. A step of applying a glass coating solution in which a methoxysilane compound or an ethoxysilane compound, which is a precursor of glass containing silicon oxide as a main component, is dissolved to a substrate, and ethoxysilane or methoxyl containing a fluorocarbon chain. Apply a fluorine coating solution in which the silane compound is dissolved to the base material,
Impregnating the ethoxysilane or methoxysilane compound containing a fluorocarbon chain in the fluorine coating liquid into the inside of the glass coating liquid applied to the base material, the method for producing a water-repellent glass coating film, A water-repellent glass coating, wherein the solvent of the glass coating solution dissolves the ethoxysilane or methoxysilane compound containing the fluorocarbon chain, and the solvent of the glass coating solution is insoluble in the solvent of the fluorine coating solution. Manufacturing method of membrane. 2. A glass coating liquid and a fluorine coating liquid are separated from each other, placed in the same container, and the substrate is immersed in the container to apply the glass coating liquid to the substrate and to apply the fluorine coating liquid to the substrate. The method for producing a water-repellent glass coat film according to claim 1, wherein the method is applied to the base material.