KR20020038968A - Method for producing water repellent glass which has high durability - Google Patents

Abstract

PURPOSE: Provided is a preparation method of water repellent glass forming an inorganic film, which has fine irregularities on the surface and uniform-sized pores on the inside, on the surface of the glass, especially large-sized substrate. Accordingly, the resultant glass is excellent in water repellency, durability, and abrasion resistivity. CONSTITUTION: The preparation method is as follows: (i) preparing a first solution by mixing 1pts.wt. of tetraethyl orthosilicate(TEOS), 1.7-17pts.wt. of alcohol such as methanol, ethanol, iso-propanol and butanol, and 0.6-6pts.wt. of HCl(1%) solution; (ii) preparing a second solution by mixing 1pts.wt. of metal(Ti, Al and Zr) alkoxide and 2-5pts.wt. of alcohol; (iii) preparing a third solution by adding the second solution to the first solution, then adding alcohol dispersed with 0.4-4.5M(based on 1M TEOS) of at least one colloidal metal oxides(10-100nm) selected from such as SiO2, TiO2, ZrO2, Al2O3, CeO and SnO2; (iv) coating a glass substrate with the third solution, and sintering at lower than 600deg.C for forming inorganic film on which fine irregularities, caused by metal oxides particles, are dispersed; (v) spreading pre-coater, silane coupling agent, over the inorganic film to improve bonding force with water repellent film; (vi) coating fluorosilane-based repellent solution, and sintering. Also, the inorganic film with fine irregularities on the surface and uniform-sized pores on the inside is prepared by adding organic polymer resin, such as polyacryl amide, polybutoxy ethylene, etc., emulsified in alcohol to the above solution of step (iii), where the pores are formed by thermal composition of polymer for homogeneous dispersion of water repellent materials, and other processes are the same as the above process.

Description

METHOOD FOR PRODUCING WATER REPELLENT GLASS WHICH HAS HIGH DURABILITY

The present invention relates to a method for producing a water-repellent glass that is applied to the surface of the substrate such as glass to form a water-repellent coating for forming a durable water-repellent coating, and using such a composition, to form a water-repellent coating with excellent weather resistance and hardness. In forming an inorganic protective film to enhance the bonding force with the water repellent material on the surface of a large substrate, such as glass, fine irregularities are formed on the surface uniformly to increase the bonding density of the water repellent material and evenly dispersed in the coating film. It is to provide a method for producing a water-repellent glass excellent in durability and wear resistance.

Water repellent coating not only reduces the frictional force by increasing the contact angle between the coated film and water droplets as much as possible, but also suppresses the generation of static electricity, so that the water droplets do not adhere well and are easily removed by external forces such as wind pressure even when attached. It can be mainly applied to the outdoor side of the molten glass. As a method of imparting water repellency to glass, in most cases, a hydrophilic glass surface composed of Si-O-Si or Si-OH is coated with a hydrocarbon-based organic molecule having a low surface energy. In particular, low surface energy -CF ₃ , -CF ₂ , -CH ₃ is used as a water repellent, and organic compounds having such a water repellent is used as a water repellent coating. In general, water repellents used in the manufacture of water-repellent glass are largely classified into FAS and fluororesin. Both types are the same in that they have CF ₃ water-repellent groups at the end, but FAS is known to have excellent film strength and affinity with glass because it can form siloxane bonds with glass.

When FAS or the like is coated on the surface of the glass substrate to coat FAS, the soda-lime-containing glass may be less durable due to alkali ions or contamination of the surface. Therefore, in order to improve the durability of the water-repellent glass, a method of synthesizing an inorganic film and a water-repellent material having excellent bonding strength with a glass substrate is mainly used, or a method of increasing the adhesion between the water-repellent material and the substrate by uneven surface of the substrate.

In Japanese Patent Laid-Open Nos. 4-338137, 5-112757, 5-35745, 55-345641, 7-257942, etc., water repellent coated on the surface of a glass substrate is disclosed. The main technique deals with a film composed of SiO ₂ as a main component and a part of nonmetallic atoms of ceramics substituted with fluoroalkyl groups. In these patents, the starting material uses a solution in which a portion of the alkyl alkoxide represented by Si (OR) ₄ and an alkyl group are substituted with a fluoroalkyl group, and a mixture of substituted silicon alkoxide, alcohol and water (or base), and in particular, durability of the coating film. In order to improve, alkoxides of metals such as TiO ₂ , Al ₂ O ₃ , and ZrO ₂ are mixed. In addition, the alkoxide of phosphorus (P) was mixed in the solution to suppress the influence of alkali diffusion of the glass substrate.

However, these methods can increase the water repellency by mixing the FAS compound with the metal alkoxide, oxidizing the alkoxide by heat treatment, and retaining the fluoroalkyl group, but the water repellent is mainly formed at the end of the substituted alkoxide after the firing treatment. Since it exists concentrated in the outermost shell, there is a disadvantage in that the difference in the initial water repellency characteristics and the characteristics after the wear is relatively large.

In Japanese Patent Laid-Open No. 4-124046, the glass substrate is immersed in 0.05-0.1% by weight of hydrofluoric acid solution for about 1 to 10 minutes to form fine irregularities that do not cause whitening on the surface. To be processed.

Japanese Patent Application Laid-Open No. 7-69680 solves the disadvantage that when hydrofluoric acid is used, the surface is easily eroded due to strong erosion of the glass surface. An acidic aqueous solution having a pH of 3.0 or less except for hydrofluoric acid is used for inorganic materials such as glass substrates. A technique for forming a water repellent coating after surface treatment by dipping in is disclosed. Since the alkali component on the surface of the substrate is removed from the acidic aqueous solution, deterioration due to alkali elution is prevented. In addition, there is a difference in degree on the surface, but microscopically, fine irregularities are formed to improve the adhesion to the water repellent film.

In another method, Japanese Laid-Open Patent Publication No. H5-24886 discloses a SiO ₂ film having a thickness of 0.2 μm on a glass surface by depositing glass in a supersaturated solution by adding boric acid to a saturated aqueous solution of silicon oxide of hydrofluoric acid. The method is etched with an aqueous hydrofluoric acid solution of% or less, fine irregularities are formed on the surface thereof, and a water repellent layer is coated thereon.

However, it has been pointed out that the surface unevenness method is not reproducible in the process or homogeneous in a large area substrate and requires an additional process using a strong acid.

Another uneven surface of the substrate is a method of forming an inorganic protective layer having sub-micron unevenness between the glass substrate and the water repellent film and coating the water repellent film thereon.

In Japanese Patent Laid-Open Nos. 5-213633 and 6-16455, a metal alkoxide-based compound and a metal acetylacetonate-based compound are used as a solution for forming a protective layer. Fine irregularities such as this occur. Through the publications of Korean Patent Application Laid-Open Nos. 7-33480 and 8-40748, a silica sol solution having an average molecular weight of several thousand and a silica sol solution having an average molecular weight of tens of thousands is obtained to obtain a SiO ₂ protective layer having an uneven surface. Said that.

In Japanese Patent Laid-Open No. 8-40748, a silica sol having a different average molecular weight is mixed to form an uneven surface SiO ₂ protective layer, and then a solution composed of Si alkoxide and FAS and SnO ₂ fine particles having a semiconductor property of 10 Onm or less. The water-repellent film was coated with the solution prepared by adding thereto.

The SiO ₂ protective layer is formed to a thickness of about 200 nm by applying a liquid composition to the surface of the transparent substrate by dipping, spraying, flow, etc., and then calcining to improve durability and abrasion resistance. The coating layer and the uncoated layer are clearly distinguished with the naked eye due to the optical interference caused by the slight difference in thickness due to the difference in refractive index between the SiO ₂ protective layer having a refractive index of about 1.42 and the glass substrate (1.5 to 1.52 in the case of general plate glass). There is a disadvantage in that defects such as rainbow light and stains occur. In addition, there is a problem that the uniformity of the entire surface cannot be guaranteed because the unevenness of the surface is caused by the difference in the average molecular weight and the distribution thereof is over a large range.

The object of the present invention is to solve the problems of the prior art as described above, in forming an inorganic protective film for enhancing the bonding force with the water-repellent material on the surface of a large substrate such as glass, as well as uniformly forming a fine irregularities on the surface However, the present invention provides a method of manufacturing a water-repellent glass having excellent water repellency, durability, and abrasion resistance by properly dispersing pores having a uniform size in the inorganic protective film to increase the bonding density of the water repellent material and evenly dispersing the coating water inside the coating film.

In addition, an object of the present invention is to improve the stability of the composition for forming an inorganic protective film on the surface of the substrate, less defects in the manufacturing process, producing a water-repellent glass that can form irregularities and pores of uniform size To provide.

In order to achieve the above object, according to the present invention, there is provided a method for producing a water-repellent glass having a fine irregularities on the surface and an inorganic protective film in which pores of uniform size are properly dispersed therein, and thus water-repellent glass.

More specifically, according to the first embodiment of the present invention, a step of preparing a first solution by mixing 1.7 to 17 parts by weight of alcohol and 0.6 to 6 parts by weight of an aqueous 1% HCl solution with respect to 1 part by weight of TEOS; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; Preparing a solution 3 by adding the solution 2 to the solution 1 and adding an alcohol having fine particles of the colloidal metal oxide dispersed therein; Applying the solution 3 to the substrate glass and baking at a temperature of 600 ° C. or lower to form an inorganic protective film on the surface of which fine irregularities are properly distributed by metal oxide fine particles; Coating a pretreatment agent on the inorganic protective film in order to improve bonding to the water repellent film, and applying an alcohol solution of a fluorosilane-based water repellent material, followed by secondary firing to form a water repellent film. A method for producing a water repellent glass having a structure in which phases are properly dispersed is provided.

In addition, according to a second embodiment of the present invention, a step of preparing a first solution by mixing 1.7 to 17 parts by weight of alcohol, 0.6% to 6 parts by weight of an aqueous 1% HCl solution with respect to 1 part by weight of TEOS; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; Adding solution 2 to solution 1, adding an alcohol emulsion of colloidal metal oxide fine particles and an alcohol emulsion of an organic polymer resin insoluble in alcohol to prepare solution 3; Applying the solution 3 to the substrate glass and baking at a temperature of 600 ° C. or lower to form an inorganic protective film on the surface of which the fine irregularities and fine pores generated by thermal decomposition of the organic polymer resin are properly distributed by the metal oxide fine particles; Coating a pretreatment agent on the inorganic protective film in order to improve bonding to the water repellent film, and applying an alcohol solution of a fluorosilane-based water repellent material, followed by secondary firing to form a water repellent film. A method for producing a water repellent glass having a structure in which phases are properly dispersed is provided.

At this time, the weight ratio of SiO ₂ of the inorganic solids in the solution 3 and solids of other inorganic components ZrO ₃ , TiO ₂ , Al ₂ O _3, etc. is 2.5 / 7.5 to 3.5 / 6.5, and the prepared inorganic protective film The refractive index of is preferably 1.50 to 1.52, in this range can eliminate the difference in refractive index with the substrate.

In addition, the above-mentioned colloidal metal oxide fine particles have a particle diameter of 10 nm to 100 nm and are preferably mixed at a ratio of 0.4 to 4.5 moles with respect to 1 mole of the TEOS. If the particle size used is less than 10 nm, Irrespective of the addition amount, it is difficult to expect the unevenness effect after the addition, and when it is 100 nm or more, the appearance is blurred after the film formation regardless of the addition amount. In addition, even when the addition amount of the oxide fine particles is 0.4 mol or less with respect to 1 mol of TEOS, it is difficult to expect the unevenness effect regardless of the size of the added particles, and when added more than 4.5 mol, the appearance becomes blurred regardless of the addition amount after the film formation. do.

As the colloidal metal oxide fine particles, one or more selected from SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , CeO, SnO _2, and the like are used.

Examples of the organic polymer resin insoluble in the alcohol include polyacrylamide, polycyclopentylethylene, polybutoxyethylene, polybenzyloxyethylene, polychloromethylbutadiene and polyvinylacetylacetate, and the average molecular weight of the organic polymer resin It is preferable that it is several hundred to several thousand silver, and the size of the particle | grain which the solution of the organic polymer resin emulsified in alcohol is 10 nm-100 nm is preferable.

As the type of alcohol, at least one or more of methanol, ethanol, isopropanol and butanol is used.

As a pretreatment agent used to improve the binding force with the water repellent membrane, at least one alcohol solution among silane coupling agents such as propyltrimethoxyoxysilane, ethyltrimethoxysilane, tetramethylorthosilicate and the like is used. The coupling agent is characterized in that it is diluted to about 1-30% by weight with respect to the alcohol solvent.

As the FAS-based water repellent material for forming the water repellent film, at least one of fluoroalkylalkoxysilane, fluoroalkyl chloride silane, and fluoroalkyl isocyanate silane is used.

Hereinafter, the content of the present invention will be described in more detail.

In the present invention, in forming the inorganic protective film for enhancing the bonding force with the water-repellent material on the surface of the glass substrate, fine irregularities are uniformly formed on the surface, and the pores of uniform size are also properly dispersed in the inorganic protective film, thereby repelling water. The material is dispersed evenly inside the coating film to enable the production of water-repellent glass excellent in water repellency, durability and wear resistance.

In other words, a solution containing a high-molecular SiO ₂ -chain is prepared by hydrolysis and condensation reaction from Si alkoxide, and at least one metal alkoxide of Ti, Al, Zr and fine particles of metal oxide are dispersed in addition to Si alkoxide. When the solution is mixed, the composition A in which the fine particles of the metal oxide are dispersed in the SiO ₂ -MO composite chain can be prepared.

On the other hand, when a solution of an organic polymer resin insoluble in alcohol is vigorously mixed in the alcohol, a composition B is prepared in the form of emulsification and dispersed in fine particles. When the A and B compositions are mixed in an appropriate ratio and coated on the substrate glass, and then fired at a temperature of 600 ° C. or less, fine concavo-convex phases are formed on the surface by the metal oxide fine particles, and the pores generated by thermal decomposition of the organic polymer resin are properly distributed inside. A composite inorganic protective film of SiO ₂ -MO is formed. When the FAS component, which is a water-repellent substance, is mixed and applied to the alcohol on the inorganic protective film and fired, a water-repellent coating having improved durability (including wear resistance and light resistance) is formed.

The mixing ratio of the fine particles of Si alkoxide, metal alkoxide and metal oxide included in Composition A is 1.50 to 1.52 after coating and firing in consideration of the composite system of metal oxide and inorganic polymer SiO ₂ -MO dispersed in particulate form. In this case, defects such as rainbow light and stains caused by optical interference between the protective film and the glass substrate can be solved.

Such a water-repellent glass according to the present invention, with respect to 1 part by weight of TEOS, 1.7 to 17 parts by weight of alcohol, 0.6% to 6 parts by weight of a 1% HCl aqueous solution to prepare a first solution; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; Preparing a solution 3 by adding the solution 2 to the solution 1 and adding an alcohol having fine particles of the colloidal metal oxide dispersed therein; Applying the solution 3 to the substrate glass and baking at a temperature of 600 ° C. or lower to form an inorganic protective film on the surface of which fine irregularities are properly distributed by metal oxide fine particles; The pretreatment agent may be coated on the inorganic protective film to improve the binding force to the water repellent film, and then coated with an alcohol solution of a fluorosilane-based water repellent material, followed by secondary firing to form a water repellent film.

In addition, to 1 part by weight of TEOS, 1.7 to 17 parts by weight of alcohol, 0.6% to 6 parts by weight of a 1% HCl aqueous solution to prepare a first solution; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; The solution 2 is added to the solution 1, an alcohol in which fine particles of a colloidal metal oxide is dispersed is added thereto, and a solution of an organic polymer resin insoluble in alcohol is mixed with the alcohol at a ratio of 5 to 30 parts by weight based on the total alkoxide. And after emulsifying, adding the particulate dispersion alcohol to prepare a solution 3; The solution 3 is applied to the substrate glass and gelled, and the coated glass substrate is first calcined at a temperature of 600 ° C. or lower, so that pores generated by thermal decomposition of fine irregularities and organic polymer resin by metal oxide fine particles on the surface are properly distributed. Forming an inorganic protective film; In order to improve the bonding strength with the water repellent film on the inorganic protective film can be prepared through the step of forming a water repellent film by coating a pretreatment agent, an alcohol solution of a fluorosilane-based water repellent material and then secondary baking.

The fine particles of the metal oxide may be produced by any method. For example, it is preferable to prepare the metal oxide fine particles through a hydrolysis and dehydration condensation reaction using, for example, a metal alkoxide-based compound or a metal acetylacenet-based compound as a starting material. Hydrolysis of the metal alkoxide with an excess of water results in dispersing the hydroxide precipitated particles in a solution and then adding an acid to form a transparent sol. The sol formed has an average molecular weight of several hundreds to thousands and a size of several nm or more. It is a particle brush composed of dense oxide particles. The metal alkoxide-based 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 thereof is substituted with a methyl group, an ethyl group, for example, a single methyl alkoxide or a single ethyl alkoxy. De, etc. are contained. In addition, the metal acetylacenet-based compound includes not only the case where only the acetylacenet group is bonded to all of the metals, but also a portion of which is substituted with a methylalkoxy group, an ethylalkoxy group or the like. Moreover, as said metal, it is especially preferable to select Si, Ti, Al, Ce, or Zr.

The metal oxide fine particles may be commercialized as a solution in which the fine particles are dispersed, and commercially available products containing SiO ₂ fine particles include CATALOID, OSCAL (Japan), LUDOX (Du Pont; USA), and SUPER CELL. (Japan), CERAMICA (Japan), HAS (COL COAT; Japan), ATLON (Japan), CGS-Dl-0600 (GISO; Japan), etc. . The trade names of the products in which the TiO ₂ fine particles are dispersed are TA-10, TA-15 (Japan), and the trade names of the products in which the ZrO ₂ fine particles are dispersed, NZS-30A and NZS-30B (日 學 化學 工業; Japan), AZS-A, AZS-NB, AZS-B (Japan), and SUNVEIL, OPTOLAKE (Japan), and the like in which the fine particles are mixed.

The organic polymer resins insoluble in the alcohol include polyacrylamide, polycyclopentylethylene, polybutoxyethylene, polybenzyloxyethylene, polychloromethylbutadiene and polyvinylacetylacetate, and the monomers of these resins are dispersed in a solution state. It may also disperse in the phosphorus alcohol and polymerize. In other words, when an acrylamide monomer which is soluble in water and insoluble in alcohol is added as an aqueous solution, a surfactant and a polymerization initiator are added and stirred in alcohol, a polymer having a polyacrylamide diameter of 0.05 to 0.3 μm is used in the alcohol. And disperse into particles swollen by water. In addition, the solvent of the polymer resin is different depending on the type of resin, it is selected from the table 1 below, it is used by mixing with alcohol in the ratio of 5 to 30% by weight relative to the total alkoxide.

Type of organic polymer resin Type of solvent Polyacrylamide water Polycyclopentylethylene Toluene, chloroform, diethyl ether Polybutoxyethylene Cyclonucleic Acid, Diethyl Ether Polybenzyloxyethylene Benzene, toluene, acetone Polychloromethylbutadiene Toluene, dichloromethane Polyvinylacetylacetate Acetone, Chloroform

The inorganic protective film is used by appropriately diluting the composition with alcohol and adjusting the viscosity according to the coating application method. The coating method may be applied to all of the immersion method, spray method, flow method, etc. that are generally used to apply a liquid composition to the substrate, it is preferable to use ethanol as the alcohol. However, in actual coating applications, when the volatilization rate of the alcohol is too high, a difference in the reaction rate of each component constituting the composition may occur, and accordingly local defects may occur in the coating film. If you make a composition solution or mix an appropriate amount using isopropyl alcohol, butyl alcohol or higher boiling point, you can control the reaction rate of each component in the SiO ₂ -MO complex system and react simultaneously. Homogeneous yet stable membranes can be produced.

As a method of applying the immersion method to the composition for water repellent coating, the glass substrate is lowered at a constant speed while being maintained in the vertical direction with respect to the liquid level of the diluted solution, immersed in the coating solution, and then after 1 to 10 lapses. Apply water repellent solution by pulling up at a rate of cm / min. In order to apply the flow method, the glass substrate is placed vertically, and the diluent of the composition is applied while flowing from the upper portion of the substrate glass to the lower portion at a flow rate of about 200 to 600 cc / min.

When the coated glass substrate is dried at room temperature, a gel film of SiO ₂ -MO composite system in which inorganic particles and polymer resin particles are dispersed is formed, and when heat-treated at a temperature of 600 ° C. or below, the surface is uneven by the inorganic particles, As a result, an inorganic protective film having pores distributed therein can be obtained.

The pretreatment agent used to improve the binding force to the water repellent membrane, characterized in that at least one alcohol solution of silane coupling agents, such as propyltrimethoxysilane, ethyltrimethoxysilane, tetramethyl orthosilicate, The silane coupling agent is preferably diluted to about 1-30% by weight based on the alcohol solvent. If it is less than 1% by weight, the effect of the bonding accelerator is less. If it is more than 30% by weight, defects such as stains on the surface are likely to occur.

As a method of coating the pretreatment agent on the inorganic protective film, a tool such as a brush or a roller can be used in addition to the spray method, the flow method, and the deposition method. Moreover, after coating, it dries at the temperature of normal temperature or 200 degrees C or less.

As the FAS-based water repellent material for forming the water repellent film on the inorganic protective film coated with the pretreatment agent, at least one selected from fluoroalkylalkoxysilane, fluoroalkyl chloride silane, and fluoroalkyl isocyanate silane is selected. The solution for preparing the water repellent membrane can be prepared by diluting the FAS-based water repellent material to about 3-10% by weight with respect to an alcoholic solvent such as ethanol, and the spray method, the flow method, and the deposition method are used as a method of coating the solution. After the coating and drying process, heat treatment at 250 ℃ for 1 hour to complete the water-repellent glass.

The following examples are provided to illustrate the present invention and are not intended to limit the scope of the present invention. Those skilled in the art can modify and change the following examples without departing from the scope and spirit of the present invention.

Example

Example 1

An inorganic protective film and a water repellent film of the present invention were prepared by the following method, and a water-repellent coating glass was produced through an application process and a baking process.

(Manufacturing process of coating solution for inorganic protective film)

The following (a)-(b) was stirred for 20 minutes.

(a) TEOS 5.7 mg

(b) 34 g of ethanol

(c) 11 g of 1 wt% hydrochloric acid aqueous solution

To this, (c) was added and mixed for about 30 minutes to proceed with the hydrolysis reaction.

Separately prepared by mixing (d). (E) and stirred for 30 minutes.

(d) TBOT 12g

(e) 34 g of ethanol

Subsequently, the solutions (d) and (e) were mixed with the solutions (a), (b) and (c) described above. The resulting mixture was mixed and stirred for 1 hour in a 25 DEG C sealed container to proceed with hydrolysis and polycondensation reactions. A composition A was prepared by adding 35 g of a solution (OSCAL 1224; dispersed in ethanol) and 200 g of ethanol in which SiO ₂ fine particles having an average particle diameter of 25 nm were dispersed in ethanol at a solid content of 20 wt%.

(Application process of composition for inorganic protective film)

The composition for protective film coating obtained above was apply | coated to the surface of a glass plate by the flow method.

The coating composition was diluted with 1,500 g of alcohol in a ethanol: butanol ratio of 9: 1 and stirred for at least 20 minutes to prepare a solution suitable for flow coating. The clear glass substrate 300mm × 300mm in size and 3mm thick is placed vertically, and the solution is applied while flowing from the top of the substrate glass to the bottom at a flow rate of about 400cc / min using a pump. It was then dried in the air to form a gel film on the glass surface.

(Primary firing process)

After the glass plate on which the film was formed was left in the air for 2 hours or more to proceed with a sufficient gelling reaction, the glass plate was maintained for 1 hour in a 400 ° C electric furnace and then heat-treated again at 540 ° C for 20 minutes.

(Application of pretreatment and water repellent solution and secondary firing process)

Dipropyl trimethoxysilane is diluted to 1 to 10 wt% with methanol, coated on the inorganic protective film by roving method and dried at room temperature. After dissolving 3 g of FAS (fluoro alkyl silane compounds) in 97 g of isopropyl alcohol, adding 0.3 g of 1 wt% aqueous hydrochloric acid solution, stirring for 30 minutes, a solution was applied on the substrate prepared by the above process by roving. It was then dried in air and fired in an oven at 150 ° C. for 30 minutes.

The refractive index value of the formed water repellent coating was 1.51. The water repellency, surface roughness, appearance and durability were compared according to the dosage of SiO ₂ fine particle dispersion contained in the solution. The water repellency was compared by measuring the contact angle with water, and the surface roughness measured the centerline average roughness Ra value and the maximum floor height Rtm. Appearance was determined by measuring the homogeneity and milkiness of the coating film by visual and cloudy values, and the durability was made in the same way as the wiper blade of the car.The durability is 60,000 round trips at a round trip speed of 1 round trip / second while spraying water with 105g load. The subsequent contact angle change was observed. In addition, CASS (saline spray) was tested for 240 hours in a saline spray system, and the weather resistance (WOM) test was conducted under the SAE J1960 condition by irradiating 0.55 W / m ² light at 340 nm using a weather meter meter of Atlas, USA. The contact angle changes were compared after a 2000 hour test.

Composition m + n (g) Water repellency Surface roughness Appearance Contact angle after durability test (°) m n Contact angle Ra (nm) Rtm (nm) Coating homogeneity Blur Wear CASS Weather Example 1 5.7 35 119 4 20 ○ ○ 100 < 100 < 100 < Comparative Example 1 2.3 40 122 5 30 △ △ 100 < 100 < 100 < Comparative Example 2 12.7 25 117 3 19 ○ ○ 100 < 100 < 100 < Comparative Example 3 16.1 15 115 2 13 ○ ○ 95-100 95-100 95-100 Comparative Example 4 23.1 10 112 One 11 ○ ○ 95-100 95-100 90-95 Comparative Example 5 30 0 110 One 10 ○ ○ 90> 90> 90> Comparative Example 6 0 0 108 One 9 ○ ○ 90> 90> 90>

In the appearance of the above table,?: Very good,?: Excellent,?: Normal, x: poor.

The prepared water-repellent membrane was transparent without any milky parts, and the homogeneity of the membrane was good. The initial contact angle was 119 °. The contact angle characteristic after the durability test was also good at 100 degrees or more.

Comparative Examples 1 to 6

In Comparative Examples 1 to 4, the other conditions were carried out in the same manner as in Example 1 except that the mixing amount of the starting solution TEOS and the SiO ₂ fine particle dispersion was changed in the composition of the inorganic protective film coating solution.

In the case of Comparative Example 1, the amount of TEOS was small and the amount of SiO ₂ fine particle dispersion added was large. In this case, the contact angle was excellent at 122 ° at the initial stage and 100 ° or more even after the durability test, but the transparency of the coating film was poor.

In Comparative Example 2, the contact angle was good at 117 °, the appearance (homogeneity and transparency) of the remaining films was good, and the durability characteristics were also excellent.

In the case of Comparative Examples 3 and 4, the amount of TEOS added is large and the amount of SiO ₂ fine particles added is small. Until this case, the effect of adding SiO ₂ fine particles was small, the contact angle was small, and the contact angle after the durability test was 100 ° or less.

In Comparative Example 5, the characteristics of the water-repellent glass specimen having a flat inorganic protective film without separately adding SiO ₂ fine particle dispersion is shown as a comparative example. In addition, Comparative Example 6 will be shown as a comparative example in which the water-repellent material was directly applied to the surface of the substrate glass without forming an inorganic protective film.

As a result of the experiment, the contact angle characteristics were also worse than those in which the SiO ₂ fine particle dispersion was added, and the contact angles after the durability test were also lower than 90 °.

Example 2

The preparation process of the coating solution for inorganic protective films was carried out as in Example 1, except that the content of TEOS was 5.7 g, and SiO ₂ fine particles having a particle size of 100 nm were dispersed in ethanol at 20 wt% of solids (OSCAL: 日本 觸) Composition A was prepared by adding 35 g of ethanol and 200 g of ethanol.

The prepared coating solution was applied and calcined in the same manner as in Example 1 to form a water repellent coating by applying a pretreatment agent and a water repellent material. The refractive index of the formed water repellent film was 1.51. The water repellency, surface roughness, appearance and durability of the water repellent membrane were compared according to the diameter size of the fine particles of the SiO ₂ fine particle dispersion contained in the solution.

Diameter of SiO ₂ Particles (nm) Water repellency Surface roughness Appearance Contact angle after durability test (°) Contact angle Ra (nm) Rtm (nm) Coating homogeneity Blur Wear CASS Weather Example 2 100 119 4 20 ○ ○ 100 < 100 < 100 < Comparative Example 7 5 108 One 9 ○ ○ 90> 90-95 90> Comparative Example 8 8 115 2 13 ○ ○ 90-95 90-95 90-95 Comparative Example 9 15 117 3 19 ○ ○ 100 < 100 < 100 < Comparative Example 10 150 122 5 30 △ △ 100 < 100 < 100 <

In appearance of the above table,?: Very good,?: Excellent,?: Normal, x: poor.

The prepared water-repellent membrane was transparent without any milky parts, and the homogeneity of the membrane was good. The initial contact angle was 119 °. The contact angle characteristic after the durability test was also good at 100 degrees or more.

Comparative Examples 7 to 10

In Comparative Examples 7 to 10, the other conditions were carried out in the same manner as in Example 2, except that the size of the particle diameter of the SiO ₂ fine particle dispersion, which was the starting additive of the coating solution for the inorganic protective film, was changed.

In the case of Comparative Examples 7, 8 and 9, the size of SiO ₂ fine particles was smaller than 100 nm of Example 2, and when the particle diameter of Comparative Example 7, 8 was 10 nm or less, the effect of the added fine particles was small and the initial contact angles were 108. And 115 ° and no more than 95 ° for the contact angle after the endurance test. On the other hand, in Comparative Example 9, when the size of the SiO ₂ fine particles was 15 nm, the initial contact angle was 117 ° and the contact angle after durability exceeded 100 °. The state of the film was also good without surface whiteness or the like.

In the case of Comparative Example 10, the contact angle of the water repellent film prepared when the diameter of the SiO ₂ fine particles was 150 nm was initially excellent at 122 ° and at least 100 ° after the durability test, but the transparency of the coating film was poor.

Example 3

The preparation process of the inorganic protective film coating solution was carried out as in Example 1, but the mixing amount with each component as follows, a solution in which SiO ₂ fine particles having an average particle diameter of 25nm dispersed in ethanol at 20% by weight of solid content (OSCAL 1224; 日本) Composition A was prepared by adding 25 g and 200 g of ethanol.

(a) 12.7 g of TEOS

(b) 34 g of ethanol

(c) 11 g of 1 wt% hydrochloric acid aqueous solution

(d) 14 g TPOZ (zirconium propoxide)

(e) 34 g of ethanol

After the composition A was mixed for 1 hour or more, a composition for coating an inorganic protective film was prepared.

The prepared coating solution was applied and calcined in the same manner as in Example 1, the pretreatment agent and the water repellent material were applied, the refractive index was 1.515, the initial contact angle was 117 °, the centerline average roughness Ra was 3 nm, and the contact angle after the durability test was the lowest. A water repellent coating of 100 ° or more was formed.

Example 4

The manufacturing process of the coating solution for inorganic protective films is the same as in Example 1, but the amount of mixing with each component as follows, a solution in which TiO ₂ fine particles having a particle size of 1Onm dispersed in a solid content of 30% by weight (SUNVEIL; 日本 化成) 6 g and 300 g of ethanol were mixed and stirred for 20 minutes to prepare composition A.

(a) TEOS 15g

(b) 34 g of ethanol

(c) 11 g of 1 wt% hydrochloric acid aqueous solution

(d) 8 g of TBOZ (zirconium butoxide)

(e) 34 g of ethanol

After the composition A was mixed for 1 hour or more, a composition for coating an inorganic protective film was prepared.

The prepared coating solution was applied and calcined in the same manner as in Example 1, the pretreatment agent and the water repellent material were applied, the refractive index was 1.515, the initial contact angle was 117 °, the centerline average roughness Ra was 3 nm, and the contact angle after the durability test was the lowest. A water repellent coating of 100 ° or more was formed.

Example 5

The following (a) ~ (b) was stirred for 20 minutes and (c) was mixed to proceed with the hydrolysis reaction for 30 minutes. Then, a composition A was prepared by mixing 15 g of solution NZS-30A (300 g of ethanol) and 300 g of ethanol, in which ZrO ₂ particles having a particle diameter of 30 nm or less were dispersed in a solid content of 30 wt%, and stirred for 20 minutes.

(a) TEOS 15g

(b) 33 g of ethanol

(c) 10 g of 3 wt% hydrochloric acid aqueous solution

The prepared coating solution was applied and calcined in the same manner as in Example 1, the pretreatment agent and the water repellent material were applied, the refractive index was 1.52, the initial contact angle was 118 °, the centerline average roughness Ra was 3 nm, and the contact angle after the durability test was the lowest. A water repellent coating of more than 95 ° was formed.

Example 6

An inorganic protective film and a water repellent film of the present invention were prepared by the following method, and a water-repellent coating glass was produced through an application process and a baking process.

(Manufacturing process of coating solution for inorganic protective film)

The following (a)-(b) are stirred for 20 minutes.

(a) 5.7 g of TEOS

(b) 34 g of ethanol

(c) 11 g of 1 wt% hydrochloric acid aqueous solution

(C) was added thereto and mixed for about 30 minutes to proceed with the hydrolysis reaction.

Separately prepared by mixing (d), (e) and stirred for 30 minutes.

(d) TBOT 12g

(e) 34 g of ethanol

The solutions (d) and (e) were then mixed with the solutions (a), (b) and (c) described above. The resulting mixture was mixed and stirred for 1 hour in a 25 DEG C sealed container to proceed with hydrolysis and polycondensation reactions. A composition A was prepared by adding 35 g of a solution [OSCAL 1223; dispersed in ethanol] and 200 g of ethanol, in which SiO ₂ fine particles having an average particle diameter of 25 nm were dispersed in ethanol at a solid content of 20% by weight.

Separately, a solution obtained by dissolving 5 g of polyvinyl acetyl acetate in 10 g of acetone was prepared, and then mixed with 100 g of alcohol, which was then strongly stirred to mix the emulsified composition B with the composition A and stirred for at least 1 hour to prepare a composition for coating an inorganic protective film. Prepared.

(Application process of composition for inorganic protective film)

The composition for protective film coating obtained above was apply | coated to the surface of a glass plate by the flow method.

The coating composition was diluted with 1,500 g of alcohol in a ethanol: butanol ratio of 9: 1 and stirred for at least 20 minutes to prepare a solution suitable for flow coating. The clear glass substrate 300mm × 300mm in size and 3mm thick is placed vertically, and the solution is applied while flowing from the top of the substrate glass to the bottom at a flow rate of about 400cc / min using a pump. It was then dried in the air to form a gel film on the glass surface.

(Primary firing process)

After the glass plate on which the film was formed was left in the air for 2 hours or more to proceed with a sufficient gelling reaction, the glass plate was maintained for 1 hour in a 400 ° C electric furnace and then heat-treated again at 540 ° C for 20 minutes.

(Application of pretreatment and water repellent solution and secondary firing process)

Dipropyl trimethoxysilane is diluted to 1 to 10 wt% with methanol, coated on the inorganic protective film by roving method and dried at room temperature. 3 g of FAS was dissolved in 97 g of isopropyl alcohol, 0.3 g of 1 wt% aqueous hydrochloric acid solution was added thereto, stirred for 30 minutes, and then a solution was applied on the substrate prepared by the above process by a roving method. It was then dried in air and fired in an oven at 150 ° C. for 30 minutes.

The refractive index of the formed water repellent film was 1.51. The water repellency, surface roughness, appearance and durability of the water repellent membrane were compared according to the dosage of the SiO ₂ fine particle dispersion contained in the solution, and the results are shown in Table 3.

The water repellency was compared by measuring the contact angle with water, and the surface roughness measured the centerline average roughness Ra value and the maximum floor height Rtm. Appearance was determined by measuring the homogeneity and milkiness of the coating film by visual and cloudy values, and the durability was made in the same way as the wiper blade of the car.The durability is 60,000 round trips at a round trip speed of 1 round trip / second while spraying water with 105g load. The subsequent contact angle change was observed. In addition, CASS (saline spray) was tested for 240 hours in a saline spray system, and the weather resistance (WOM) test was conducted under the SAE J1960 condition by irradiating 0.55 W / m ² light at 340 nm using a weather meter meter of Atlas, USA. The contact angle changes were compared after a 2000 hour test.

Composition m + n (g) Polymer resin addition amount (g) Water repellency Surface roughness Appearance Contact angle after durability test (°) Contact angle Ra (nm) Rtm (nm) Coating homogeneity Blur Wear CASS Weather m n Example 6 5.7 35 5 120 5 23 ○ ○ 100 < 100 < 100 < Comparative Example 11 2.3 40 5 124 6 32 △ △ 100 < 100 < 100 < Comparative Example 12 12.7 25 5 119 4 22 ○ ○ 100 < 100 < 100 < Comparative Example 13 16.1 15 5 117 3 15 ○ ○ 100 < 100 < 100 < Comparative Example 14 23.1 10 5 114 2 12 ○ ○ 95-100 95-100 90-95 Comparative Example 15 16.1 15 0 115 2 13 ○ ○ 95-100 95-100 95-100 Comparative Example 16 30 0 0 110 One 10 ○ ○ 90> 90> 90> Comparative Example 17 30 0 0 108 One 9 ○ ○ 90> 90> 90>

In the appearance of the above table,?: Very good,?: Excellent,?: Normal, x: poor.

The prepared water-repellent membrane was transparent without any white areas, and the homogeneity of the membrane was good. The initial contact angle was 120 °. The contact angle characteristic after the durability test was also good at 100 degrees or more.

Comparative Examples 11 to 17

In Comparative Examples 11 to 14, the other conditions were carried out in the same manner as in Example 6, except that the mixing amount of the starting solution TEOS and the SiO ₂ fine particle dispersion was changed in the composition of the inorganic protective film coating solution.

In Comparative Example 11, the amount of TEOS was small and the amount of SiO ₂ fine particle dispersion added was large. In this case, the contact angle was initially excellent at 124 ° and more than 100 ° even after the durability test, but the coating film had good transparency.

In Comparative Examples 12 and 13, the contact angles were good at 119 ° and 117 °, and the remaining films had good appearance (homogeneity and transparency) and excellent durability properties.

In the case of Comparative Example 14, the amount of TEOS added is large, and the amount of SiO ₂ fine particles added is small. Until this time, the addition effect of the SiO ₂ fine particles and the addition of the polymer resin were small, and the initial contact angle was as small as 114 ° and the contact angle after the durability test was 100 ° or less.

In Comparative Example 15, only the SiO ₂ fine particle dispersion was added without adding the polymer resin emulsion. In Comparative Example 16, the water-repellent glass specimen having the flat inorganic protective film without separately adding the SiO ₂ fine particle dispersion and the polymer resin emulsion was added. Will be shown as a comparative example. In addition, Comparative Example 17 will be shown as a comparative example in which the water-repellent material was directly applied to the surface of the substrate glass without forming an inorganic protective film. As a result of the experiment, the initial contact angle was smaller than 115 ° and the contact angle characteristic after the durability test was also less than 95 °.

Example 7

The preparation process of the inorganic protective film coating solution was carried out in the same manner as in Example 6, except that the SiO ₂ fine particles having a particle size of 5.7 g and a particle size of 100 nm were dispersed in ethanol at 20% by weight of solids (OSCAL: 日本 觸) Composition A was prepared by adding 35 g of ethanol and 200 g of ethanol.

The prepared coating solution was applied and fired in the same manner as in Example 6, and a pretreatment agent and a water repellent material were applied to form a water repellent coating having a refractive index of 1.51. The water repellency, surface roughness, appearance and durability of the water repellent membrane were compared according to the dosage of the SiO ₂ fine particle dispersion contained in the solution.

Size of SiO ₂ Particles (nm) Polymer resin addition amount (g) Water repellency Surface roughness Appearance Contact angle after durability test (°) Contact angle Ra (nm) Rtm (nm) Coating homogeneity Blur Wear CASS Weather Example 7 100 5 120 4 20 ○ ○ 100 < 100 < 100 < Comparative Example 18 5 5 109 One 9 ○ ○ 90> 90-95 90> Comparative Example 19 8 5 117 2 13 ○ ○ 95-100 95-100 95-100 Comparative Example 20 15 5 119 3 19 ○ ○ 100 < 100 < 100 < Comparative Example 21 150 5 122 5 30 △ △ 100 < 100 < 100 < Comparative Example 22 8 0 115 2 13 ○ ○ 90-95 90-95 90-95 Comparative Example 23 8 10 119 2 13 ○ ○ 100 < 100 < 100 <

In the appearance of the above table,?: Very good,?: Excellent,?: Normal, x: poor.

The prepared water-repellent membrane was transparent without any white areas, and the homogeneity of the membrane was good. The initial contact angle was 120 °. The contact angle characteristic after the durability test was also good at 100 degrees or more.

Comparative Examples 18 to 23

In Comparative Examples 18 to 21, the other conditions were carried out in the same manner as in Example 7, except that the size of the fine particles in the SiO ₂ fine particle dispersion, which was the starting additive of the coating solution for the inorganic protective film, was changed.

In the case of Comparative Examples 18, 19, and 20, the size of SiO ₂ fine particles was smaller than 100 nm of Example 7, and when the particle diameters of Comparative Examples 18 and 19 were 10 nm or less, the effect of the added fine particles was small and the initial contact angle was 109 °, 117 ° and less than 100 ° for the contact angle after durability test. On the other hand, in the case of Comparative Example 20, when the size of the SiO 2 fine particles was 15 nm, the initial contact angle was 119 ° and the contact angle after durability exceeded 100 °. The state of the film was also good without surface whiteness or the like.

In the case of Comparative Example 21, the contact angle of the water repellent film prepared when the diameter of the SiO2 fine particles was 150 nm was initially excellent at 122 ° and at least 100 ° after the durability test, but the transparency of the coating film was poor.

In the case of Comparative Example 22, only the SiO ₂ fine particle dispersion was added without adding the polymer resin emulsion, and in the case of Comparative Example 23, 10 g of the polymer resin emulsion was added as a comparative example. In Comparative Example 22, the initial contact angle of the prepared water repellent membrane was 115 ° and the contact angle after the durability test was 95 ° or less. On the other hand, in Comparative Example 23, even though the initial contact angle was 119 ° and the contact angle after the durability test exceeded 100 °, and the SiO2 fine particle size was small (8 nm), the initial contact angle and durability characteristics of the final water repellent membrane improved with addition of the polymer resin.

Example 8

The manufacturing process of the coating solution for inorganic protective film was carried out as in Example 6, but the mixing amount with each component as follows, a solution in which SiO ₂ fine particles having an average particle diameter of 25 nm dispersed in ethanol with a solid content of 20% by weight (OSCAL 1224; 日本 觸) Composition A was prepared by adding 25 g and 200 g of ethanol.

(a) 12.7 g of TEOS

(b) 34 g of ethanol

(c) 11 g of 1 wt% hydrochloric acid aqueous solution

(d) 14 g TPOZ (zirconium propoxide)

(e) 34 g of ethanol

A solution obtained by dissolving 5 g of polyacrylamide in 10 g of water was prepared, and this was mixed with 100 g of alcohol and strongly stirred to emulsify the composition B, which was mixed with the composition A, and stirred for at least 1 hour to prepare a composition for coating an inorganic protective film.

The prepared coating solution was applied and calcined in the same manner as in Example 6, the pretreatment agent and the water repellent material were applied, the refractive index was 1.515, the initial contact angle was 119 °, the centerline average roughness Ra was 4 nm, and the contact angle after the durability test was the lowest. A water repellent coating of 105 ° or more was formed.

Example 9

The preparation process of the inorganic protective film coating solution was carried out as in Example 6, but the mixing amount with each component as follows, a solution in which TiO ₂ fine particles having a particle size of 1Onm dispersed in a solid content of 30% by weight (SUNNEIL; 曰 本 觸媒 化成) 6 g and 300 g of ethanol were mixed and stirred for 20 minutes to prepare composition A.

(a) TEOS 15g

(b) 34 g of ethanol

(c) 10 g of 3 wt% hydrochloric acid aqueous solution

(d) 8 g of TBOZ (zirconium butoxide)

(e) 34 g of ethanol

A solution obtained by dissolving 5 g of polyacrylamide in 10 g of water was prepared, and this was mixed with 100 g of alcohol and vigorously stirred to emulsify the composition B, which was mixed with the composition A, and stirred for at least 1 hour to prepare a composition for coating an inorganic protective film.

The prepared coating solution was applied and calcined in the same manner as in Example 6, the pretreatment agent and the water repellent material were applied, the refractive index was 1.515, the initial contact angle was 118 °, the centerline average roughness Ra was 4 nm, and the contact angle after the durability test was the lowest. A water repellent coating of 105 ° or more was formed.

Example 10

The following (a)-(b) was stirred for 20 minutes, (c) was mixed, and the hydrolysis reaction was advanced for 30 minutes. Then, a composition A was prepared by mixing 15 g of a solution NZS-30A (30 g of NZS-30A) and 30Og of ethanol in which ZrO ₂ particles having a particle diameter of 30 nm or less were dispersed in a solid content of 30 wt%, and stirred for 20 minutes.

(a) TEOS 15g

(b) 33 g of ethanol

(c) 10 g of 3 wt% hydrochloric acid aqueous solution

A solution obtained by dissolving 5 g of polyacrylamide in 10 g of water was prepared, and this was mixed with 100 g of alcohol and vigorously stirred to emulsify the composition B, which was mixed with the composition A, and stirred for at least 1 hour to prepare a composition for coating an inorganic protective film.

The prepared coating solution was applied and calcined in the same manner as in Example 6, and then coated with a pretreatment agent and a water-repellent material. The refractive index was 1.52, the initial contact angle was 119 °, the centerline average roughness Ra was 4 nm, and the contact angle after the durability test was A water repellent coating of at least 95 ° was formed.

According to the present invention, by adjusting the refractive index value of the inorganic protective film having a fine concavo-convex shape on the surface to 1.50 to 1.52, not only is it applicable to a large substrate, but also enhances the binding force with the water-repellent material, and the water-repellent material is evenly dispersed in the coating film. A water repellent glass is provided which is excellent in water repellency, durability and wear resistance.

Claims (12)

To 1 part by weight of TEOS, 1.7 to 17 parts by weight of alcohol, 0.6% to 6 parts by weight of a 1% HCl aqueous solution to prepare a first solution; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; Preparing a solution 3 by adding the solution 2 to the solution 1 and adding an alcohol having fine particles of the colloidal metal oxide dispersed therein; Applying the solution 3 to the substrate glass and baking at a temperature of 600 ° C. or lower to form an inorganic protective film on the surface of which fine irregularities are properly distributed by metal oxide fine particles; Coating a pretreatment agent on the inorganic protective film in order to improve bonding to the water repellent film, and applying an alcohol solution of a fluorosilane-based water repellent material, followed by secondary firing to form a water repellent film. A method for producing a water repellent glass having a structure in which phases are appropriately dispersed. To 1 part by weight of TEOS, 1.7 to 17 parts by weight of alcohol, 1% HCl aqueous solution was mixed to 0.6 to 6 parts by weight to prepare a first solution; Preparing a second solution by mixing 2 to 5 parts by weight of alcohol with respect to 1 part by weight of at least one metal alkoxide of Ti, Al, and Zr; Adding solution 2 to solution 1, to which solution 3 is prepared by adding an alcohol emulsion of colloidal metal oxide fine particles and an alcohol emulsion of an organic polymer resin insoluble in alcohol; Applying the solution 3 to the substrate glass and baking at a temperature of 600 ° C. or lower to form an inorganic protective film on the surface of which the fine irregularities and fine pores generated by thermal decomposition of the organic polymer resin are properly distributed by the metal oxide fine particles; Coating a pretreatment agent on the inorganic protective film in order to improve bonding to the water repellent film, and applying an alcohol solution of a fluorosilane-based water repellent material, followed by secondary firing to form a water repellent film. A method for producing a water repellent glass having a structure in which phases are appropriately dispersed. The method according to claim 1 or 2, The weight ratio of SiO ₂ of the inorganic solids in the prepared solution 3 to solids ZrO ₃ , TiO ₂ , Al ₂ O _3, etc., of the other inorganic components is 2.5 / 7.5 to 3.5 / 6.5, and the refractive index of the prepared inorganic protective film is 1.50 to 1.52 method for producing a water-repellent glass, characterized in that. The method according to claim 1 or 2, The colloidal metal oxide fine particles have a particle diameter of 10 nm to 100 nm, and are mixed at a ratio of 0.4 to 4.5 moles with respect to 1 mole of the TEOS. The method according to claim 1 or 2, The colloidal metal oxide fine particles are SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , CeO, SnO _{2 A} method for producing a water-repellent glass, characterized in that at least one selected from the group. The method according to claim 1 or 2, The alcohol is methanol. A method for producing a water-repellent glass, characterized in that at least one of ethanol, isopropanol and butanol. The method according to claim 1 or 2, The pretreatment agent used to improve the binding force to the water repellent membrane is a water-repellent glass, characterized in that at least one alcohol solution of the silane coupling agent of propyltrimethoxysilane, ethyltrimethoxysilane, tetramethyl orthosilicate Manufacturing method. The method of claim 7, wherein The silane coupling agent is a method for producing a water-repellent glass, characterized in that diluted to about 1-10% by weight with respect to the alcohol solvent. The method according to claim 1 or 2, The method for producing a water-repellent glass, characterized in that at least one of a fluoroalkylalkoxy silane, a fluoroalkyl chloride silane, and a fluoroalkyl isocyanate silane as the fluorosilane-based water repellent material for forming the water repellent film. The method of claim 2, The organic polymer resin insoluble in the alcohol is polyacrylamide, polycyclopentylethylene, polybutoxyethylene, polybenzyloxyethylene, polychloromethylbutadiene and polyvinylacetylacetate. The method of claim 2, A method for producing a water-repellent glass, characterized in that the average molecular weight of the organic polymer resin insoluble in the alcohol is several hundred to several thousand. The method of claim 2, The particle size of the particles of the alcohol insoluble in the alcohol of the organic polymer resin insoluble in the alcohol is characterized in that the particle size of 100nm to 100nm.