JP2008156157A - Water repellent oil repellent antifouling glass plate, method of manufacturing the same and vehicle and building using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water repellent oil repellent antifouling glass plate having improved durability such as wear resistance and weather resistance, improved water sliding property and antifouling property, a method of manufacturing the same and vehicles and buildings using the same. <P>SOLUTION: The water repellent oil repellent antifouling glass plate 10 is manufactured by forming a water repellent oil repellent antifouling coating film 8 on the surface of a fine particle fused glass base material 7 obtained by applying a fine particle dispersed solution in which transparent fine particles 4 are dispersed on the surface of the glass base material 5, drying and heat-treating in an oxygen-containing atmosphere. The vehicles and buildings use the same. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a glass plate having a highly durable, water-repellent, oil-repellent and antifouling coating formed on the surface thereof, a method for producing the same, and vehicles and buildings using the same.

In general, a chemical adsorption solution consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular film-like water / oil repellent / antifouling chemical adsorption film. Is already well known (see, for example, Patent Document 1).

The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of chlorosilane-based adsorbents. It is in.

JP-A-4-132737

However, since the conventional chemical adsorption film uses only the chemical bond between the adsorbent and the flat substrate surface, the contact angle of the water droplet is only about 120 degrees, and the water droplets and dirt are naturally removed. Has the problem of poor water and oil repellency and antifouling properties and water separation. Moreover, the subject that durability, such as abrasion resistance and a weather resistance, was also scarce occurred.

The present invention relates to a glass plate for a window of a vehicle such as an automobile or a building that requires a water / oil repellent / antifouling function and a glass plate for an optical device filter. The purpose is to improve durability such as water resistance (also referred to as water slidability) and abrasion resistance and weather resistance.

A water and oil repellent and antifouling glass plate according to a first invention provided as means for solving the above problems is a plate-like glass substrate and a water and water repellent material fused to the surface of the glass substrate. It has oil-repellent transparent fine particles and a water- and oil-repellent and antifouling coating covering a portion of the surface of the glass substrate where the transparent fine particles are not fused.

In the water- and oil-repellent and antifouling glass plate according to the first invention, a part of the surface of the transparent fine particles is fused to the surface of the glass substrate, and the other exposed part is the water-repellent part. It is preferably covered with an oil repellent antifouling film.

In the water / oil repellent / antifouling glass plate according to the first invention, the water / oil repellent / antifouling coating is preferably covalently bonded to the surface of the transparent fine particles and the glass substrate.

In the water / oil repellent / antifouling glass plate according to the first invention, the transparent fine particles having different particle diameters may be mixed and used.

In the water / oil repellent / antifouling glass plate according to the first aspect of the present invention, the water / oil repellent / antifouling coating preferably contains a —CF ₃ group.

In the water- and oil-repellent and antifouling glass plate according to the first invention, the transparent fine particles are translucent, and the softening temperature thereof is higher than the softening temperature of the glass substrate surface. Preferably it is either.

In the water / oil repellent / antifouling glass plate according to the first aspect of the invention, it is preferable that the transparent fine particles have a particle size of less than 400 nm.

In the water- and oil-repellent and antifouling glass plate according to the first invention, the contact angle with water is preferably 140 degrees or more.

In the water- and oil-repellent and antifouling glass plate according to the first aspect of the present invention, the transparent fine particles are formed on the glass substrate via a metal oxide transparent film that is fused to the transparent fine particles at a temperature lower than that of the glass substrate. Preferably, the water- and oil-repellent and antifouling coating covers the portion where the transparent fine particles are not fused via the transparent coating.

The vehicle according to the second invention is equipped with the water / oil repellent / antifouling glass plate according to the first invention.

The building according to the third invention is equipped with the water / oil repellent antifouling glass plate according to the first invention.

The method for producing a water / oil / oil repellent antifouling glass plate according to the fourth invention comprises a step C of preparing a fine particle dispersion in which transparent fine particles are dispersed, and the fine particle dispersion is applied to the surface of the glass substrate and dried. The process D for attaching the transparent fine particles to the surface of the glass substrate, and the glass substrate with the transparent fine particles attached to the surface are heat-treated at a temperature lower than the softening temperature of the transparent fine particles, A step E of fusing the transparent fine particles to the surface of the glass substrate, a step F of washing and removing the transparent fine particles not fused to the surface of the glass substrate, and a fine particle fusion in which the transparent fine particles are fused. And a step G of forming a water / oil repellent / antifouling coating on the surface of the glass substrate.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, before the step D, the surface of the glass base material is not dissolved in the fine particle dispersion and is more than the glass base material. You may further have the process B which forms the transparent film of the metal oxide fuse | melted with the said transparent fine particle at low temperature.
In the present invention, “metal” includes a so-called metalloid element such as boron (B) or silicon (Si).

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, a sol-gel method may be used for forming the transparent film.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the metal alkoxide solution used for forming the transparent film by the sol-gel method contains either one or both of phosphoric acid and boric acid. May be.

In the method for producing a water / oil repellent / antifouling glass plate according to the fourth invention, the heat treatment temperature in the step E is 250 ° C. or higher and lower than the softening temperature of the glass substrate and the transparent fine particles. preferable.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the first silane compound containing a linear group and a non-aqueous organic solvent are included before Step C. The first silane compound is obtained by dispersing transparent fine particles a (original transparent fine particles) in the chemical adsorption liquid and reacting the silyl group of the first silane compound with the reactive group on the surface of the transparent fine particles a. It is preferable that the step A for producing the transparent fine particles whose surface is covered with the monomolecular film of Step A and the heat treatment in the step E are performed in an atmosphere containing oxygen.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, an organic solvent is used for the fine particle dispersion, and the linear group may be a fluorocarbon group.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the fine particle dispersion is one of water and alcohol or a mixture of both, and the linear group is carbonized. It may be a hydrogen group.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the formation of the water- and oil-repellent and antifouling coating film in the step G is performed with a second silane compound containing a fluorocarbon group and non- A second chemical adsorption liquid containing an aqueous organic solvent is brought into contact with the fine particle fused glass substrate, and a silyl group of the second silane compound and a reactive group on the surface of the fine particle fused glass substrate are obtained. It is preferable to carry out by this reaction.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, after the reaction between the silyl group and the reactive group in the step G, the unreacted second silane compound is washed away. May be.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively, An alkoxysilane compound may be used.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively, It may be a halosilane compound.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively, It may be an isocyanate silane compound.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the first and second chemical adsorption liquids containing the alkoxysilane compound further include a metal carboxylate as a condensation catalyst. 1 or 2 or more compounds selected from the group consisting of a carboxylate metal salt, a carboxylate metal salt polymer, a carboxylate metal salt chelate, a titanate ester, and a titanate ester chelate may be included.
Further, the promoter may contain one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds.

In the method for producing a water- and oil-repellent and antifouling glass plate according to the fourth invention, the first and second chemical adsorption liquids containing the alkoxysilane compound include a ketimine compound and an organic acid as a condensation catalyst. , An aldimine compound, an enamine compound, an oxazolidine compound, and one or more compounds selected from the group consisting of aminoalkylalkoxysilane compounds may be further included.

The water / oil repellent / antifouling glass plate according to claims 1 to 9 and the water / oil repellent / antifouling glass plate according to claims 12 to 27 are required to have a water / oil repellent / antifouling function. It is possible to provide a water / oil-repellent and antifouling glass plate excellent in durability such as water-drop separation (also referred to as water slidability), antifouling properties, abrasion resistance, and weather resistance in glass plates for windows of vehicles and buildings. .

A water repellent / oil repellent antifouling glass plate according to claim 1, a vehicle according to claim 10, a building according to claim 11, and a water repellent / oil repellent antifouling glass plate according to claim 12-27. In the manufacturing method, since the surface of the glass substrate is covered with fused water- and oil-repellent and antifouling transparent fine particles, the water- and oil-repellent and antifouling glass plate exhibits a complex surface shape having irregularities. . Therefore, it has high water and oil repellency and antifouling properties due to the so-called “lotus leaf effect”.

In particular, the water- and oil-repellent and antifouling glass plate according to claim 2 has a complex uneven structure on the surface because the transparent fine particles are fused to the surface of the glass substrate at a part of the surface. Since the exposed portion is covered with a water / oil repellent / antifouling film, it has high water / oil repellent / antifouling properties.

The water / oil repellent / antifouling glass plate according to claim 3 can be improved in durability because the water / oil repellent / antifouling coating is covalently bonded to the surface of the transparent fine particles and the glass substrate.

Since the water repellent / oil repellent and antifouling glass plate according to claim 4 is used by mixing transparent fine particles having different particle diameters, the surface shape of the water / oil repellent and antifouling glass plate has fractal properties. Water and oil repellency can be improved.

The water / oil repellent / antifouling glass plate according to claim 5 can improve the water / oil repellent / antifouling property since the water / oil repellent / antifouling coating film contains —CF ₃ groups.

The water / oil repellent / antifouling glass plate according to claim 6 is silica, alumina, or zirconia in which the transparent fine particles are translucent and the softening temperature thereof is higher than the softening temperature of the glass substrate surface. It can be fused to the surface of the glass substrate without impairing the shape of the fine particles.

In the water and oil repellent and antifouling glass plate according to the seventh aspect, since the particle diameter of the transparent fine particles is less than 400 nm, which is smaller than the wavelength of visible light, there is little scattering of visible light and high translucency can be maintained.

The water / oil / oil / repellency antifouling glass plate according to claim 8 has a contact angle with water of 140 degrees or more, so the falling angle of the water droplet becomes small and the water droplet does not substantially adhere.

Since the water- and oil-repellent and antifouling glass plate according to claim 9 is formed on the surface of the glass substrate, a metal oxide transparent film that is fused to the transparent fine particles at a temperature lower than that of the glass substrate is formed. The heat treatment temperature at the time of fusion can be lowered, and the thermal deformation of the transparent fine particles at the time of fusion can be suppressed.

Since the vehicle according to claim 10 is equipped with the water- and oil-repellent antifouling glass plate according to claims 1 to 9, it is possible to prevent adhesion of raindrops and to improve the visibility outside the vehicle in rainy weather.

Since the building according to claim 11 is equipped with the water- and oil-repellent antifouling glass plate according to claims 1 to 9, it is possible to prevent adhesion of raindrops and to improve outdoor visibility in rainy weather.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claims 12 to 27, by applying a fine particle dispersion on the surface of the glass substrate and drying, the transparent fine particles are adhered to the surface of the glass substrate, Next, this is heat-treated to produce a fine-particle fused glass substrate, and a water-repellent / oil-repellent / fouling-resistant film is formed thereon, so that the entire surface is substantially uniformly covered with transparent fine particles, A water- and oil-repellent and antifouling glass plate excellent in visibility, transparency and durability can be obtained.
Moreover, since the heat treatment temperature is lower than the softening temperature of the transparent fine particles, thermal deformation of the transparent fine particles at the time of fusion can be suppressed.

The method for producing a water- and oil-repellent and antifouling glass plate according to claim 13, wherein the transparent fine particles are not dissolved in the fine particle dispersion on the surface of the glass substrate before Step D, but at a temperature lower than that of the glass substrate. Therefore, the heat treatment in the step E can be performed at a lower temperature.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 14, since the sol-gel method is used for forming the metal oxide transparent coating, the metal oxide transparent coating can be easily formed.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 15, the metal alkoxide solution used for forming the transparent film by the sol-gel method contains one or both of phosphoric acid and boric acid. The softening point of the transparent oxide film is lowered, and the heat treatment temperature during fusion can be lowered.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 16, the heat treatment temperature in step E is 250 ° C. or higher and lower than the softening temperature of the glass substrate and transparent fine particles. The deformation of the transparent fine particles can be suppressed.

The method for producing a water- and oil-repellent and antifouling glass plate according to claim 17 comprises a first chemistry comprising a first silane compound containing a linear group and a non-aqueous organic solvent before Step C. Transparent fine particles in which transparent fine particles a are dispersed in an adsorbent and the surfaces are covered with a monomolecular film of the first silane compound by the reaction between the silyl group of the first silane compound and the reactive groups on the surface of the transparent fine particles a In the step C, transparent fine particles whose surface is covered with a monomolecular film of the first silane compound are used in the step C, so that the transparent fine particles in the fine particle dispersion are used. Can be dispersed uniformly.
In addition, since the heat treatment in step E is performed in an atmosphere containing oxygen, the monomolecular film of the first silane compound can be completely decomposed and removed at a low heating temperature.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 18, an organic solvent is used for the fine particle dispersion, and the linear group of the first silane compound is a fluorocarbon group. The surface energy of the fine particles is reduced, and the aggregation of the transparent fine particles can be reliably suppressed.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 19, either one of water and alcohol or a mixture of both is used for the fine particle dispersion, and the linear group of the first silane compound is used. Since is a hydrocarbon group, the cost required for the preparation of the fine particle dispersion can be reduced, and the safety of the fine particle acid solution is further increased.

21. The method for producing a water / oil / oil / repellency / antifouling glass plate according to claim 20, wherein the formation of the water / oil / oil / repellency / antifouling coating in Step G is performed by applying a second silane compound containing a fluorocarbon group to the fine particle fused glass. Since it is carried out by the reaction between the silyl group of the second silane compound and the reactive group on the surface of the fine particle fused glass substrate in contact with the substrate, the durability of the water / oil repellent / antifouling coating is improved. Can do.

In the method for producing a water- and oil-repellent and antifouling glass plate according to claim 21, the unreacted second silane compound is washed away after the reaction between the silyl group and the reactive group in Step G. By forming only the water / oil repellent / antifouling coating film covalently bonded to the surface of the glass substrate, the water / oil / oil repellent / antifouling property and durability of the water / oil repellent / antifouling glass plate can be improved.

In the method for producing a water- and oil-repellent and antifouling glass according to claim 22, one or both of the first and second silane compounds do not generate harmful hydrogen chloride upon reaction with a reactive group. Since it is an alkoxysilane compound, it is possible to manufacture a water / oil repellent and antifouling glass plate more safely, and to suppress the corrosion of production equipment and the generation of acidic waste liquid.

In the method for producing a water- and oil-repellent and antifouling glass according to claim 23, either one or both of the first and second silane compounds are halosilane compounds highly reactive with a reactive group. The production of the water / oil repellent and antifouling glass plate can be carried out more efficiently, and the addition of a catalyst becomes unnecessary.

25. The method for producing a water / oil repellent / antifouling glass plate according to claim 24, wherein one or both of the first and second silane compounds generate harmful hydrogen chloride upon reaction with a reactive group. In addition, since it is a highly reactive isocyanate silane compound, corrosion of production facilities and generation of acidic waste liquid can be suppressed, and addition of a catalyst becomes unnecessary.

The method for producing a water- and oil-repellent antifouling glass according to claim 25, wherein the first and second chemical adsorption liquids containing an alkoxysilane compound are further used as a condensation catalyst as a carboxylic acid metal salt or a carboxylic acid ester. Since it contains one or more compounds selected from the group consisting of metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates, alkoxysilane compounds and reactive groups The reaction time can be shortened, and the production of the water / oil / oil / repellency antifouling glass plate can be carried out more efficiently.

28. The method for producing a water- and oil-repellent and antifouling glass according to claim 26 and 27, wherein the first and second chemical adsorption liquids containing an alkoxysilane compound are ketimine compounds, organic acids, aldimine compounds, enamine compounds. 1 or 2 or more compounds selected from the group consisting of an oxazolidine compound and an aminoalkylalkoxysilane compound further reduce the reaction time between the alkoxysilane compound and the active hydrogen group, resulting in water and oil repellency and antifouling properties The glass plate can be produced with higher efficiency. In particular, when both of these compounds and the above condensation catalyst are included, the reaction time can be further shortened.

Hereinafter, a water / oil repellent / antifouling glass plate according to an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, a water- and oil-repellent and antifouling glass plate 10 according to an embodiment of the present invention includes a plate-shaped glass substrate 5 and a transparent film of metal oxide on the surface of the glass substrate 5. Silica fine particles 1a (an example of water- and oil-repellent / antifouling transparent fine particles) fused through a silica-based transparent film 6 as an example, and a water- and oil-repellent and anti-repellent agent covering a portion where silica fine particles are not fused. And a chemisorbed monomolecular film 8 containing a fluorocarbon group, which is an example of a dirty coating.

As shown in FIGS. 2A and 2B, the method for producing the water / oil repellent / antifouling glass plate 10 includes a first silane compound containing a linear group and a non-aqueous organic solvent. Silica fine particles 1 as an example of transparent fine particles (original transparent fine particles a) are dispersed in the first chemical adsorption liquid, and the silyl group of the first silane compound and the hydroxyl group 2 (reactive group) on the surface of the silica fine particles 1 are dispersed. Step A for producing the silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound by reaction with the first example), and as shown in FIG. As shown in FIG. 4A, a step B for forming the transparent coating 6, a step C for preparing a fine particle dispersion in which the silica fine particles 4 whose surfaces are covered with the monomolecular film 3 of the first silane compound are dispersed. The fine particle content on the surface of the glass substrate 5 (specifically, the surface of the silica-based transparent coating 6). Applying and drying the liquid, the process D for attaching the silica fine particles 4 on the silica-based transparent coating 6 on the surface of the glass substrate 5, and the glass substrate 5 with the silica fine particles 4 attached to the surface are heat-treated, Silica fine particles 4 are fused to the surface of a glass substrate 5 through a silica-based transparent coating 6 to produce an uneven glass substrate (an example of a fine-particle fused glass substrate) 7 covered with the fused silica fine particles 1a. Step E, step F for washing and removing silica fine particles 4 that have not been fused to the surface of the glass substrate 5, and formation of a chemisorption monomolecular film 8 containing a fluorocarbon group on the surface of the concavo-convex glass substrate 7. Process G to be performed.
Hereinafter, steps A to G will be described in more detail.

In step A, silica fine particles 4 whose surfaces are covered with the monomolecular film 3 of the first silane compound are produced.
In order not to impair the transparency of the water / oil repellent / antifouling glass plate 10 to be produced, the diameter of the silica fine particles 1 used for producing the silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound. Is preferably smaller than the visible light wavelength (380 to 700 nm). Specifically, the diameter of the fine particles is preferably 10 to 400 nm, more preferably 10 to 300 nm, and even more preferably 10 to 100 nm. The silica fine particles 1 used may have a single particle diameter, but when mixed with two or more silica fine particles having different particle diameters, the surface thereof has a fractal structure. 11 (see FIG. 5) is obtained, and the water / oil repellency / antifouling property is improved.

In the present embodiment, silica fine particles are used as the transparent fine particles. However, the surface has active hydrogen groups (an example of reactive groups) that react with alkoxysilyl groups and halosilyl groups, such as hydroxyl groups and amino groups. Any fine particles that are light and have a softening point higher than that of the glass substrate can be used. Examples of transparent fine particles that can be used other than silica include fine particles such as alumina and zirconia.

The first chemical adsorption liquid used for the production of the silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound includes the first silane compound, the silyl group, and the hydroxyl group 2 on the surface of the silica fine particle 1. It is prepared by mixing a condensation catalyst for accelerating the condensation reaction with a non-aqueous organic solvent.

As the first silane compound, an alkoxysilane compound represented by any one of the following chemical formulas 1 and 2 is used.

In the above chemical formulas 1 and 2, m represents an integer of 5 to 20, n represents an integer of 0 to 9, and R represents an alkyl group having 1 to 4 carbon atoms.
Y represents (CH ₂ ) _k (k represents an integer of 1 to 3) and a single bond, and Z represents O (ether oxygen), COO, Si (CH ₃ ) ₂ , and a single bond. Represents one of the bonds.

Specific examples of the alkoxysilane compound that can be used as the first silane compound include alkoxysilane derivatives containing a fluorocarbon group shown in the following (1) to (12), and the following (21) to (32). And alkoxysilane derivatives containing the hydrocarbon group shown in FIG.

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(5) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(8) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(9) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(10) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

(21) CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
(22) CH 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{(23) CH 3 (CH 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
(24) CH ₃ (CH ₂ ) ₉ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(25) CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(26) CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) _{3
(27) CH 3 CH 2 O} (CH 2) 15 Si (OC 2 H 5) 3
_{(28) CH 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(29) CH 3 (CH 2} ) 7 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
_{(30) CH 3 (CH 2} ) 9 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(31) CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(32) CH 3 (CH 2} ) 7 Si (OC 2 H 5) 3

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

When the silica fine particles 1 are dispersed in the first chemical adsorption liquid containing the alkoxysilane compound and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl groups 2 on the surface of the silica fine particles 1 cause a condensation reaction, and A monomolecular film 3 of the first silane compound having a structure as shown in either Chemical Formula 3 or Chemical Formula 4 is generated. The three single bonds extending from the oxygen atom are bonded to the surface of the silica fine particle 1 or the silicon (Si) atom of the adjacent silane compound, at least one of which is bonded to the silicon atom on the surface of the silica fine particle 1. is doing.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the silica fine particles 1, and it is preferable to remove these impurities in advance by thoroughly washing and drying the silica fine particles 1.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, as a condensation catalyst, silica fine particles 4 whose surface is covered with a monomolecular film 3 of a first silane compound under the same conditions except that H3 of Japan Epoxy Resin Co., which is a ketimine compound, is used instead of dibutyltin oxide. When the production of is carried out, the reaction time can be shortened to about 1 hour without impairing the quality.

Further, as a condensation catalyst, a mixture of H3 and dibutyltin bisacetylacetonate (Japan epoxy resin) (mixing ratio is 1: 1) was used, and the other conditions were the same, and the monomolecular film 3 of the first silane compound was used. When the silica fine particles 4 whose surface is covered are manufactured, the reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

For the preparation of the first chemical adsorption solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

A preferable concentration of the alkoxysilane compound in the first chemical adsorption solution is 0.5 to 3% by mass.

After the reaction, washing with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface yields silica fine particles 4 covered with the monomolecular film 3 of the first silane compound. FIG. 2B shows a schematic diagram of a cross-sectional structure of the silica fine particles 4 covered with the monomolecular film 3 of the first silane compound thus manufactured. FIG. 2B shows an example of the monomolecular film 3 of the first silane compound having a structure represented by the following chemical formula 5.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, if the silica fine particles 4 covered with the monomolecular film 3 of the first silane compound produced are left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is absorbed in the air. The resulting silanol group undergoes a condensation reaction with the alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the silica fine particles 4 covered with the monomolecular film 3 of the first silane compound. This polymer film is not fixed by covalent bonding to the surface of the silica fine particles 4 covered with the monomolecular film 3 of the first silane compound, but does not particularly hinder the manufacturing process after the process A.

Although the case where an alkoxysilane compound is used as the first silane compound has been described in this embodiment, a halosilane compound or an isocyanate silane compound having a fluorocarbon group may be used. When these silane compounds are used, a condensation catalyst and a co-catalyst are not required, alcohol solvents cannot be used, and they are more susceptible to hydrolysis than alkoxysilane compounds. Except that the reaction is carried out at a humidity of 30% or less, the first chemical adsorption solution can be prepared and the silica fine particles covered with the monomolecular film of the first silane compound can be produced in the same manner as the alkoxysilane compound. .
Examples of the halosilane compound and isocyanate silane compound that can be used as the first silane compound include compounds shown in the following (41) to (52).

(41) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(42) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(43) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(44) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(45) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(46) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(47) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(48) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(49) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(50) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(51) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(52) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(Step A).

In step B, a silica-based transparent coating 6 that does not dissolve in the fine particle dispersion (used in step C) and is fused to the transparent fine particles 4 at a temperature lower than that of the glass substrate 5 is formed on the surface of the glass substrate 5. (See FIG. 3).
There is no restriction | limiting in particular about the material of the glass base material 5 to be used, a shape, and a magnitude | size, Arbitrary window glass materials used in a vehicle and a building can be used. Moreover, as long as an active hydrogen group exists on the surface, a surface film may be formed. The active hydrogen group may be a hydroxyl group, but may be another functional group having an active hydrogen such as an amino group.

The silica-based transparent film 6 formed on the surface of the glass substrate 5 is preferably a silica dry gel film formed by a sol-gel method.
Since there are more free hydroxyl groups on the surface and inside of the unsintered dry gel film than on the surface of the glass substrate 5 having no transparent coating, the silica fine particles 4 and Can be fused.

The formation of a silica dry gel film is performed by using a sol solution (an example of a metal alkoxide solution) obtained by mixing a tetraalkoxysilane such as tetramethoxysilane (Si (OCH ₃ ) ₄ ), a condensation catalyst, and a solvent with a glass substrate. 5 can be applied by evaporating the solvent.
As a result, a condensation reaction occurs between the hydroxyl group generated by hydrolysis of the alkoxyl group by moisture in the air and the alkoxyl group, and a transparent dry gel film of silica (silica-based transparent film 6) is formed on the surface of the glass substrate 5. Example) is formed.
Since the condensation catalyst, cocatalyst, solvent type, tetraalkoxysilane concentration, and addition amount of the catalyst that can be used are the same as those in the first chemical adsorption solution, description thereof is omitted.

The application of the sol solution can be performed by an arbitrary method such as a dip coating method, a spin coating method, a spray method, or a screen printing method.
Moreover, although the film thickness of a dry gel film is based also on the particle size of the silica fine particle 1 used for manufacture of the water-repellent / oil-repellent antifouling glass plate 10, 10-50 nm is preferable.
FIG. 3 shows a schematic diagram of a cross-sectional structure of the glass substrate 5 having the silica dried gel film thus produced.
When the glass substrate 5 having a silica dry gel film as a transparent film is used to produce the water / oil repellent / antifouling glass plate 10, the heat treatment in the step E can be performed at a low temperature of 300 ° C. or less. The concavo-convex glass substrate 7 to which the silica fine particles 1a are fused can be produced without deteriorating the strengthening degree of the glass that has been tempered in advance with air cooling.

In the present embodiment, a dry gel film of silica is formed as the transparent film. However, the silica fine particles 1 can be fused at a temperature lower than that of the glass substrate 5 with transparency. A transparent film can be formed and used. Examples of the transparent film that can be used include dry gel films such as alumina and titanium oxide.
Moreover, when phosphoric acid or boric acid is added to the sol solution at several percents, a dry gel film of phosphorus silicate glass (PSG) or boron silicate glass (BSG) is formed, and the heat treatment temperature in step E is 250 ° C. It can be reduced to the extent (step B above).

In step C, a fine particle dispersion in which silica fine particles 4 whose surfaces are covered with the monomolecular film 3 of the first silane compound is dispersed is prepared.
The silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound are added to the solvent, and vigorously stirred by any stirring means such as a stirring spring or a magnetic stirrer, or by ultrasonic irradiation. The silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound are uniformly dispersed in the solvent.
As a solvent that can be used for the preparation of the fine particle dispersion, any solvent that can uniformly disperse the silica fine particles 4 and that can be easily removed by evaporation after coating on the glass substrate 5 is used. Can do.

When a silane compound having a fluorocarbon group represented by the chemical formula 1 (for example, the above (1) to (12)) is used as the first silane compound, any water and alcohol-based solvents can be excluded. A non-aqueous organic solvent is preferable, and when using a silane compound having a hydrocarbon group represented by Chemical Formula 2 (for example, the above (21) to (32)), any organic material including water and an alcohol-based solvent is used. Although a solvent can be used, water and alcohol solvents are preferable from the viewpoint of low toxicity and ease of waste disposal.

The mass ratio in the fine particle dispersion of the silica fine particles 4 whose surface is covered with the monomolecular film 3 of the first silane compound is preferably 0.5 to 5% by mass. When the mass ratio is less than 0.5% by mass, a large amount of the fine particle dispersion is required, and when it exceeds 5% by mass, it is difficult to uniformly disperse the silica fine particles 4, which is not preferable.

The monomolecular film 3 of the first silane compound covering the surface of the silica fine particles 4 has an effect of reducing the surface energy of the silica fine particles 4, and has an effect of suppressing aggregation in the fine particle liquid and improving dispersibility.
In the present embodiment, the silica fine particles 4 whose surfaces are covered with the monomolecular film 3 of the first silane compound produced in the process A are used. However, the silica fine particles 1 are directly removed by omitting the process A. Even when a fine particle dispersion is prepared by dispersing in a solvent, although the defect density on the surface of the concavo-convex glass substrate 7 produced in the step E is slightly increased, the water-repellent / oil-repellent / antifouling glass plate 10 is produced. There will be no major hindrance (step C).

In step D, the fine particle dispersion is applied to the surface of the glass substrate 5 (the surface of the silica-based transparent coating 6) and dried, whereby the silica fine particles 4 are formed on the surface of the glass substrate 5 via the silica-based transparent coating 6. Adhere.
The fine particle dispersion can be applied by an arbitrary method such as a dip coating method, a spin coating method, a spray method, or a screen printing method. Further, for the evaporation of the solvent, known methods such as air drying, reduced pressure drying, heat drying and the like can be used alone or in appropriate combination depending on the boiling point, vapor pressure and the like of the solvent used.
FIG. 4 is a schematic diagram of the cross-sectional structure of the glass substrate 5 having the silica-based transparent coating 6 to which the silica fine particles 4 whose surfaces are covered with the monomolecular film 3 of the first silane compound attached are obtained in this manner. Shown in (a) (step D above).

In step E, a glass substrate 5 having a silica-based transparent coating 6 on which silica fine particles 4 whose surfaces are covered with a monomolecular film 3 of a first silane compound is mounted is heat-treated in an atmosphere containing oxygen, and silica The silica fine particles 4 were fused by decomposing the monomolecular film 3 of the first silane compound covering the surfaces of the fine particles 4 and fusing the silica-based transparent coating 6 and the silica fine particles 4 on the surface of the glass substrate 5. The concavo-convex glass substrate 7 (that has the fused silica fine particles 1a on the surface) (see FIG. 4B) is manufactured.
The heat treatment is performed in an oxygen-containing atmosphere at a temperature higher than the temperature at which the glass substrate 5 and the silica fine particles 4 are fused and lower than the melting temperature of the glass substrate 5 and the silica fine particles 4. The higher the heat treatment temperature, the stronger the silica particles 4 can be fused to the surface of the glass substrate 5. However, when the temperature is too high, the silica particles are buried in the glass substrate 5 (or the transparent coating 6). Therefore, it is not preferable.
When the glass substrate 5 has the silica-based transparent coating 6, heat treatment can be performed at a low temperature of about 250 to 300 ° C. for fusing the glass substrate 5 and the silica fine particles 4. However, in order to completely decompose the monomolecular film 3 of the first silane compound covering the surface of the silica fine particles 4, it is necessary to perform a heat treatment at 350 to 400 ° C.
When the first silane compound has a fluorocarbon group, it is necessary to perform heat treatment at about 400 ° C. in order to completely decompose the monomolecular film, but in the case of having a hydrocarbon group, 350 ° C. The monolayer can be completely decomposed to a certain degree. Therefore, when the 1st silane compound containing a hydrocarbon group is used in the process A, even if it uses tempered glass as the glass base material 5, since the effect of the air-cooling strengthening process is not impaired, it is preferable.
A schematic diagram of the cross-sectional structure of the concavo-convex glass substrate 7 thus obtained is shown in FIG.

In the present embodiment, the glass substrate 5 on which the silica-based transparent coating 6 is formed is used. However, the step B may be omitted and the glass substrate 5 not having the silica-based transparent coating 6 may be used as it is. Good. When blue plate glass is used as the glass substrate 5, a preferable heat treatment temperature is about 650 degrees. The treatment time is 30 minutes when heat treatment is performed in air at 650 ° C. (step E above).

In step F, the silica fine particles 4 that have not been fused to the surface of the glass substrate 5 are removed by washing. Although any solvent can be used for washing, water that is harmless and can easily be disposed of is most preferable (step F).

In step G, a chemically adsorbed monomolecular film 8 containing a fluorocarbon group is formed on the surface of the concavo-convex glass substrate 7 having the fused silica fine particles 1a to produce a water- and oil-repellent and antifouling glass plate 10.

The second chemisorption liquid used for forming the chemisorption monomolecular film 8 containing a fluorocarbon group is composed of an alkoxysilane compound (an example of the second silane compound) containing a fluorocarbon group and the concavo-convex glass substrate 7. It is prepared by mixing a condensation catalyst for promoting a condensation reaction between a hydroxyl group on the surface (an example of a reactive group) and an alkoxysilyl group and a non-aqueous organic solvent.

Examples of the alkoxysilane compound containing a fluorocarbon group include the alkoxysilane compounds represented by the general formula (Formula 1).

Concentrations of the condensation catalyst, cocatalyst and combinations thereof that can be used for the second chemical adsorption solution, solvent type, alkoxysilane compound, condensation catalyst, and cocatalyst concentration, reaction conditions and reaction time are Since it is the same as a chemical adsorption liquid, description is abbreviate | omitted.

In the chemisorption monomolecular film 8 having a fluorocarbon group, the exposed portion of the fused silica fine particles 1a and the silica fine particles 1a on the surface of the glass substrate 5 (the surface of the silica-based transparent coating 6) are not fused. It is covalently attached to the part.

Although the case where an alkoxysilane compound is used as the second silane compound has been described in this embodiment, a halosilane compound or an isocyanate silane compound having a fluorocarbon group may be used. When a halosilane compound is used, a condensation catalyst and a cocatalyst are not required, an alcohol solvent cannot be used, and it is more susceptible to hydrolysis than an alkoxysilane compound. %), The second chemical adsorption solution can be prepared and reacted with the concavo-convex glass substrate 7 in the same manner as the alkoxysilane compound.
FIG. 1 shows a schematic diagram of a cross-sectional structure of the water / oil repellent / antifouling glass plate 10 thus obtained. In addition, in FIG. 1, what has the structure represented by said Chemical formula 5 is shown as an example of the chemisorption monomolecular film 8 containing a fluorocarbon group (the above process G).

Since the film thickness of the chemical adsorption monomolecular film 8 having a fluorocarbon group is at most about 1 nm, the unevenness of about 50 nm formed on the surface of the glass substrate covered with the fused silica fine particles 1a is Almost no damage. In addition, due to this unevenness effect (so-called “lotus leaf effect”), the apparent surface energy of the water / oil repellent / antifouling glass plate 10 can be reduced, and the water droplet contact angle is 140 degrees or more (this embodiment). Is about 150 degrees), and super water repellency can be realized.

Further, since the silica fine particles 1a having a hardness higher than that of the glass are fused to the surface of the base glass 5 of the water / oil repellent / antifouling glass plate 10 via the silica-based transparent coating 6, the wear resistance is increased. Has also improved significantly.
Further, in the water / oil repellent / antifouling glass plate 10, the thickness of the coating including the silica fine particles 1 a fused to the surface of the glass substrate 5 and the chemical adsorption monomolecular film 8 having a fluorocarbon group is as a whole. Since it is about 100 nm, the transparency of the glass substrate 5 is not impaired.

After the reaction, when the generated water / oil / oil repellent and antifouling glass plate 10 is left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air and formed. The resulting silanol group causes a condensation reaction with the alkoxysilyl group. As a result, an extremely thin polymer film made of polysiloxane is formed on the surface of the water / oil repellent / antifouling glass plate 10. Unlike the monomolecular film, the polymer film is not entirely fixed to the surface of the water / oil / oil / fouling and anti-fouling glass plate 10 by a covalent bond, but has a fluorocarbon group. It has oil repellency and antifouling properties. Therefore, it can be used as the water / oil repellent / antifouling glass plate 10 in this state as long as the durability is somewhat inferior.

Moreover, as an alkoxysilane compound containing the fluorocarbon group which can be used in the process G, the compound shown to said (1)-(12) is mentioned.

Examples of the halosilane compound and isocyanate silane compound containing a fluorocarbon group that can be used in Step G include the compounds shown in the above (41) to (52).

From the relationship between the contact angle to the water droplet on the water-repellent surface and the falling angle obtained from the experiment using water droplets of different volumes (0.02 to 0.08 ml), when the water droplet contact angle is 150 degrees or more, It is known that the falling angle is 15 degrees or less regardless of the volume.
Therefore, it can be seen that when the water / oil repellent / antifouling glass plate 10 is used as a window glass plate for a vehicle or a building, most of the water droplets cannot fall on the surface and fall down.

The water / oil / oil / repellency antifouling glass plate 10 is excellent in durability such as abrasion resistance and weather resistance, water droplet separation (sliding), and antifouling, and is required to have a water / oil / oil repellent and antifouling function. It can be used as a glass plate for windows of vehicles and buildings.
Vehicles that can use the water- and oil-repellent and antifouling glass plate 10 include automobiles, railway vehicles, ships, etc., and are used as window glass plates for all windows regardless of whether they are driver seats or cabins. Can do.
Moreover, as a building which can use the water-repellent / oil-repellent antifouling glass plate 10, any building such as a detached house, an apartment house, and an office building can be cited.

Examples carried out for confirming the effects of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
(1) Production of silica fine particles covered with a monomolecular film having a fluorocarbon group Silica fine particles having an average particle diameter of 100 nm were prepared, washed thoroughly and dried.
(Heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (Chemical Formula 6, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.99 parts by weight, and dibutyltin bisacetylacetonate (condensation catalyst) 0.01 weight Parts were weighed and dissolved in 100 parts by weight of hexamethyldisiloxane solvent to prepare a first chemical adsorption solution.

このようにして得られた第１の化学吸着液に乾燥したシリカ微粒子を混入撹拌して空気中（相対湿度４５％）で２時間程度反応させた。
その後、クロロホルムで洗浄し、過剰なアルコキシシラン化合物およびジブチルスズビスアセチルアセトナートを除去した。

The first chemisorbed liquid thus obtained was mixed and stirred with dried silica fine particles and reacted in air (relative humidity 45%) for about 2 hours.
Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(2) Formation of a silica-based transparent coating on the surface of a glass substrate An automotive window glass plate (front screen, side screen, and rear screen) was prepared, washed thoroughly, and dried.
0.99 parts by weight of tetramethoxysilane (Si (OCH ₃ ) ₄ ) and 0.01 parts by weight of dibutyltin diacetylacetonate (condensation catalyst) were weighed and dissolved in 100 parts by weight of hexamethyldisiloxane solvent, A sol solution was prepared. When the sol solution thus obtained is applied to the surface of an automotive window glass plate and the solvent is evaporated, tetramethoxysilane is hydrolyzed and dealcoholized, resulting in silica containing a large amount of hydroxyl groups having a film thickness of about 50 nm. A system transparent film (silica dry gel film) was formed.

(3) Adding 1 part by weight of silica fine particles, the surface of which is coated with a monomolecular film containing a fluorocarbon group, prepared in (1), to the surface of a glass substrate, in 99 parts by weight of xylene, A fine particle dispersion was prepared by vigorous stirring.
After applying the fine particle dispersion on the surface of the automotive window glass plate having a transparent coating of silica dry gel film formed in (2), the solvent is evaporated and the surface is covered with a monomolecular film containing a fluorocarbon group. A glass substrate having silica fine particles adhered to the surface was obtained.

(4) Production of concavo-convex glass base material fused with silica fine particles A glass base material with silica fine particles whose surface is covered with a monomolecular film containing a fluorocarbon group adhered to the surface is baked at 500 ° C. in air for 30 minutes. Then, the monomolecular film containing the fluorocarbon group covering the surface of the silica fine particles was decomposed and removed, and the silica fine particles were fused to the glass substrate surface. Thereafter, when washed with water, silica fine particles that were not fused to the surface of the glass substrate were removed, and an uneven glass substrate fused with a single layer of silica fine particles was obtained.

(5) Formation of a monomolecular chemical adsorption film containing a fluorocarbon group (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane (Chemical Formula 7, manufactured by Shin-Etsu Chemical Co., Ltd.) It melt | dissolved in 100 weight part of dehydrated nonane, and prepared the 2nd chemical adsorption liquid.
The second chemically adsorbed liquid was applied to the surface of the automobile window glass plate produced in (4), on which silica fine particles were fused and fixed, in dry air having a relative humidity of 30% or less and reacted. After the reaction, it was washed with a fluorocarbon solvent to remove the unreacted trichlorosilane compound.

The apparent water droplet contact angle of the water-repellent / oil-repellent antifouling automotive window glass plate thus obtained was about 151 degrees.
For comparison, a water / oil repellent / antifouling film was formed on the surface of an automotive window glass plate to which silica fine particles had not been fused in the same manner as in (5), and the water droplet contact angle was measured. The contact angle was about 115 degrees.

(Example 2)
As silica fine particles, a mixture of 1 part by weight of silica fine particles having an average particle diameter of 200 nm and 10 parts by weight of silica fine particles having an average particle diameter of 50 nm is used, and the same operations as in (1) to (5) of Example 1 are performed. As a result, a water / oil / oil / fouling and anti-fouling glass plate 11 having a fractal structure on the surface and a water / water / oil / fouling / antifouling effect with a water droplet contact angle of about 160 degrees could be produced (see FIG. 5).

(Example 3)
Water and oil repellent and water repellent having a water droplet contact angle of about 150 degrees (similar effect was obtained if the water droplet contact angle was 140 degrees or more for practical use) prepared under the same conditions as the glass plate prepared in Example 1. Dirty glass plates are installed as front window glass for passenger cars (also called windshield, tilt angle is approximately 45 degrees), side window glass (tilt angle is approximately 70 degrees), and rear window glass (tilt angle is approximately 30 degrees). I tried an experiment.

First, the state of attachment of rain water droplets while stopped was confirmed, but almost no water droplets having a diameter of about 5 mm or more were observed on any glass.

Next, running experiments were conducted at 45 km / hour and 60 km / hour.
When the state of attachment of rainwater droplets during traveling at 45 km / hour was confirmed, there was almost no adhesion of waterdrops having a diameter of about 2 mm or more on the side window glass and the rear window glass. Further, on the front window glass, a large amount of raindrops adhered continuously during traveling, but the waterdrops having a diameter of about 2 mm or more quickly moved upward and did not remain so as to scatter and obstruct the view.
When the speed was further increased to 60 km / hour, water droplets having a diameter of about 2 mm or more were instantaneously scattered and almost completely removed.

In addition, while using a door mirror during a running experiment and visually confirming the visibility of the rear through the side window glass plate, the distortion of visibility and the deterioration of visibility due to rain water droplets were hardly felt.

In addition, the visibility outside the vehicle with and without a coating (including alumina fine particles and water / oil repellent / antifouling coating) was compared in clear weather, and the transparency of the coating was 97% with respect to light having a wavelength of 400 to 700 nm. Because of the above, deterioration in visibility was not felt even when compared with a car without a coating. In addition, the wear resistance against the wiper can be significantly improved because the alumina fine particles have a higher hardness than when the water-repellent coating is formed with the glass as it is.

From the above experiments, it was confirmed that a car equipped with a water- and oil-repellent and antifouling glass plate exerts a special effect on safe driving in rainy weather.

Example 4
A water-repellent / oil-repellent / fouling-resistant glass plate having a water droplet contact angle of 152 degrees, which was prepared in the same manner as in Example 1, was attached to a window glass of a building, and the raindrop adhesion in rainy weather was confirmed. The raindrops did not attach at all. In addition, dust and dirt that had adhered to in fine weather were washed away by raindrops, and the glass became clean.

It is explanatory drawing which represented typically the cross-section of the water repellent / oil repellent antifouling glass plate which concerns on one embodiment of this invention. In the manufacturing method of the water / oil repellent / antifouling glass plate, a conceptual diagram expanded to a molecular level for explaining a process of forming a fluorocarbon monomolecular film on the surface of silica fine particles, (a) is a reaction The cross-sectional structure of the previous silica fine particle, (b) represents the cross-sectional structure of the silica fine particle on which a monomolecular film containing a fluorocarbon group is formed. It is a schematic diagram showing the cross-sectional structure of the glass base material in which the silica type transparent coating film was formed in the manufacturing method of the said water-repellent | oil-repellent | antifouling | fouling-proof glass plate. (A) is explanatory drawing of the state in which the silica fine particle coat | covered with the fluorocarbon type | system | group monomolecular film has adhered to the glass substrate surface in which the silica type transparent film was formed in the process D, (b) is in the process E It is explanatory drawing which shows typically the state which the silica fine particle fuse | melted. It is explanatory drawing which represented typically the cross-sectional state of the water repellent and oil-repellent antifouling glass plate which has a fractal structure on the surface.

Explanation of symbols

1: silica fine particles, 1a: fused silica fine particles, 2: hydroxyl group, 3: monomolecular film of first silane compound, 4: silica fine particles, 5: glass substrate, 6: silica-based transparent coating, 7: irregularities Glass substrate, 8: chemical adsorption monomolecular film containing fluorocarbon group, 10: water / oil repellent / antifouling glass plate, 11: water / oil / oil repellent / antifouling glass plate having a fractal structure on the surface

Claims (27)

Covers the plate-shaped glass substrate, the water- and oil-repellent antifouling transparent fine particles fused to the surface of the glass substrate, and the portion of the surface of the glass substrate where the transparent fine particles are not fused. A water / oil / oil repellent / anti-fouling glass plate having a water / oil / oil / repellent / anti-fouling coating. 2. The water / oil repellent / antifouling glass plate according to claim 1, wherein a part of the surface of the transparent fine particles is fused to the surface of the glass substrate, and the other exposed part is the water / oil repellent. A water- and oil-repellent and antifouling glass plate which is covered with an oil and antifouling coating. The water / oil repellent / antifouling glass plate according to claim 2, wherein the water / oil repellent / antifouling coating is covalently bonded to the surface of the transparent fine particles and the glass substrate. Oil-repellent antifouling glass plate. The water / oil repellent / antifouling glass plate according to any one of claims 1 to 3, wherein the transparent fine particles having different particle diameters are mixed and used. Oil-resistant antifouling glass plate. 5. The water / oil repellent / antifouling glass plate according to claim 1, wherein the water / oil repellent / antifouling coating contains —CF ₃ groups. Dirty glass plate. The water / oil repellent / antifouling glass plate according to any one of claims 1 to 5, wherein the transparent fine particles are translucent and have a softening temperature higher than the softening temperature of the glass substrate surface. A water- and oil-repellent antifouling glass plate characterized by being any one of silica, alumina, and zirconia. The water / oil repellent / antifouling glass plate according to claim 1, wherein the transparent fine particles have a particle size of less than 400 nm. The water / oil repellent / antifouling glass plate according to claim 1, wherein the water contact angle is 140 ° or more. The water / oil repellent / antifouling glass plate according to any one of claims 1 to 8, wherein the transparent fine particles are transparent metal oxides fused to the transparent fine particles at a temperature lower than that of the glass substrate. It is fused to the surface of the glass substrate through a coating, and the water and oil repellent antifouling coating covers a portion where the transparent fine particles are not fused through the transparent coating. Characteristic water and oil repellent antifouling glass plate. A vehicle equipped with the water / oil repellent / antifouling glass plate according to claim 1. A building comprising the water- and oil-repellent antifouling glass plate according to any one of claims 1 to 9. Step C for preparing a fine particle dispersion in which transparent fine particles are dispersed, and Step D for attaching the transparent fine particles to the surface of the glass substrate by applying and drying the fine particle dispersion on the surface of the glass substrate. The glass substrate on which the transparent fine particles adhere to the surface is heated at a temperature lower than the softening temperature of the transparent fine particles, and the transparent fine particles are fused to the surface of the glass substrate; and the glass substrate A step F for cleaning and removing the transparent fine particles not fused to the surface of the material, and a step G for forming a water / oil repellent antifouling film on the surface of the fine particle fused glass substrate to which the transparent fine particles are fused. A method for producing a water- and oil-repellent and antifouling glass plate, comprising: 13. The method for producing a water / oil repellent / antifouling glass plate according to claim 12, wherein before the step D, the surface of the glass substrate is not dissolved in the fine particle dispersion and is lower than the glass substrate. A method for producing a water- and oil-repellent and antifouling glass plate, further comprising a step B of forming a transparent film of a metal oxide fused with the transparent fine particles at a temperature. 14. The method for producing a water / oil repellent / antifouling glass plate according to claim 13, wherein a sol-gel method is used for forming the transparent film. The method for producing a water- and oil-repellent and antifouling glass plate according to claim 14, wherein the metal alkoxide solution used for forming the transparent film by a sol-gel method contains one or both of phosphoric acid and boric acid. A method for producing a water- and oil-repellent antifouling glass plate. 16. The method for producing a water / oil repellent / antifouling glass plate according to claim 15, wherein the heat treatment temperature in the step E is 250 ° C. or higher and lower than the softening temperature of the glass substrate and the transparent fine particles. A method for producing a water- and oil-repellent antifouling glass plate. In the manufacturing method of the water-repellent / oil-repellent and antifouling glass plate according to any one of claims 12 to 16, before the step C, the first silane compound containing a linear group and a non-aqueous system. Transparent fine particles a are dispersed in a first chemical adsorption solution containing an organic solvent, and the first silane compound is reacted with a silyl group of the first silane compound and a reactive group on the surface of the transparent fine particles a. A process A for producing the transparent fine particles whose surface is covered with a monomolecular film, and the heat treatment in the process E is performed in an oxygen-containing atmosphere. Manufacturing method of glass plate. 18. The method for producing a water / oil repellent antifouling glass plate according to claim 17, wherein an organic solvent is used for the fine particle dispersion, and the linear group is a fluorocarbon group. A method for producing a water / oil repellent antifouling glass plate. 18. The method for producing a water / oil repellent / antifouling glass plate according to claim 17, wherein the fine particle dispersion is one of water and alcohol or a mixture thereof, and the linear group is a hydrocarbon. A method for producing a water- and oil-repellent and antifouling glass plate, characterized in that it is a base. 20. The method for producing a water / oil repellent / antifouling glass plate according to any one of claims 12 to 19, wherein the formation of the water / oil repellent / antifouling coating film in the step G includes a fluorocarbon group. A second chemical adsorption liquid containing a second silane compound and a non-aqueous organic solvent is brought into contact with the fine particle fused glass substrate, so that the silyl group of the second silane compound and the fine particle fused glass substrate are brought into contact with each other. A method for producing a water- and oil-repellent and antifouling glass plate, which is carried out by a reaction with a reactive group on the surface. 21. The method for producing a water- and oil-repellent and antifouling glass plate according to claim 20, wherein after the reaction between the silyl group and the reactive group in the step G, the unreacted second silane compound is washed away. A method for producing a water- and oil-repellent and antifouling glass plate. The method for producing a water- and oil-repellent and antifouling glass plate according to any one of claims 20 and 21, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Either or both of them are alkoxysilane compounds, A method for producing a water / oil repellent antifouling glass plate. The method for producing a water- and oil-repellent and antifouling glass plate according to any one of claims 20 and 21, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Any one or both of these are a halosilane compound, The manufacturing method of the water repellent and oil repellent antifouling glass plate characterized by the above-mentioned. The method for producing a water- and oil-repellent and antifouling glass plate according to any one of claims 20 and 21, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Any one or both of these are an isocyanate silane compound, The manufacturing method of the water / oil repellent antifouling glass plate characterized by the above-mentioned. The method for producing a water- and oil-repellent and antifouling glass plate according to claim 22, wherein the first and second chemical adsorption liquids containing the alkoxysilane compound further include a metal carboxylate as a condensation catalyst, Water repellent and water repellent characterized by comprising one or more compounds selected from the group consisting of carboxylate metal salts, carboxylate metal salt polymers, carboxylate metal salt chelates, titanate esters, and titanate ester chelates. Manufacturing method of oil-proof antifouling glass plate. 23. The method for producing a water- and oil-repellent and antifouling glass plate according to claim 22, wherein the first and second chemical adsorption liquids containing the alkoxysilane compound are a ketimine compound, an organic acid, an aldimine as a condensation catalyst. A method for producing a water / oil repellent / antifouling glass plate, further comprising one or more compounds selected from the group consisting of a compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. 26. The method for producing a water / oil repellent / antifouling glass plate according to claim 25, wherein the cocatalyst is further selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds. A method for producing a water- and oil-repellent and antifouling glass plate, comprising one or more compounds.

Images