JP2007126332A - Water-repellent glass plate, its producing method, and vehicle or glass window using the glass plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve durability such as wear resistance or weatherability, water droplet releasing property (called also as planing property), and antifouling property for a glass plate for windows of vehicles such as automobiles or of buildings, which is required to have water-repellent, oil-repellent and anti-fouling functions. <P>SOLUTION: A water-repellent glass plate, covered with water-repellent transparent fine particles covalently bonded to the surface of the plate, is characterized in that a major portion of the surface of each water-repellent transparent fine particle covalently bonded to the surface of the glass plate is covered with a water-repellent coat, and a portion of the water-repellent transparent fine particles are covalently bonded to the surface of a base glass plate through an organic film a part of which contains a reactive functional group at one end and is covalently bonded to the surface of each transparent fine particle through Si at the other end, and an organic film which contains a reactive functional group at one end and is covalently bonded to the base glass plate through Si at the other end. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a glass plate having a highly durable and water-repellent coating formed on the surface thereof. More specifically, the present invention relates to a glass plate for a vehicle such as a vehicle or a window of a building that requires a water / oil repellent / antifouling function. Furthermore, it relates to a vehicle and a glass window using the same.

It is already well known that a chemisorbed liquid 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 water-repellent chemisorbed film. (For example, refer to 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.
Japanese Patent Laid-Open No. 02-258032

However, since the conventional chemical adsorption film uses only the chemical bond between the adsorbent and the substrate surface, there is a problem that the wear resistance and water repellency are poor.

The present invention relates to a glass plate for vehicles and buildings such as automobiles that require a water and oil repellent and antifouling function, durability such as wear resistance and weather resistance, water droplet separation (also referred to as water slidability), and antifouling. The purpose is to improve performance.

A first invention provided as means for solving the above-mentioned problems is a water-repellent glass plate characterized by being covered with water-repellent transparent fine particles covalently bonded to the surface.

According to a second invention, in the first invention, most of the water-repellent transparent fine particles covalently bonded to the surface are covered with a water-repellent coating, and one part includes a reactive functional group at one end. An organic film covalently bonded to the surface of the transparent fine particle through Si at the end and an organic film covalently bonded to the base glass plate through Si at one end and a reactive functional group at the other end It is a water-repellent glass plate characterized by being covalently bonded to the surface of the glass plate.

A third invention is the water-repellent glass plate according to the second invention, wherein at least the water-repellent film is covalently bonded to the surface of the transparent fine particles.

A fourth invention is the water-repellent glass plate according to the third invention, wherein the water-repellent coating on the surface of the transparent fine particles contains a -CF ₃ group.

According to a fifth invention, in the second invention, the organic film covalently bonded to the surface of the transparent fine particle through Si at one end and a reactive functional group at one end contains at least N and the reactive functional group at one end. The organic film that is covalently bonded to the base glass plate through Si at the other end contains at least O, or has a reactive functional group at one end and is covalently bonded to the transparent fine particle surface through Si at the other end. The organic film containing at least O, the reactive functional group at one end, and the organic film covalently bonded to the substrate glass plate via Si at the other end are at least N and covalently bonded to each other. It is a water-repellent glass plate characterized.

A sixth invention is the water-repellent coating according to the second invention, and an organic film which has a reactive functional group at one end and is covalently bonded to the surface of the transparent fine particle via Si at the other end and / or at one end. The water-repellent glass plate is characterized in that an organic film containing a reactive functional group and covalently bonded to the base glass plate via Si at the other end is a monomolecular film.

A seventh invention is a water-repellent glass plate according to the first to seventh inventions, wherein the transparent fine particles are translucent silica, alumina, or zirconia.

An eighth invention is a water-repellent glass plate according to the first to seventh inventions, wherein the size of the transparent fine particles is at least smaller than the wavelength of visible light.

A ninth invention is the water-repellent glass plate according to any one of the first to eighth inventions, wherein a contact angle with respect to water is controlled to 150 degrees or more.

A tenth aspect of the present invention is the vehicle according to any one of the first to ninth aspects, wherein the water-repellent glass is attached.

An eleventh aspect of the invention is a glass window for a building according to any one of the first aspect to the ninth aspect, wherein water-repellent glass is attached.

According to a twelfth aspect of the present invention, an epoxy group or imino group is prepared by bringing a glass plate into contact with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. It is a manufacturing method of the reactive glass plate characterized by including the process of reacting the alkoxysilane compound containing this, and the glass plate surface.

   In a thirteenth invention, transparent fine particles are dispersed in a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an imino group or an epoxy group, a silanol condensation catalyst, and a non-aqueous organic solvent, and an imino group or A method for producing reactive transparent fine particles, comprising a step of reacting an alkoxysilane compound containing an epoxy group with the surface of the transparent fine particles.

In the fourteenth aspect of the invention, at least an epoxy group or an alkoxysilane compound containing an imino group, a silanol condensation catalyst, and a non-aqueous organic solvent are mixed to bring a glass plate into contact with an epoxy group, or A process of producing an epoxy group or a reactive glass plate containing an imino group by reacting an alkoxysilane compound containing an imino group with the surface of the glass plate, an alkoxysilane compound containing an imino group or an epoxy group, and a silanol condensation catalyst Transparent fine particles are dispersed in a chemisorbed liquid prepared by mixing a non-aqueous organic solvent with an imino group or an epoxy group by reacting an alkoxysilane compound containing an imino group or an epoxy group with the surface of the transparent fine particle. A process for producing reactive transparent fine particles containing, a reactive glass plate containing the epoxy group, and an imino group. A step of bringing the reactive transparent fine particles or reactive glass plate containing imino groups into contact with the reactive transparent fine particles containing epoxy groups and heating to bond the reactive glass plate and the reactive transparent fine particles; Prepared by mixing a chlorosilane compound containing a fluorocarbon group and trichlorosilyl group and a non-aqueous organic solvent, or mixing an alkoxysilane compound containing a fluorocarbon group and alkoxysilyl group, a silanol condensation catalyst, and a non-aqueous organic solvent. And a step of forming a water-repellent film by bringing the chemically adsorbed liquid into contact with a glass plate having transparent fine particles bonded to the surface thereof.

According to a fifteenth invention, in the fourteenth invention, a glass plate is attached to a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or an imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of producing an epoxy group or a reactive glass plate containing an imino group by reacting an alkoxysilane compound containing an epoxy group or imino group with a glass plate surface, and an imino group or an epoxy group Dispersing transparent fine particles in a chemical adsorption solution prepared by mixing an alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and reacting the surface of the transparent fine particles with an alkoxysilane compound containing an imino group or an epoxy group. A process for producing reactive transparent fine particles containing an imino group or an epoxy group, and a reactive glass containing the epoxy group A plate and the reactive transparent fine particle containing the imino group, or a reactive glass plate containing the imino group and the reactive transparent fine particle containing the epoxy group are brought into contact with each other and heated to bring the reactive glass plate and the reactive transparent fine particle into contact with each other. Step of bonding, chlorosilane compound containing fluorocarbon group and trichlorosilyl group and non-aqueous organic solvent are mixed, or alkoxysilane compound containing fluorocarbon group and alkoxysilyl group, silanol condensation catalyst and non-aqueous type In the process of forming a water-repellent coating by contacting a chemical adsorption solution prepared by mixing organic solvents with a glass plate having transparent fine particles bonded to the surface, excess chemical adsorption solution is washed away. It is a manufacturing method of a water-repellent glass plate.

The sixteenth invention is the twelfth to fifteenth invention, wherein at least selected from a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound as a co-catalyst for the silanol condensation catalyst. The method for producing a water-repellent glass sheet according to claim 9, wherein one is used in combination.

Hereinafter, the gist of the above invention will be described. The present invention relates to a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or an imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. A reactive glass plate containing an epoxy group or an imino group by reacting an alkoxysilane compound containing an epoxy group or an imino group with a glass plate surface, and an alkoxy containing an imino group or an epoxy group Transparent fine particles are dispersed in a chemical adsorption solution prepared by mixing a silane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the surface of the transparent fine particles is reacted with an alkoxysilane compound containing an imino group or an epoxy group. Or the process of manufacturing the reactive transparent fine particle containing an epoxy group, and the reactive glass containing the said epoxy group And the reactive transparent fine particle containing the imino group, or the reactive glass plate containing the imino group and the reactive transparent fine particle containing the epoxy group are brought into contact with each other and heated to bond the reactive glass plate and the reactive transparent fine particle. Or a step of mixing a chlorosilane compound containing a fluorocarbon group and trichlorosilyl group and a non-aqueous organic solvent, or an alkoxysilane compound containing a fluorocarbon group and alkoxysilyl group, a silanol condensation catalyst, and a non-aqueous type solvent. It is covered with water-repellent transparent fine particles covalently bonded to the surface by contacting a chemical adsorption solution prepared by mixing an organic solvent with a glass plate having transparent fine particles bonded to the surface to form a water-repellent coating. The gist of the invention is to provide a water-repellent glass plate that is highly durable and excellent in water-drop separation (also referred to as water slidability).

The water-repellent glass plate mounted with the highly durable and water-repellent water-repellent glass plate as a window glass, wherein the surface of the water-repellent glass plate is made of water-repellent transparent fine particles covalently bonded to the glass plate surface. The gist of the invention is to provide a vehicle such as an automobile or a glass window of a building that is covered and whose water contact angle is controlled to 150 degrees or more.

  At this time, the surface of most of the water-repellent transparent fine particles covalently bonded to the surface is covered with a water-repellent coating, and one part contains a reactive functional group at one end and the other surface through Si at the other end When covalently bonded to the glass plate surface via an organic film covalently bonded to the organic film and a reactive functional group at one end and an organic film covalently bonded to the base glass plate via Si at the other end It is convenient for improving durability.

In addition, it is convenient to improve durability and water repellency when at least the water-repellent coating is covalently bonded to the surface of the transparent fine particles.
Furthermore, it is convenient for improving the water repellency that the water-repellent coating on the surface of the transparent fine particles contains —CF ₃ groups.

Furthermore, the organic film covalently bonded to the surface of the transparent fine particle via Si at one end and containing a reactive functional group at one end contains at least N and contains a reactive functional group at one end via Si at the other end. The organic film covalently bonded to the substrate glass plate contains at least O, or the organic film covalently bonded to the surface of the transparent fine particle via Si at one end and a reactive functional group at the other end is at least O. It is convenient for improving the durability when the organic film having a reactive functional group at one end and being covalently bonded to the base glass plate through Si at the other end and at least N is covalently bonded to each other. Good.

In addition, a water-repellent film, an organic film having a reactive functional group at one end and covalently bonding to the surface of the transparent fine particle through Si at the other end, Si having a reactive functional group at one end and Si at the other end When at least one of the organic films covalently bonded to the base glass plate is a monomolecular film, it is convenient to improve water repellency and durability.

Furthermore, it is convenient to improve the wear resistance of the water-repellent coating by using light-transmitting and high hardness silica, alumina, or zirconia as the transparent fine particles.

Further, when the size of the transparent fine particles is at least smaller than the wavelength of visible light, it is convenient for improving the transparency.

In addition, at the time of production, a glass plate is brought into contact with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent, and contains an epoxy group or imino group. A process of producing an epoxy group or an imino group-containing reactive glass plate by reacting an alkoxysilane compound and the glass plate surface; an imino group or an alkoxysilane compound containing an epoxy group; a silanol condensation catalyst; and a non-aqueous system. Reactive transparent particles containing imino groups or epoxy groups by dispersing transparent fine particles in a chemical adsorption solution prepared by mixing organic solvents and reacting the surface of the transparent fine particles with an alkoxysilane compound containing imino groups or epoxy groups. A step of producing fine particles, a reactive glass plate containing the epoxy group and a reactivity containing the imino group A step of bringing the reactive glass plate containing bright fine particles or imino groups into contact with the reactive transparent fine particles containing the epoxy group and heating to bond the reactive glass plate and the reactive transparent fine particles; Chemistry made by mixing a chlorosilane compound containing a trichlorosilyl group and a non-aqueous organic solvent, or a mixture of an alkoxysilane compound containing a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a non-aqueous organic solvent. In the process of forming a water-repellent film by contacting the adsorbent with a glass plate with transparent fine particles bonded to the surface, it is convenient to improve the water repellency, transparency, and durability by washing and removing excess chemical adsorbent. Is good.

Further, instead of a silanol condensation catalyst, or as a cocatalyst, at least one selected from ketimine compounds, or organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, aminoalkylalkoxysilane compounds, alone or in combination, The use of an alkoxysilane compound is advantageous because the reaction time can be shortened.

  As described above, according to the present invention, in glass plates for automobiles and buildings that require water and oil repellent and antifouling functions, durability such as abrasion resistance and weather resistance, water droplet separation (both water slidability) It has the effect of providing a water-repellent glass plate excellent in antifouling property and an automobile using the same.

In the present invention, a glass plate is brought into contact with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. A process for producing a reactive glass plate containing an epoxy group or an imino group by reacting the alkoxysilane compound containing the glass plate surface, an alkoxysilane compound containing an imino group or an epoxy group, a silanol condensation catalyst and a non-aqueous system Dispersion of transparent fine particles in a chemisorbed liquid prepared by mixing organic solvents with the reaction of an alkoxysilane compound containing an imino group or epoxy group with the surface of the transparent fine particle to react with an imino group or an epoxy group A step of producing transparent fine particles, a reactive glass plate containing the epoxy group and a reactivity containing the imino group A step of bringing the reactive glass plate containing bright fine particles or imino groups into contact with the reactive transparent fine particles containing the epoxy group and heating to bond the reactive glass plate and the reactive transparent fine particles; Prepared by mixing a chlorosilane compound containing a trichlorosilyl group and a nonaqueous organic solvent, or mixing an alkoxysilane compound containing a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent. A water-repellent glass plate covered with water-repellent transparent fine particles covalently bonded to the surface is provided by contacting the chemically adsorbed liquid with a glass plate having transparent fine particles bonded to the surface to form a water-repellent coating. Is.

  Therefore, in the present invention, for glass plates for automobiles and buildings that require water and oil repellent and antifouling functions, durability such as wear resistance and weather resistance, water droplet water separation (also referred to as water slidability), It has the effect of providing a water-repellent glass plate with excellent dirtiness and an automobile with excellent visibility outside the vehicle when running in the rain. In addition, it is possible to provide a window that can achieve the same effect in a building window.

  Hereinafter, although the detail of this invention is demonstrated using an Example, this invention is not restrict | limited at all by these Examples.

  In addition, although the glass regarding this invention has the glass plate for vehicles, such as vehicles, and a window of a building, the window glass of a motor vehicle is taken up and demonstrated as a typical example below.

  First, the glass plate 1 used for a window glass for automobiles was prepared, washed well and dried. Next, a functional functional group reactive as a chemical adsorbent, for example, an agent having an epoxy group at one end and an alkoxysilyl group at the other end, for example, 99 wt% of an agent represented by the following chemical formula (Formula 1), As the silanol condensation catalyst, for example, each of dibutyltin diacetylacetonate is weighed so as to be 1% by weight, and a total concentration of about 1% by weight in a silicone solvent, for example, hexamethyldisiloxane solvent (preferably the concentration of the chemical adsorbent is , About 0.5 to 3%) to prepare a chemical adsorption solution.

This adsorbed liquid was applied to the surface of the glass plate 1 and allowed to react for about 2 hours in normal air (relative humidity 45%). At this time, since the surface of the glass plate 1 contains a large number of hydroxyl groups 2 (FIG. 1A), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group 2 are silanol condensation catalysts. Chemical adsorption including epoxy groups chemically bonded to the surface over the entire glass surface by reacting in the presence of alcohol (in this case, de-CH ₃ OH) to form bonds as shown in the following chemical formula (Chemical Formula 2) The monomolecular film 3 is formed with a film thickness of about 1 nanometer.

Thereafter, when the substrate was washed with a chlorine-based solvent such as chloroform, a glass plate 4 covered with a chemically adsorbed monomolecular film having a reactive epoxy group on the surface could be produced (FIG. 1 (b)).

If it is taken out and left in the air without washing, the solvent is evaporated and the chemical adsorbent remaining on the surface of the glass plate reacts with moisture in the air on the surface of the glass plate, and the particle surface is made of the above-mentioned chemical adsorbent. A polymer film was formed. Even with this coating, the reactivity was hardly changed.

On the other hand, alumina fine particles 5 having an average particle size smaller than the wavelength of visible light and about 100 nm were prepared and dried well. Next, an agent containing an imino group (—NH) that reacts with an epoxy group at the functional site as a chemical adsorbent and an alkoxysilyl group at the other end, for example, the following chemical formula containing an amino group at the terminal Weighing 99% by weight of the drug and 1% by weight of acetic acid, which is an organic acid instead of the silanol condensation catalyst, a solvent in which the same amount of silicone and dimethylformamide are mixed, for example, 50% hexamethyldisiloxane and dimethylformamide A chemical adsorption solution was prepared by dissolving in a 50% solution to a total concentration of about 1% by weight (preferably the concentration of the chemical adsorbent is about 0.5 to 3%).

The adsorbed liquid was mixed with the anhydrous alumina fine particles and stirred and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the surface of the alumina fine particle 5 contains a large number of hydroxyl groups 6 (FIG. 2A), the —Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are removed in the presence of acetic acid. A chemisorbed monomolecular film containing an amino group 7 chemically bonded to the surface over the entire surface of the fine particles by forming a bond as shown in the following chemical formula (Chemical Formula 4) by reacting with alcohol (in this case, de-CH ₃ OH) 8 is formed with a film thickness of about 1 nanometer.

Thereafter, when chloroform or n-methylpyrrolidinone as a chlorinated solvent is added and washed with stirring, as in Example 1, the surface is coated with a chemisorbed monomolecular film having a reactive functional group such as an amino group on the surface. The broken alumina fine particles 9 could be formed (FIG. 2B). Here, when an adsorbent containing an amino group is used, it is better to use an organic acid such as acetic acid because a precipitate is generated in the tin-based catalyst. The amino group contains an imino group, but pyrrole derivatives, imidazole derivatives, and the like can be used as substances containing imino groups in addition to amino groups. Furthermore, when a ketimine derivative was used, an amino group could be easily introduced by hydrolysis after film formation.

In addition, since the monomolecular film formed by this treatment was extremely thin with a film thickness of nanometer level as in Example 1, the particle diameter and surface shape of the alumina fine particles were not impaired.
Note that the reactivity does not substantially change when it is taken out into the air without washing, but the chemical adsorbent remaining on the particle surface reacts with the moisture in the air on the particle surface, and the chemical is adsorbed on the particle surface. Alumina fine particles on which an ultrathin polymer film made of an adsorbent was formed were obtained.

Next, the alumina fine particles covered with the chemical adsorption monomolecular film having amino groups are dispersed and applied to the surface of the glass plate covered with the chemical adsorption monomolecular film having the epoxy group, and the ethanol is evaporated. Then, when heated at about 100 ° C. for about 30 minutes, an epoxy group and an amino group undergo an addition reaction by the reaction shown in the following chemical chemical formula (Chemical Formula 5), and the glass and alumina fine particles pass through two monomolecular films. And fixed.
Thereafter, further washing with an organic solvent such as chloroform removes the alumina fine particles covered with the chemisorption monomolecular film having an extra unreacted amino group, and the surface of the glass plate 1 and the alumina fine particles 5 become the two monomolecules. A glass plate 10 in which only one layer was covalently bonded through the membrane was obtained (FIG. 3A).

Next, when a monomolecular film is formed, a chemical adsorbent containing a fluorocarbon group (functional site) and a chlorosilyl group (active site) that has a critical surface energy of 10 mN / m or less, such as CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ was dissolved in a non-aqueous solvent (for example, dehydrated nonane) at a concentration of about 1% by weight to prepare a chemical adsorption solution (hereinafter referred to as an adsorption solution). This adsorption solution, when in a dry atmosphere (a relative humidity of 30% or less were preferred.) In applied to the glass plate surface to react, covered alumina fine particles 4 of the glass plate 4 surface in a number of amino groups 7 (FIG. 3 (a)), a dehydrochlorination reaction occurs between the chlorosilyl group (SiCl) group of the chemical adsorbent and the amino group (—NH ₂ ) on the surface of the alumina fine particles. A bond represented by the following chemical formula (Formula 6) is formed. Next, when washed with a fluorocarbon solvent, a glass plate 12 covered with a water-repellent monomolecular film 11 made of the chemical adsorbent was obtained.

When taken out into the air without cleaning, the chemical adsorbent remaining on the glass plate surface reacts with moisture in the air when the solvent evaporates, and the ultrathin polymer consisting of the chemical adsorbent on the particle surface. A film was formed. Even with this coating, the water repellency was hardly changed.

Since the film thickness of this monomolecular film is at most about 1 nm, the unevenness of about 50 nm on the surface of the glass plate formed by the alumina fine particles was hardly damaged. Also, due to the unevenness effect, the apparent water droplet contact angle of this glass plate was about 160 degrees, and super water repellency was realized.

The critical surface energy of a monomolecular film made of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ on the flat substrate surface is about 6 mN / m, and the maximum water droplet contact angle is 115 degrees. It was about.

On the other hand, alumina fine particles have a higher hardness than glass and are bonded to the glass plate surface by covalent bonds, so they are made directly on the glass plate surface using CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl _3. Compared to the monomolecular film, the wear resistance was greatly improved.
Further, since the total thickness of the coating film was about 100 nm, the transparency was not impaired.

As in Example 1, after preparing a glass plate in which only one layer of alumina fine particles was covalently bonded to the surface of the glass plate, a drug containing a fluorocarbon group (—CF ₃ ) at one end and an alkoxysilyl group at the other end, For example, 99% by weight of the chemical represented by CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ and 1% by weight of dibutyltin diacetylacetonate, for example, using silanol condensation catalyst Then, a chemical adsorption solution is prepared by dissolving in a silicone solvent, for example, a hexamethyldisiloxane solvent to a concentration of about 1% by weight (preferably the concentration of the chemical adsorbent is about 0.5 to 3%). After immersing a glass plate in which only one layer of alumina fine particles is covalently bonded to the glass plate and reacting for about 2 hours, the excess adsorbent is washed and removed. Thus, the same water-repellent glass as in Example 1 could be produced.

On the other hand, in the same manner as in Example 1, a chemisorption monomolecular film having an amino group is formed on the glass plate surface in the same manner, and a chemisorption monomolecular film having an epoxy group is formed on the surface of the alumina fine particles. Then, when one layer of alumina fine particles is fixed on the glass plate surface and finally CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ is reacted, the SiCl group also reacts with the epoxy group. The water-repellent glass can be manufactured.

In Examples 1 to 3, the substances shown in (Chemical Formula 1) and (Chemical Formula 3) were used as chemical adsorbents containing reactive groups, but in addition to the above, the following (1) to ( The substances shown in 16) were available.
(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(2) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(3) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(6) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
(7) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) _{3
(8) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(9) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(11) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(12) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(15) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(16) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) — group represents a functional group represented by the following formula (Chemical Formula 7), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by the following formula (Chemical Formula 8). Represents a functional group.

In Examples 1 and 3, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ was used as the fluorocarbon-based chemical adsorbent, but in addition to the above, hydrocarbons were included. The substances shown in the following (21) to (26) were available.
(21) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(22) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(23) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(24) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(25) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(26) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
Furthermore, in Example 2 above, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ was used as the fluorocarbon-based chemical adsorbent. The materials shown in () to (42) were available.

(31) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(32) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(33) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(34) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(35) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(36) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(37) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(38) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(39) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(40) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(41) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(42) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

In Examples 1 to 3, silanol condensation catalysts include 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. Is available. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate could be used.

In addition, as a solvent for the film-forming solution, an organic chlorine-based solvent, a hydrocarbon-based solvent, a fluorocarbon-based solvent or a silicone-based solvent that does not contain water, regardless of whether the chemical adsorbent is an alkoxysilane-based or chlorosilane-based Alternatively, it was possible to use a mixture thereof. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC.

Specific solvents that can be used are non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl in the case of chlorosilane. Examples include silicone, alkyl-modified silicone, polyether silicone, and dimethylformamide.
Further, when the adsorbent is an alkoxysilane type and the organic film is formed by evaporating the solvent, an alcohol type solvent such as methanol, ethanol, propanol, or a mixture thereof can be used in addition to the solvent.

Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.

On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the treatment time is reduced to about half to 2/3 even at the same concentration. did it.

Further, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The processing time can be further shortened several times, and the film forming time can be reduced to a fraction.

For example, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 1 hour. Results were obtained.

Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio was 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 20 minutes.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity is further increased when one of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is mixed with a silanol condensation catalyst.

Here, the ketimine compound that can be used is not particularly limited. For example, 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-pentadeca Diene, 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.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

In the above three embodiments, the alumina fine particles have been described as an example. However, the present invention is not limited as long as the surface contains active hydrogen, that is, fine particles containing hydrogen of a hydroxyl group, an amino group, or hydrogen of an imino group. It was applicable to any fine particles.

Specifically, it goes without saying that silica, zirconia, and the like can be applied as transparent fine particles harder than glass in addition to alumina.

A water-repellent glass plate having a water droplet contact angle of about 160 degrees (similar effect was obtained if the water droplet contact angle was 150 or more for practical use) prepared under the same conditions as the glass plate prepared in Example 1 was used for passenger cars. A front window glass (also referred to as a windshield, tilt angle of about 45 degrees), a side window glass (tilt angle of about 70 degrees), and a rear window glass (tilt angle of about 30 degrees) were mounted, and a rainy running experiment was attempted.

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

Next, a running experiment was attempted. First, when the speed was 45 km / hour, the adhesion of raindrops was confirmed. There was almost no adhesion of water droplets having a diameter of about 2 mm or more on the side window glass and the rear window glass. Also, on the windshield, a large amount of raindrops adhered continuously during traveling, but water droplets with a diameter of about 2 mm or more moved quickly upward and rearward, and did not remain so as to scatter and obstruct visibility. . 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 the running experiment, the rear view was confirmed through a side window glass plate using a door mirror, but there was almost no visual distortion or visibility deterioration due to raindrops.

In addition, we compared external visibility with or without a coating in fine weather, but the transparency of the coating was 97% or more with respect to light with a wavelength of 400 to 700 nm. Was not felt at all. 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 the automobile of the present invention exerts a special effect on safe driving in rainy weather.

As a reference, FIG. 3 shows the relationship between the contact angle (including data obtained using other substances) with respect to water droplets obtained in various experiments and the falling angle. As is clear from this data, it can be seen that, when the water droplet contact angle is 150 degrees or more, most water droplets in contact with the window glass surface flow down naturally.

In Example 1 of this invention, it is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the monomolecular film containing an epoxy group on the glass surface, (a) is the figure of the glass surface before reaction, ( b) shows the figure after the monomolecular film containing an epoxy group is formed. BRIEF DESCRIPTION OF THE DRAWINGS It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the monomolecular film containing an amino group in the alumina fine particle surface in Example 1 of this invention, (a) is the figure of the glass surface before reaction, ( b) shows the figure after the monomolecular film containing amino groups has been formed. In Example 1 of the present invention is a conceptual diagram enlarged to the molecular level in order to explain the step of binding alumina fine particles to the glass substrate surface and further forming a water-repellent monomolecular film on the surface of the alumina fine particles, (A) is the figure which the glass substrate surface and the alumina fine particle couple | bonded, (b) shows the figure after the water-repellent monomolecular film was formed through the amino group. The figure which plotted the data obtained by the preliminary experiment in performing this invention, and showed the relationship between the contact angle with respect to water, and a fall angle.

Explanation of symbols

1 Glass plate 2 Hydroxyl group 3 Monomolecular film containing epoxy group
4 Glass plate covered with chemisorption monomolecular film containing epoxy group 5 Alumina fine particles 6 Hydroxyl group 7 Amino group 8 Chemisorption monomolecular film containing amino group
Alumina fine particles covered with a chemisorbed monolayer containing 9 amino groups
10 A glass plate in which only one layer of alumina fine particles is covalently bonded through two monomolecular films 11 Water repellent monomolecular film
12 Glass plate covered with water-repellent monomolecular film

Claims (16)

A water-repellent glass plate which is covered with water-repellent transparent fine particles covalently bonded to the surface. The surface of most of the water-repellent transparent fine particles covalently bonded to the surface is covered with a water-repellent coating, and one part contains a reactive functional group at one end and is covalently bonded to the surface of the transparent fine particle via Si at the other end. It is covalently bonded to the surface of the substrate glass plate through an organic film that has a reactive functional group at one end and an organic film that is covalently bonded to the substrate glass plate through Si at the other end. The water-repellent glass plate according to claim 1, wherein The water repellent glass plate according to claim 2, wherein at least the water repellent coating is covalently bonded to the surface of the transparent fine particles. 4. The water-repellent glass plate according to claim 3, wherein the water-repellent coating on the surface of the transparent fine particles contains —CF ₃ groups. An organic film that includes a reactive functional group at one end and is covalently bonded to the surface of the transparent fine particle via Si at the other end includes at least N, and includes a reactive functional group at one end and a substrate via Si at the other end. The organic film covalently bonded to the glass plate contains at least O, or the organic film covalently bonded to the transparent fine particle surface via Si at one end and reactive functional group at the other end. The organic film including a reactive functional group at one end and covalently bonding to the base glass plate via Si at the other end includes at least N and is covalently bonded to each other. The water-repellent glass plate described. A water-repellent coating and an organic film containing a reactive functional group at one end and covalently bonded to the surface of the transparent fine particle through Si at the other end and / or a reactive functional group at one end and Si at the other end The water-repellent glass plate according to claim 2, wherein the organic film covalently bonded to the substrate glass plate via a monomolecular film is a monomolecular film. 7. The water-repellent glass plate according to claim 1, wherein the transparent fine particles are translucent silica, alumina, or zirconia. The water repellent glass plate according to claim 1, wherein the size of the transparent fine particles is at least smaller than the wavelength of visible light. 9. The water-repellent glass plate according to claim 1, wherein a contact angle with water is controlled to 150 ° or more. 10. A vehicle equipped with the water-repellent glass according to claim 1. 10. A window glass of a building equipped with the water-repellent glass according to claim 1.
A glass plate is brought into contact with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent, and an alkoxysilane compound containing an epoxy group or imino group and glass. A method for producing a reactive glass plate, comprising a step of reacting a plate surface. An alkoxysilane containing an imino group or an epoxy group in which transparent fine particles are dispersed in a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an imino group or an epoxy group, a silanol condensation catalyst, and a non-aqueous organic solvent. A method for producing reactive transparent fine particles, comprising a step of reacting a compound and the surface of transparent fine particles. An alkoxysilane compound containing an epoxy group or imino group by contacting a glass plate with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. A reactive glass plate containing an epoxy group or an imino group by reacting the surface of the glass plate with an alkoxysilane compound containing an imino group or an epoxy group, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of producing reactive transparent fine particles containing an imino group or an epoxy group by dispersing transparent fine particles in a chemically adsorbed liquid prepared and reacting an alkoxysilane compound containing an imino group or an epoxy group with the surface of the transparent fine particles; A reactive glass plate containing the epoxy group and a reactive transparent fine particle containing the imino group, Contacting a reactive glass plate containing an imino group with the reactive transparent fine particles containing the epoxy group and heating to bond the reactive glass plate and the reactive transparent fine particles; and a fluorocarbon group and a trichlorosilyl group. A chemisorbed liquid and a surface prepared by mixing a chlorosilane compound containing nitrogen and a non-aqueous organic solvent, or mixing an alkoxysilane compound containing a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a non-aqueous organic solvent. And a step of forming a water-repellent film on the surface by contacting a glass plate to which transparent fine particles are bonded. An alkoxysilane compound containing an epoxy group or imino group by contacting a glass plate with a chemical adsorption solution prepared by mixing an alkoxysilane compound containing at least an epoxy group or imino group, a silanol condensation catalyst, and a non-aqueous organic solvent. And a process for producing a reactive glass plate containing an epoxy group or an imino group by reacting the surface of the glass plate with an alkoxysilane compound containing an imino group or an epoxy group, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of producing reactive transparent fine particles containing an imino group or an epoxy group by dispersing transparent fine particles in a chemically adsorbed liquid prepared and reacting an alkoxysilane compound containing an imino group or an epoxy group with the surface of the transparent fine particles; A reactive glass plate containing the epoxy group and a reactive transparent fine particle containing the imino group, Contacting a reactive glass plate containing an imino group with the reactive transparent fine particles containing the epoxy group and heating to bond the reactive glass plate and the reactive transparent fine particles; and a fluorocarbon group and a trichlorosilyl group. A chemisorbed liquid and a surface prepared by mixing a chlorosilane compound containing nitrogen and a non-aqueous organic solvent, or mixing an alkoxysilane compound containing a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a non-aqueous organic solvent. 15. The method for producing a water-repellent glass plate according to claim 14, wherein in the step of forming a water-repellent coating by contacting a glass plate to which transparent fine particles are bonded, excess chemical adsorption solution is washed away. 16. The co-catalyst used for the silanol condensation catalyst is a ketimine compound, or at least one selected from organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds. A method for producing the water-repellent glass plate as described.

Images