JP2008247700A - Water-repellent, oil-repellent contamination preventive antireflection film and method for manufacturing the same, and lens, glass sheet, glass, optical equipment, device using solar energy, and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent, oil-repellent contamination preventive antireflection film having water-repellent, oil-repellent and contamination preventive properties, water drop release property and durability, and a method for manufacturing the film, to provide a lens, a glass sheet and glass having the water-repellent, oil-repellent contamination preventive antireflection film formed thereon, and to provide optical equipment, a device using solar energy and a display using them. <P>SOLUTION: The water-repellent, oil-repellent contamination preventive antireflection film 12 includes: water-repellent, oil-repellent contamination preventive transparent fine particles 5 melt sticking to the surface of a planar base 1; and a coating 11 of a water-repellent, oil-repellent contamination preventive substance covering a part of the base 1 where the transparent fine particles 1a are not melt sticking. The transparent fine particles 5 are melt sticking in a part of their surfaces to the surface of the base 1, while the other exposed part is covered with the water-repellent, oil-repellent contamination preventive coating 11. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a highly durable, water- and oil-repellent antifouling antireflection film and a method for producing the same, a lens, a glass plate, glass having a water-repellent, oil-repellent and antifouling antireflection film formed on the surface, glass, The present invention relates to an optical device, a solar energy utilization device, and a display on which they are mounted.

It is already well known that when a solution of a chlorosilane compound having a fluorocarbon group is brought into contact with the surface of a glass substrate, a monomolecular film-like water-repellent coating can be formed by a surface reaction (see, for example, Patent Document 1). .
The principle of production of such a water-repellent coating is to form a siloxane bond by a dehydrochlorination reaction between active hydrogen such as a hydroxyl group (silanol group) on the surface of the glass substrate and a chlorosilyl group.

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 provides a lens for an optical device that requires a water / oil repellent / antifouling function, a surface glass plate of a solar energy utilization device such as a solar cell or a solar water heater, or a display face plate such as a CRT, PDP, or LCD. The purpose of the glass is to provide an antireflection function and to improve durability such as wear resistance and weather resistance, water drop water separation (also referred to as water slidability), oil repellency, and antifouling properties.

The water / oil repellent / antifouling antireflective coating according to the first invention provided as means for solving the above-mentioned problems comprises water / oil repellent / antifouling transparent fine particles fused to the surface of a glass substrate. Including.
Here, “fusion” refers to a state where a glass substrate and a part of transparent fine particles are bonded together by eutectic fusion.

In the water / oil repellent / antifouling antireflection film according to the first invention, it is preferable that the transparent fine particles having different particle diameters are mixed and used.

In the water / oil repellent / antifouling antireflection film according to the first aspect of the invention, it is preferable that the water / oil repellent / antifouling coating is covalently bonded to at least the surface of the transparent fine particles.

In the water / oil repellent / antifouling antireflection film according to the first aspect of the invention, it is preferable that the water / oil repellent / antifouling coating contains a —CF ₃ group.

In the water- and oil-repellent and antifouling antireflection film according to the first invention, the transparent fine particles are preferably translucent and any one of silica, alumina, and zirconia having a higher softening point than the glass substrate. .

In the water / oil repellent / antifouling antireflection film according to the first invention, the transparent fine particles preferably have a particle size of less than 400 nm.

In the water / oil repellent / antifouling antireflection film according to the first aspect of the invention, the contact angle with respect to water is preferably 140 degrees or more.

In the water / oil repellent / antifouling antireflection film according to the first aspect of the invention, the transparent fine particles are formed through the metal oxide transparent film fused to the transparent fine particles at a temperature lower than that of the glass substrate. It may be fused to the surface of the substrate.

The lens according to the second invention has the water / oil repellent antifouling antireflection film according to the first invention formed on the surface thereof.
The glass plate according to the third invention has the water / oil repellent / antifouling antireflection film according to the first invention formed on the surface thereof.
The glass according to the fourth invention has the water / oil repellent / antifouling antireflection film according to the first invention formed on the surface thereof.
An optical device according to a fifth aspect of the present invention is equipped with a lens on which the water / oil / oil repellent antifouling antireflection film according to the first aspect is formed.
A solar energy utilization apparatus according to a sixth aspect is equipped with a glass plate on which the water / oil / oil repellent / antifouling antireflection film according to the first aspect is formed.
A display according to a seventh aspect is equipped with a glass on which the water / oil / oil repellent / antifouling antireflection film according to the first aspect is formed.

According to an eighth aspect of the present invention, there is provided a method for producing a water / oil / oil repellent antifouling antireflective film, wherein a first chemical adsorption solution containing a first silane compound containing a first functional group and a non-aqueous organic solvent is glass. A reactive glass group that is brought into contact with a substrate and whose surface is covered with a monomolecular film of the first silane compound by a reaction between the silyl group of the first silane compound and the active hydrogen group on the surface of the glass substrate. A second chemisorbed solution comprising a step A for producing a material, a second silane compound containing a second functional group that reacts with the first functional group to form a covalent bond, and a non-aqueous organic solvent Reactive transparent in which transparent fine particles are dispersed therein and the surface is covered with a monomolecular film of the second silane compound by the reaction of the silyl group of the second silane compound and the active hydrogen group on the surface of the transparent fine particle Step B for producing fine particles;
Heating the reactive glass substrate and the reactive transparent fine particles in contact with each other to react the first functional group and the second functional group, and forming the transparent fine particles through the formed covalent bond The glass substrate having the surface bonded to the surface C, and the glass substrate having the transparent fine particles bonded to the surface in the step C are heat-treated in an atmosphere containing oxygen, and the surface of the glass substrate A step D for producing a glass substrate having a surface covered with the fused transparent fine particles, a third silane compound containing a fluorocarbon group, and a non-aqueous organic solvent. The third chemical adsorption liquid containing was brought into contact with the glass substrate whose surface was covered with the fused transparent fine particles, and the surface was covered with the fused silyl groups of the third silane compound and the fused transparent fine particles. By reaction with active hydrogen groups on the surface of glass substrate Serial and a step E of forming a water-repellent, oil-repellent, soil-resistant coating formed of fluorocarbon group.
The “active hydrogen group” refers to any functional group that forms a bond with a silyl group by a condensation reaction.

In the method for producing a water / oil / oil repellent antifouling antireflection film according to the eighth invention, one of the first and second functional groups may be an epoxy group and the other may be an amino group or an imino group.

In the method for producing a water / oil repellent antifouling antireflective film according to the eighth invention, in any one of 1, 2 or 3 of the steps A, B and E, the silyl group and the active hydrogen group After the reaction, unreacted substances are removed by washing.
The “reaction between the silyl group and the active hydrogen group” refers to the reaction between the silyl group of the first silane compound and the active hydrogen group on the surface of the glass substrate in the step A, and the reaction in the step B. The surface of the glass substrate whose surface is covered with the transparent fine particles fused with the silyl group of the third silane compound in the step E in the reaction between the silyl group of the silane compound 2 and the active hydrogen group on the surface of the transparent fine particles. Means a reaction with an active hydrogen group. Further, the “unreacted substance” means an unreacted first silane compound in the step A, an unreacted second silane compound in the step B, and an unreacted third silane compound in the step E. Means each.

In the method for producing a water / oil / oil repellent antifouling antireflection film according to the eighth invention, before the step A, a transparent coating of metal oxide which is fused to the transparent fine particles at a temperature lower than that of the glass substrate. Step F may be further formed on the surface of the glass substrate.
In the present invention, “metal” includes so-called semi-metal elements such as boron (B) and silicon (Si).
It is preferable to use a sol-gel method for forming the transparent film in the step F.

In the method for producing a water / oil repellent antifouling antireflection film according to the eighth invention, the first, second and third silanes contained in the first, second and third chemical adsorption liquids, respectively. Any one, two, or three of the compounds may be an alkoxysilane compound.
The “alkoxysilane compound” refers to a silane compound having an alkoxysilyl group represented by the general formula —SiOR (R represents an alkyl group).

In the method for producing a water / oil repellent antifouling antireflection film according to the eighth invention, the first, second and third silanes contained in the first, second and third chemical adsorption liquids, respectively. Any one, two, or three of the compounds may be halosilane compounds.
The “halosilane compound” refers to a silane compound having a halosilyl group represented by the general formula —SiX (X represents any one of chlorine, bromine, and iodine).

In the method for producing a water / oil / oil repellent / antifouling antireflection film according to the eighth invention, the first, second and third chemical adsorption liquids containing the alkoxysilane compound are further carboxylic acid 1 or 2 or more compounds selected from the group consisting of metal salts, carboxylate metal salts, carboxylate metal salt polymers, carboxylate metal salt chelates, titanate esters and titanate ester chelates may be included as a condensation catalyst. Good.
In this case, it is preferable that the cocatalyst further includes 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 / oil / oil repellent / antifouling antireflection film according to the eighth invention, the first, second and third chemical adsorption liquids containing the alkoxysilane compound are ketimines as a condensation catalyst. One or more compounds selected from the group consisting of compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds may be further included.

According to the water- and oil-repellent and antifouling antireflection film according to claim 1 and the method for producing the water and oil repellent and antifouling antireflection film according to claims 15 to 24, the surface of the plate-like substrate Is covered with a coating of water- and oil-repellent antifouling transparent fine particles and a water-repellent oil-repellent antifouling substance, so that the surface of the base material is given water and oil repellent antifouling properties, water droplet separation and durability. can do.

The water / oil / oil repellent antifouling antireflection film according to claim 1, the lens according to claim 9, the glass plate according to claim 10, the glass according to claim 11, the optical device according to claim 12, 13. The solar energy utilization apparatus according to claim 13, the display according to claim 14, and the method for producing a water / oil / oil / repellency antifouling antireflection film according to claims 15 to 24, wherein Since the surface of the glass substrate is covered with the fused water- and oil-repellent and antifouling transparent fine particles, the water- and oil-repellent and antifouling antireflection film exhibits a complex surface shape with irregularities, and so High water and oil repellent antifouling property due to "lotus leaf effect".

In particular, since the water / oil / oil / repellency / antifouling antireflection film according to claim 2 is used by mixing transparent fine particles having different particle diameters, the surface shape of the water / oil / oil / repellency / antifouling antireflection film is fractal. The water and oil repellency and antifouling properties can be improved.

The water / oil repellent / antifouling antireflective coating according to claim 3 can improve the durability since the water / oil repellent / antifouling coating is covalently bonded to at least the surface of the transparent fine particles.

The water / oil repellent / antifouling antireflection film according to claim 4 can improve the water / oil repellent / antifouling property since the water / oil repellent / antifouling coating film contains —CF ₃ group.

The water / oil / oil repellent / antifouling antireflection film according to claim 5 is made of silica, alumina, or zirconia having transparent fine particles having a light-transmitting property and a softening point higher than that of the glass substrate, so that the shape of the fine particles is not impaired. Can be fused to the surface of the glass substrate.

The water / oil / oil repellent / antifouling antireflective film according to claim 6 has a transparent particle size of less than 400 nm, which is smaller than the wavelength of visible light, and therefore can hardly scatter visible light and maintain high translucency.

The water / oil / oil / repellency antifouling antireflection film according to claim 7 has a contact angle with respect to water of 140 ° or more, so that the drop angle of the water droplet becomes small and the water droplet does not substantially adhere.

9. The water / oil / oil repellent antifouling antireflection film according to claim 8, wherein the transparent fine particles are adhered to the surface of the glass substrate through a transparent film of metal oxide which is fused to the transparent fine particles at a temperature lower than that of the glass substrate. Since it is fused, thermal deformation of the transparent fine particles at the time of fusion is suppressed.

In the lens according to claim 9, the glass plate according to claim 10, and the glass according to claim 11, the surface is covered with a water-repellent / oil-repellent / antifouling antireflection film. It can impart antifouling properties, water droplet water separation and durability.

In the optical device according to claim 12, since the lens having the water / oil repellent / antifouling antireflective film formed thereon is mounted, the lens is provided with water / oil repellent / antifouling property, water-drop-off property, and Durability can be imparted. As a result, maintenance work of the optical device can be reduced and the life of the optical device can be extended.

In the solar energy utilization apparatus according to claim 13, since the glass plate having the water repellent / oil repellent / antifouling antireflection film formed thereon is mounted, the water / oil repellent / antifouling property, water droplets are attached to the glass plate. Water release and durability can be imparted. As a result, the absorption efficiency of sunlight is improved, the maintenance work is reduced, and the efficiency and operating rate of the solar energy utilization device are improved.

In the display according to claim 14, since the glass on which the water / oil repellent / antifouling antireflection film is formed is attached, the glass is provided with water / oil / oil repellent / antifouling property, water droplet repellent property, and durability. Sex can be imparted. As a result, a clear image can be seen on the display, and the maintenance work of the display (face plate cleaning work) can be reduced.

In the method for producing a water / oil / oil repellent antifouling antireflection film according to claims 15 to 24, the first functional group and the second functional group are reacted to form transparent fine particles on the surface via the formed covalent bond. A bonded glass substrate is manufactured, and then this is heat-treated to produce a glass substrate whose surface is covered with fused transparent fine particles, on which a water and oil repellent and antifouling film is formed. Therefore, it is possible to obtain a water / oil repellent antifouling antireflection film which is substantially uniformly covered with transparent fine particles over the entire surface and is excellent in visibility, transparency and durability.

The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 16, wherein one of the first and second functional groups is an epoxy group and the other is an amino group or an imino group. The glass substrate and the transparent fine particles can be firmly bonded and fixed through the covalent bond formed by the reaction between the functional groups.

In the method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 17, the unreacted material is washed away after the reaction between the silyl group and the active hydrogen group, so that the surface is covered with fused transparent fine particles. By forming only the water- and oil-repellent and antifouling film covalently bonded to the surface of the glass substrate, the water and oil and oil repellent and antifouling properties and durability of the water and oil and oil repellent and antireflective film can be improved. .

The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 18, wherein before step A, a step of forming a metal oxide transparent coating fused to transparent fine particles at a temperature lower than that of the glass substrate. Since it has F, the heat treatment in the step D can be performed at a lower temperature.

In the method for producing a water- and oil-repellent and antifouling antireflection film according to claim 19, since the sol-gel method is used for forming the transparent film, the transparent film can be easily formed.

The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 20, wherein any of the first, second and third silane compounds contained in the first, second and third chemical adsorption liquids, respectively. , 1, 2 or 3 is an alkoxysilane compound that does not generate harmful hydrogen chloride upon reaction with active hydrogen groups, so that it is safer to produce a water and oil repellent antifouling antireflective coating It is possible to suppress the corrosion of production equipment and the generation of acidic waste liquid.

The water / oil / oil repellent / antifouling antireflection film according to claim 21, wherein any of the first, second and third silane compounds contained in the first, second and third chemical adsorption liquids, respectively. 1, 2, or 3 is a halosilane compound that is highly reactive with active hydrogen groups, so that it is possible to produce a water- and oil-repellent antifouling antireflective coating more efficiently and to add a catalyst. Is no longer necessary.

The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 22, wherein the first, second and third chemical adsorption liquids containing an alkoxysilane compound are further used as a condensation catalyst as a carboxylic acid. Since it contains one or more compounds selected from the group consisting of metal salts, carboxylate metal salts, carboxylate metal salt polymers, carboxylate metal salt chelates, titanate esters and titanate ester chelates, alkoxysilane compounds and The reaction time with the active hydrogen group can be shortened, and the production of the water / oil / oil / antifouling antireflection film can be carried out more efficiently.

25. The method for producing a water- and oil-repellent and antifouling antireflection film according to claim 23 and 24, wherein the first, second and third chemical adsorption liquids containing an alkoxysilane compound are ketimine compounds, organic acids. 1 or 2 or more compounds selected from the group consisting of an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. The production of a water / oil repellent antifouling antireflection film can be carried out more efficiently. 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 antireflection film according to an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the water / oil repellent / antifouling antireflective coating 12 according to one embodiment of the present invention has a silica fine particle 5 (water repellent) having a water / oil repellent / antifouling coating 11 formed on the surface thereof. An example of the oil repellent antifouling transparent fine particles) has a structure fused to the surface of the glass substrate 1. The water / oil repellent / antifouling coating 11 is composed of a silane compound containing a perfluorooctyl group (CF ₃ (CF ₂ ) ₇ —), which is an example of a fluorocarbon group containing a CF ₃ group, and fused silica fine particles. It is covalently bonded to the surface by reaction with a hydroxyl group (an example of a functional group having active hydrogen (an active hydrogen group)) on the surface of the glass substrate 1a covered with the surface.

The method for producing the water / oil repellent / antifouling antireflection film 12 includes an alkoxysilane compound, which is an example of a first silane compound containing an epoxy group 3, which is an example of a first functional group, a condensation catalyst, and a non-aqueous system. A first chemical adsorption solution prepared by mixing an organic solvent is brought into contact with the glass substrate 1 and schematically shown in FIG. 2 (a) and an alkoxysilyl group (an example of a silyl group) of the alkoxysilane compound. Epoxy group 3 is introduced into the surface by reaction with hydroxyl group 2 (an example of an active hydrogen group) on the surface of glass substrate 1, that is, the surface is covered with monomolecular film 3 a of an alkoxysilane compound containing epoxy group 3. Step A for producing the broken reactive glass substrate 4 (FIG. 2B) and a second containing an amino group 7 which is an example of a second functional group that reacts with the epoxy group 3 to form a covalent bond. Arco is an example of a silane compound Silica fine particles 5 are dispersed in a second chemical adsorption solution prepared by mixing a silane compound, a condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilyl group of the alkoxysilane compound is schematically shown in FIG. The amino group 7 was introduced into the surface by the reaction with the hydroxyl group 6 (an example of the active hydrogen group) on the surface of the silica fine particle 5 shown specifically, that is, the monomolecular film 8 of the alkoxysilane compound containing the amino group 7 Process B for producing reactive silica fine particles (an example of reactive transparent fine particles) 9 (FIG. 3B) with the surface covered, and the reactive glass substrate 4 and the reactive silica fine particles 9 are in contact with each other. Step C for producing a glass substrate 10 (FIG. 4) in which the silica fine particles are bonded to the surface through covalent bonds by reacting with epoxy groups 3 and amino groups 7 by heating with silica, and the silica fine particles via covalent bonds On the surface The combined glass substrate 10 is heat-treated in an oxygen-containing atmosphere to produce a glass substrate 1a (see FIG. 5) whose surface is covered with fused silica fine particles, and a fluorocarbon group. Glass whose surface is covered with silica fine particles fused with a third chemisorbed liquid prepared by mixing an alkoxysilane compound, which is an example of a third silane compound, a condensation catalyst, and a non-aqueous organic solvent The water- and oil-repellent and antifouling coating film 11 is brought into contact with the substrate 1a by the reaction between the alkoxysilyl group of the alkoxysilane compound and the hydroxyl group on the surface of the glass substrate 1a whose surface is covered with fused silica fine particles. And step E of forming (see FIG. 1).
Hereinafter, the processes A to E will be described in more detail.

In step A, the reactive glass substrate 4 whose surface is covered with the monomolecular film 3a having an epoxy group is manufactured.
There is no restriction | limiting in particular about the material of the glass base material 1 used for manufacture of the reactive glass base material 4, 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. In the present embodiment, the active hydrogen group is the hydroxyl group 2, but may be an amino group containing active hydrogen or the like.

The first chemical adsorption liquid used for the production of the reactive glass substrate 4 is for accelerating the condensation reaction between the alkoxysilane compound containing the epoxy group 3 and the alkoxysilyl group and the hydroxyl group 2 on the surface of the glass substrate 1. It is prepared by mixing a condensation catalyst and a non-aqueous organic solvent.

The alkoxysilane compound containing an epoxy group 3 has a functional group containing an epoxy group (oxirane ring) and an alkoxysilyl group at both ends of a linear alkylene group, and is represented by the following general formula (Formula 1). Preferred are alkoxysilane compounds.

In the above formula, E represents a functional group containing an epoxy group, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.

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 first chemical adsorption solution is applied to the surface of the glass substrate 1 and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group 2 on the surface of the glass substrate 1 cause a condensation reaction, and the following chemical formula 2 A monomolecular film 3a including an epoxy group having a structure as shown in FIG. The three single bonds extending from the oxygen atom are bonded to the surface of the glass substrate 1 or the silicon (Si) atom of the adjacent silane compound, at least one of which is a silicon atom on the surface of the glass substrate 1. Is combined with.

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 glass substrate 1, so that these impurities can be removed in advance by thoroughly washing and drying the glass substrate 1. preferable.
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, when the reactive glass substrate 4 is produced by using H3 of Japan Epoxy Resin Co., Ltd. which is a ketimine compound instead of dibutyltin oxide as the condensation catalyst and the other conditions are the same, The reaction time can be shortened to about 1 hour without losing quality.

Furthermore, when the reactive glass substrate 4 is produced by using a mixture of H3 and dibutyltin bisacetylacetonate (mixing ratio is 1: 1) of Japan Epoxy Resin Co., Ltd. as the condensation catalyst, and other conditions are the same. 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 as unreacted materials yields a reactive glass substrate 4 whose surface is covered with a monomolecular film 3a containing an epoxy group. It is done. A schematic view of the cross-sectional structure of the reactive glass substrate 4 manufactured in this way is shown in FIG. 2B shows an example of a monomolecular film 3a having an epoxy group having a structure represented by the following chemical formula 3.

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, when the generated reactive glass substrate 4 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 the generated silanol groups are Causes a condensation reaction with an alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the reactive glass substrate 4. Although this polymer film is not fixed to the surface of the reactive glass substrate 4 by a covalent bond, it contains an epoxy group 3 and therefore is similar to the monomolecular film 3 a containing an epoxy group with respect to the reactive silica fine particles 9. It has the reactivity of. Therefore, even if it does not wash | clean, the manufacturing process of the water repellent / oil repellent antifouling anti-reflective film 12 after the process C will not be particularly hindered (process A above).

In step B, reactive silica fine particles 9 whose surface is covered with a monomolecular film 8 having an amino group are produced.
In order not to impair the transparency of the water / oil repellent / antifouling glass plate 12 to be produced, the diameter of the silica fine particles 5 used for the production of the reactive silica fine particles 9 should be smaller than the visible light wavelength (380 to 700 nm). preferable. 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 5 used may have a single particle diameter, but when silica fine particles having two or more different particle diameters are mixed and used, the surface of the resulting water / oil repellent / antifouling antireflection film 12 is used. Is preferable because it has fractal properties and improves water and oil repellency and antifouling properties.

In the present embodiment, silica fine particles are used as the transparent fine particles. However, the surface has active hydrogen groups that react with alkoxysilyl groups and halosilyl groups, such as hydroxyl groups and amino groups, and are translucent from a glass substrate. Also, any fine particles having a high softening point can be used. Examples of transparent fine particles that can be used in addition to silica include fine particles such as silica and zirconia.

The second chemical adsorption liquid used for the production of the reactive silica fine particles 9 is a condensation catalyst for promoting the condensation reaction between the alkoxysilane compound containing amino groups 7 and the alkoxysilyl groups and the hydroxyl groups 6 on the surface of the silica fine particles 5. And a non-aqueous organic solvent.

As the alkoxysilane compound containing an amino group 7, an alkoxysilane compound having an amino group and an alkoxysilyl group at both ends of a linear alkylene group and represented by the following general formula (Formula 4) is preferable.

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms. The amino group 7 may be protected by a protecting group in order to avoid side reactions with the alkoxysilyl group. The protecting group is preferably one that can be easily removed by hydrolysis or the like, and examples thereof include a ketimine derivative produced by the reaction between a ketone and an amino group.
The amino group 7 may be a secondary amine other than the primary amine as shown in Chemical Formula 4, and an alkoxysilane compound containing a functional group having an imino group such as a pyrrole group or an imidazole group instead of the amino group 7 may be used. Can be used.

When the silica fine particles 5 are dispersed in the second chemical adsorption liquid and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl groups 6 on the surface of the silica fine particles 5 cause a condensation reaction, which is represented by the following chemical formula 5. A monomolecular film 8 including an amino group having such a structure is generated. The three single bonds extending from the oxygen atom are bonded to the surface of the glass substrate 1 or the silicon (Si) atom of the adjacent silane compound, at least one of which is a silicon atom on the surface of the glass substrate 1. Is combined with.

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 5, and it is preferable to remove these impurities in advance by thoroughly washing and drying the silica fine particles 5.
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.

Among the condensation catalysts that can be used in the first chemical adsorption solution, the compound containing a tin (Sn) salt reacts with the amino group 7 contained in the alkoxysilane derivative to form a precipitate. It cannot be used as a condensation catalyst in a liquid.
Therefore, in the second chemisorbed liquid, the same compounds as those in the first chemisorbed liquid are used alone, except for the carboxylic acid tin salt, the carboxylic acid ester tin salt, the carboxylic acid tin salt polymer, and the carboxylic acid tin salt chelate. Two or more types can be mixed and used as a condensation catalyst.
The types of cocatalysts that can be used in the second chemisorbed liquid and combinations thereof, the types of solvents, alkoxysilane compounds, condensation catalysts, and the concentrations of cocatalysts, reaction conditions, and reaction times, the first chemisorbed liquid Since it is the same as that, the description is omitted.

After the reaction, washing with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface yields reactive silica fine particles 9 whose surface is covered with a monomolecular film 8 containing amino groups. A schematic diagram of the cross-sectional structure of the reactive silica fine particles 9 produced in this way is shown in FIG. FIG. 3B shows an example of a monomolecular film 8 having an amino group having a structure represented by the following chemical formula 6.

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, when the generated reactive silica fine particles 9 are 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 the generated silanol groups are converted to alkoxy. Causes a condensation reaction with a silyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the reactive silica fine particles 9. Although this polymer film is not fixed to the surface of the reactive silica fine particle 9 by a covalent bond, it contains an amino group 7 and therefore is similar to the monomolecular film 8 containing an amino group with respect to the reactive glass substrate 4. It has the reactivity of. Therefore, even without cleaning, the manufacturing process of the water / oil repellent / antifouling antireflective film 12 after Step C is not particularly hindered (Step B).

As an example of the alkoxysilane compound which has an epoxy group which can be used in process A, the compound shown to following (1)-(11) is mentioned. Moreover, as an example of the alkoxysilane compound which has an amino group which can be used in the process B, the compound shown to following (12)-(18) is mentioned.

_{(1) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OCH 3) 3
_{(2) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
_{(3) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OCH 3) 3
_{(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(6) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(7) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
_{(8) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OC 2 H 5) 3
_{(9) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(10) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(11) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3
(12) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(15) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(16) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(17) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(18) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) CH ₂ O— group represents a functional group (glycidoxy group) represented by Chemical Formula 7, and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by Chemical Formula 8. Functional group (3,4-epoxycyclohexyl group).

In this embodiment, an epoxy group is used as the first functional group and an amino group is used as the second functional group. However, the amino group is used as the first functional group and the epoxy is used as the second functional group. Each group may be used.

In step C, the reactive glass substrate 4 and the reactive silica fine particles 9 are heated in contact with each other to react the epoxy groups 3 and the amino groups 7 so that the silica fine particles are bonded to the surface via covalent bonds. The glass substrate 10 is manufactured.
The reactive silica fine particles 9 are dispersed in the dispersion liquid, and after coating on the reactive glass substrate 4, the dispersion liquid is evaporated. When heated thereafter, the glass substrate 10 in which the silica fine particles are bonded to the surface through a covalent bond is obtained by an addition reaction between an epoxy group and an amino group as shown in Chemical Formula 9.

As the dispersion liquid of the reactive silica fine particles 9, the monomolecular film 3 a and amino group containing epoxy groups that do not cause side reactions with the epoxy groups 3 and amino groups 7 and cover the surfaces of the glass substrate 1 and the silica fine particles 5, respectively. Any liquid that does not destroy the monomolecular film 8 containing groups can be used. A preferred dispersion includes ethanol.
In the case of a reaction between an epoxy group and an amino group, a preferable reaction temperature is 100 ° C., and a preferable reaction time is 30 minutes.

After the reaction, when washed with a washing solvent, unreacted reactive silica fine particles 9 are removed, and a glass substrate 10 in which the silica fine particles are bonded to the surface through covalent bonds is obtained. FIG. 4 shows a schematic diagram of a cross-sectional structure of the glass substrate 10 in which the silica fine particles thus produced are bonded to the surface through covalent bonds.
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. (Step C).

In step D, the glass substrate 10 on which the silica fine particles are bonded to the surface via a covalent bond is heat-treated in an atmosphere containing oxygen to decompose the monomolecular film covering the surfaces of the glass substrate 1 and the silica fine particles 5. In addition, the glass substrate 1a (see FIG. 5) whose surface is covered with the fused single layer silica fine particles is manufactured by fusing the glass substrate 1 and the silica fine particles 5 together.
The heat treatment temperature is higher than the temperature at which the monomolecular film covering the surfaces of the glass substrate 1 and the silica fine particles 5 is decomposed, and the temperature at which the glass substrate 1 and the silica fine particles 5 are fused, and the glass substrate 1 And the melting temperature of the silica fine particles 5 must be lower. When blue plate glass is used as the glass substrate 1, a preferable heat treatment temperature is about 650 degrees. The reaction time is 30 minutes when heat treatment is performed in air at 650 ° C.
FIG. 5 shows a schematic diagram of the cross-sectional structure of the glass substrate 1a whose surface is covered with the fused silica fine particles thus obtained (step D).

In step E, the water / oil / oil / repellency / antifouling coating 11 is formed on the surface of the glass substrate 1a whose surface is covered with the fused silica fine particles, and the water / oil / oil / repellency / antifouling antireflection film 12 is produced.

The third chemical adsorption liquid used for the production of the water / oil repellent / antifouling antireflective film 12 is composed of an alkoxysilane compound containing a fluorocarbon group and a glass substrate 1a whose surface is covered with fused silica fine particles. It is prepared by mixing a condensation catalyst for accelerating the condensation reaction between the surface hydroxyl group and the alkoxysilyl group and a non-aqueous organic solvent.

Examples of the alkoxysilane compound containing a fluorocarbon group include an alkoxysilane compound represented by the following general formula (Formula 10).

In the above formula, m represents an integer of 0 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.

Condensation catalyst that can be used for the third chemical adsorption solution, types of promoters and combinations thereof, solvent types, alkoxysilane compounds, condensation catalysts, and concentrations of promoters, reaction conditions, and reaction time Since it is the same as a chemical adsorption liquid, description is abbreviate | omitted.

Although the case where an alkoxysilane compound is used has been described in this embodiment mode, a halosilane 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 reaction with the glass substrate 1a whose surface is covered with silica fine particles prepared and fused with the third chemisorbed liquid can be performed in the same manner as the alkoxysilane compound.
A schematic view of the cross-sectional structure of the water / oil / oil repellent / antifouling antireflection film 12 obtained in this manner is shown in FIG. In addition, in FIG. 1, what has the structure represented by following Chemical formula 11 as an example of the water repellent / oil repellent antifouling film 11 is shown.

Since the film thickness of the monomolecular water-repellent / oil-repellent antifouling film 11 is at most about 1 nm, it is about 50 nm formed on the surface of the glass substrate 1a covered with fused silica fine particles. The unevenness is hardly damaged. In addition, due to this unevenness effect (so-called “lotus leaf effect”), the apparent surface energy of the water / oil repellent / antifouling antireflective coating 12 can be reduced, and the water droplet contact angle is 140 degrees or more (this embodiment) In the form, it is about 150 degrees), and super water repellency can be realized.

In addition, since the silica fine particles 5 having a hardness higher than that of the glass are fused on the surface of the base glass of the water / oil / oil repellent / antireflective antireflection film 12, the wear resistance is greatly improved.
Further, in the water / oil / oil / repellency / antifouling antireflection film 12, the total thickness of the coating including the silica fine particles 5 and the water / oil / oil / repellency / antifouling coating 11 formed on the surface of the glass substrate 1 is about 100 nm. Therefore, the transparency of the glass substrate 1 is not impaired.

After the reaction, when the generated water / oil / oil repellent anti-reflective coating 12 is left in the air without washing with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, The produced silanol group causes a condensation reaction with the alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the water / oil / oil repellent / antifouling antireflection film 12. Unlike the monomolecular film, the polymer film is not entirely fixed to the surface of the water / oil / oil / fouling / antireflection film 12 by a covalent bond, but has a fluorocarbon group. It has water and oil repellency and antifouling properties. Therefore, it can be used as the water / oil repellent / antifouling antireflective film 12 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 E, the compound shown to following (21)-(32) is mentioned.

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

Moreover, as a halosilane compound containing the fluorocarbon group which can be used in the process E, the compound shown to following (41)-(46) is mentioned.

(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 SiCl ₃

In the present embodiment, the glass substrate 1 is used as it is for the production of the reactive glass substrate 4 in the step A. However, a coating for fusing the silica fine particles 5 at a lower temperature than the glass substrate 1 is used as the glass substrate. The process F formed on the surface of 1 may be performed before the process A.
As the coating, any coating (transparent coating) that has transparency and can fuse the silica fine particles 5 at a temperature lower than that of the glass substrate 1 can be used. Silicon oxide formed by a sol-gel method can be used. A dry gel film of a metal oxide such as aluminum oxide is preferred.
When a solution of a metal alkoxide containing a condensation catalyst is applied to the surface of the glass substrate 1 and the solvent is evaporated, a condensation reaction takes place between the hydroxyl group generated by hydrolysis of the alkoxyl group by moisture in the air and the alkoxyl group, and the glass A transparent dry gel film of metal oxide is formed on the surface of the substrate 1.
Since there are more free hydroxyl groups than the glass substrate 1 on the surface and inside of the unsintered dry gel film, the silica fine particles 5 can be fused at a temperature lower than that of the glass substrate 1.

Formation of a dry gel film of silica, which is an example of a transparent film, is obtained by mixing a sol solution obtained by mixing a tetraalkoxysilane such as tetramethoxysilane (Si (OCH ₃ ) ₄ ), a condensation catalyst and a solvent with the glass substrate 1. It can be performed by applying to the surface and evaporating the solvent.
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 5 used for manufacture of water-repellent oil-repellent antifouling antireflection film 12, 10-50 nm is preferred.
When the water-repellent / oil-repellent / antifouling antireflective film 12 is produced using the glass substrate 1 having the silica dry gel film thus obtained on the surface, the heat treatment in the step D is performed at 300 ° C. or less. It becomes possible to carry out at a low temperature, and the glass substrate 1a whose surface is covered with silica fine particles fused can be manufactured without deteriorating the strengthening degree of the glass which has been tempered by air cooling in advance.

In addition to the dry gel film of silica, any transparent film that has transparency and can fuse the silica fine particles 1 at a temperature lower than that of the glass substrate 1 can be formed and used. Examples of the transparent film that can be used include dry gel films such as silica 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. Can be reduced to the extent

The water / oil repellent antifouling antireflection film 12 has a water droplet contact angle of about 150 degrees.
As a reference, FIG. 6 shows the relationship between the contact angle with respect to water droplets on the water-repellent surface and the falling angle, obtained from experiments using water droplets (0.02 to 0.08 ml) of different volumes. As is apparent from this graph, when the water droplet contact angle is 150 degrees or more, the falling angle is 15 degrees or less regardless of the volume of the water droplet.
Therefore, it can be seen that when the water / oil / oil repellent antifouling antireflection film 12 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 repellent / antifouling anti-reflective coating 12 has excellent durability such as abrasion resistance and weather resistance, water repellency (sliding property), and antifouling properties, and requires a water / oil repellent / antifouling function. It can be used as a glass plate for windows of vehicles and buildings.
Vehicles that can use the water / oil repellent / antifouling antireflective coating 12 include automobiles, railway vehicles, ships, etc., and are used as glass plates for windows of any windows, regardless of driver seats, cabins, etc. be able to.
In addition, examples of buildings that can use the water / oil repellent / antifouling antireflective coating 12 include arbitrary buildings such as single-family houses, apartment houses, and office buildings.

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.

The glass substrate according to the present invention includes a lens for an optical device, a glass plate for a solar energy utilization device, and a face plate for a display. As a representative example, a glass plate for a solar water heater will be described below. .

Example 1
(1) Preparation of reactive glass substrate A glass plate for a solar water heater was prepared, washed thoroughly and dried.
0.99 parts by weight of 3-glycidoxypropyltrimethoxysilane (Chemical Formula 12, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed, and this was 100 parts by weight. A first chemical adsorption solution was prepared by dissolving in a hexamethyldisiloxane solvent.

The first chemisorbed liquid thus obtained was applied to the surface of an automotive window glass plate 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) Preparation of reactive silica fine particles Silica fine particles having an average particle diameter of 100 nm were prepared, washed thoroughly and dried.
0.99 parts by weight of 3-aminopropyltrimethoxysilane (Chemical 13 manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 part by weight of acetic acid (condensation catalyst) were weighed, and 100 parts by weight of hexamethyldisiloxane- A second chemisorbed solution was prepared by dissolving in a dimethylformamide mixed solvent (1: 1 v / v).

The dried fine silica particles were mixed and stirred in the second chemisorbed liquid thus obtained 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.

(3) Bonding and fixing silica fine particles to the surface of a glass plate for solar water heater by reaction of epoxy group and amino group The reactive silica fine particles prepared in (2) are dispersed in ethanol, and the reaction prepared in (1) It apply | coated to the surface of a property glass base material. After evaporating the ethanol, it was heated at about 100 ° C. for about 30 minutes. Then, it wash | cleaned with chloroform and the silica fine particle which was not couple | bonded and fixed to the surface of the window glass plate for motor vehicles was removed.

(4) Glass for solar water heater prepared by fusing silica fine particles to the surface of a glass plate for solar water heater (3), wherein silica fine particles are bonded and fixed on the surface through reaction between epoxy groups and amino groups The plate was heated in air at 650 ° C. for about 30 minutes. It was confirmed by scanning electron microscope observation that alumina fine particles were fused and fixed on the surface of a glass plate for a solar water heater.

(5) Formation of water- and oil-repellent and antifouling film (heptadecafluoro-1,1,2,2-tetrahydrodecyl) 1 part by weight of trichlorosilane (Chemical Formula 14) is dissolved in 100 parts by weight of dehydrated nonane. A third chemisorbed liquid was prepared.
The third chemical adsorption solution was applied and reacted in dry air with a relative humidity of 30% or less on the surface of the automotive window glass plate prepared in (4) and fused with silica fine particles on the surface. After the reaction, it was washed with a fluorocarbon solvent to remove the unreacted trichlorosilane compound.

The apparent water droplet contact angle of the glass plate for a solar water heater on which the water / oil / oil repellent / antifouling antireflection film thus obtained was formed was about 150 °.
For comparison, an attempt was made to create a water / oil repellent / antifouling film using CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ on the surface of a flat substrate. The surface energy was about 6 mN / m, and the maximum water droplet contact angle was about 115 degrees. On the other hand, in this invention, 140 degree | times or more was realizable by the uneven | corrugated effect similar to a lotus leaf.

On the other hand, transparent silica fine particles are harder than glass and are directly fused to the glass plate surface, so they are made directly using CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ on the glass plate surface. Compared to the monomolecular film, the wear resistance was greatly improved.
Moreover, since the total thickness of the fine particle coating was about 100 nm, the transparency was not impaired.
Furthermore, since such an antireflection film has a small refractive index in the vicinity of the surface and can be increased stepwise as it approaches the substrate surface, the surface reflection, which is usually about 4%, can be greatly reduced to the 1% level. .

(Example 2)
The same processing as in (1) to (4) of Example 1 was performed to prepare a glass plate for a solar water heater in which silica fine particles were fused and fixed on the surface.
The formation of the water / oil repellent / antifouling film was performed as follows.
0.99 parts by weight of (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (Chemical Formula 15) and 0.011% by weight of dibutyltin diacetylacetonate (condensation catalyst) were weighed, A third chemical adsorption solution was prepared by dissolving in 100 parts by weight of a methyldisiloxane solvent. A glass plate for a solar water heater with silica fine particles fused and fixed on the surface was immersed in a third chemical adsorption solution and reacted for about 2 hours. Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(Example 3)
On the other hand, a chemisorption monomolecular film having an amino group instead of an epoxy group is formed on the glass plate surface in the same manner as in Example 1, and a chemisorption monomolecular film having an epoxy group instead of an amino group on the surface of the silica fine particles When a layer of silica fine particles is fixed to the glass plate surface by the reaction of an epoxy group and an amino group, and finally CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ is reacted, the SiCl group is Since it also reacts with the epoxy group, the same water / oil repellent antifouling glass as in Example 1 could be produced.

Example 4
Using the same method as in Example 1, an uneven substrate with fine particles fused in advance to the surface of a transparent base material during the production of a solar cell, and after forming the solar cell, a water / oil / oil / antifouling antireflection film is formed. An antireflection film having a water droplet contact angle of about 150 degrees (similar effect was obtained if the water droplet contact angle was 140 or more in practical use) was formed, and a practical test was conducted. As a result, even after half a year, dust in the air and dirt due to rainwater hardly adhered, and the light utilization efficiency was improved by about 3% on average compared to the case where ordinary glass was attached. Further, in the case of ordinary glass, the surface becomes dirty and the light utilization efficiency is reduced by about 30% when used for one year. However, in this solar cell, the efficiency is hardly reduced even after one year.

(Example 5)
On the other hand, in Example 1, when a hydrophilic coating having a lower melting point than the glass plate for fine particle fusion, such as a silica-containing film using a sol-gel method, is formed in advance on the glass plate surface, the firing temperature is set. Even at a low temperature of 300 ° C. or less, the fine particles can be indirectly fused and fixed to the surface of the glass substrate through this film with almost no loss of the shape of the fine particles.
That is, with this method, even if a glass plate that has been tempered in advance with air cooling is used, a glass plate with an uneven surface can be produced without degrading the degree of strengthening.

Therefore, a silica-containing film was formed on a glass substrate tempered in advance by air-cooling using a sol-gel method.
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 the air-cooled tempered glass that has been thoroughly washed and dried, and the solvent is evaporated, tetramethoxysilane is hydrolyzed and dealcoholized, resulting in a large amount of about 50 nm. A silica-based transparent film (silica dry gel film) containing the hydroxyl group of was formed.
A fine particle film is formed on the silica-based transparent film thus obtained by the same method as in Example 1 and baked at 280 ° C., and then the water- and oil-repellent and antifouling method by the same method as in Example 1. When a water-soluble monomolecular film was formed, a glass plate having a water-drop contact angle of about 145 degrees and a water / oil / oil / antifouling property and an antireflection function was obtained.

Furthermore, when this water and oil repellent antifouling and antireflective glass plate is mounted on a solar water heater and tested for practical use, dirt from the dust and rainwater in the air hardly adheres, and ordinary glass The heat collection efficiency was improved by about 3% on average as compared with the case where the device was installed. In the case of ordinary glass, the surface becomes dirty and the light utilization efficiency is reduced by about 30% when used for one year. However, in this solar water heater, the efficiency was hardly reduced even after one year.

The above experimental results show that the solar cell and the solar water heater using the water / oil repellent / antifouling antireflection film of the present invention are extremely efficient and highly durable.

In addition, in the above Examples 4 and 5, although illustrated about the use of a solar cell or a solar water heater, the application of this invention is not limited to these uses, For example, the apparatus using solar energy, for example, a greenhouse Needless to say, this can also be applied.

(Example 6)
Using the same method as in Example 1, a lens having a water / oil repellent / antifouling antireflective coating was fabricated and mounted on an optical device for test use. The rate was the same as that of the anti-reflection multi-coated film, and a comparable lens could be produced.

(Example 7)
Furthermore, a CRT having a water / oil / oil / antifouling antireflection film formed on the surface was produced using the same method as in Example 1 and was used for testing. It was possible to reduce the reflection of fluorescent lights, etc., and the visibility was greatly improved.
Needless to say, this technique can be applied to the display surface of a PDP or LCD based on the same principle.

As described above, according to the present invention, durability, such as wear resistance and weather resistance, in lenses for optical devices, glass plates for solar energy utilization devices, and face plates for displays that require water / oil repellent / antifouling functions. Water-repellent / oil-repellent / anti-fouling anti-reflective coating excellent in water resistance, water-drop separation (also referred to as water slidability) and anti-fouling properties
Therefore, the present invention provides durability such as wear resistance and weather resistance on the lens surface of an optical device, a glass plate of a solar energy utilization device and a glass plate used for a face plate of a display, which are required to have a water and oil repellent and antifouling function. Water and oil repellent and anti-fouling anti-reflective coatings with excellent water repellency (also called water slidability) and antifouling properties, optical devices with excellent optical performance, and solar energy utilization devices with excellent light utilization efficiency A display having excellent visibility and antifouling properties can be provided.

It is explanatory drawing which represented typically the cross-sectional structure of the water repellent / oil repellent antifouling | reflective antireflection film which concerns on one embodiment of this invention. In the manufacturing method of the same water-repellent / oil-repellent antifouling antireflection film, it is a schematic view enlarged to a molecular level to explain a step of forming a monomolecular film containing an epoxy group on the surface of a glass substrate, (a ) Represents the cross-sectional structure of the glass surface before the reaction, and (b) represents the cross-sectional structure of the reactive glass substrate on which a monomolecular film containing an epoxy group is formed. FIG. 5 is a schematic diagram enlarged to the molecular level for explaining a step of forming a monomolecular film containing an amino group on the surface of silica fine particles in the method for producing the water / oil repellent / antifouling antireflection film; Represents the cross-sectional structure of the silica fine particles before the reaction, and (b) represents the cross-sectional structure of the reactive silica fine particles on which a monomolecular film containing an amino group is formed. In the method for producing the water / oil / oil / antifouling antireflection film, the cross-sectional structure is expanded to the molecular level in order to explain the process of producing a glass substrate in which silica fine particles are bonded to the surface through covalent bonds. FIG. It is a schematic diagram showing the cross-sectional structure of the glass base material in which the surface was covered with the fused silica fine particles.

Explanation of symbols

1: glass substrate, 1a: glass substrate whose surface is covered with fused silica fine particles, 2: hydroxyl group, 3: epoxy group, 3a: monomolecular film containing epoxy group, 4: reactive glass substrate, 5: Silica fine particles, 6: Hydroxyl group, 7: Amino group, 8: Monomolecular film containing amino group, 9: Reactive silica fine particles, 10: Glass substrate in which silica fine particles are bonded to the surface through covalent bonds, 11 : Water / oil repellent / antifouling coating, 12: Water / oil repellent / antifouling anti-reflective coating

Claims (24)

A water / oil repellent / antifouling antireflection film comprising water / oil repellent / antifouling transparent fine particles fused to the surface of a glass substrate. The water / oil repellent / antifouling antireflective film according to claim 1, wherein the transparent fine particles have different particle diameters. . The water / oil / oil / repellency / antifouling antireflection film according to claim 1, wherein the water / oil / oil / repellency / antifouling coating is covalently bonded to at least the surface of the transparent fine particles. Water and oil repellent antifouling antireflective coating. The water / oil / oil / repellency / antifouling antireflection film according to claim 3, wherein the water / oil / oil / repellency / antifouling coating comprises —CF ₃ groups. 5. The water / oil / oil repellent / antifouling antireflection film according to claim 1, wherein the transparent fine particles are translucent and have a softening point higher than that of the glass substrate, such as silica, alumina, and zirconia. A water / oil repellent antifouling antireflective film characterized by being either. The water / oil repellent / antifouling antireflection film according to any one of claims 1 to 5, wherein the transparent fine particles have a particle size of less than 400 nm. film. The water / oil repellent / antifouling antireflective film according to claim 1, wherein the water contact angle is 140 ° or more. . The water / oil repellent / antifouling antireflective film according to claim 1, wherein the transparent fine particles are made of a metal oxide that is fused to the transparent fine particles at a temperature lower than that of the glass substrate. A water / oil repellent antifouling antireflective film, which is fused to the surface of the glass substrate through a transparent film. A lens, wherein the water / oil / oil repellent / antifouling antireflective film according to claim 1 is formed on a surface thereof. A glass plate, characterized in that the water / oil repellent / antifouling antireflective film according to claim 1 is formed on a surface thereof. A glass characterized in that the water / oil / oil repellent / antifouling antireflection film according to claim 1 is formed on a surface thereof. An optical device comprising the lens according to claim 9. A solar energy utilization apparatus, comprising the glass plate according to claim 10. A display comprising the glass according to claim 11. A first chemical adsorption liquid containing a first silane compound containing a first functional group and a non-aqueous organic solvent is brought into contact with a glass substrate, and the silyl group of the first silane compound and the glass substrate Step A for producing a reactive glass substrate whose surface is covered with a monomolecular film of the first silane compound by reaction with active hydrogen groups on the surface;
Dispersing transparent fine particles in a second chemical adsorption liquid containing a second silane compound containing a second functional group that reacts with the first functional group to form a covalent bond and a non-aqueous organic solvent, Step B for producing reactive transparent fine particles whose surface is covered with a monomolecular film of the second silane compound by a reaction between the silyl group of the second silane compound and the active hydrogen group on the surface of the transparent fine particles;
Heating the reactive glass substrate and the reactive transparent fine particles in contact with each other to react the first functional group and the second functional group, and forming the transparent fine particles through the covalent bond formed Step C for producing a glass substrate having a surface bonded to the surface,
The glass substrate in which the transparent fine particles are bonded to the surface in the step C is heat-treated in an atmosphere containing oxygen, and the transparent fine particles are fused to the surface of the glass substrate. Step D for producing a glass substrate whose surface is covered;
A third chemisorbed liquid containing a third silane compound containing a fluorocarbon group and a non-aqueous organic solvent is brought into contact with the glass substrate whose surface is covered with the fused transparent fine particles, and the third The water- and oil-repellent and antifouling coating composed of the fluorocarbon group is formed by the reaction between the silyl group of the silane compound and the active hydrogen group on the surface of the glass substrate whose surface is covered with the fused transparent fine particles. A process for producing a water- and oil-repellent and antifouling antireflective film comprising the step E. 16. The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 15, wherein one of the first and second functional groups is an epoxy group and the other is an amino group or an imino group. A method for producing a water / oil repellent antifouling antireflection film. The method for producing a water / oil repellent / antifouling antireflective film according to any one of claims 15 and 16, wherein in any one of the steps A, B and E, 1, 2 or 3, the silyl group A method for producing a water- and oil-repellent antifouling antireflection film, wherein unreacted substances are washed away after the reaction between the water and the active hydrogen group. The method for producing a water / oil repellent / antifouling antireflection film according to any one of claims 15 to 17, wherein the transparent fine particles are fused to the glass substrate at a temperature lower than that of the glass substrate before the step A. A process for producing a water- and oil-repellent antifouling antireflection film, further comprising a step F of forming a transparent film of metal oxide on the surface of the glass substrate. 19. The method for producing a water / oil / oil / repellency / antifouling antireflection film according to claim 18, wherein a sol-gel method is used for forming the transparent film in the step F. Production method. 20. The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 15, wherein the first, second, and third chemical adsorption liquids each include the first, Any one of 1, 2 or 3 of the second and third silane compounds is an alkoxysilane compound. A method for producing a water / oil repellent antifouling antireflection film, wherein 20. The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 15, wherein the first, second, and third chemical adsorption liquids each include the first, Any one of 1, 2 or 3 of the second and third silane compounds is a halosilane compound. A method for producing a water- and oil-repellent antifouling antireflection film, wherein The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 20, wherein the first, second and third chemical adsorption liquids containing the alkoxysilane compound are further used as a condensation catalyst. It includes one or more compounds selected from the group consisting of a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate. A method for producing a water- and oil-repellent antifouling antireflection film. 21. The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 20, wherein the first, second and third chemical adsorption liquids contain the alkoxysilane compound as a condensation catalyst. Water repellent / oil repellent / antifouling antireflective coating, further comprising one or more compounds selected from the group consisting of organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds Manufacturing method. 23. The method for producing a water / oil / oil repellent / antifouling antireflection film according to claim 22, further comprising, as a co-catalyst, a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. A method for producing a water- and oil-repellent antifouling antireflective film, further comprising one or more selected compounds.

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