JP5572803B2 - Water repellent and oil repellent antifouling glass, method for producing the same, glass window using them, solar energy utilization apparatus and optical instrument - Google Patents

Description

The present invention relates to a water- and oil-repellent antifouling glass, a method for producing the same, a glass window using the same, a solar energy utilization device, and an optical instrument, and more specifically, a highly durable and water-repellent and oil-repellent antifouling property. The present invention relates to a water- and oil-repellent antifouling glass having a coating film formed thereon, a method for producing the same, a glass window using them, a solar energy utilization device, and an optical instrument.

In order to impart water repellency, oil repellency and antifouling properties to the surfaces of various members, a solution comprising a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent is used for chemical adsorption in the liquid phase. It is already well known that a molecular film-like water- and oil-repellent antifouling chemical adsorption film monomolecular film can be formed (for example, see Patent Document 1).

The manufacturing principle of such a monomolecular film in a solution is to form a monomolecular film by using a dehydrochlorination reaction between active hydrogen such as hydroxyl group on the substrate surface and chlorosilyl group of chlorosilane-based adsorbent. is there.

JP-A-4-132737

However, when the adsorbent is applied to a flat glass substrate, the chemical adsorption film described in Patent Document 1 has a water droplet contact angle of only about 120 degrees, so that water droplets and dirt can be removed naturally. Has the problem of insufficient water and oil repellency, antifouling properties and water separation. Further, the water / oil repellent antifouling glass to which the chemical adsorption film monomolecular film described in Patent Document 1 is applied has a problem of poor durability such as wear resistance and weather resistance.

The present invention has been made in view of such circumstances, in addition to water / oil repellent and antifouling functions, durability such as wear resistance and weather resistance, water droplet separation (also referred to as water slidability), oil repellency and antifouling properties. An object of the present invention is to provide a water- and oil-repellent and antifouling glass having improved water resistance, a method for producing the same, a glass window using them, a solar energy utilization device, and an optical instrument.

The first aspect of the present invention that meets the above-mentioned object is bonded and fixed to the surface of the glass substrate so as to cover at least part of the surface of the transparent glass substrate, and has a melting point higher than the softening temperature of the glass substrate. and high transparent first fine particles, the first surface of the fine particles of coupled fixed to the first surface of the particles so as to cover at least a part, a Do transparent small particle size than the first particulate and second microparticles, have a said first and second water- and oil-repellent formed on the surface antifouling particle film, the particle diameter of the first fine particle is at 50nm or more 400nm or less, wherein The surface of the first fine particles in which the particle size of the second fine particles is 1/100 or more and 1/5 or less of the particle size of the first fine particles, and the first fine particles are bonded to the surface of the substrate. providing water and oil repellency and antifouling glass, characterized in that not bind to It is intended to further solve the above problems.
A surface structure having complex irregularities can be formed by bonding and fixing the first fine particles to the surface of the glass substrate and further bonding and fixing the second fine particles to the surface of the first fine particles. Therefore, the water / oil repellency / antifouling property can be improved as compared with the case of having a flat surface. In addition, by forming a water- and oil-repellent and antifouling thin film on at least the surfaces of the first and second fine particles, it is possible to impart water repellency, oil repellency and antifouling properties to the surface of a generally hydrophilic glass substrate. .

In the water / oil repellent antifouling glass according to the first aspect of the present invention, the first fine particles have a particle size of 100 nm or more and 5 mm or less, and the second fine particles have a particle size of the first fine particles. the particle size of the 1/100 more than 1/5 Ru der below.
By using two types of fine particles with different particle diameters as described above, a surface structure with a so-called fractal structure can be obtained, so that water- and oil-repellent and antifouling glasses with significantly superior water and oil and oil repellency are provided. it can.

In the water / oil repellent antifouling glass according to the first aspect of the present invention, the glass substrate, the first and second fine particles are all transparent, and the particle size of the first fine particles is 400 nm or less. der Ru.
The glass substrate, the first and second fine particles are both transparent, the particle size of the first fine particles is smaller than the shortest wavelength (400 nm) of visible light (preferably about 100 nm), and the second fine particles Since the particle size is several nm to several tens of nm (preferably about 5 to 25 nm), it is possible to provide a water / oil repellent and antifouling glass excellent in transparency and optical properties, which suppresses scattering and irregular reflection of incident light.

In the water / oil repellent antifouling glass according to the first aspect of the present invention, the first fine particles are made of a material that can be fused to the glass substrate, and are fused to the surface of the glass substrate. Also good.
Alternatively, the first fine particles may be bonded and fixed to the surface of the glass substrate via a binder.
Since the first fine particles are bonded and fixed to the surface of the glass substrate through fusing or a binder, the wear resistance and weather resistance of the surface of the water / oil repellent / antifouling glass can be improved.

In the water / oil repellent / antifouling glass according to the first aspect of the present invention, the second fine particles are made of a material that can be fused to the first fine particles, and are fused to the surface of the first fine particles. It may be.
Alternatively, the second fine particles may be bonded and fixed to the surface of the first fine particles via a binder.
Since the second fine particles are bonded and fixed to the surface of the first fine particles through fusion or a binder, it is possible to improve the wear resistance and weather resistance of the surface of the water / oil repellent / antifouling glass.

In the water and oil repellent antifouling glass according to the first aspect of the present invention, the first and second fine particles are made of a material selected from the group consisting of glass, silica, alumina and zirconia. Also good.
Since the first and second fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia, the surface durability of the water / oil repellent / antifouling glass can be improved.

In the water / oil repellent / antifouling glass according to the first aspect of the present invention, the water / oil repellent / antifouling thin film is preferably a monomolecular film.
Since the water / oil repellent / antifouling thin film is a monomolecular film, the color tone and transparency of the obtained water / oil repellent / antifouling glass are not impaired.

In the water / oil repellent antifouling glass according to the first aspect of the present invention, the lower the critical surface energy of the surface, the better, but it is preferably 1 mN / m or more and 3 mN / m or less.
Since the critical surface energy of the surface is in the above range, all of the water repellency, oil repellency and antifouling property of the obtained water / oil repellent / antifouling glass can be improved.

In the second aspect of the present invention, the first dispersion liquid containing the first fine particles dispersed in the solvent is applied to the surface of the glass substrate, and after the solvent is evaporated, Step A for bonding and fixing the first fine particles, and second particles containing second fine particles dispersed in a solvent and having a particle size of 1/100 or more and 1/5 or less of the particle size of the first fine particles . A dispersion is applied to the surface of the glass substrate to which the first fine particles are bonded and fixed, and after the solvent is evaporated, the first fine particles are bonded to the surface of the glass substrate to which the first fine particles are bonded and fixed. And a step B of forming a water- and oil-repellent and antifouling thin film on the surface of the glass substrate on which the first and second fine particles are bonded and fixed. The above-mentioned problems are solved by providing a method for producing a water- and oil-repellent and antifouling glass. .
In steps A and B, complex irregularities can be formed on the surface of the glass substrate by bonding and fixing the first and second fine particles to the surface of the glass substrate. Therefore, the water repellency, oil repellency and antifouling property can be improved as compared with the glass substrate in which only the flat glass substrate and the first fine particles are bonded and fixed to the surface. Further, in Step C, the water and oil repellency and antifouling properties can be further improved by forming a water and oil and oil repellency and antifouling thin film on at least the surfaces of the first and second fine particles.

In the method for producing a water- and oil-repellent and antifouling glass according to the second aspect of the present invention, in the step A, the first fine particles may be fused to the surface of the glass substrate.
Alternatively, the first solution includes a first binder precursor that generates a binder by evaporation of a solvent and / or subsequent chemical reaction, and in the step A, the surface of the glass substrate is interposed via the binder. The first fine particles may be bound and fixed.
Since the first fine particles are bonded and fixed to the surface of the glass substrate through fusion or a binder, the wear resistance and weather resistance of the surface of the water / oil repellent / antifouling glass can be improved.

In the method for producing a water- and oil-repellent and antifouling glass according to the second aspect of the present invention, in the step B, the second fine particles are attached to the surface of the glass substrate to which the first fine particles are bonded and fixed. It may be fused.
Alternatively, the glass in which the second solution includes a second binder precursor that generates a binder by evaporation of a solvent and / or subsequent chemical reaction, and in which the first fine particles are bonded and fixed in the step B. The second fine particles may be bonded and fixed to the surface of the base material via a binder.
Since the second fine particles are bonded and fixed to the surface of the first fine particles via fusing or a binder, the wear resistance and weather resistance of the surface of the water / oil repellent / antifouling glass can be improved.

In the method for producing a water- and oil-repellent and antifouling glass according to the second aspect of the present invention, wherein the first and / or second fine particles are bonded and fixed through a binder in the step A and / or B. The second binder precursor may be a metal sol precursor that forms a transparent metal oxide by a sol-gel method.
By using a metal sol precursor that forms a transparent metal oxide by a sol-gel method as a binder precursor, the first and second fine particles are obtained without impairing the transparency of the water / oil repellent / antifouling glass produced. Can be bonded and fixed to the surfaces of the glass substrate and the first fine particles, respectively.

In the method for producing a water- and oil-repellent and antifouling glass according to the second aspect of the present invention, after the step A and / or B, the first and / or second fine particles not bonded and fixed are washed. It may be removed.

In the method for producing a water- and oil-repellent and antifouling glass according to the second aspect of the present invention, in the step C, the glass substrate reacts with the surface functional groups of the first and second fine particles to bond. A reaction liquid containing a compound having a reactive group to be formed and a fluorocarbon group is brought into contact with the surface of the glass substrate to which the first and second fine particles are bonded and fixed, and the surface functional group, the reactive group, You may form the film of the said compound fixed to this surface through the coupling | bonding formed of this reaction.
The water / oil repellent / antifouling thin film is bonded and fixed to the surfaces of the first and second fine particles through a bond formed by the reaction between the surface functional group and the reactive group. The durability of can be improved.

In this case, the reactive group is an alkoxysilyl group, and the reaction solution is
(1) one or two or more compounds selected from the group consisting of 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, and / or Alternatively, (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds may be included as a condensation catalyst.
By using an alkoxysilyl group as a reactive group, it is possible to prevent the formation of harmful by-products such as hydrogen halide during the reaction, and the reaction solution contains a condensation catalyst. The processing time required for forming the thin film can be shortened.

Further, after the step C, the excess reaction solution may be removed by washing.
By washing and removing excess reaction liquid, the water / oil / oil / repellency antifouling thin film can be made into a monomolecular film, so that the transparency of the produced water / oil / oil / repellency / antifouling glass is not impaired.

The third aspect of the present invention is the water repellency according to the first aspect of the present invention, wherein the glass substrate, the first and second fine particles are both transparent, and the particle size of the first fine particles is 400 nm or less. The above-described problems are solved by providing a glass window having an oil-repellent antifouling glass.
In addition to water repellency, oil repellency and antifouling properties, a glass window having excellent transparency and durability can be provided.

The fourth aspect of the present invention is the water repellency according to the first aspect of the present invention, wherein the glass substrate, the first and second fine particles are both transparent, and the particle size of the first fine particles is 400 nm or less. The above-described problems are solved by providing a solar energy utilization device having oil-repellent antifouling glass.
In addition to water repellency, oil repellency, and antifouling properties, it is possible to provide a solar energy utilization device that is excellent in durability and weather resistance and that is excellent in light energy utilization efficiency because scattering and diffuse reflection of incident light are suppressed.

The fifth aspect of the present invention is the water repellency according to the first aspect of the present invention, wherein the glass substrate, the first and second fine particles are both transparent, and the particle size of the first fine particles is 400 nm or less. The above-described problems are solved by providing an optical device having an oil-repellent antifouling glass.
In addition to water repellency, oil repellency and antifouling properties, it is excellent in durability and weather resistance, and since scattering and diffuse reflection of incident light are suppressed, an optical device excellent in transparency and optical characteristics can be provided.

According to the present invention, in addition to the water / oil repellent / antifouling function, the water / oil repellent has improved durability, such as abrasion resistance and weather resistance, water-drop-off property (also referred to as water slidability), oil repellency and antifouling properties An antifouling glass and a method for producing the same are provided. Further, according to the present invention, in addition to water repellency, oil repellency and antifouling properties, in addition to glass windows excellent in transparency and durability, water repellency, oil repellency and antifouling properties, weather resistance and utilization of light energy A solar energy utilization device having excellent efficiency and an optical device having excellent durability, transparency, and optical characteristics in addition to water repellency, oil repellency and antifouling properties are provided.

It is explanatory drawing which demonstrated typically the cross-section of the water repellent / oil repellent antifouling glass which concerns on one embodiment of this invention. It is explanatory drawing of the process of fuse | melting 1st microparticles | fine-particles on the surface of a glass base material in the manufacturing method of the said water-repellent | oil-repellent antifouling glass. In the manufacturing method of the said water-repellent | oil-repellent | oil-repellent | antifouling | stain-resistant glass, it is explanatory drawing of the process of carrying out the bond fixation which makes a 2nd microparticles | fine-particles through the binder on the surface of the glass base material on which the 1st microparticles | fusion were melt | fused. 2 is a scanning electron microscope (SEM) photograph of the surface of the water / oil repellent / antifouling glass produced in Example 1. FIG.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention. 1 to 3 are merely schematic explanatory views, and the size of the compound that forms the glass substrate, the first and second fine particles, and the water / oil repellent / antifouling thin film is not necessarily the actual size. Does not reflect the ratio.
As shown in FIG. 1, a water / oil repellent antifouling glass 10 according to an embodiment of the present invention is fused (bonded and fixed) to a surface of a glass substrate 11 so as to cover at least a part of the surface. For example, the first fine particles 12a bonded and fixed to the surface so as to cover at least a part of the surface of the first fine particles 12a fused to the surface of the glass substrate (11). The second fine particles 13 having a smaller particle diameter and the water and oil repellent and antifouling thin film 15a formed on the surfaces of the first and second fine particles 12a and 13 are included. The second fine particles 13 are bonded and fixed to the surface of the first fine particles 12a fused to the surface of the glass substrate (11) through a silica film 14 formed by a sol-gel method which is an example of a binder. ing.

The water / oil repellent / antifouling glass 10 is formed by applying a first dispersion liquid containing the first fine particles 12 dispersed in a solvent to the surface of the glass substrate 11 and evaporating the solvent. Step A (see FIG. 2) for fusing the first fine particles 12 to the surface of the film (see FIG. 2), the second fine particles 13 dispersed in a solvent, tetraalkoxysilane (an example of a binder precursor), Is applied to the surface of the glass substrate 11a to which the first fine particles are bonded and fixed. After the solvent is evaporated, the first dispersion is applied to the surface of the glass substrate 11a to which the first fine particles are bonded and fixed. Step B (see FIG. 3) for bonding and fixing the second fine particles 13 via a silica film (an example of a binder) 14 formed by a sol-gel method, and the glass substrate 11, the first and second fine particles Reactive groups that react with surface functional groups of 12a and 13 to form bonds A reaction liquid containing a compound 15 having a fluorocarbon group is brought into contact with the surface of the glass substrate 11b to which the first and second fine particles are bonded and fixed, and the glass group in which the first and second fine particles are bonded and fixed. Step C (see FIG. 1) of forming a water / oil repellent / antifouling thin film 15a bonded and fixed to the surface of the material 11b through a bond formed by a reaction between a surface functional group and a reactive group. It is manufactured by the method which has.
Hereinafter, each process will be described in more detail.

(1) Process A
There is no restriction | limiting in particular about the shape of the glass base material 11 used in the process A, The thing of shapes other than flat form, such as a lens and a prism, can also be used. Moreover, there is no restriction | limiting in particular also about the magnitude | size of the glass base material 11, The thing of arbitrary magnitude | sizes can be used. Furthermore, there is no restriction | limiting in particular also about the material of the glass base material 11, The thing of arbitrary materials, such as soda lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, can be used, from polymethyl methacrylate etc. An organic material such as acrylic glass (plexiglass) can also be used.

Before bringing into contact with the first dispersion, it is preferable to clean the surface of the glass substrate 11 and remove the dirt adhering to the surface. For the cleaning, any method such as immersion in a cleaning solution (heating, stirring, ultrasonic irradiation or the like may be used in combination), excimer laser irradiation, or the like can be used.

Similar to the glass substrate 11, the shape of the first fine particles 12 used in the step A is not particularly limited, but is preferably spherical or substantially spherical. The size of the first fine particles 12 is 50 nm to 5 mm, preferably 50 nm to 400 nm, and more preferably 100 to 200 nm. In particular, for the production of the water and oil repellent antifouling glass 10 that requires transparency for use in glass windows, solar energy utilization devices, optical instruments, etc., the transparency is reduced due to scattering or irregular reflection of incident light. In order to suppress, the size of the first fine particles 12 needs to be 400 nm or less, which is shorter than the wavelength of visible light. The material of the first fine particles 12 is not particularly limited, and any material such as soda lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, silica, alumina, zirconia, etc. can be used. An organic material such as acrylic glass (plexiglass) made of methyl methacrylate or the like can also be used. In particular, when fine particles made of a hard inorganic oxide such as silica, alumina, or zirconia are used, the hardness and wear resistance of the surface of the obtained water / oil repellent / antifouling glass 10 can be improved.

For the preparation of the first dispersion, an arbitrary solvent is used as long as the first fine particles 12 can be uniformly dispersed and do not react with the glass substrate 11 and the first fine particles 12 or cause swelling or deformation. However, from the viewpoints of volatility, safety, environmental load, economy, and the like, lower alcohol solvents such as water, ethanol, isopropyl alcohol, and mixed solvents thereof are preferable. The amount of the solvent depends on the size and specific gravity of the first fine particles 12 and is therefore difficult to determine uniquely. For example, the amount of the solvent is 4 to 200 times the weight of the first fine particles 12 (first The concentration of the first fine particles 12 contained in the dispersion is about 0.5 to about 20% by weight), preferably 10 to 100 times, more preferably 10 to 50 times. If the amount of the solvent is too small, the resulting first dispersion becomes a slurry, making it difficult to uniformly disperse the first fine particles 12 on the surface of the glass substrate 11, and conversely if too much, Efficiency is reduced.

When the first dispersion liquid is applied to the surface of the glass substrate 11 and then the solvent is evaporated, the first fine particles 12 can be uniformly dispersed on the surface of the glass substrate 11 (see FIG. 2B). . For the application of the first dispersion, any method such as a dip coating method, a spin coating method, a spray method, a screen printing method, or the like can be used.

Next, the surface of the glass substrate 11 is heated to obtain a glass substrate 11a in which the first fine particles (12) are fused to the surface. Although the heating temperature and the heating time depend on the glass substrate 11 and the material of the first fine particles 12 used, it is difficult to determine uniquely. For example, as the glass substrate 11, soda-lime glass, When silica fine particles are used as the first fine particles 12, the glass substrate 11 a in which the first fine particles (12) are fused to the surface is obtained by heating at 650 ° C. for about 30 minutes to 1 hour (FIG. 2). (See (C)). FIG. 2C shows a state in which the vicinity of the interface between the glass substrate 11 and the first fine particles 12a fused to the surface is fused together as an example, but there is an interface between the two. It may be.

(2) Process B
Although there is no restriction | limiting in particular about the shape of the 2nd fine particle 13 used in the process B, It is preferable that it is spherical or substantially spherical. The size of the second fine particles 13 is 1/100 or more and 1/5 or less of the particle size of the first fine particles 12, and is 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 5 to 50 nm. In particular, for the production of the water and oil repellent antifouling glass 10 that requires transparency for use in glass windows, solar energy utilization devices, optical instruments, etc., the transparency is reduced due to scattering or irregular reflection of incident light. In order to suppress, the size of the second fine particles 13 needs to be 400 nm or shorter, which is shorter than the wavelength of visible light, and 1/100 or more and 1/5 or less of the particle size of the first fine particles 12. The material of the second fine particles 13 is not particularly limited, and any material such as soda lime glass, crystal glass, quartz glass, borosilicate glass, glass ceramics, silica, alumina, zirconia, and the like can be used. An organic material such as acrylic glass (plexiglass) made of methyl methacrylate or the like can also be used. In particular, when fine particles made of a hard inorganic oxide such as silica, alumina, or zirconia are used, the hardness and wear resistance of the surface of the obtained water / oil repellent / antifouling glass 10 can be improved.

As the binder precursor used for the preparation of the second dispersion, a substance capable of forming a transparent metal oxide film by a sol-gel method, more specifically, tetraalkoxysilane Si (OR) ₄ (R is , Lower alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, etc.), boric acid trialkoxide B (OR) ₃ , aluminum trialkoxide Al (OR) ₃ , titanium tetraalkoxide Ti (OR) _{4 and} other metal alkoxides, and mixtures thereof.

For the preparation of the second dispersion, the second fine particles 13 can be uniformly dispersed, react with the glass substrate 11a and the second fine particles 13 fused with the first fine particles, or cause swelling or deformation. In addition, a solvent that can dissolve the metal alkoxide and does not decompose by reacting with the metal alkoxide is used. Specific examples of the solvent that can be used include lower alcohol solvents such as methanol, ethanol, and isopropyl alcohol, and mixed solvents thereof.

The amount of the solvent used for the preparation of the second dispersion is difficult to determine uniquely because it depends on the size and specific gravity of the second fine particles 13. 4 to 200 times the weight (the concentration of the second fine particles 13 contained in the second dispersion is about 0.5 to about 20% by weight), preferably 10 to 100 times, more preferably 10 to 50 times . If the amount of the solvent is too small, the obtained second dispersion becomes a slurry, and it becomes difficult to uniformly disperse the first fine particles 12 on the surface of the glass substrate 11. Efficiency is reduced.

When the second dispersion is applied to the surface of the glass substrate 11a to which the first fine particles (12) have been fused and then the solvent is evaporated, a sol is formed on the surface of the glass substrate 11a to which the first fine particles have been fused. -The second fine particles 13 can be bonded and fixed in a state of being uniformly dispersed through a silica film (hereinafter sometimes abbreviated as “silica film”) 14 formed by a gel method (see FIG. 3B). ). For the application of the second dispersion, any method such as a dip coating method, a spin coating method, a spray method, a screen printing method, or the like can be used. Next, when the heat treatment is further performed to sinter the silica coating 14, the second fine particles 13 can be more firmly bonded and fixed to the surface of the glass substrate 11a to which the first fine particles are fused. When the sintering temperature is increased, the silica coating 14 is melted or softened, and the second fine particles 13 can be fused. At this time, if phosphoric acid or boric acid of about 5% of the metal alkoxide is added to the second dispersion, the melting point of the silica coating 14 can be lowered to about 500 ° C. By sintering for about 30 minutes, the second fine particles 13 can be fused to the surface of the glass substrate 11a fused with the first fine particles.

In the present embodiment, the first fine particles 12 are directly fused on the surface of the glass substrate 11 in the step A, and the silica coating 14 is interposed on the surface of the glass substrate 11a on which the first fine particles are fused in the step B. The second fine particles 13 are bonded and fixed, but both methods can be used for bonding and fixing the first and second fine particles 12 and 13 in both steps A and B. In addition, even when one of the glass substrate 11 and the first and second fine particles 12 and 13 is an organic material, it is possible to perform bonding and fixing by fusion if possible. However, since the organic material has a lower melting point and softening temperature than the inorganic material and easily undergoes thermal decomposition, the heating temperature needs to be lower than that of the inorganic material. Furthermore, a photocurable resin or an adhesive (epoxy adhesive or cyanoacrylate adhesive) may be used as the binder.

In the present embodiment, the glass substrate 11 is used as it is for the production of the glass substrate 11a in which the first fine particles are fused in the process A, but the temperature is lower than that of the glass substrate 11 before the process A. A film for fusing the first fine particles 12 may be formed on the surface of the glass substrate 11. As the coating, any coating (transparent coating) that has transparency and can fuse the first fine particles 12 at a temperature lower than that of the glass substrate 11 can be used, but it was formed by a sol-gel method. A dry gel film of a metal oxide such as silicon oxide or aluminum oxide is preferred.

When a metal alkoxide solution containing a condensation catalyst (details will be described later) is applied to the surface of the glass substrate 11 and then the solvent is evaporated, hydroxyl groups and alkoxyl groups generated by hydrolysis of the alkoxyl groups by moisture in the air. A condensation reaction takes place between them and a transparent dry gel film of metal oxide is formed on the surface of the glass substrate 11. Since there are more free hydroxyl groups than the glass substrate 11 on the surface and inside of the unsintered dry gel film, it can be fused with the first fine particles 12 at a temperature lower than that of the glass substrate 11.

The 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 11. It can be performed by applying to the surface and evaporating the solvent.
Condensation catalysts, cocatalysts, solvent types, tetraalkoxysilane concentrations, and catalyst addition amounts that can be used will be described later.

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 1st microparticles | fine-particles 12 used for manufacture of the water repellent / oil repellent antifouling glass 10, 5-50 nm is preferable. When the water-repellent / oil-repellent antifouling glass 10 is produced using the glass substrate 11 having a silica dry gel film on the surface thus obtained, the heat treatment in the step A is performed at a low temperature of 300 ° C. or less. Can be done. Therefore, even when the glass substrate 11 that has been tempered in advance with air cooling is used, it is possible to manufacture the glass substrate 11a in which the first fine particles are fused without deteriorating the strengthening degree by heating at a high temperature.

(3) Process C
Water / oil / oil repellent / antifouling bonded and fixed to the surface of the glass substrate 11b to which the first and second fine particles are bonded and fixed through a bond formed by the reaction of the surface functional group and the reactive group. The reaction liquid used for forming the water-soluble thin film 15a and producing the water / oil / oil repellent glass 10 is an alkoxysilane compound containing a fluorocarbon group (an example of a compound having a reactive group and a fluorocarbon group). A condensation catalyst for promoting a condensation reaction between a hydroxyl group (an example of a surface functional group) and an alkoxysilyl group on the surface of the glass substrate 11b to which the first and second fine particles are bonded and fixed, and a non-aqueous system It is prepared by mixing with an organic solvent.

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

_{(I) CF 3 (CF 2} ) n -Y-Z- (CH 2) m -Si (OR) 3

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.

Examples of the alkoxysilane compound containing a fluorocarbon group represented by the formula (I) include compounds shown in the following (1) to (12).

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

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 reaction solution was applied to the surface of the glass substrate 11b to which the first and second fine particles were bonded and fixed and reacted in air at room temperature, the alkoxysilyl group and the first and second fine particles were bonded and fixed. The hydroxyl group on the surface of the glass substrate 11b undergoes a condensation reaction to produce a water / oil repellent / antifouling thin film 15a containing a fluorocarbon group having a structure as shown in Chemical Formula 1 below. The three single bonds extending from the oxygen atom are bonded to the surface of the glass substrate 11b to which the first and second fine particles are bonded and fixed, or to the silicon (Si) atom of the adjacent silane compound, of which at least One is bonded to a silicon atom on the surface of the glass substrate 1.

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 water adhering to the surface of the glass substrate 11b to which the first and second fine particles are bonded and fixed. Therefore, the glass in which the first and second fine particles are bonded and fixed. It is preferable to remove these impurities in advance by thoroughly washing and drying the substrate 11b.
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 H3 from Japan Epoxy Resin Co., which is a ketimine compound, is used as the condensation catalyst instead of dibutyltin oxide and the other conditions are the same, the reaction time can be reduced to about 1 hour.

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.

The organic acid that can be used is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and malonic acid.

For the preparation of the reaction 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.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, the substrate is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted materials, and the surface is covered with a water- and oil-repellent and antifouling thin film 15a. Glass 10 is obtained.

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

After the reaction, if the excess reaction solution is left in the air without being washed away with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group becomes an alkoxysilyl group. Causes a condensation reaction. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the water / oil repellent antifouling glass 10. This polymer film is not fixed to the surface of the water / oil / oil / repellency antifouling glass 10 by a covalent bond, but has water / oil / oil repellent / antifouling properties because it has a fluorocarbon group. Therefore, it can be used as the water / oil repellent / antifouling glass 10 in this state as long as the durability is somewhat inferior.

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 solution can be prepared and reacted with the glass substrate 11a to which the first fine particles are fused in the same manner as the alkoxysilane compound.

Since the film thickness of the monomolecular water-repellent / oil-repellent antifouling thin film 15a is at most about 1 nm, it is about 5 to 50 nm formed on the surface of the glass substrate 11b to which the first and second fine particles are fused. The unevenness of is almost unaffected. In addition, due to the unevenness effect (so-called “lotus leaf effect”), the apparent surface energy of the water / oil repellent / antifouling glass 10 can be reduced, and the water droplet contact angle is 140 ° or more (in this embodiment). About 150 °) and super water-repellent properties can be realized.

Moreover, as a halosilane compound containing the fluorocarbon group which can be used in the process C, the compound shown to following (21)-(26) is mentioned. Moreover, the isocyanate silane compound shown to following (27)-(32) can also be used.

(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
(27) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(28) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(29) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(30) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(31) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(32) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃

The water / oil repellent antifouling glass 10 has a water droplet contact angle of about 150 degrees. From the study results using various volumes of water droplets (0.02-0.08 ml), it was confirmed that 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 droplets. Yes. Therefore, when the water / oil repellent / antifouling glass 10 is used as a window glass plate for a vehicle or a building, most water droplets cannot fall on the surface and fall down.

The water / oil repellent / antifouling glass 10 is excellent in durability such as wear resistance and weather resistance, water droplet separation (sliding), and antifouling properties, and is required to have a water / oil repellent / antifouling function. It can be used for glass windows in vehicles and buildings. Vehicles that can use the water- and oil-repellent and antifouling glass 10 include automobiles, railway vehicles, ships, and the like, and can be used as window glass plates for all windows regardless of driver seats, cabins, etc. it can. In particular, when used for a glass window for a driver's seat, it also has an effect of improving visibility from the driver's seat. Moreover, as a building which can use the water-repellent / oil-repellent antifouling glass 10, any building such as a detached house, an apartment house, and an office building can be cited.

Further, when the water and oil repellent antifouling glass 10 is passed to a solar energy utilization device, it is possible to suppress a decrease in utilization efficiency of solar energy due to adhesion of dirt, scattering of incident light, irregular reflection, etc., and durability and weather resistance. Provided is a solar energy utilization device that is excellent in performance and can be used for a long time even under harsh outdoor environments. Specific examples of the solar energy utilization device include a solar water heater, a solar battery, and a greenhouse.

Further, the water / oil repellent / antifouling glass 10 can also be applied to a member for an optical device that requires a water / oil repellent / antifouling function. Examples of members for optical equipment include lenses for cameras, spectrometers, etc., prisms, mirrors, faceplates of display devices such as PDPs, etc., durability such as wear resistance and weather resistance, water droplet separation (water sliding properties) It is also possible to form a water / oil repellent antifouling antireflection film excellent in antifouling property, and to provide an optical device excellent in optical performance, a PDP display with less surface reflection, and the like.

Next, examples carried out for confirming the effects of the present invention will be described. These examples are illustrative only and are not intended to limit the scope of the invention.
Example 1: Production of water and oil repellent antifouling glass (1)
First silica fine particles having an average particle diameter of about 130 nm were dispersed in ethanol to prepare a first dispersion. This is applied to the surface of a glass plate for a solar water heater, which is a flat glass substrate, and after evaporating the ethanol solvent, it is heated at 630 ° C. for 25 minutes to place the first silica fine particles on the surface of the glass substrate. Fused. Since the melting point of silica was 2000 ° C. or higher, the first silica fine particles were not fused together. On the other hand, the first silica fine particles in contact with the surface of the glass base material were intruded into the surface of the glass base material and fused to the surface along with the softening of the glass. Thereafter, the surface of the glass substrate on which the first silica fine particles were fused was washed, and the first silica fine particles not fused on the surface were removed.

Next, a sol-gel solution (silica concentration 2%) prepared by adding a trace amount of water and phosphoric acid to a methanol solution of tetramethoxysilane was applied to the surface of the glass substrate on which the first silica fine particles were fused and then dried. And the silica film which has a film thickness of about several nanometers was formed. After the second silica fine particles having an average particle size of about 15 nm are dispersed in ethanol and applied to the entire surface of the silica coating, the ethanol is evaporated and further sintered at 600 ° C. for 30 minutes, and then not fused to the surface. The second silica fine particles were removed by washing.

At this time, if phosphoric acid or boric acid is added to the sol-gel solution in a solid content of about 5%, the melting point of the silica coating can be reduced to about 500 ° C. The second silica fine particles were sufficiently fused at the sintering temperature. In addition, the unevenness derived from the first silica fine particles was not impaired under this heating condition.

After weighing 99 parts by weight of heptadecafluorodecyltrimethoxysilane CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , 1 part by weight of dibutyltin diacetylacetonate (condensation catalyst), A reaction solution having a concentration of about 1% by weight was dissolved in siloxane. The reaction solution was applied to the surface of the glass substrate on which the first and second silica fine particles were fused, and reacted at room temperature. At this time, since the surface of the first and second silica fine particles and the silica coating contains a large number of hydroxyl groups, the heptadecafluorodecyltrimethoxysilane-Si (OCH ₃ ) group and the hydroxyl group are converted into the condensation catalyst. It reacts in the presence of alcohol (in this case, de-CH ₃ OH) to form a bond as shown in the following chemical formula (Chemical Formula 2), and the water- and oil-repellent and antifouling thin film containing a fluorocarbon group is on the surface. The film was formed with a film thickness of about 1 nanometer in a state of being chemically bonded to the film.

After that, the excess reaction solution is washed and removed with dichloromethane, and then the water and oil repellent, covered with a water and oil repellent and antifouling thin film (monomolecular film) containing fluorocarbon groups chemically bonded to the surface over the entire surface. A water and oil repellent antifouling glass for solar water heaters having antifouling and antireflection functions could be produced. FIG. 4 shows a scanning electron microscope (SEM) photograph of the surface of the water / oil / oil repellent antifouling glass thus obtained. As the first and second silica fine particles are fused to the surfaces of the glass substrate and the first silica fine particles, respectively, complex irregularities are formed on the surface. It was confirmed that the water repellency, oil repellency and antifouling property were improved as compared with the case where a water / oil repellent / antifouling thin film was formed on the surface. However, since the sizes of the first and second silica fine particles used for the production were both shorter than the wavelength of visible light, the transparency was hardly deteriorated.

Note that the firing temperature at the time of fusing the first and second silica fine particles is 250 ° C. or higher and lower than the softening temperature of the base material, so that the fine particles can be firmly fused to the glass surface. Silica fine particles were buried in the silica coating or inside the glass substrate. Therefore, the heating temperature must be about the softening degree of the substrate or less.

On the other hand, at this time, the formed water- and oil-repellent and antifouling thin film on the surface of the fine particles has the effect of reducing the surface energy of the silica fine particles, and the apparent surface of the substrate surface along with the unevenness having a fractal structure. It has the effect of greatly reducing energy. When the water droplet contact angle was actually measured, although some variation was observed, the contact angle was about 150 ° and the critical surface energy was about 1 to 3 mN / m.

When the water- and oil-repellent and antifouling glass obtained in this way is installed in a solar water heater and tested for practical use, dirt in the air and dirt from rainwater hardly adhere to it, and ordinary glass is attached Compared with the initial value, the heat collection efficiency was improved by about 3% on average. In addition, 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 reduction due to the dirt is 5% or less even after one year. .

Example 2: Production of water and oil repellent antifouling glass (2)
Using the same method as in Example 1, fine particles of different sizes (silica fine particles having an average particle diameter of 50 nm and silica fine particles having an average particle diameter of 10 nm were previously added to the surface of the transparent glass substrate used for the light incident surface when manufacturing the solar cell. The glass substrate was fused and used to form a solar cell, and after forming a solar cell, a water- and oil-repellent and antifouling thin film containing a fluorocarbon group was formed. Anti-reflection with a fractal structure in the vicinity of the surface, high water and oil repellency (water contact angle of 153 degrees) and high light transmission (the transmittance of light near 500 nm was about 98%). A solar cell covered with a functional film could be manufactured. Furthermore, as a result of conducting a practical use test with this cell, even after half a year, dirt in the air and dirt due to rainwater hardly adhered, and the average light utilization efficiency is about 3% compared to the case where ordinary glass is attached. I was able to improve. 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. Although the water droplet contact angle at this time was about 153 °, practically similar effects were obtained when the water droplet contact angle was 140 ° or more.

Example 3: Production of water and oil repellent antifouling glass (3)
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 the optical characteristics were not inferior and lenses with excellent antifouling properties could be produced.

Example 4: Production of water and oil repellent antifouling glass (4)
A PDP (Plasma Display Panel) face plate with a water / oil / oil repellent / anti-fouling anti-reflective coating formed on the surface using the same method as in Example 1 was tested and used. In addition, it was possible to efficiently reduce the reflection of indoor fluorescent lamps and the like onto the face plate surface, and the visibility was greatly improved.

The present invention provides a condensing member for solar energy utilization devices such as glass windows, solar water heaters, solar cells, and greenhouses in buildings and vehicles that require durability and weather resistance in addition to water repellency, oil repellency, and antifouling properties. It can be suitably applied to optically transmissive members of optical devices and display devices.

DESCRIPTION OF SYMBOLS 10 Water repellent / oil repellent antifouling glass 11 Glass substrate 11a Glass substrate 11b in which the first fine particles are fused Glass substrate 12 in which the first and second fine particles are bonded and fixed to the surface 12 First fine particles 12a Glass First fine particles 13 second fine particles 14 fused to the surface of the base material 14 Silica coating 15 formed by the sol-gel method 15a Compound having reactive groups and fluorocarbon groups Water repellent and oil repellent antifouling thin film

Claims (21)

Transparent first fine particles bonded and fixed to the surface of the glass substrate so as to cover at least a part of the surface of the transparent glass substrate, and having a melting point higher than the softening temperature of the glass substrate ;
Transparent second fine particles having a particle diameter smaller than that of the first fine particles, which are bonded and fixed to the surface of the first fine particles so as to cover at least part of the surface of the first fine particles;
Said first and second possess a water-repellent, oil-repellent antifouling film formed on the surface of fine particles, the particle size of the first particles is at 50nm or more 400nm or less, the second grain particles The diameter is 1/100 or more and 1/5 or less of the particle diameter of the first fine particles, and the first fine particles are not bonded to the surface of the first fine particles bonded to the surface of the substrate. Water repellent and oil repellent antifouling glass. Wherein the first particles consist of fusible material on the glass substrate, water-repellent, oil-repellent antifouling glass according to claim 1, characterized in that it fused to the surface of the glass substrate. The first fine particles, water-repellent, oil-repellent antifouling glass of claim 1, wherein the through binder are bound and fixed to the surface of the glass substrate. Said second particles are made of fusible material in the first fine particle, from claim 1, characterized in that it is fused to the surface of the first fine particles 3 of any one of claims Water and oil repellent antifouling glass. The second fine particles, water-repellent, oil-repellent antifouling glass according to any one of claims 1 to 3, characterized in that via a binder which is coupled fixed to the surface of the first particles. 6. The water and water repellency according to any one of claims 1 to 5 , wherein the first and second fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia. Oil antifouling glass. The water / oil repellent / antifouling glass according to any one of claims 1 to 6 , wherein the water / oil repellent / antifouling thin film is a monomolecular film. The water / oil repellent / antifouling glass according to any one of claims 1 to 7 , wherein the surface has a critical surface energy of 1 mN / m or more and 3 mN / m or less. A first dispersion containing first fine particles dispersed in a solvent is applied to the surface of the glass substrate, and after evaporating the solvent, the first fine particles are bonded and fixed to the surface of the glass substrate. Step A,
The first fine particles are bound and fixed to a second dispersion liquid containing second fine particles dispersed in a solvent and having a particle size of 1/100 or more and 1/5 or less of the particle size of the first fine particles. Applying to the surface of the glass substrate, evaporating the solvent, and then bonding and fixing the second fine particles to the surface of the glass substrate to which the first fine particles are bonded and fixed; and
And a step C of forming a water- and oil-repellent and antifouling thin film on the surface of the glass substrate to which the first and second fine particles are bonded and fixed. Production method. The method for producing a water / oil repellent / antifouling glass according to claim 9 , wherein in the step A, the first fine particles are fused to the surface of the glass substrate. The first solution includes a first binder precursor that generates a binder by evaporation of a solvent and / or a subsequent chemical reaction. In the step A, the first solution is formed on the surface of the glass substrate via the binder. 10. The method for producing a water- and oil-repellent and antifouling glass according to claim 9, wherein 1 fine particle is bonded and fixed. The water repellent according to any one of claims 9 to 11 , wherein in the step B, the second fine particles are fused to the surface of the glass substrate to which the first fine particles are bonded and fixed. Manufacturing method of oil-repellent antifouling glass. The glass substrate on which the second solution includes a second binder precursor that generates a binder by evaporation of a solvent and / or a subsequent chemical reaction, and the first fine particles are bonded and fixed in the step B The method for producing a water / oil repellent / antifouling glass according to any one of claims 9 to 11 , wherein the second fine particles are bonded and fixed to the surface of the glass using a binder. 14. The water / oil repellent and oil repellent according to claim 11 or 13, wherein the first and / or second binder precursor is a metal sol precursor that forms a transparent metal oxide by a sol-gel method. A method for producing dirty glass. Wherein after step A and / or B, water repellency of any one of claims 9 14, characterized in that washing removes the that was not coupled fixed first and / or second particulate A method for producing oil-proof antifouling glass. In the step C, a reaction liquid containing a compound having a reactive group that forms a bond by reacting with the surface functional groups of the glass substrate and the first and second fine particles and a fluorocarbon group is added to the first and second A film of the compound bonded to and fixed to the surface via a bond formed by a reaction between the surface functional group and the reactive group is brought into contact with the surface of the glass substrate to which the second fine particles are bonded and fixed. The method for producing a water / oil repellent / antifouling glass according to any one of claims 9 to 15 , wherein the glass is formed. The reactive group is an alkoxysilyl group, and the reaction solution is
(1) one or two or more compounds selected from the group consisting of 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, and / or Or (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. 16. A method for producing a water- and oil-repellent antifouling glass according to 16 . 18. The method for producing a water / oil repellent / antifouling glass according to claim 16 or 17, wherein after the step C, the excess reaction solution is washed away. Any one water-repellent, oil-repellent, a glass window having a fouling property glass according to claims 1 to 8. The solar energy utilization apparatus which has the water repellent and oil repellent antifouling glass of any one of Claim 1 to 8 . Optical apparatus having a water-repellent, oil-repellent antifouling glass of any one of claims 1 8.

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