JP2012219004A - Wear-resistant water-ultrarepellent, oil-repellent antifouling glass, method for manufacturing the same, glass window using the same, solar energy utilization device, optical equipment and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repelling and oil-repelling antifouling glass which has improved durability such as wear resistance and weatherability, water droplet repellency, oil repellency, and antifouling performance in addition to water-repelling and oil-repelling functions, a method for manufacturing the same, and a glass window using the same, a solar energy utilization device, and optical equipment.SOLUTION: A wear-resistant, water-ultrarepellent and oil-repellent antifouling glass 10 has a glass substrate 14 having a plurality of confetti-like projections 11 and a water-repellent, oil-repellent and antifouling thin film 15a bonded to at least one part of the surface of the glass substrate 14 having a confetti-like projection 11, and the confetti-like projection 11 is composed of a substantially hemispherical first projection 12 and a plurality of conically-shaped or bamboo shoot shaped second projection 13 which are formed on the surface of the first projection 12 and have a smaller diameter of the bottom face than the first projection 12.

Description

The present invention relates to a wear-resistant super water- and oil-repellent antifouling glass, a method for producing the same, a glass window using the same, a solar energy utilization device, an optical device, and a display device, and more specifically, has high durability and TECHNICAL FIELD The present invention relates to a wear-resistant super water- and oil-repellent antifouling glass having a water-repellent and oil-repellent antifouling coating formed on the surface, a method for producing the same, a glass window using the same, a solar energy utilization device, an optical device, and a display .

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. 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 wear-resistant water- and oil-repellent and antifouling glass to which the chemical adsorption film monomolecular film described in Patent Document 1 is applied has a problem that durability such as wear resistance and weather resistance is poor.

Therefore, the present inventor fused to the surface of the plate-like base material, the water- and oil-repellent antifouling transparent fine particles made of a hard material such as silica, alumina, zirconia, and the surface of the base material Water / oil / oil / repellency / antifouling anti-reflective coating having a coating of a water / oil / oil / repellency / antifouling substance covering a portion where fine particles as a transparent core are not fused, and an optical device using the same A solar energy utilization device and a display have been proposed (see Patent Document 2). The transparent fine particles fused to the surface of the base material provide unevenness on the surface of the base material and improve wear resistance, so that in addition to water and oil repellency and antifouling properties, it is possible to improve wear resistance. Have.

Further, in order to further improve the water / oil repellency / antifouling property by forming a surface structure having complicated irregularities on the surface of the glass substrate, fine particles as the first core are formed on the surface of the glass substrate. After the bonding and fixing, the second fine particles are bonded and fixed to the surface of the glass substrate to which the first core fine particles are bonded and fixed, and the first and second fine particles are bonded and fixed. Produced by forming a water- and oil-repellent and antifouling thin film on the surface, and a first fine particle serving as a core bonded and fixed to the surface of the glass substrate so as to cover at least a part of the surface of the glass substrate; A second fine particle having a diameter smaller than that of the first fine particle serving as a core, and fixed to the surface of the fine particle so as to cover at least a part of the surface of the first fine particle, and the first and second fine particles Water and oil repellent antifouling thin film formed on the surface of Water-repellent, oil-repellent antifouling glass proposed (see Patent Document 3).

JP-A-4-132737 JP 2008-247699 A JP 2010-222199 A

However, in the production method described in Patent Document 3, it is difficult to bond and fix the second fine particles to the surface of the first fine particles that are the core. For example, the water and oil repellency is high and the water droplet contact angle exceeds 160 °. The problem that it is not possible to express soiling remains.

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. It is an object of the present invention to provide a wear-resistant super water- and oil-repellent antifouling glass having improved resistance, a method for producing the same, a glass window using the same, a solar energy utilization device, an optical device, and a display device.

According to the first aspect of the present invention, the glass substrate having a plurality of confetti-like protrusions and a water / oil / oil repellent and antifouling thin film bonded to at least a part of the surface of the glass substrate having the protrusions. The scallop-shaped projections are formed on the surface of the substantially hemispherical first projection as a core and the surface of the first projection, and the diameter of the bottom surface is smaller than the diameter of the first projection. The object is solved by providing a wear-resistant super water- and oil-repellent and antifouling glass comprising a plurality of conical or bamboo shoot-like second protrusions.
A surface structure having complex irregularities can be formed by bonding and fixing fine particles as cores on the surface of the glass substrate to form first protrusions, and further bonding and fixing second protrusions on the surface. 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 surface of the confetti-like protrusions, it is possible to impart water repellency, oil repellency and antifouling properties to the surface of a generally glass substrate having hydrophilicity.

In the wear-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention, the first protrusion is formed by fusing a fine particle having a spherical or substantially spherical core to the surface of the glass substrate. Alternatively, they may be formed by bonding via a binder.
Since the first fine particles as the core are bonded and fixed to the surface of the glass substrate through fusion or binder, the wear resistance, weather resistance, etc. of the surface of the wear-resistant super water- and oil-repellent antifouling glass Can be improved.

In the wear-resistant super water- and oil-repellent antifouling glass according to the first aspect of the present invention, the glass substrate, the scalloped projections and the binder are all transparent,
The diameter of the core fine particles is 30 to 100 nm,
The second protrusion may have a height of 10 to 30 nm.
Both the glass substrate and the confetti-like protrusion are transparent, the diameter of the core fine particle is smaller than the shortest wavelength (400 nm) of visible light (preferably about 100 nm), and the diameter of the second protrusion is several nm. Since it is ˜several tens nm (preferably 10 to 30 nm), it is possible to provide a wear-resistant super water / oil repellent / antifouling glass excellent in transparency and optical properties because scattering and irregular reflection of incident light are suppressed.

In the wear-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention, the height of the second protrusion is 1/10 or more and 1/2 or less of the height of the first protrusion. It may be.

In the wear-resistant super water / oil / oil repellent glass according to the first aspect of the present invention, the second protrusion may be made of zinc oxide.

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

In the wear-resistant super 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- and oil-repellent and antifouling thin film is a monomolecular film, the color tone and transparency of the resulting wear-resistant super water- and oil-repellent and antifouling glass are not impaired.

In the wear-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention, the lower the critical surface energy of the surface, the better, but it may be 1 mN / m or more and 3 mN / m or less. preferable.
Since the critical surface energy of the surface is in the above range, it is possible to improve all of the water repellency, oil repellency and antifouling property of the resulting wear-resistant super water / oil / oil repellent glass.

According to a second aspect of the present invention, there is provided a step A in which spherical or substantially spherical core particles dispersed in a solvent are sprayed on the surface of a glass substrate, and the glass substrate on which the core particles are sprayed. Heating to bond and fix or fuse the fine particles as the core to the surface of the glass substrate to form a substantially hemispherical first protrusion; and to the surface of the first protrusion, the first protrusion Forming a plurality of conical or bamboo shoot-like second protrusions having a bottom diameter smaller than the diameter of one protrusion, and a confetti-like protrusion comprising the first and second protrusions; By providing a process D for forming a water- and oil-repellent and antifouling thin film on the surface of the glass substrate, the method for producing a wear-resistant super water- and oil-repellent and antifouling glass is provided. The present invention solves the above problems.
In Steps A to C, complex irregularities can be formed on the surface of the glass substrate by forming a plurality of confetti-like projections bonded or fused 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 core 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 repellency and antifouling property thin film on at least the surface of the confetti-like protrusions.

In the method for producing a wear-resistant super water- and oil-repellent antifouling glass according to the second aspect of the present invention, the glass substrate and the first and second protrusions are both transparent, The height of the protrusion may be 30 to 300 nm.

In the above case, it is preferable that the diameter of the core fine particle is 30 to 100 nm, and the height of the second protrusion is 10 to 30 nm.

In the method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to the second aspect of the present invention, in the step B, the glass substrate after the dispersion is applied is not less than the softening point of the glass substrate. The core fine particles may be fused to the surface of the glass substrate by heating at a temperature equal to or lower than the melting point of the core fine particles.

In the method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to the second aspect of the present invention, the dispersion comprises a binder precursor that generates a binder by evaporation of a solvent and / or subsequent chemical reaction. In addition, in the step B, the core fine particles may be bonded and fixed or fused to the surface of the glass substrate via the binder.
Since the core fine particles are bonded, fixed, or fused to the surface of the glass substrate via fusing or a binder, the wear resistance, weather resistance, etc. of the surface of the abrasion-resistant super water- and oil-repellent antifouling glass are improved. it can.

In the process for producing a wear-resistant super water- and oil-repellent and antifouling glass according to the second aspect of the present invention in which the fine particles as the core are bonded and fixed via a binder in the step B, the binder precursor is a sol-gel It may be a metal sol precursor that forms a transparent metal oxide by a 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 The second fine particles can be bonded and fixed to the surface of the glass substrate and the fine particles serving as the first core, respectively.

In the method for producing a wear-resistant super water- and oil-repellent antifouling glass according to the second aspect of the present invention, after the step B, the core fine particles that are not bonded and fixed may be washed away. .

In the method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to the second aspect of the present invention, in the step B, the core adhered, bonded, or fused to the surface of the glass substrate; It is preferable to form the protrusions made of zinc oxide on the surface of the fine particles to be formed using an atmospheric pressure plasma method.

In the method for producing a wear-resistant super water- and oil-repellent antifouling glass according to the second aspect of the present invention, in the step D, it reacts with the surface functional groups of the glass substrate and the confetti-like protrusions to bond. A surface of the glass substrate on which the first and second fine particles are bonded and fixed, and a reaction solution containing a compound having a reactive group for forming a fluorinated carbon group or a dimethylsilyl group. A film of the compound bonded and fixed to the surface may be formed through a bond formed by a reaction between the compound and the reactive group.
Durability of water- and oil-repellent antifouling thin film by bonding and fixing the water-repellent and oil-repellent antifouling thin film to the surface of confetti-like protrusions through a bond formed by the reaction between the surface functional group and the reactive group 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- and oil-repellent and antifouling thin film can be made into a monomolecular film, thus impairing the transparency of the abrasion-resistant super water- and oil-repellent and antifouling glass produced. There is no.

In the method for producing an abrasion-resistant super water / oil / oil repellent glass according to the second aspect of the present invention, the step C may be performed before the step B.

In the third aspect of the present invention, the glass substrate, the confetti-like protrusion and the binder are all transparent, the diameter of the core fine particle is 30 to 100 nm, and the height of the conical or bamboo-like protrusion is high. The object is solved by providing a glass window having a wear-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention having a thickness of 10 to 30 nm.
In addition to water repellency, oil repellency and antifouling properties, a glass window having excellent transparency and durability can be provided.

In the fourth aspect of the present invention, the glass substrate, the confetti-like protrusion and the binder are all transparent, the diameter of the core fine particle is 30 to 100 nm, and the height of the conical or bamboo shoot-like protrusion is high. The above-mentioned problems are solved by providing a solar energy utilization device having the wear-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention having a thickness of 10 to 30 nm.
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.

In the fifth aspect of the present invention, the glass substrate, the confetti-like protrusions and the binder are all transparent, the diameter of the core fine particles is 30 to 100 nm, and the height of the conical or bamboo shoot-like protrusions is The above-mentioned problems are solved by providing an optical apparatus having the abrasion-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention having a thickness of 10 to 30 nm.
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.

In the sixth aspect of the present invention, the glass substrate, the confetti-like projections and the binder are all transparent, the diameter of the core fine particles is 30 to 100 nm, and the height of the conical or bamboo shoot-like projections is The above-mentioned problems are solved by providing a display device having an abrasion-resistant super water- and oil-repellent and antifouling glass according to the first aspect of the present invention having a thickness of 10 to 30 nm.
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, a display device excellent in transparency and optical characteristics can be provided.

According to the present invention, in addition to the water / oil repellent / antifouling function, durability such as wear resistance and weather resistance, water-drop separation (also referred to as water slidability), oil repellency, and antifouling properties are improved. A water- and oil-repellent 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 Provided are a solar energy utilization device with excellent efficiency, and an optical device excellent in durability, transparency and optical characteristics in addition to water repellency, oil repellency and antifouling properties, and a display device excellent in fingerprint resistance. .

It is explanatory drawing which demonstrated typically the cross-section of the abrasion-resistant super water-repellent oil-repellent antifouling glass which concerns on one embodiment of this invention. It is explanatory drawing of the process of fuse | melting the microparticles | fine-particles used as a core on the surface of a glass base material in the manufacturing method of the abrasion-resistant super water-repellent oil-repellent antifouling glass. It is explanatory drawing of the process of forming a several cone-shaped protrusion on the surface of the microparticles | fine-particles used as the core fused | fused to the surface of the glass base material in the manufacturing method of the abrasion-resistant super water-repellent oil-repellent antifouling glass. 2 is a scanning electron microscope (SEM) photograph of the surface of the wear-resistant super water- and 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 illustrations, and the size of the compound that forms the glass substrate, the first and second protrusions, and the water / oil repellent / antifouling thin film is not necessarily an actual size. The ratio is not reflected.
As shown in FIG. 1, a wear-resistant super water- and oil-repellent and antifouling glass 10 according to a first embodiment of the present invention includes a glass substrate 14 on which a plurality of confetti-like protrusions 11 are formed, It has a water- and oil-repellent and antifouling thin film 15 a bonded to at least a part of the surface of the glass substrate 14 a having the protrusions 11. The confetti-like projections 11 are formed on the surface of a substantially hemispherical first projection 12 as a core and the surface of the first projection 12, and a plurality of conical shapes having a bottom diameter smaller than the diameter of the first projection 12. Or it is comprised by the 2nd protrusion 13 of a bamboo shoot shape.

The abrasion resistant super water / oil repellent antifouling glass 10 has a step A in which spherical or substantially spherical fine particles 16 dispersed in a solvent are dispersed on the surface of the glass substrate 14, and the fine particles 16 as the core are formed. A step B of heating the dispersed glass substrate 14 to bond or fix the core fine particles 16 to the surface of the glass substrate 14 to form a first hemispherical first protrusion 12; A plurality of bamboo shoot-like protrusions 13 (conical or bamboo shoot-like) having a bottom diameter smaller than the diameter of the first protrusion 12 are attached to the surface of the first protrusion 12 attached, bonded, fixed or fused to the surface of the material 14. An example of the second projection of the first projection: Hereinafter, the process C for forming the projection may be abbreviated as “projection”), and a hemispherical projection (the first projection of the first projection) formed by the fused fine particles 16a. Example) Consists of 12 and bamboo shoot-like projections 13 Produced by the process and a step D of forming a water-repellent oil-repellent antifouling thin film 15a on the surface of the candy-like projections 11 are formed glass substrate 14a to be.
Hereinafter, the processes A to D will be described in more detail.

(1) Process A
There is no restriction | limiting in particular about the shape of the glass base material 14 used for manufacture of abrasion-resistant super water-repellent oil-repellent antifouling glass 10, 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 14, 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 14, 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 spraying the fine particles 16, it is preferable to clean the surface of the glass substrate 14 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), corona treatment, oxygen plasma treatment, or excimer light irradiation can be used.

The fine particles 16 serving as the core used in the production of the wear-resistant super water / oil repellent antifouling glass 10 are spherical or substantially spherical, and have a diameter of 10 nm to 5 mm, preferably 20 nm to 400 nm, more preferably 30 to 30 nm. 100 nm. In particular, for the production of the abrasion-resistant super water- and oil-repellent antifouling glass 10 that requires transparency for use in display devices such as glass windows, solar energy utilization devices, optical devices, touch panels, etc. In order to suppress a decrease in transparency due to light scattering and irregular reflection, the diameter of the core fine particle 16 needs to be 400 nm or less, which is shorter than the wavelength of visible light, and the most preferable diameter range is 30 to 30 above. 100 nm.

There are no particular restrictions on the material of the core fine particles 16, 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 acid can also be used. In particular, when using fine particles as the core composed of hard inorganic oxides such as silica, alumina, zirconia, etc., the hardness and wear resistance of the surface of the resulting wear-resistant super water- and oil-repellent antifouling glass 10 are reduced. It can be improved.

The dispersion of the fine particles 16 serving as the core can be performed using any method. For example, a method of evaporating the solvent after applying a dispersion liquid in which the fine particles 16 serving as the core are dispersed in a solvent to the glass substrate 14 is available. Preferably used.
For the preparation of the dispersion, any solvent can be used as long as it can uniformly disperse the fine particles 16 serving as the core and does not react with the glass substrate 14 and the fine particles 16 serving as the core or cause swelling or deformation. However, from the viewpoints of volatility, safety, environmental burden, economy, and the like, lower alcohol solvents such as water, ethanol, isopropyl alcohol, and mixed solvents thereof are preferable. Although the amount of the solvent depends on the size and specific gravity of the fine particles 16 serving as the core, it is difficult to uniquely determine. For example, the amount of the solvent is 4 to 200 times the weight of the fine particles 16 serving as the core (first The concentration of the fine particles 16 serving as the core 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 fine particles 16 serving as the core on the surface of the glass substrate 14, and conversely if too much, Efficiency is reduced.

When the solvent is evaporated after applying the dispersion on the surface of the glass substrate 14, the fine particles 16 serving as the core can be uniformly dispersed on the surface of the glass substrate 14. 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.

(2) Process B
Next, the surface of the glass substrate 14 on which the fine particles 16 serving as the core are dispersed is heated at a temperature not lower than the softening point of the glass substrate 14 and not higher than the melting point of the fine particles 16 serving as the core. A fused glass substrate 14a is obtained. Although the heating temperature and the heating time depend on the glass substrate 14 used and the material of the fine particles 16 serving as the core, it is difficult to determine uniquely. For example, as the glass substrate 14, soda lime glass, the core In the case where silica fine particles are used as the fine particles 16 to be used, a glass substrate in which the core fine particles 16 are fused to the surface by heating at 650 ° C. for about 30 minutes to 1 hour, and the core fine particles are fused. The material 14b is obtained.

The dispersion may contain a binder precursor that generates a binder that can be bonded to the surfaces of the glass substrate 14 and the core fine particles 16 by evaporation of the solvent and / or subsequent chemical reaction. As the binder precursor, a substance capable of forming a transparent metal oxide film by a sol-gel method, more specifically, tetraalkoxysilane Si (OR) ₄ (R is methyl group, ethyl group, n-propyl). Group, lower alkyl group such as i-propyl group, etc.), metal alkoxide such as boric acid trialkoxide B (OR) ₃ , aluminum trialkoxide Al (OR) ₃ , titanium tetraalkoxide Ti (OR) ₄ , and These mixtures are mentioned.

When the dispersion is applied to the surface of the glass substrate 14 and then the solvent is evaporated, a silica coating (hereinafter referred to as “silica coating”) formed on the surface of the glass substrate 14 by a sol-gel method may be used. )), The fine particles 16 as the core can be bonded and fixed in a uniformly dispersed state. In this case, a silica coating may also be formed on the surface of the fine particles 16 serving as the core as long as the shape of the fine particles 16 serving as the core is not impaired and the size is within a desired range. In addition, the solution containing a binder precursor is prepared separately from the dispersion, and after applying the binder precursor solution, the solvent is evaporated, and the surface of the glass substrate 14 on which the silica coating has been formed in advance is not included. A dispersion may be applied.

Subsequently, when a heat treatment at about 200 to 500 ° C. is further performed to sinter the silica coating, the fine particles 16 serving as the core can be bonded and fixed to the surface of the glass substrate 14 more firmly. When the sintering temperature is increased to such an extent that the base glass is softened, the silica coating is melted or softened, and the fine particles 16 serving as the core can be fused. At this time, if phosphoric acid or boric acid of about 5% of the metal alkoxide is added to the dispersion, the melting point of the silica coating can be lowered to about 500 ° C., so that the base glass is softened. The fine particles 16 serving as the core can be fused to the surface of the glass substrate 14 by sintering at 500 to 600 ° C. for about 30 minutes.

Even when either the glass substrate 14 or the fine particles 16 serving as the core is an organic material, bonding and fixing by fusion can be performed as long as heat resistance can be ensured. 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 14 is used as it is for the production of the glass substrate 14b in which the core fine particles are fused in the steps A and B, but before the step A, the glass substrate 14 is used. Alternatively, a film for fusing the fine particles 16 serving as the core at a low temperature may be formed on the surface of the glass substrate 14. As the coating, any coating (transparent coating) having transparency and capable of fusing the fine particles 16 serving as the core at a temperature lower than that of the glass substrate 14 can be used. However, the coating 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 14 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 the glass substrate 14 and a transparent dry gel film of metal oxide is formed on the surface of the glass substrate 14. Since there are more free hydroxyl groups than the glass substrate 14 on the surface and inside of the unsintered dry gel film, it can be fused to the fine particles 16 at a lower temperature than the glass substrate 14.

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 14. 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 sol solution can be applied by an arbitrary method such as a dip coating method, a spin coating method, a spray method, an ink jet method, or a screen printing method. Moreover, although the film thickness of a dry gel film is based also on the diameter of the fine particle 16 used as the core used for manufacture of abrasion-resistant super water-repellent oil-repellent antifouling glass 10, 5-50 nm is preferable. When the glass substrate 14 having a silica dry gel film thus obtained is used to produce the wear-resistant super water / oil / oil repellent glass 10, the heat treatment in the step A is performed at 300 ° C. It becomes possible to carry out at the following low temperature. Therefore, even when a glass substrate 14 that has been tempered in advance with air cooling is used, it is possible to produce a glass substrate 14b in which fine particles as cores are fused without degrading the degree of strengthening by heating at a high temperature.

Process C
Next, a plurality of conical shapes having a bottom diameter smaller than the diameter of the core fine particles 16 on the surface of the core fine particles 16 (or 16a) attached, fixed, or fused to the surface of the glass substrate 14 or A bamboo shoot-like projection 13 is formed. For the formation of the protrusions 13, a chemical vapor deposition (CVD) method of zinc oxide using an atmospheric pressure plasma method is preferably used from the viewpoint of productivity, ease of enlargement, and the like. For forming the projections 13 made of zinc oxide using the plasma CVD method, a linear plasma torch can be used, a zinc complex or an organic zinc compound can be used as a zinc source, and helium, argon, or the like can be used as a carrier gas. Specific examples of the zinc complex or metal zinc compound include diethyl zinc (Zn (C ₂ H ₅ ) ₂ ), diacetylacetonate zinc (Zn (acac) ₂ ), bis (2-methoxy-6-methyl-3,5). -Heptane dionate) zinc (Zn (MOPD) ₂ ) and the like.

The protrusion 13 formed in this way has a conical or bamboo shoot shape, and the diameter of the bottom surface is, for example, 1/100 or more and 1/5 or less of the diameter of the fused fine particles 16a. 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 10 to 20 nm. The aspect ratio of the protrusion 13 defined by the ratio of the height of the protrusion 13 to the diameter of the bottom surface of the protrusion 13 is, for example, 1 or more and 5 or less. If the aspect ratio is too large, the second protrusions 23 are easily broken, and if the aspect ratio is too small, the fractal property of the surface shape of the wear-resistant super water / oil repellent / antifouling glass 10 is reduced. However, sufficient water / oil repellent and antifouling performance is hardly exhibited.

In particular, for the production of the abrasion-resistant super water- and oil-repellent antifouling glass 10 that requires transparency for use in display devices such as glass windows, solar energy utilization devices, optical devices, touch panels, etc. In order to suppress a decrease in transparency due to light scattering or irregular reflection, the height of the protrusion 13 is preferably 10 to 30 nm.

Note that, as shown in FIG. 3, bamboo shoot-like protrusions 13 may be formed on the surface of the glass substrate 14. Here, even if the process C is performed before the process B, a similar surface shape can be formed.

Process D
A water- and oil-repellent and oil-repellent material that is bonded and fixed to the surface of the glass substrate 14a on which the gold-peel-like protrusions (11) are formed through a bond formed by a reaction between a surface functional group (not shown) and a surface reactive group. The reaction liquid used for forming the antifouling thin film 15a and producing the abrasion-resistant super water / oil repellent antifouling glass 10 is an alkoxysilane compound containing a fluorocarbon group (surface reactive group and fluorocarbon group). In order to promote the condensation reaction between the hydroxyl group (an example of the surface functional group) and the alkoxysilyl group on the surface of the glass base material 14a on which the gold-peeled projection (11) is formed. It is prepared by mixing a condensation catalyst of the above and a non-aqueous 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 is applied to the surface of the glass substrate 14a on which the confetti protrusions (11) are formed and reacted in air at room temperature, the glass substrate on which the alkoxysilyl groups and the confetti protrusions (11) are formed. The hydroxyl group on the surface of the material 14a 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 atoms are bonded to the surface of the glass substrate 14a on which the confetti-like protrusions (11) are formed or to the silicon (Si) atoms of the adjacent silane compound, and at least one of them is bonded. The book is bonded to silicon atoms 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 inhibited by oils and fats or moisture adhering to the surface of the glass base material 14a on which the confetti-like projections (11) are formed, so that the glass base material on which the confetti-like projections (11) are formed. It is preferable to remove these impurities in advance by thoroughly washing and drying 14a.
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 surface is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances, and then the surface is covered with a water and oil repellent and antifouling thin film 15a. Oil-stain-resistant 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 wear-resistant super water / oil / oil repellent glass 10. This polymer film is not fixed to the surface of the wear-resistant super water / oil / oil repellent antifouling glass 10 by covalent bonds, but has water and oil / oil repellent / antifouling properties because it has a fluorocarbon group. ing. Therefore, it can be used as the wear-resistant super water / oil repellent / antifouling glass 10 even in this state, except that 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. %) Or less), the reaction with the glass substrate 14a on which the preparation of the reaction solution and the confetti-like protrusions (11) are formed can be carried out similarly to the alkoxysilane compound.

Since the film thickness of the monomolecular water- and 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 14a on which the confetti-like projections (11) are formed. The unevenness of is almost unaffected. In addition, this uneven effect (the so-called “lotus leaf effect”) can reduce the apparent surface energy of the wear-resistant super water- and oil-repellent and antifouling glass 10, and the water droplet contact angle is 140 ° or more (present) In the embodiment, it is about 150 °), and super water repellency can be realized.

Moreover, as a halosilane compound containing the fluorocarbon group which can be used in the process D, 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 abrasion resistant super 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 to 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 droplet. Yes. Therefore, when the wear-resistant super water / oil / oil repellent glass 10 is used as a window glass plate for a vehicle or a building, most of the water droplets cannot fall on the surface and fall down.

The wear-resistant super water- and oil-repellent antifouling glass 10 is excellent in durability, such as abrasion resistance and weather resistance, water-dropping property (water slidability), and antifouling properties, and has a water and oil repellent and antifouling function. Can be used for glass windows for vehicles and buildings that require high speed. Vehicles that can use the abrasion-resistant super water / oil repellent antifouling glass 10 include automobiles, railway vehicles, ships, etc., and glass plates for windows of any windows, regardless of driver seats, cabins, etc. Can be used as 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 abrasion-resistant super water-repellent oil-repellent antifouling glass 10, arbitrary buildings, such as a detached house, an apartment house, and an office building, are mentioned.

Further, when the wear-resistant super water / oil repellent antifouling glass 10 is passed to the solar energy utilization device, it is possible to suppress a decrease in the utilization efficiency of solar energy due to adhesion of dirt, scattering of incident light, irregular reflection, etc. Provided is a solar energy utilization device that is excellent in durability and weather resistance and can be used for a long period of 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 wear-resistant super water / oil repellent / antifouling glass 10 can also be applied to members for optical devices that require water / oil repellent / antifouling functions. 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 Abrasion Resistant Super Water / Oil Repellent Antifouling Glass (1)
[1] Fusion of silica fine particles as a core to the glass substrate surface A sol-gel solution (silica concentration 2%) prepared by adding a trace amount of water and phosphoric acid to a methanol solution of tetramethoxysilane is used as a glass substrate. The silica film having a film thickness of about several nanometers was formed by drying after coating on the surface. Silica fine particles having an average diameter of about 130 nm are dispersed in ethanol, applied to the entire surface of the silica coating, ethanol is evaporated, and further sintered at 600 ° C. for 30 minutes, and then the silica fine particles not fused to the surface are washed. Removed.

At this time, if phosphoric acid or boric acid is added to the above sol-gel solution in a solid content of about 5%, the melting point of the silica coating can be reduced to about 500 ° C., so it is about 550-600 ° C. for about 30 minutes. The silica fine particles could be sufficiently fused at the sintering temperature. Further, the unevenness derived from the fused composite fine particles was not impaired under these heating conditions.

Bis (2-methoxy-6-methyl-3,5-heptanedionate) zinc ((Zn (MOPD) ₂ (C ₁₈ H ₃₀ O ₆ Zn), manufactured by Ube Industries)) is used as a zinc source, and helium is used as a plasma gas. The bamboo shoot-like protrusions made of zinc oxide were formed on the surface of the glass substrate on which silica fine particles were fused (see FIG. 4). Here, the conditions of the atmospheric pressure plasma method are as follows: It was as follows.
Vaporizer temperature 100 ° C
Substrate temperature 210 ° C
Plasma He gas flow rate 1400ccm
Carrier He gas flow rate 250ccm
Total He gas flow 1650ccm
Oxygen flow rate 50ccm
Gap (gap between cathode electrode and substrate) 0.5mm
Power supply High frequency pulse power supply Applied voltage 1kV
Frequency 20kHz
Stage moving speed 1mm / s (reciprocating motion between 20mm)
Deposition time 180min

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 fused composite fine particles were fused, and reacted at room temperature. At this time, since the surface of the fused composite fine particles and the silica coating contains a large number of hydroxyl groups, the heptadecafluorodecyltrimethoxysilane-Si (OCH ₃ ) group and the hydroxyl group are removed in the presence of the condensation catalyst. Alcohol (in this case, de-CH ₃ OH) was reacted to form a bond as shown in the following chemical formula (Chemical Formula 8), and the water- and oil-repellent and antifouling thin film containing a fluorocarbon group was chemically bonded to the surface. The film was formed in a thickness of about 1 nanometer.

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 wear-resistant super 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 abrasion-resistant super water / oil / oil repellent glass thus obtained. The fused composite fine particles are fused to the surfaces of the glass substrate and the first silica fine particles, respectively, thereby forming complex irregularities on the surface. As will be described later, the surface of the flat glass substrate is water repellent. It was confirmed that a water droplet contact angle of 160 ± 4 degrees excellent in water repellency, oil repellency and antifouling property can be realized as compared with a water droplet contact angle of about 110 degrees when the oil-repellent antifouling thin film is formed. Moreover, since the size of the fused composite fine particles used for the production was all shorter than the wavelength of visible light, the transparency was hardly deteriorated.

The higher the firing temperature at the time of fusing silica fine particles is 250 ° C. or higher and lower than the softening temperature of the substrate, the stronger the fine particles can be fused to the glass surface. Silica fine particles have been buried inside the 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 drop contact angle was actually measured, although some variation was observed, the contact angle was about 160 ° and the critical surface energy was about 1 to 3 mN / m.

When the wear-resistant super water-repellent oil-repellent antifouling glass obtained in this way is installed in a solar water heater and tested for practical use, dirt from air dust and yellow sand hardly adheres and it rains. For example, self-cleaning and surface reflection of the glass can be reduced by fine surface irregularities, and the heat collection efficiency can be improved by about 3% on average as compared with the case where normal glass is mounted. 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 Abrasion Resistant Super Water / Oil Repellent Antifouling Glass (2)
Similar to Example 1 except that two types of silica fine particles having different diameters (silica fine particles having an average diameter of 50 nm and silica fine particles having an average diameter of 10 nm were used in a mixture of about 1:10) were used. On the surface of the glass plate, confetti-like protrusions were formed. When a water-repellent / oil-repellent / anti-fouling thin film containing a fluorocarbon group is formed after forming this solar cell, the cross section near the surface of the solar cell has a fractal structure and a high water / oil repellent effect (with a water droplet contact angle). 158 °) and a solar cell covered with a film having an antireflection function having high light transmittance (the transmittance of light near 500 nm was about 98%). 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 yellow sand hardly adhere, and if it rains, it is self-cleaned, and furthermore, the glass is formed by fine surface irregularities. The surface reflection can be reduced, and the light utilization efficiency can be improved by about 6% on average as compared with the case of mounting ordinary glass. 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 158 °, practically similar effects were obtained when the water droplet contact angle was 140 ° or more.

Example 3 Production of Abrasion Resistant Super Water / 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 testing purposes. There was almost no adhesion, and the light transmittance was the same as that of the anti-reflection multi-coated film, and the lens was excellent in antifouling property without being inferior in optical characteristics.

Example 4 Production of Abrasion Resistant Super Water / 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 transmittance was 92% or more over the entire wavelength region of visible light.

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

DESCRIPTION OF SYMBOLS 10 Abrasion resistant super water-repellent oil-repellent antifouling glass 11 Gold flat sugar-like protrusion 12 Semi-spherical protrusion 13 Bamboo-like protrusion 14 Glass base material 14a Glass base material 14b with gold flat sugar-like protrusion Fused glass substrate 15 Compound having surface reactive group and fluorocarbon group 15a Water- and oil-repellent antifouling thin film 16 Fine particle 16a serving as the core Fine particle serving as the core fused to the glass substrate

Claims (24)

A glass substrate having a plurality of confetti-like protrusions;
A water- and oil-repellent and antifouling thin film bonded to at least part of the surface of the glass substrate having the protrusions,
The confetti-shaped projections are formed on a substantially hemispherical first projection comprising fine particles as a core and on the surface of the first projection, and a plurality of bottom diameters smaller than the diameter of the first projection. A wear-resistant super-water- and oil-repellent and antifouling glass comprising a conical or bamboo shoot-like second protrusion. 2. The first protrusion is formed by fusing a fine particle, which is a spherical or substantially spherical core, to the surface of the glass base material or by bonding it through a binder. Wear resistant super water and oil repellent antifouling glass. The glass substrate, the confetti protrusions and the binder are all transparent,
The diameter of the core fine particles is 30 to 100 nm,
The wear-resistant super water- and oil-repellent and antifouling glass according to claim 2, wherein the height of the second protrusion is 10 to 30 nm. 4. The wear-resistant super water / oil / oil repellent according to claim 1, wherein a height of the second protrusion is 1/10 or more and 1/2 or less of a height of the first protrusion. Dirty glass. The wear-resistant super water- and oil-repellent and antifouling glass according to any one of claims 1 to 4, wherein the second protrusion is made of zinc oxide. The wear-resistant super water-repellent material according to any one of claims 1 to 5, wherein the core fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia. Oil repellent antifouling glass. The wear-resistant super water / oil / oil repellent and antifouling glass according to any one of claims 1 to 6, wherein the water / oil / oil repellent / antifouling thin film is a monomolecular film. The wear-resistant super water- and oil-repellent and 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 step A of dispersing fine particles, which are the cores of a spherical or substantially spherical core dispersed in a solvent, onto the surface of the glass substrate;
The glass base material on which the core microparticles serving as the core are dispersed is heated to bond and fix or fuse the core microparticles on the surface of the glass base, so that the first hemispherical first A step B of forming a protrusion of
Forming a plurality of conical or bamboo shoot-like second protrusions having a bottom diameter smaller than the diameter of the first protrusion on the surface of the first protrusion; and
And a step D of forming a water- and oil-repellent and antifouling thin film on the surface of the glass substrate on which the confetti-like projections composed of the first and second projections are formed. A method for producing a wearable super water- and oil-repellent antifouling glass. The transparent wear resistance according to claim 9, wherein the glass substrate and the first and second protrusions are both transparent, and the height of the scallop-like protrusions is 30 to 300 nm. A method for producing super water and oil repellent antifouling glass. 11. The wear-resistant super water / oil / oil repellent glass according to claim 10, wherein the core fine particles have a diameter of 30 to 100 nm and the second protrusions have a height of 10 to 30 nm. Manufacturing method. In the step B, the glass substrate after application of the dispersion is heated at a temperature equal to or higher than the softening point of the glass substrate and below the melting point of the core fine particles, and the core fine particles are melted on the surface of the glass substrate. The method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to any one of claims 9 to 11, wherein the glass is worn. The dispersion includes a binder precursor that generates a binder by evaporation of a solvent and / or a subsequent chemical reaction, and in the step B, the fine particles serving as the core are bonded to the surface of the glass substrate through the binder. The method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to any one of claims 9 to 12, wherein the glass is fixed or fused. 14. The method for producing a wear-resistant super water / oil repellent / antifouling glass according to claim 13, wherein the binder precursor is a metal sol precursor that forms a transparent metal oxide by a sol-gel method. . 15. The wear-resistant super-water / oil-repellent / anti-repellent agent according to any one of claims 9 to 14, wherein after the step B, the core fine particles that have not been fixed or fused are washed and removed. A method for producing dirty glass. In the step B, the protrusions made of zinc oxide are formed on the surface of the core fine particles adhered, bonded, or fused to the surface of the glass substrate using an atmospheric pressure plasma method. The method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to any one of claims 9 to 15. In the step D, a reaction solution containing a compound having a reactive group that reacts with a surface functional group of the glass substrate and the saccharoid-like protrusion to form a bond, and a fluorocarbon group or a dimethylsilyl group, A film of the compound that is brought into contact with the surface of the glass substrate on which the first and second protrusions are formed, and is bonded and fixed to the surface via a bond formed by a reaction between the surface functional group and the reactive group The method for producing a wear-resistant super water- and oil-repellent and antifouling glass according to any one of claims 9 to 16, wherein The reactive group is an alkoxysilyl group, and the reaction solution is
(1) one 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. 18. A process for producing a wear-resistant super water- and oil-repellent antifouling glass according to 17. 19. The method for producing a wear-resistant super water / oil repellent / antifouling glass according to claim 17 or 18, wherein the excess reaction solution is washed away after the step C. The method for producing a wear-resistant super water / oil repellent / antifouling glass according to any one of claims 9 to 19, wherein the step C is performed before the step B. A glass window comprising the abrasion-resistant super water- and oil-repellent antifouling glass according to any one of claims 3 to 8. The solar energy utilization apparatus which has the abrasion-resistant super water-repellent oil-repellent antifouling glass of any one of Claim 3 to 8. An optical device comprising the abrasion-resistant super water- and oil-repellent antifouling glass according to any one of claims 3 to 8. A display device comprising the abrasion-resistant super water- and oil-repellent and antifouling glass according to claim 3.