JP4572150B2 - Method for producing water-repellent glass material - Google Patents

Description

The present invention relates to a method for producing a water-repellent glass material .

  A glass material that is installed in the atmosphere and exposed to an environment in which the temperature rises and falls repeatedly tends to cause condensation on the surface due to moisture contained in the atmosphere. In particular, the main components constituting the glass material are silicon, sodium and the like. It is known that the surface of the glass material becomes thin and cloudy when water and the components constituting the glass material react. That is, it is considered that the water turbidity on the surface of the glass material is suppressed if water droplets such as condensation existing on the surface of the glass material flow quickly without remaining on the surface.

  In order to keep the water droplets from staying on the surface of the glass material, it is considered desirable to drop the water droplets by their own weight by increasing the contact angle between the water droplets and the surface as much as possible. For this reason, a method of increasing the contact angle by the surface tension of water droplets that are formed by forming fine irregularities on the surface of the glass material and various water repellent glasses using these methods have been proposed.

  Incidentally, when the contact angle between the water droplet and the surface of the glass material is around 120 °, it is called a water repellent state, and when the contact angle is around 150 °, it is called a super water repellent state.

  As a method for improving water repellency, a water repellent film in which a petal-like transparent alumina film (amorphous alumina film) is formed on a transparent glass substrate and covered with a water repellent film has been reported (see Patent Document 1). In addition, a water-repellent coating has been reported in which a preparation liquid composed of dimethyl silicon alkoxide is applied on a transparent glass substrate to form a transparent silica film (see Patent Document 2). Furthermore, a method for producing a coated substrate in which a coating solution obtained by mixing thermally decomposable resin fine particles in water glass is coated on a transparent glass substrate has also been reported (see Patent Document 3). According to the methods described in Patent Documents 1 to 3, any of them requires baking and heating, which is not always a simple method in terms of process management and equipment.

  In addition, a super water-repellent substrate including a substrate, a base film mainly composed of silicon oxide, and a water-repellent coating film containing a fluoroalkyl group has been reported as a technique that omits baking and heating (Patent Document). 4). According to the technique of Patent Document 4, it has been pointed out that there is a possibility of super water repellency and transparency being impaired due to restrictions due to the atmosphere (temperature, humidity) when forming a base film on a substrate.

Based on the above knowledge, the inventor has strongly formed fine irregularities on the surface of the glass material, and has proposed a water-repellent glass material comprising a simple production method and a production method thereof.
JP-A-9-202650 Japanese Patent Laid-Open No. 10-259037 JP 2005-81292 A International publication WO03 / 039856

The present invention has been made in view of the above, the fine irregularities formed on the surface of the glass material is firmly fixed to increase the water repellency, water repellency glass can be produced relatively easily A method for manufacturing a material is provided.

The invention according to claim 1 is a silane coupling agent coating step for coating a glass material surface with a silane coupling agent containing an organosilane, and a silane coupling for drying the glass material coated with the silane coupling agent. An agent drying step, a surface modification step in which a flame of a fuel gas containing a modifying substance is sprayed on the glass material surface coated with the silane coupling agent to disperse the modifying substance on the glass material surface, and the modification A water repellent coating step for coating a water repellent containing a fluororesin polymer on the surface of a glass material in which a porous material is dispersed, and a water repellent drying step for drying the water repellent applied on the surface of the glass material And a method for producing a water-repellent glass material.

The invention of claim 2, wherein the organosilane is 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyl trimethoxy silane, according to claim 1 which is selected from any one or more vinyl trimethoxysilane The present invention relates to a method for producing a water-repellent glass material.

The invention of claim 3 relates to the method for producing a water-repellent glass material according to claim 1 or 2 , wherein the modifying substance is either one or both of an alkylsilane compound and an alkoxysilane compound.

Invention of Claim 4 concerns on the manufacturing method of the water-repellent glass material of any one of Claim 1 thru | or 3 whose spraying time of the flame of the fuel gas containing the said modifying material is less than 5 second.

Invention of Claim 5 concerns on the manufacturing method of the water-repellent glass material of any one of Claim 1 thru | or 4 whose solvent of the water repellent containing the said fluororesin polymer is hydrofluoroether.

According to the method for producing a water-repellent glass material according to the first aspect of the present invention, a silane coupling agent coating step of coating an organosilane-containing silane coupling agent on the surface of the glass material, and applying the silane coupling agent A silane coupling agent drying step for drying the applied glass material, and a flame of a fuel gas containing the modifying substance is sprayed on the surface of the glass material coated with the silane coupling agent, so that the modifying substance is applied to the glass material surface. A surface modifying step for dispersing, a water repellent applying step for applying a water repellent containing a fluororesin polymer on the surface of the glass material in which the modifying substance is dispersed, and a repellent applied on the surface of the glass material. Since it includes a water repellent drying step for drying the liquid agent, it is possible to form water and water repellent performance by forming fine irregularities on the surface of the glass material relatively easily. Moreover, it is difficult to be influenced by the atmosphere such as temperature and humidity during manufacturing, and management of manufacturing conditions becomes easy.

According to the method for producing a water-repellent glass material according to the invention of claim 2, in the invention of claim 1 , the organosilane is 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Since it is selected from one or more of vinyltrimethoxysilane, it can be estimated that the modification substance dispersed on the surface is promoted to be fixed and the fine irregularities formed on the surface of the glass material are firmly fixed. .

According to the method for producing a water-repellent glass material according to the invention of claim 3, in the invention of claim 1 or 2 , the modifying substance is either one or both of an alkylsilane compound and an alkoxysilane compound. Good meltability and mixing with fuel gas.

According to the method for producing a water-repellent glass material according to the invention of claim 4, in the invention of any one of claims 1 to 3 , the spraying time of the flame of the fuel gas containing the reforming substance is within 5 seconds Therefore, it is possible to achieve both water repellency based on the average roughness of the glass material surface and translucency.

According to the method for producing a water-repellent glass material according to the invention of claim 5, in the invention according to any one of claims 1 to 4 , the solvent of the water-repellent agent containing the fluororesin polymer is hydrofluoroether. Therefore, the compatibility with the fluororesin polymer contained in the water repellent is good, and the coatability is good.

The present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a schematic process diagram of a method for producing a water-repellent glass material according to an embodiment of the present invention, FIG. 2 is a conceptual diagram showing a contact angle on the surface of a glass material, and FIG. 3 is a schematic diagram of a surface modifying apparatus.

The physical properties of the water- repellent glass material are such that when the glass material is a colorless transparent smooth glass plate and the thickness thereof is 1.2 mm, the light transmittance near a wavelength of 350 nm satisfies 75% or more, and the wavelength of 360 to 360 The transmittance at 700 nm satisfies 80% or more. At the same time, as shown in FIG. 2, the water-repellent glass material 10 has a water-repellent surface 11 such that the contact angle θ of the water droplet 20 of distilled water is 125 ° or more. Furthermore, as will be apparent from examples described later, the super water repellency may be exhibited with a contact angle θ of 150 ° or more. That is, the water-repellent glass material in this case has good translucency and water-repellent performance.

  Here, the glass material to which water repellency is imparted corresponds to glass materials such as lead glass (crystal glass), borosilicate glass, and quartz glass in addition to soda lime glass that is widely used. Of course, considering the transmittance as described above, the glass material is best colorless and transparent. However, if the transmittance is not strictly determined, a colored transparent glass material or an opaque glass material can also be used, and water repellency can be imparted thereto.

  Various methods are used for evaluating the water repellency. In the embodiment, a droplet method that is relatively widely used and easy to evaluate is adopted. That is, a drop of distilled water was transferred (dropped) onto the surface of the glass material and imaged, and the contact angle was measured from the image (see FIG. 4 described later).

As described above in the background art, there are fine irregularities on the surface of the glass material as a factor of the water repellency. Therefore , as will be apparent from Examples described later, the arithmetic average roughness (Ra) of the glass material surface satisfies 15 nm to 90 nm. The arithmetic average roughness is an index of surface irregularities. For this measurement, a scanning probe microscope, an atomic force microscope (AFM) or the like is mainly used.

As for the water-repellent glass material having the above physical properties, the production method for exerting the water-repellent performance is shown in FIG. 1 and, as defined in the invention of claim 1 , a silane coupling agent coating step (S1), silane This is because the coupling agent drying step (S2), the surface modification step (S3), the water repellent coating step (S4), and the water repellent drying step (S5) are included. As described above, soda lime glass, lead glass (crystal glass), borosilicate glass, quartz glass and the like are preferably used as the glass material to which water repellency is imparted in consideration of the transmittance. However, for the purpose of providing only water repellency, a colored transparent glass material and an opaque glass material can also be used.

In the silane coupling agent coating step (S1), the surface of the glass material is washed in advance and the surface of the glass material is kept clean. Painted. As defined in the invention of claim 2 , as the organosilane, 3-glycidoxypropyltrimethoxysilane (see the structure (I) of Chemical Formula 1), 3-methacryloxypropyltrimethoxysilane (the structure of Chemical Formula 2 (II)) )) And vinyltrimethoxysilane (see Structure (III) of Chemical Formula 3). These organosilanes are mainly diluted with a solvent such as alcohol and prepared to a concentration of about 0.5 to 5%.

  As a method for applying the silane coupling agent, there are a method in which the glass material is immersed in an organosilane solution diluted with alcohol, and a method in which the glass material is spray-coated, which are appropriate. Needless to say, various organosilanes other than the above-mentioned organosilanes are preferably used. In addition, each organosilane is used as a single species in the examples, but it is also possible to use a mixture of a plurality of species.

  In the silane coupling agent drying step (S2), the silane coupling agent on the surface of the glass material is dried. In this step, the film is dried by a known dryer at about 100 ° C. for about 30 minutes. Alternatively, it may be left still and air dried.

  The surface modification step (S3) is a kind of combustion chemical vapor deposition (CCVD), and a flame of combustion gas containing a modifying substance is sprayed on the surface of a glass material coated with a silane coupling agent. As a result, the modifying substance is dispersed and attached to the surface of the glass material. A good example of the process of the step S3 is the itro process (Itro (registered trademark)) of the surface modification method for solid substances disclosed in Japanese Patent No. 3557194.

  FIG. 3 is a diagram schematically showing the surface modification apparatus 100. The surface reforming apparatus 100 includes a supply unit 101 that supplies a fuel gas such as air or propane, a storage unit 110 (tank) that stores a melt reforming substance 115, and a burner 103 (a jetting unit). 102 is connected. Reference numeral 104 denotes a mixing unit of the supply unit and the storage unit. Reference numeral 111 denotes a heating unit that heats the melt-modified material in the storage unit. The air / combustible gas and the melt-modifying substance are mixed and ejected from the burner 103 as a flame F. Therefore, the flame F comes into contact with the surface 151 of the glass material 150 before the treatment, and at the same time, the modifying substance in the flame F is scattered while being oxidized and attached to the surface 151. Reference numeral 152 denotes a surface after adhesion.

As the modifying substance used in the surface modification step of S3, as defined in the invention of claim 3 , one or both of an alkylsilane compound and an alkoxysilane compound are used. These are melted by being heated (heated) by the heating unit, and mixed with the fuel gas such as air or propane supplied from the supply unit at a suitable concentration ratio. Examples of the alkylsilane compound include tetramethylsilane, tetraethylsilane, 1,2-dichlorotetramethylsilane, 1,2,3-trichlorotetramethylsilane, and the like. Examples of the alkoxysilane compound include tetramethoxysilane and dimethyldiethoxysilane. The modifying substance is preferably an alkylsilane compound or an alkoxysilane compound having a boiling point of less than 100 ° C. from the viewpoint of meltability and mixing with fuel gas. In addition to the above, the modifying substance may include an alkyl titanium compound and an alkyl titanium compound.

Modified substances containing Si such as alkylsilane compounds and alkoxysilane compounds are not necessarily dispersed on the surface of the glass material as they are, but Si is oxidized due to the oxidation reaction caused by the combustion of fuel gas, etc. It is considered that the fine particles mainly containing SiO ₂ are dispersed on the surface. In addition, as characterized in the production method of the present invention, the above-mentioned silane coupling agent is presumed to act as a scaffold (anchor) for the modifying substance dispersed on the surface. Therefore, it is assumed that fine particles mainly composed of SiO ₂ are firmly fixed on the surface of the glass material, and the friction resistance is confirmed as is apparent from the examples described later. Since various forms dispersed on the surface of the glass material are assumed, it is assumed that the modifying substance is dispersed and attached to the surface of the glass material.

As will be appreciated from FIG. 3, Ru flame fuel gas containing a reforming material is found blown to the surface of the glass material. In such a case, a difference occurs in the amount of modifying substance (amount of SiO ₂ or the like) dispersed and adhered to the glass material surface depending on the spraying time. Of course, the average roughness of the glass material surface increases (roughens) as the flame spraying time increases. However, if the flame spraying time is extremely increased, white turbidity occurs due to the scattered light on the surface of the glass material, and the transmittance as the glass material decreases. Therefore, in applications where translucency is desired, consideration is given to both water repellency and translucency based on the average roughness of the glass material surface. Based on the above, the invention is defined as the invention of claim 4 and , as is clear from the examples described later, it is desirable that the flame spraying time be within 5 seconds.

In the water repellent coating step (S4), a water repellent containing a fluororesin polymer is coated on the surface of the glass material in which the modifying substance is dispersed as described above. As the water repellent solvent, hydrofluoroether is used as defined in the invention of claim 5 . Preferable examples of the hydrofluoroether include C ₄ F ₉ OCH ₃ , C ₄ H ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF _{2 and the} like. As a method for applying the water repellent, there are a method of immersing a glass material in a water repellent, a method of spray coating, and brush coating as in the case of the silane coupling agent of S1, which are appropriate. Thus, since hydrofluoroether is a solvent, compatibility with the fluororesin polymer contained in the water repellent is good, and coating properties are good. In addition, each hydrofluoroether can be used as a single species or a mixture of a plurality of species.

  In the water repellent drying step (S5), the water repellent on the surface of the glass material is dried. In this step, the film is dried by a known dryer at about 100 to 150 ° C. for about 30 minutes. Alternatively, it may be left still and air dried.

  As described above, the water-repellent glass material produced by the method for producing a water-repellent glass material is excellent in water repellency, and water droplets are prevented from staying on the glass material surface. Therefore, it is suitable when it is installed and constructed in a place that directly contacts the atmosphere. Further, in the manufacturing method, heating up to several hundred degrees C. is not performed, and the surface modification process is performed by a relatively simple apparatus. For this reason, the burden on facilities such as a firing furnace is reduced during production. Furthermore, as understood from the manufacturing method described above, since the drying process and the surface modification process are included, it is considered that the atmosphere such as temperature and humidity during the manufacturing has little influence on the product performance, and the manufacturing conditions Management is easy.

[Glass material]
As a glass material imparting water repellency, a glass slide made of soda lime glass (Matsunami Glass Co., Ltd .: S-1225, size—length 26 mm × width 65 mm × thickness 1.2 mm) was used. Prior to the treatment, the surface of the slide glass was washed with ethanol and quickly wiped off with a paper towel (Crecia Co., Ltd .: Kimwipe).

[Preparation, coating and drying of silane coupling agent]
Acetic acid was added to methanol at 1% of its weight, and about 1.0 to 2.0% of its weight was added to the methanol solution and mixed to prepare a silane coupling agent diluted with organosilane.

  Therefore, a silane coupling agent whose organosilane is 3-glycidoxypropyltrimethoxysilane (see structure (I)) is used as the A agent. Similarly, a silane coupling agent that is 3-methacryloxypropyltrimethoxysilane (see structure (II)) is used as B agent, and a silane coupling agent that is vinyltrimethoxysilane (see structure (III)) is used as C agent. did. Incidentally, the water repellent glass material composed of the A agent was designated as “Prototype Example A”, the water repellent glass material comprised of the B agent was designated as “Prototype Example B”, and the water repellent glass material comprised of the C agent was designated as “Prototype Example C”.

  A glass material (slide glass) was dipped into each of the three types of silane coupling agents (A agent, B agent, C agent) prepared as described above, and quickly taken out. Subsequently, each glass material coated with a silane coupling agent was carried into a dryer and dried while applying hot air at 100 ° C. for 30 minutes.

[Surface modification of glass materials]
After drying, each glass material coated with a silane coupling agent was subjected to surface modification using an apparatus manufactured by Ishimat Japan Co., Ltd. The reforming substances were tetramethylsilane and tetramethoxysilane, and a fuel gas flame containing them was sprayed. In the surface modification, a single flame is applied to the glass material (slide glass) for about 1 second. Therefore, spraying was performed twice (2 seconds) on each of the glass materials using the silane coupling agent (A agent, B agent, C agent) to obtain prototype examples A2, B2, and C2. Similarly, spraying was performed 5 times (for 5 seconds) to obtain prototype examples A5, B5, and C5. The air pressure: 0.018 MPa, gas pressure: 3.6 KPa, DFM:. 0.35 L / min.

[Water repellent coating and drying]
A prototype manufactured by Sumitomo 3M Co., Ltd. as a water repellent: Novec EGC-1720 (containing 0.1% by weight of a fluororesin polymer, and the solvent is mainly composed of C ₄ F ₉ OCH ₃ ) and subjected to the above treatment. Each of A2, B2, C2, A5, B5, and C5 was dipped and quickly taken out. Subsequently, each prototype example coated with a water repellent was carried into a dryer and dried while hot air of 100 to 150 ° C. was applied for 30 minutes, and the prototypes A2, B2, C2, A5, B5, C5 An aqueous glass material was obtained.

[Create comparative example]
In the comparative example, without performing the surface modification described above, using the same glass material as the prototype example (slide glass (manufactured by Matsunami Glass Co., Ltd .: S-1225)), applying a silane coupling agent, etc. Comparative examples H1 to H8 were prepared. In each comparative example, the drying conditions are the same as in the prototype.

  In Comparative Example H1, a silane coupling agent (agent A) was applied and dried, and then Aerosil (N972 manufactured by Nippon Aerosil Co., Ltd .: R972) dispersed in 0.5% by weight of n-hexane was applied. The primary average particle diameter of hydrophobic silica of the aerosil is 16 nm. In Comparative Example H2, after applying a silane coupling agent (C agent) and drying, Aerosil prepared in the same manner as in Comparative Example H1 was applied.

  In Comparative Example H3, a silane coupling agent (agent A) was applied and dried, and then methanol-organosilica sol manufactured by Nissan Chemical Industries, Ltd .: XBA-ST (particle size 10-15 nm, colloidal silica solid content 30%, dispersed) A solution prepared by adding 1.0% (medium xylene / n-butanol) was applied and dried. In Comparative Example H4, the silane coupling agent was changed to the B agent from Comparative Example H3, and the subsequent procedure was the same as Comparative Example H3. In Comparative Example H5, the silane coupling agent was changed to C agent compared to Comparative Example H3, and the subsequent procedure was the same as Comparative Example H3.

  In Comparative Example H6, a silane coupling agent (agent A) was applied and dried, and then the organosilica sol manufactured by Nissan Chemical Industries, Ltd .: methanol silica sol (particle size 10 to 15 nm, colloidal silica solid content 30%, dispersed in methanol) A solution prepared by adding 1.0% methanol) was applied and dried. In Comparative Example H7, the silane coupling agent was changed to B agent from Comparative Example H6, and thereafter, the same procedure as in Comparative Example H6 was performed. In Comparative Example H8, the silane coupling agent was changed to C agent compared to Comparative Example H6, and thereafter, the same procedure as in Comparative Example H6 was performed.

[Measurement of contact angle]
The contact angle was measured by using an automatic contact meter “CA-Z type” manufactured by Kyowa Interface Science Co., Ltd. under the conditions of a temperature of 21.1 ° C. and a relative humidity of 60% RH. A fluororesin-coated female syringe was attached to the automatic contact meter, and 4 μL of distilled water was added dropwise. However, when the contact angle was measured by dropping distilled water, the water repellency was quite high, so the water droplets at the tip of the fluororesin-coated female syringe of the automatic contact meter were forcibly pressed against the surface of each glass material. It was measured. The photograph in FIG. 4A is immediately before the water droplet at the tip is cut off. The photograph in FIG. 4B shows a state where water droplets are forcibly transferred to the surface of the glass material.

  Five glass materials (slide glass) were used for each prototype and comparative example, and three points were measured for each glass material. Therefore, for Prototype Example A2, the contact angle for 15 times was measured as 5 sheets × 3 points. Table 1 below shows simple average values, maximum values, minimum values, and standard deviations obtained by measuring contact angles (°) for each of 15 trial manufacture examples A2, B2, C2, A5, B5, and C5. Table 2 shows simple average values, maximum values, minimum values, and standard deviations obtained by measuring contact angles (°) for 15 times of Comparative Examples H1 to H8.

As is apparent from the contact angle measurement results, the prototypes generally have a high contact angle. Looking at the average value of the prototypes, the majority is around 150 °, and it can be considered that the super-water-repellent performance is almost obtained. Incidentally, although there are variations when Looking at minimum is not less 120 ° or more contact angle with any prototype example, it is certainly have a water repellency. On the other hand, as is clear from the average value of the comparative example, it cannot be said that water repellency is sufficient. From this result, it can be said that the surface modification of the glass material surface is effective in improving the water repellency.

[Observation of surface]
The inventor has convinced that the difference in the contact angle is caused by the surface roughness of the glass material surface. Then, in order to grasp | ascertain the shape of the glass material surface, the inventor observed by AFM (DFM) mode and the scanner: 20 micrometers using the probe microscope (SII nanotechnology Co., Ltd .: SPI-3700 SPA-300). FIG. 5 shows an image by AFM.

  FIG. 5A shows a single glass material before treatment used in the prototype and the comparative example. This Ra = 0.14 nm. FIG. 5B is a prototype example B2, where Ra = 17.4 nm. FIG. 5C shows a prototype example B5, where Ra = 83.8 nm. Ra is the arithmetic mean roughness and was calculated using the calculation method of JIS-B-0601. In each image diagram, the measurement area is 10 μm × 10 μm, and the maximum height of the scale in the Z direction is 1000 nm.

  As is obvious from the figure, an increase in the surface roughness can be confirmed by accompanying the surface modification of the glass material. In particular, from the comparison between FIGS. 5B and 5C, the increase in the surface roughness depends on the number of surface modifications.

[Measurement of transmittance]
The transmittance was measured for the above-mentioned three types of samples (glass material before processing, prototype B2 and prototype B5) observed with a probe microscope. An ultraviolet-visible spectrophotometer (JASCO Corporation: V560) was used for the measurement. A deuterium discharge tube was used as a light source for a wavelength of 340 nm or less, and a tungsten iodine lamp was used as a light source for 340 to 900 nm. The result of the transmittance is the graph of FIG. The blank in FIG. 6 is a glass material before processing.

  As understood from the graph, the transmittance in the vicinity of a wavelength of 350 nm is 75% or more and the transmittance at a wavelength of 360 to 700 nm satisfies 80% or more in any prototype. From comparison with the prototype example B2 and the prototype example B5, the transmittance tends to decrease as the number of surface treatments (2 times and 5 times) increases. That is, the transmittance decreases due to the increase in surface roughness accompanying the surface modification of the glass material. Accordingly, considering the securing of good transmittance and the acquisition of water repellency, it can be said that the number of surface treatments is 5 times or less (that is, the flame spraying time is within 5 seconds). In addition, the reflection suppression effect by application | coating of a water repellent can be considered as a factor in which the transmittance | permeability of prototype example B2 exceeded the blank (glass material before a process) in a graph.

[Evaluation of friction resistance]
The inventor predicts that the silane coupling agent acts as a scaffold (anchor) for the modifying substance dispersed on the surface of the glass material, and the modification substance (fine particles mainly composed of SiO ₂ ). The sticking property was evaluated by wiping. Therefore, the surface of Prototype Example B2 is lightly wiped with a paper towel (Crecia Co., Ltd .: Kimwipe), and before and after this wiping, the surface of the water-repellent glass material of the Prototype Example is FESEM, that is, a field emission scanning electron microscope (JEOL). Observed by JSM6700F NT).

  The observation results are as shown in FIG. In either case, the acceleration voltage is 3.0 kv and the image is SEI (secondary electron image). FIG. 7A is a photograph before wiping at a magnification of 50000 times, and FIG. 7B is a photograph at a magnification of 100000 times in FIG. FIG. 7C is a photograph at a magnification of 50000 times after wiping of FIG. 7A, and FIG. 7D is a photograph at a magnification of 100000 times in FIG.

  As can be seen from the photographs before and after the wiping, a reduction in the modifying substance dispersed on the surface of the glass material is observed, but it still remains. Therefore, the friction resistance of the surface of the water-repellent glass material was confirmed by the presence of the silane coupling agent and the surface modification treatment (blowing of flame containing organosilane). Accordingly, the inventor expects the water repellent function of the surface of the water repellent glass material to be maintained in actual use.

It is a schematic process drawing of the manufacturing method of the water-repellent glass material which concerns on one Example of this invention. It is a conceptual diagram which shows the contact angle of the glass material surface. It is a schematic diagram of a surface modification apparatus. It is a photograph which shows the measurement condition of the contact angle of the glass material surface. It is an image image by AFM of a water-repellent glass material. It is a graph which shows the measurement result of the transmittance | permeability. It is a photograph by FESEM before and after wiping off a water-repellent glass material.

DESCRIPTION OF SYMBOLS 10 Water-repellent glass material 11 Surface 20 Water drop 100 Surface modification apparatus 103 Burner 110 Storage part 150 Glass material before a process

Claims (5)

A silane coupling agent application step of applying an organosilane-containing silane coupling agent to the glass material surface;
A silane coupling agent drying step of drying the glass material coated with the silane coupling agent;
A surface modification step of dispersing the reforming substance on the glass material surface by spraying a flame of a fuel gas containing the reforming substance on the glass material surface coated with the silane coupling agent;
A water repellent coating step of coating a water repellent containing a fluororesin polymer on the surface of the glass material in which the modifying substance is dispersed;
And a water repellent drying step for drying the water repellent applied to the surface of the glass material. The method for producing a water-repellent glass material according to claim 1 , wherein the organosilane is selected from one or more of 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and vinyltrimethoxysilane. . The method for producing a water-repellent glass material according to claim 1 or 2 , wherein the modifying substance is one or both of an alkylsilane compound and an alkoxysilane compound. The method for producing a water-repellent glass material according to any one of claims 1 to 3 , wherein a spray time of the flame of the fuel gas containing the modifying substance is within 5 seconds. The method for producing a water-repellent glass material according to any one of claims 1 to 4 , wherein a solvent of the water-repellent agent containing the fluororesin polymer is hydrofluoroether.

Images