JPH05170487A - Water repelling treatment of substrate and water-repellent substrate - Google Patents

Abstract

PURPOSE:To easily obtain high water repellency by applying a prescribed soln. to the surface of a substrate, carrying out thermal decomposition, bonding and sticking a vapor-deposited film to the surface of the substrate. CONSTITUTION:A fluorine-contg. silane compd. such as CF3(CH2)2Si(OMe)3 having <=100 deg.C b.p. is diluted with methanol, etc., to obtain a soln. for vapor deposition having 0.1wt.% concn. This soln. is applied to the surface of a substrate such as plate glass, thermal decomposition is carried out by heating at 100-400 deg.C and a vapor-deposited film is bonded and stuck to the surface of the substrate in the form of a monomolecular layer. A water-repellent substrate is easily produced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to various substrates, particularly a treatment method for imparting water-repellent performance to the surface of a glass plate, and a water-repellent substrate which is water-repellent treated by the treatment method. Regarding the water-based glass plate, the water-repellent substrate, especially the water-repellent glass plate can be used in a wide variety of applications such as building window materials or wall materials exposed to wind and rainwater, and vehicle window materials, and is useful. It is to provide something.

[0002]

2. Description of the Related Art Various techniques have been known for imparting water repellency by forming an organic fluoride coating film such as a fluorine-containing silane compound on the surface of a glass substrate or a steel plate.

For example, JP-A-60-231442 describes a water-repellent treated glass, which is a polymer of an organosilicon compound having a siloxane bond as an adhesive component on the glass surface (eg, tetramethylsilane), and As a water repellent component, a water repellent coating film composed of both an organosilicon compound having a larger carbon composition ratio or a smaller oxygen composition ratio than the organosilicon compound (eg tetraethoxysilane) or a polymer of a fluorine compound is formed. In the glass side portion of the water repellent treated film, a polymer having good adhesion to glass is mainly arranged, and in the outer side portion of the treated film, a polymer having high water repellency is mainly arranged. What has been done is disclosed.

Further, for example, Japanese Patent Application Laid-Open No. 3-247537 describes a method for producing water-repellent glass. After polishing and cleaning the surface of a glass substrate, 5% or more of hydrogen atoms in an alkyl group of polydialkylsiloxane are fluorine atoms. Disclosed is a method comprising applying a silicone-based water repellent substituted for to a glass substrate to form a coating film, and curing the film to adhere to the glass substrate to form a water repellent cured film having a film thickness of 0.1 to 2 μm. ing.

Further, for example, JP-A-3-247538 describes a method for producing water-repellent glass, which has a viscosity of 10
A water repellent solution in which a water repellent of a silicone polymer of 0 to 10 million cs is dissolved is applied to the surface of a glass substrate to form a coating film, and then cured to form a water repellent film on the glass substrate. A method consisting of doing is disclosed.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in the water-repellent treated glass described in JP-A-60-231442, a plasma polymerization method is required for production, and the treated film also has a considerable thickness. It is necessary, and is disclosed in
In the method for producing water-repellent glass described in Japanese Laid-Open Patent Publication No. 247537 and Japanese Laid-Open Patent Publication No. 3-247538, it is necessary to apply a dipping method, a roll coating method, or the like, and it is necessary to apply it to a glass plate by rubbing it into a thick film. These are not sufficient in terms of the mechanical strength of the coating, and it is no exaggeration to say that the scratch resistance is inferior, and their applications are becoming limited.
In some cases, it is often difficult to use it.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and has a boiling point of 100 °.
A fluorinated silane compound solution with a specific dilution concentration of C or less is heated at a specific temperature to evaporate and fixedly bond to the surface of the base material, and uniformly treated while maintaining the surface shape or state of various base materials without being damaged. In addition to being able to impart water-repellent performance, the water-repellent treated substrate can be formed as a monomolecular layered film on the surface, so that its mechanical strength, etc. The strength of the base material itself is almost the same as that of the base material itself, and the originality of the base material such as glass plate can be maintained. A water repellent treatment method and a water repellent substrate thereof are provided.

That is, according to the present invention, when a fluorine-containing silane compound solution is vapor-deposited and bonded and fixed on the surface of a substrate, the concentration of the fluorine-containing silane compound is adjusted to 0.1 wt% or more with a diluting solvent to form a vapor deposition solution. And heating temperature 10
A water repellent treatment method for a base material, which comprises thermally decomposing at 0 to 400 ° C., vapor depositing on the surface of the base material, and bonding and fixing the base material. And the above-mentioned water repellent treatment method for a substrate, wherein the substrate is a glass plate.

Further, a water-repellent substrate characterized in that at least a vapor-deposited film is formed on the surface of the substrate in the form of a monomolecular layer by the water-repellent treatment method for the substrate. And the above-mentioned water-repellent substrate, wherein the substrate is a glass plate.

As the fluorine-containing silane compound,
Is CF₃(CH₂)₂Si (OMe)₃, CF₃(C
F₂)_Five(CH₂)₂Si (OMe)₃, CF₃(CF
₂) ₇(CH₂)₂Si (OMe)₃, CF₃(C
F₂)₇(CH₂)₂SiMe (OMe)₂, CF
₃(CF₂)₇(CH₂)₂SiCl₃, CF₃(CF
₂)₇(CH₂)₂Si (NH₂)₃Etc., boiling point is 100
° C or less, for example 85 to 90 ° C
Any luxide or modified type may be used.

Further, the diluting solvent is preferably a lower alcohol such as methanol, ethanol or isopropyl alcohol. Further, the concentration of the fluorine-containing silane compound was set to 0.1 wt% or more with a diluting solvent to obtain a solution for vapor deposition. When it is less than 0.1 wt%, sufficient water repellency cannot be expressed and the contact angle with water is 90 to 90%. This is because only about 95 ° can be obtained, and only a value less than this can be obtained. Basically, if 0.1 wt% or more, the contact angle is 1
There is almost no change at around 10 °, and the upper limit is not particularly limited, but from the viewpoint of economy or liquid stability, if it is set, it is about 10 wt%.

Furthermore, the heating temperature is 100 to 400.
10 ° C was used for thermal decomposition and vapor deposition at ° C.
If the temperature is lower than 0 ° C, the volatilization tends to be insufficient and the efficiency is deteriorated. Below the boiling point is not a problem, and high water repellency cannot be exhibited. On the other hand, if the temperature exceeds 400 ° C., the monomolecular layered film once formed is decomposed and evaporated, and the water repellency is significantly reduced.

Furthermore, it can be inferred from the result of the elemental analysis of the surface that the film is a fixed monomolecular layered film, and it is inferred from the fact that it is not detected other than C or F element. For example, Auger electron spectroscopy or secondary ion mass spectrometry. It is checked by the detection depth of the F component by the method or the like.

Furthermore, the base material is any of various inorganic base materials, especially transparent glass plates, and is not particularly limited to colorless or colored, its kind, color tone, shape, etc. It can be used not only as plate glass, but also as various tempered glass, strength-up glass, flat plate and single plate, as well as double glazing or laminated glass, for various resin plates, steel plates or ceramic plates, and various articles. Needless to say, it can be adopted.

[0015]

As described above, according to the water repellent treatment method for a base material of the present invention, a water repellent group (hydrophobic group) is vapor-deposited on the surface of the base material by thermal decomposition to impart water repellency to the base material. The water-repellent treated substrate, especially the water-repellent treated glass, can maintain the same surface condition as untreated glass, and its mechanical strength, abrasion resistance, scratch resistance, optical characteristics, etc. are basically glass. Excellent water repellency of the base material, such as the ability to express the same performance as the surface and the extremely simple process, which makes it possible to process large area substrates inexpensively and efficiently. The treatment method and a useful and unique water-repellent substrate can be widely provided.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 Clear size 100 mm x 100 mm, thickness 2 mm
The surface of the float glass plate was sequentially washed with a neutral detergent and water rinse, dried and then degreased with acetone to obtain a vapor deposition surface.
Then, a fluoroalkylsilane [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OM
e) ₃ ] in a volume ratio display, the fluoroalkylsilane 1 is diluted with isopropyl alcohol 50 and nitric acid 1 to give a fluorine-containing silane compound concentration of about 0.1 w.
Separately pre-prepared solution for vapor deposition 1 at t%
g onto a glass petri dish (8 cm diameter round shape), and put it on the glass plate so that the vapor deposition surface of the above-mentioned glass plate is on the lower side, and then put it in an electric furnace at about 100 ° C for about 1
After holding for 0 minute, the vapor deposition solution was thermally decomposed and evaporated to firmly bond to the vapor deposition surface of the glass plate. Furthermore, the heating temperature is about 200 ° C, about 300 ° C and about 450 ° C.
The same procedure as described above was carried out at ° C.

The water repellency of the obtained glass plate with a vapor-deposited film is measured by placing water on the vapor-deposited surface of the glass plate with a vapor-deposited film and measuring the contact angle with a CA-A type manufactured by Kyowa Interface Science Co., Ltd. The accelerated weather resistance is D.I. P. W accelerated weathering test by Suga Shikenki Co., Ltd.
The heating temperature is 200 ° C under the conditions of cycle time of about 75 ° C and UV irradiation power of 3.0 mW for about 8 hours. The durability is 30 ° C in the usual outdoor exposure test.
It was carried out using the one at 0 ° C.

The results show that the relationship between heating temperature and water repellency is shown in Table 1, accelerated weathering resistance is shown in Table 2, and durability by outdoor exposure is shown in Table 3. That is, except for those having a heating temperature of 450 ° C., they have sufficient water repellency, have sufficient weather resistance and durability, and the film thickness of the vapor-deposited film was measured. It is a monomolecular layered film, and when the film strength was variously investigated by scratching strength (JISK6718), etc., it showed mechanical strength equal to or almost equal to that of the surface of the glass plate, and it could withstand even wipers of automobiles, for example. Therefore, there was an adhesive force and the state of the surface of the substrate could be utilized.

Example 2 As a fluorine-containing silane compound, CF ₃ (CF ₂ ) ₇ (CH
₂ ) ₂ SiCl ₃ was used, and otherwise the same as in Example 1.

With respect to the obtained vapor-deposited glass plate, the water repellency, the contact angle of water, the accelerated weather resistance and the durability were examined in the same manner as in Example 1. The results are shown in Tables 1 to 3 as in Example 1.
It had the same characteristics as.

Example 3 Instead of the glass plate of Example 1, a non-glare glass plate having a gloss value of 148% (for example, a glass plate having a ground glass surface by etching etc.) was used, and the same procedure as in Example 2 was performed. Then, the vapor deposition film was applied.

The water vapor repellency of the obtained glass plate with a vapor-deposited film was examined in the same manner as in Example 1. The results are shown in Table 1, which shows the same water repellency as in Example 1. Then, the film thickness of the vapor-deposited film was measured, and it was not possible to measure with a normal one, and it was a monomolecular layered film, and various investigations of the film strength revealed that it was a machine equivalent to or almost equivalent to the surface of the glass plate. It has a mechanical strength, and can withstand even a windshield wiper of an automobile, has scratch resistance and adhesion, and the surface condition such as visible light transmittance and light scattering state of the glass before and after the treatment is visually and scanning electron microscope ( It was unchanged by observation with Hitachi, Ltd .: x700 times), and the surface condition of the base material was utilized without changing the non-glare performance of the substrate.

Example 4 Instead of the glass plate of Example 1, a glass plate with a SiO ₂ thin film (film thickness of about 100 nm) having micropits on the surface was used, and the deposited film was formed in the same manner as in Example 2. gave.

When the obtained glass plate with a vapor deposition film was examined in the same manner as in Example 3, the same results as in Example 3 were obtained. The scanning electron microscope (manufactured by Hitachi, Ltd.) has a magnification of 20,000.

In the water repellent treatment method for a substrate of the present invention, for example, a water repellent film can be simultaneously applied to both front and back surfaces by placing a glass plate on the sheer.

[0027]

[Table 1]

Comparative Example 1 A metal alkoxide [Si (OEt) ₄ ] solution was added to a fluorine silane compound [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si.
(OMe) ₃ ] in a molar ratio display
A glass plate is immersed in a solution added at a ratio of metal alkoxide of 0.5 / 1 and pulled up at a constant speed (about 1 mm / sec) to form a gel film on the glass plate, and then about 380 °
A water-repellent thin film was obtained by heating at C for about 30 minutes in an electric furnace.

The obtained glass plate with a thin film was subjected to the accelerated weather resistance test of water repellency and the durability test by outdoor exposure in the same manner as in Example 1, and the results are shown in Tables 2 and 3. It was almost the same as in Examples 1 and 2. However, compared to Examples 1 and 2,
Its film thickness is quite thick, but it is much thinner than other conventional ones.
Although it is better than the other conventional ones, it is not always said that the surface condition of the substrate can be fully utilized.

Comparative Example 2 Fluorine silane compound [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂
The partially hydrolyzed solution of Si (OMe) ₃ ] was directly applied to a glass plate by a rubbing method to obtain a water-repellent thin film.

The obtained glass plate with a thin film was subjected to the accelerated weather resistance test of water repellency and the durability test by outdoor exposure in the same manner as in Comparative Example 1, and Tables 2 and 3
And was almost the same as in Examples 1 and 2. However, compared with Examples 1 and 2, the film thickness is considerably thicker, but is far thinner than the other conventional ones, and it is not always said that the surface condition of the substrate can be fully utilized although it is better than the other conventional ones. It was difficult to say, and it was difficult to say that it had a sufficient adhesive force.

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

As described above, according to the present invention,
It is a simple and easy method for water repellent treatment on the surface of a substrate, and it can give high water repellency without changing the surface condition of the substrate itself. PV for the purpose of controlling the optical characteristics in advance.
Widely applied to various coating films such as automobile window materials, various glass articles, etc., such that water repellency can be imparted to the surface of the base material film coated by the D method or the CVD method without deteriorating its characteristics. The present invention provides a useful water-repellent treatment method for a base material and a water-repellent base material having high utility value which can be adopted.

Claims (4)

[Claims] 1. When a fluorine-containing silane compound solution is vapor-deposited on a surface of a substrate by thermal decomposition to bond and fix it, the concentration of the fluorine-containing silane compound is adjusted to 0.1 wt% or more with a diluting solvent to obtain a vapor deposition solution, and a heating temperature is set. A water repellent treatment method for a base material, which comprises thermally decomposing at 100 to 400 ° C., vapor deposition on the surface of the base material, and bonding and fixing. 2. The water repellent treatment method for a substrate according to claim 1, wherein the substrate is a glass plate. 3. A water-repellent substrate, which is formed by forming at least a vapor-deposited film in a monomolecular layer on the surface of the substrate by a water-repellent treatment method for the substrate. 4. The water-repellent substrate according to claim 3, wherein the substrate is a glass plate.