JPH08319137A - Water-repellent glass article and its production - Google Patents

Abstract

PURPOSE: To obtain the subject article excellent in water-repelling performance, wear resistance, oil repellency and stainproofness by providing the surface of a glass substrate with a specific water-repelling film. CONSTITUTION: This article is obtained by providing the surface of a glass substrate with a water-repelling film pref. 4-1,000μm thick composed of a fluoroalkylsilane condensate (e.g. a condensed hydrolyzate obtained by mixing heptadecafluorodecyl trimethoxysilane with isopropyl alcohol and hydrochloric acid) (pref. plus 0.01-30wt.%, based on the condensate, of a fluororesin such as tetrafluoroethylene polymer). It is preferable that a film predominant in a silicon oxide be held between the glass substrate and the water-repelling film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent glass article, particularly a windshield for automobiles, vehicles, aircraft, ships, etc., a building window, an aquarium, a road panel such as a ship bottom window and a soundproof wall, glass tableware, glass. The present invention relates to a low-friction and high-durability water-repellent glass article used for ornaments and the like.

[0002]

2. Description of the Related Art By imparting water repellency to the surface of a glass article, water droplets containing contaminants are less likely to adhere to and remain on the glass surface, so that the glass can be prevented from being contaminated or burnt. Further, by using this water-repellent glass for a windshield, a side glass or the like of an automobile, rainwater adhering to the surface is blown away by wind pressure when traveling in the rain, so that the driver's view is secured and safety is improved.

Conventionally, in the production of such a water-repellent film, a liquid-phase adsorption method or a vapor-phase adsorption method has been used with a silicone or fluorosilicone water-repellent agent having reactivity with a silanol group on the surface of a glass substrate as a raw material. Has been. Examples of the liquid phase adsorption method include a rubbing method known as a commercially available product, for example, a dipping method disclosed in JP-A-4-221630, and a sol-gel method disclosed in JP-A-3-23493. . The rubbing method is a method in which a water repellent agent is dropped on a substrate and then directly spread with a cloth and wiped up. The dipping method is to form a water-repellent layer on the surface of a substrate by immersing the substrate in a solution prepared by adding a water-repellent agent to water or an organic solvent and pulling it up at a constant speed. In addition, the sol-gel method uses tetraethoxysilane (TEO
The substrate is coated with a mixed aqueous solution of a SiO ₂ forming component such as S) and a water repellent component such as fluorosilane. In the vapor phase adsorption method, a fluoroalkylsilane (trichloro terminal) atmosphere is created in a decompression chamber maintained at a constant temperature, a substrate is held therein, and a water repellent layer is formed on the substrate surface.

[0004]

A water repellent of silicone type,
In the case of a base material treated with an alkylsilane-based water repellent, the initial coefficient of friction is small and the water droplets have excellent falling properties, but the durability is not good. For example, when a float glass substrate is treated with an alkylsilane-based water repellent, the critical inclination angle of water droplets is about 10 ° before being exposed outdoors for about 1 month and is 3 °.
It becomes 0 ° or more and the falling property of water drops becomes worse. Also, in the abrasion test, the flannel cloth was abraded 3000 times, and the contact angle of water, which was about 100 ° before the abrasion test, became 80 ° or less, and the water repellency was significantly reduced.

When treated with a fluorosilicone water repellent or a fluoroalkylsilane water repellent, the weather resistance and abrasion resistance are excellent, but the initial friction coefficient is large. For example, when a float glass substrate is treated with a fluoroalkylsilane water repellent, the contact angle is 80 ° or more even after 1 year of outdoor exposure, and the abrasion resistance test shows that the contact angle is 8 after a wear of 3000 times.
Shows 0 ° or more and maintains water repellent performance. However, in the initial stage, the critical inclination angle of the water droplet is 30 ° or more, and the falling property of the water droplet is not good.

When treated with a fluoroalkylsilane-alkylsilane mixed water repellent, the friction coefficient becomes smaller than when treated with a fluoroalkylsilane system, and the initial critical sliding angle is improved to about 20 ° to 25 °. It However, the contact angle after 1 year of the outdoor exposure test and the contact angle after 3000 abrasion resistance tests are lower than those when treated with the fluoroalkylsilane system.

In order to increase the adhesive force between the substrate and the sheet, a method of sticking a fluororesin sheet surface-treated with an alkali metal solution, amalgam, or sputter etching to a glass base material makes the fluororesin sheet have an optical thickness of not more than the optical thickness. Difficult to wear, and as a result of wear during use,
Wear scratches are very noticeable and have difficulty in optical characteristics. Even in the case of a fluorine enamel coat, if it is attempted to increase the adhesive strength between the base material and the water repellent layer, the film thickness becomes more than the optical thickness, and like the fluorine sheet, abrasion scratches are very conspicuous and there is a problem with the optical characteristics.

An object of the present invention is to provide a transparent water repellent glass article having excellent water repellency and abrasion resistance.

[0009]

The present invention is a water-repellent glass article having a water-repellent film containing a fluoroalkylsilane compound condensate and a fluororesin on the surface of a glass substrate.

The condensate of the fluoroalkylsilane compound used in the water-repellent film in the present invention is a substance obtained by hydrolyzing and condensing a silane compound having a fluoroalkyl group.
The fluoroalkylsilane compound has a silicon atom as a center and has a fluoroalkyl group, 0 to 2 alkyl groups, and at least one functional group, and specifically, the following chemical formulas (1) and (2) ) Fluoroalkylsilane compounds represented by

R _f ¹ QSi (CH ₃ ) _p (Z) _3-p (1) where R _f ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms Q :-( CH ₂ ) _y- (y is integer from 2 to _{5) Z: -OCH 3, -OC 2} H 5, -OCOCH 3, -OCO
C ₂ H _5, -NCO, -Cl or -OH p,: 0,1 or 2

[(R _f ² Q) _a Si (R ¹ ) _b (NR ³ ) _{(4-ab) / 2} ] _m・ [(R _f ² Q) _c Si (R ² ) _d (R ³ ) _e O _{(4-cde) / 2} ] _n (2) where R ¹ and R ² may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R ^3: a hydrogen atom or an alkyl group R _f ^2: perfluoroalkyl ether group of a perfluoroalkyl group or a -C 2-35 carbon atoms _{1~20 Q :-( CH 2) y -} (y is 2 An integer of 5) a: an integer of 1 to 3 b: an integer of 0 to 2, and a + b is 1 to 3 c: an integer of 0 to 2 d: an integer of 1 to 3, and c + d is 1 Is an integer of m, n: 1 or more

Examples of the fluoroalkylsilane compound represented by the above chemical formula (1) include CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
i (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃
Cl ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OCH
₃ ) _{2 and the} like, among which fluoroalkyltrialkoxysilanes, especially CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si
Cl ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
Is particularly preferable because it has excellent water repellency.

The fluoroalkylsilane compound is added with water for causing hydrolysis, an acidic or basic catalyst for hydrolysis, and a solvent represented by alcohols, and the mixture is stirred for a predetermined time. As a result, a hydrolysis / condensation reaction is caused to form a condensate.

Next, the fluororesin contained in the water repellent film of the present invention will be described. Examples of the fluororesin include homo- or copolymers of fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, trichlorofluoroethylene, vinylidene fluoride and vinyl fluoride, or copolymers of these with a polymerizable ethylenically unsaturated compound. Examples of the polymer include a tetrafluoroethylene polymer (PTFE), a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), and a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA). As the fluororesin, one having a molecular weight of 500 to 1,000,000 can be used, but if the molecular weight of the fluororesin is too low, the heat resistance of the water-repellent film is likely to deteriorate, and conversely if it is too high, the Since the melting temperature becomes high and it becomes difficult to allow the fluororesin to uniformly exist in the water repellent film, 50
Fluororesin having a molecular weight of 00 to 100,000 is particularly preferable. Although usually fluororesin end groups are also included other than CF ₃ group, preferred for the introduction of all CF ₃ group in the terminal group of the fluorine resin by fluorine gas treatment is further enhanced water repellency. This tendency becomes remarkable as the molecular weight becomes lower.

The proportion of the fluoroalkylsilane compound condensate and the fluororesin in the water-repellent film of the present invention is such that if the fluoroalkylsilane compound condensate is too much (the fluororesin is too little), the water-repellent performance, especially water droplet If the amount of the fluoroalkylsilane compound condensate is too small (the amount of the fluororesin is too large), the adhesive force between the water-repellent layer and the base material is likely to be lowered. Therefore, the content of the fluororesin in the condensate of the fluoroalkylsilane compound is preferably 0.01 to 30% by weight, and more preferably 0.1 to 10% by weight.

The water-repellent film of the present invention comprises two phases of a condensate of a fluoroalkylsilane compound and a fluororesin, and in the film, the fluororesin in the fluoroalkylsilane condensate matrix has various fine particles of 2 nm to 1000 nm. The size has a phase morphology (domain structure). The morphology varies depending on the type and amount of the fluoroalkylsilane condensate matrix and the fluororesin.
Cylindrical, lamellar, or interpenetrating (IP
N) takes a phase form.

The water-repellent film of the present invention may contain a polydimethylsiloxane, an alkoxysilane condensate, etc., in addition to the fluoroalkylsilane compound condensate and the fluororesin. However, if the amount of these components is too large, the weather resistance of the water-repellent film and the adhesion of the water-repellent film tend to deteriorate, so the total amount of the fluoroalkylsilane compound condensate and the fluororesin is at least 30% by weight in the water-repellent film. %, Preferably 60% by weight, more preferably 90% by weight or more.

If the thickness of the water-repellent film of the present invention is too small, the water-repellent performance will be poor, and if it is too large, the transparency of the film will be impaired. Therefore, the water-repellent film should be 4nm-2000n
It preferably has a thickness of m, more preferably 10
It has a thickness of ~ 200 nm.

In the present invention, a base film may be provided between the glass substrate and the water repellent film. In order to improve the adhesion of the water repellent film and the abrasion resistance of the water repellent film, it is preferable to provide a film containing silicon oxide as a main component. This film can be formed by a known sol-gel method such as hydrolysis / condensation of a metal alkoxide such as silicon or a metal acetylacetonate before coating the water repellent film. Preferably, a fine metal oxide such as colloidal silica is dispersed in a metal alkoxide or a metal acetylacetonate to form a base film having fine irregularities on the surface, which further improves the abrasion resistance of the water-repellent film. Can be increased.

The water-repellent glass article of the present invention is produced by spraying a water-repellent agent containing a fluoroalkylsilane compound and a fluororesin on the surface of a glass substrate heated to a high temperature as described below. You can It can also be produced by immersing and pulling up a glass base material heated to a high temperature in a bath of the water repellent agent kept at a high temperature.

The water repellent is a hydrolyzate of the fluoroalkylsilane compound; a fluororesin; a solvent in which the fluoroalkylsilane compound is soluble, such as an alcohol or a ketone;
And a solution or suspension liquid of a fluororesin, for example, Freon, alcohol. Actually, the water repellent is a mixture of a fluoroalkylsilane compound solution, a fluororesin suspension (or solution) and, if necessary, a diluent, polydimethylsiloxane, and an alkoxysilane condensate. The fluororesin suspension is stirred so that the diameter of the fluororesin in the liquid is 1000 nm or less, preferably 100 nm or less. The total solid content of the fluoroalkylsilane compound and the fluororesin is usually 0.1 to 90 relative to the water repellent.
It is diluted to give a weight percentage. And the ratio of the fluoroalkylsilane compound to the fluororesin is preferably 0.01 to 30% by weight of the fluororesin with respect to the condensate of the fluoroalkylsilane compound, like the ratio in the water-repellent film. A more preferred range is 0.1-10
% By weight.

In the case of the spraying method, the water repellent agent is sprayed onto a glass substrate kept at 300 ° C. to 700 ° C. by a sprayer such as a spray gun for paint. The temperature of the glass substrate is more preferably maintained at a temperature of 450 ° C. or higher, which is the decomposition temperature of the oroalkylsilane compound in the water repellent. The diameter of mist when spraying a water repellent is 0.1 to 30 μm
Adjust to be within the range. Here, the mist is defined as including mist in which several to several tens of water-repellent molecules are aggregated into an energy-stable cluster state. It is preferable to adjust the mist diameter in the range of 0.1 to 1 μm and spray so that the diameter is as uniform as possible, since a smooth water-repellent film can be obtained. When producing heat-strengthened and / or bent glass for automobile window glass, it is necessary to heat the glass plate in a heating furnace, but if the water repellent is sprayed immediately after this heating, a water repellent film is formed. Can be incorporated into the process of heat strengthening and / or bending, which simplifies the process.

As described above, when the base material is once heated to the decomposition temperature of the water repellent agent or more and then immediately subjected to the water repellent treatment by spraying, (1) the hydrocarbon-based contaminants adhered to the base material are Since it is decomposed and removed by heating the material, it is not necessary to consider reattachment of contaminants, and therefore the water repellent treatment can be performed in a very good condition of the base material. (2) Water repellent agent (fluoroalkylsilane compound) The above-mentioned heating achieves passage through the temperature range (about 200 to about 400 ° C.) necessary for forming a strong siloxane bond with the base material, whereby the strong chemical bond density is dramatically increased. As a result, the adhesive strength between the water-repellent layer and the base material is significantly increased, and (3) the melting point of the fluororesin (2
(70 to 330 ° C.), the fluoroalkylsilane matrix and the fluororesin are mixed in a liquid-liquid system at a temperature higher than 70 to 330 ° C., and as a result, the fluororesin is firmly retained in the fluoroalkylsilane condensate matrix while having various phase structures, Further, (4) the diameter of the fluororesin can be set to 1 μm or less, and thus the thickness of the water-repellent film can be set to 1 μm or less (optical thickness or less).

If the water repellent agent is applied or sprayed to the substrate and then heated, the application or spraying is performed at a low temperature, so that the fluororesin is applied or sprayed as a solid. The fluororesin silane compound is no longer incorporated into the fluoroalkylsilane compound, so that the fluororesin is immediately separated from the film, and a predetermined water-repellent film cannot be obtained.

[0026]

【Example】

Example 1 Hereinafter, the water-repellent glass according to the example of the present invention shown in FIG. 1 will be described in detail. FIG. 1 shows a cross section of a glass substrate of SiO ₂ coat / soda lime glass having a water repellent film formed on the surface thereof. Reference numeral 1 is a glass substrate, 2 is a coating layer made of SiO ₂ , and 3 is a water repellent layer made of a water repellent.

Formation of SiO ₂ Underlayer Film Hydrolysis product of tetraethoxysilane (molecular weight of about 300
0, solid content concentration about 30% by weight) About 30 g diluted with about 100 g isopropyl alcohol to a solution of 50 mm x 50
Dip a soda lime silicate glass substrate of mm × 2 mm and pull out the substrate at a speed of 100 cm / min to about 27
Heated at 0 ° C for about 10 minutes and made SiO about 50nm thick
_{2 A} base film was formed on the surface of the substrate.

Preparation of Fluoroalkylsilane / Fluorine Resin-Containing Spray Liquid Heptadecafluorodecyltrimethoxysilane 10
g, 1N hydrochloric acid 10 g, isopropyl alcohol 20 g
After mixing, the mixture was kept at room temperature for 4 days to obtain a hydrolyzed condensate. 12 g of this hydrolysis-condensation product is diluted with 88 g of isopropyl alcohol to obtain a first liquid. Primary particle size 0.1μ
m of PTFE (average molecular weight; 10,000) was suspended in acetone to obtain an acetone suspension containing 6 wt% of PTFE, which was designated as the second liquid. The first liquid and the second liquid were mixed and stirred to obtain a spray suspension.

Formation of Water-Repellent Film The glass substrate on which the above-mentioned SiO ₂ base film was formed was placed in a baking furnace without being washed, and the substrate was heated to about 650 ° C. Immediately after taking out the substrate from the baking furnace, the sprayed spray gun (Iwata spray gun # 88) was used to spray the above sprayed suspension onto the surface of the substrate so that the diameter of the suspension droplets was about 1000-.
Substrate temperature is about 300 ° C after spraying at 10000 nm
Continued spraying until. As a result, a water repellent film having a thickness of about 10 nm was obtained. The water-repellent film was composed of 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate and 1% by weight of PTFE.

The water-repellent performance of this water-repellent film was evaluated by measuring the contact angle, the critical inclination angle and the friction coefficient. The critical tilt angle is defined as the tilt angle of the substrate just before the water drops start rolling after slowly dropping the water drop having a diameter of about 5 mm on a horizontal substrate. Further, in order to examine the durability of the film, a reciprocating abrasion test with a flannel cloth was performed 3000 to 20000 times. The results are shown in Table 1.

[0031]

[Table 1] =================================== Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative example 3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Contact angle (degree) 108 104 109 105 125 121 Critical inclination angle (degree) 10 28 10 28 15 32 Friction coefficient 0.1 0.3 0.1 0.3 0.3 0.5 −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−− Contact angle (degree) after abrasion test After abrasion 3000 times 103 91 101 90 120 110 After abrasion 5000 times 100 80 98 75 115 100 After abrasion 10000 times 95 50 92 40 108 90 After abrasion 20000 times After 95-90-102 80 =====================================

Example 2 Hereinafter, the water-repellent glass according to the example of the present invention shown in FIG. 2 will be described in detail. FIG. 2 shows a cross section of a glass substrate of soda lime glass having a water repellent film formed on its surface. Reference numeral 1 is a glass substrate, and 3 is a water-repellent layer made of a water-repellent agent.

The soda lime glass substrate was put into a firing furnace without being washed, and the substrate was heated to about 650.degree. Then, the substrate was taken out from the firing furnace, and immediately after that, the same spraying suspension as in Example 1 was sprayed under the same conditions as in Example 1. The water-repellent performance of the obtained water-repellent film was evaluated by measuring a contact angle, a critical inclination angle, and a friction coefficient. In addition, a reciprocating wear test using a flannel cloth was conducted to examine the durability of the film. The results are shown in Table 1.
Shown in

Example 3 Hereinafter, the water-repellent glass according to the example of the present invention shown in FIG. 3 will be described in detail. FIG. 3 shows a cross section of a water-repellent glass plate having a water-repellent film formed on its surface. Reference numeral 1 is a glass substrate, 2 is an uneven layer made of SiO ₂ , and 3 is a water repellent layer made of a water repellent.

Formation of Undercoat Film First, a method for preparing the undercoat film composition will be described. The following (a) ~
Mix (b) and stir for 20 minutes. (A) TEOS 52.10g (b) Isopropanol 383.00g For the above (a)-(b) mixture, the following (c),
Add (d) and stir for 2 hours. (C) Water 10.58g (d) 1N hydrochloric acid aqueous solution 2.70g

The above solution was placed in a sealed container and kept at 50 ° C. for 3 hours.
After stirring for an hour, the mixture is further stirred at 20 ° C. for 15 hours.
Then, the following (e) and (f) are added to this, and further 2
A composition for a base film was obtained by stirring at 0 ° C. for 5 hours. (E) Colloidal silica (“Snowtex OL” manufactured by Nissan Chemical Industry, particle diameter 50 nm, solid content 20% by weight) 73.70 g (g) Isopropanol 449.80 g

(Coating Process) A 70 × 150 × 3.4 mm float glass substrate was degreased, washed and dried to obtain washed glass. The washed glass substrate was immersed in the composition for a base film obtained above and pulled up at a pulling rate of 100 mm / min to prepare a wet coating film.

(Firing Step) The glass substrate on which the above wet coating film is formed is kept in an air atmosphere at 120 ° C. for 20 minutes to evaporate water and ethanol in the wet coating film,
The temperature was further raised to 250 ° C., and the temperature was maintained for 1 hour to form a siliceous base film having a thickness of about 50 nm. In this base film, colloidal silica fine particles having a diameter of about 50 nm are densely aggregated two-dimensionally, and each fine particle is TEOS.
It is firmly attached to the substrate by silica derived from. Then, irregularities having a height of about 25 nm were formed on the surface of the base film due to the arrangement of colloidal silica fine particles.
The substrate to which the base film was attached was placed in a baking furnace without being washed, and the substrate was heated to about 650 ° C. Then, the substrate was taken out from the firing furnace, and the same spraying suspension as in Example 1 was sprayed under the same conditions as in Example 1. The water-repellent performance of the obtained water-repellent film was evaluated by measuring a contact angle, a critical inclination angle, and a friction coefficient. In addition, a reciprocating wear test using a flannel cloth was conducted to examine the durability of the film. The results are shown in Table 1.

Comparative Example 1 A soda lime glass substrate on which SiO ₂ was formed by the liquid phase film forming method was subjected to ultrasonic cleaning for 10 minutes and UV-ozone cleaning for 3 minutes in the same manner as in Example 1, and then the following liquid was used. Water repellent treatment was performed by the phase adsorption method.

After the heptadecafluorodecyltrichlorosilane CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ was dissolved in the solvent hexafluorometaxylene at a concentration of 2%, the washed substrate was immersed in the adsorbent for about 2 hours. A heat treatment was performed at 300 ° C. for 30 minutes to obtain a sample. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement as in Example 1. In addition, a reciprocating wear test using a flannel cloth was conducted to examine the durability of the film. The results are shown together in Table 1.

Comparative Example 2 A soda lime glass substrate was ultrasonically cleaned for 10 minutes under UV-
After performing ozone cleaning for 3 minutes, water repellent treatment was performed by a liquid phase adsorption method using the same hexafluorometaxylene solution of heptadecafluorodecyltrichlorosilane as in Comparative Example 1. After water repellent treatment, heat treatment was performed at 300 ° C. for 30 minutes to obtain a sample.

The water-repellent performance of the obtained water-repellent film was evaluated in Example 2.
The contact angle measurement, the critical tilt angle measurement, and the friction coefficient measurement were performed in the same manner as in. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results are shown together in Table 1.

Comparative Example 3 In the same manner as in Example 3, a sol-gel SiO ₂ liquid in which 50 nm colloidal silica was dispersed was applied to the substrate by flow coating, and 50 nm colloidal silica was two-dimensionally densely aggregated. After forming the uneven film on the soda lime glass,
It was baked at 500 ° C. for 30 minutes. After cooling to room temperature, UV-
What was performed for 3 minutes by ozone cleaning was subjected to water repellent treatment by a liquid phase adsorption method using the same hexafluorometaxylene solution of heptadecafluorodecyltrichlorosilane as in Comparative Example 1.
After the water repellent treatment, heat treatment was performed at 300 ° C. for 30 minutes.

The water-repellent performance of the obtained water-repellent film was evaluated in Example 3
The contact angle measurement, the critical tilt angle measurement, and the friction coefficient measurement were performed in the same manner as in. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results are shown together in Table 1.

When comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, the Examples were compared in terms of initial friction coefficient and critical inclination angle. Better than the example. Moreover, it can be seen that the contact angle after the abrasion test is larger in the example than in the comparative example, and the abrasion durability is also excellent.

The reasons are as follows: 1) The ideal chemical bond density between the water-repellent layer and the substrate was obtained. 2) The fluororesin domain is firmly introduced. Can be considered. Therefore, it is considered that the hydrophilic groups on the surface were remarkably reduced, and the initial friction coefficient and the critical inclination angle were smaller than those in Comparative Examples. It is considered that the wear resistance performance was also improved due to the smaller friction coefficient.

Comparative Example 4 In the preparation of the spray liquid of Example 1, instead of the spray liquid containing fluoroalkylsilane / fluorine resin, an acetone suspension containing 6% by weight of low-molecular-weight PTFE having a primary particle size of 0.1 μm was used alone. The same operation as in Example 1 was performed except that the above was performed. When the amount of sprayed liquid was increased, the resulting water repellent film became optically opaque. Moreover, it flaked off when worn with flannel cloth. On the other hand, when the amount of the sprayed liquid was gradually reduced so as to become transparent, the contact angle was 50 to 70 ° and the water repellency was insufficient. It is considered that the fluororesin itself hardly reacts with the silanol on the substrate surface and no bond is generated.

Example 4 A soda lime glass substrate was put into a suspension strengthening furnace without being washed, heated to about 650 ° C., taken out, immediately bent, and immediately air-blow strengthened by air blow. . Then, when the plate temperature reached 370 ° C., the same blowing suspension as in Example 1 was sprayed in the same manner as in Example 1 to obtain a bent tempered glass having a water repellent film with a thickness of about 10 nm. The water-repellent film was composed of 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate and 1% by weight of PTFE.

The water-repellent performance of the obtained water-repellent film was evaluated by measuring the contact angle, the critical inclination angle and the friction coefficient. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 2.

Example 5 In the same manner as in Example 1, the soda lime glass substrate on which SiO ₂ was formed by the liquid phase film forming method was put into a hanging and strengthening furnace without being washed, heated to 650 ° C., and then taken out. And immediately bent, and immediately air-blow strengthened by air blow. Then, when the plate temperature reached 370 ° C., the same sprayed suspension as in Example 1 was sprayed by the same method as in Example 1 to obtain a water-repellent film having a thickness of about 10 nm. The water-repellent film is a condensate of heptadecafluorodecyltrimethoxysilane 9
It was composed of 0% by weight and 10% by weight of PTFE.

The water-repellent performance of the obtained water-repellent film was evaluated by measuring a contact angle, a critical inclination angle and a friction coefficient. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 1.

Example 6 A soda lime glass substrate was placed in a horizontal strengthening furnace without being washed, heated to 650 ° C., and then subjected to gravity bending. Immediately after the bending work, the same blowing suspension as in Example 1 was sprayed by the same method as in Example 1 simultaneously with the air cooling strengthening by the air blow to simultaneously perform the air cooling strengthening and the water repellent treatment.
In this way, a bent tempered glass having a water repellent film with a thickness of about 10 nm was obtained. The water-repellent film is composed of 99% by weight of heptadecafluorodecyltrimethoxysilane condensate, and PTF.
It was composed of 1% by weight of E. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 2.

Example 7 As in Example 1, a soda lime glass substrate on which SiO ₂ was formed by the liquid phase film forming method was placed in a horizontal strengthening furnace without being washed, heated to 650 ° C., and then weighed by itself. Bending was performed. Immediately after the bending work, the same blowing suspension as in Example 1 was sprayed by the same method as in Example 1 simultaneously with the air cooling strengthening by the air blow to simultaneously perform the air cooling strengthening and the water repellent treatment. Thus, a water repellent film having a thickness of about 10 nm was obtained. The water-repellent film was composed of 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate and 1% by weight of PTFE. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement. In addition, a reciprocating wear test was conducted to examine the durability of the film. Results are in Example 1.
Was the same as

Example 8 After forming a lead-containing crystal glass tumbler, the tumbler is placed in a slow cooling furnace (electric furnace) to remove residual strain and is once heated to 450.degree. Then, during the slow cooling, when the glass temperature reached about 350 ° C., the same spraying suspension as in Example 1 was sprayed in the same manner as in Example 1, and the thickness was about 10 nm.
The water repellent film of was obtained. The water-repellent film is 90% by weight of heptadecafluorodecyltrimethoxysilane condensate, and PTFE.
It was composed of 10% by weight. This water-repellent film had a water contact angle of 105 ° and an octane contact angle of 82 °, and had not only water-repellent performance but also oil-repellent performance. In fact, when the glass was directly held by the hand, fingerprints remained much less than the untreated glass, and even when lipstick or the like adhered, it was much easier to remove than the untreated glass. From the viewpoint of antifouling performance combining water and oil repellency, it can be said that the treated one is obviously superior to the untreated one.

Example 9 After four holes were drilled in a soda-lime glass substrate used in the point support method, the soda-lime glass substrate was put into a tempering furnace without being washed, and 60
After heating to 0 to 700 ° C., it was taken out and immediately subjected to air cooling for strengthening by air blow. And the plate temperature is 3
When the temperature reached 00 to 450 ° C, the same spraying suspension as in Example 1 was sprayed in the same manner as in Example 1 to give a thickness of about 10
A water repellent film having a thickness of nm was obtained. The water-repellent film is 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate, and PT
It was composed of 1% by weight of FE. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 2.

This water-repellent film showed an octane contact angle of 80 ° and had not only water-repellent performance but also oil-repellent performance.
Therefore, in terms of antifouling performance that combines water repellent performance and oil repellent performance, it is considered that the treated one is superior to the untreated one.

Example 10 During the gradual cooling process of the continuous band-shaped soda lime glass plate coming out of the float kiln, the same spray suspension as in Example 1 was used as in Example 1 when the glass temperature reached 300 to 400 ° C. By spraying in the same manner, a water-repellent film having a thickness of about 10 nm was obtained. The water-repellent film was composed of 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate and 1% by weight of PTFE. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 2.

This water-repellent film showed an octane contact angle of 80 ° and had not only water-repellent performance but also oil-repellent performance.
Therefore, when viewed as antifouling performance that combines water repellent performance and oil repellent performance, it is considered that the treated one is superior to the untreated one.

Example 11 Formation of SiO ₂ Underlayer Film A 50 mm × 50 mm × 2 mm soda lime silicate glass substrate was treated in the same manner as in Example 1 to form an SiO ₂ underlayer film on the surface of the substrate.

Preparation of Dip Coating Solution Containing Fluoroalkylsilane / Fluorine Resin Heptadecafluorodecyltrimethoxysilane 500
g and 1 N hydrochloric acid (500 g) were mixed, and the mixture was kept at 50 ° C. for 4 days to obtain a hydrolyzate. This was mixed with 50 g of low molecular weight PTFE having a primary particle size of 0.1 μm and heated to 350 ° C. to obtain a dip coating solution.

Formation of Water-Repellent Film The glass substrate on which the SiO ₂ base film was formed was subjected to ultrasonic cleaning for 10 minutes and UV-ozone cleaning for 3 minutes, and then 300 to
Heated to 350 ° C. The dip coating solution is 350 ℃
The above-mentioned heated glass substrate was immersed in a bath heated to 1, and pulled up at a speed of 100 mm / min. After cooling to room temperature, the excess liquid on the substrate surface was removed with a solvent to obtain a water-repellent film having a thickness of about 10 nm. The water-repellent film was composed of 99% by weight of a heptadecafluorodecyltrimethoxysilane condensate and 1% by weight of PTFE. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results were the same as in Example 1.

Example 12 The same amount of FE was used instead of PTFE in the preparation of the fluoroalkylsilane / fluorine resin-containing spray solution of Example 1.
Example 1 except that P (average molecular weight; 10,000) was used
The same operation was performed. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement as in Example 3. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results are shown together in Table 2.

[0063]

[Table 2]

Example 13 In the preparation of the fluoroalkylsilane / fluorine resin-containing spray liquid of Example 1, the same amount of PF was used instead of PTFE.
Example 1 except that A (average molecular weight: 10,000) was used
The same operation was performed. The water-repellent performance of the obtained water-repellent film was evaluated by contact angle measurement, critical tilt angle measurement, and friction coefficient measurement as in Example 3. In addition, a reciprocating wear test was conducted to examine the durability of the film. The results are shown together in Table 2.

[0065]

As described above, the water-repellent glass article of the present invention is superior to the conventional water-repellent glass made of a fluoroalkylsilane compound in the initial critical inclination angle, abrasion resistance, and oil repellency. It is clear that it also has antifouling properties.

Therefore, the water-repellent glass according to the present invention can be suitably used for windshields for automobiles, architectural windows, water tanks, road panels such as bottom windows and soundproof walls, glass tableware, and glass ornaments.

[Brief description of drawings]

FIG. 1 is a sectional view conceptually showing the structure of one embodiment of the water-repellent glass of the present invention.

FIG. 2 is a sectional view conceptually showing the water-repellent glass structure of the present invention.

FIG. 3 is a sectional view conceptually showing the water-repellent glass structure of the present invention.

[Explanation of symbols]

 1 glass substrate 2 silicon oxide film 3 water repellent layer

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[Procedure amendment]

[Submission date] May 29, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

[(R _f ² Q) _a Si (R ¹ ) _b (NR ³ ) _{(4-ab) / 2} ] _m・ [(R _f ² Q) _c Si (R ² ) _d (R ³ ) _e O _{(4-cde) / 2} ] _n (2) where R ¹ and R ² may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R ^3: a hydrogen atom or an alkyl group R _f ^2: perfluoroalkyl ether group of a perfluoroalkyl group or a -C 2-35 carbon atoms _{1~20 Q :-( CH 2) y -} (y is 2 An integer of 5) a: an integer of 1 to 3 b: an integer of 0 to 2, and a + b is 1 to 3. c: an integer of 0 to 2 d: an integer of 1 to 3, and c + d is 1 to 3 e: a number of 0 to 3, preferably a decimal number of 0.01 to 0.5 m, n: 1 Greater than or equal to integer

Claims (6)

[Claims] 1. A water-repellent glass article having a water-repellent film containing a condensate of a fluoroalkylsilane compound and a fluororesin on the surface of a glass substrate. 2. The fluororesin is contained in the water-repellent film in an amount of 0.01 to 30 relative to the condensate of the fluoroalkylsilane compound.
The water-repellent glass article according to claim 1, wherein the water-repellent glass article is contained by weight. 3. The water repellent glass article according to claim 1, wherein the water repellent film has a thickness of 4 nm to 1000 nm. 4. Between the glass substrate and the water repellent film,
The water-repellent glass article according to claim 1, which has a film containing silicon oxide as a main component. 5. The water-repellent glass article according to claim 1, wherein the layer containing silicon oxide as a main component contains silica fine particles. 6. A process for producing a water-repellent glass article having a water-repellent film, which comprises spraying a liquid containing a hydrolyzate of a fluoroalkylsilane compound and a fluororesin on the surface of a glass substrate heated to a high temperature. Method.