JPH05319868A - Water repellent for glass substrate and treatment for water repellency - Google Patents

Abstract

PURPOSE:To efficiently obtain water-repellent glass at low cost without causing coating irregularity even by a simple coating method, and to improve dropping property of water drops, adhesive strength, weather resistance, scratching resistance, etc., thereof without decreasing optical characteristics. CONSTITUTION:In the water repellent obtd. by partly hydrolyzing a mixture liquid of fluoroalkyl silane compd. and boric acid or alkoxide of boric acid, the mixture liquid containing 0.05-5mol boric acid or alkoxide of boric acid to 1mol fluoroalkyl silane compd. is diluted with a diluting solvent to 0.5-10wt.% diluted concn., and then water and/or acid catalyst are added by 1 to 10 times mol or the total mol of fluoroalkyl silane compd. and boric acid or alkoxide of boric acid to obtain the objective water repellent. The obtd. water repellent is applied on the surface of glass and heated at 100-400 deg.C to obtain water- repellent glass having the film of a single molecule thickness to 5nm film thickness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a water repellent treatment agent for a glass surface, which has excellent water repellency, reduced slipperiness (falling inclination angle) of water drops, and excellent weather resistance or scratch resistance, and the water repellent agent. The present invention relates to a water repellent treatment method of applying a water treatment agent to a glass substrate, and is useful for window glass for vehicles, ships, aircraft, construction, and the like.

[0002]

2. Description of the Related Art In order to improve the water repellency of glass, attempts have been made to apply a compound such as a fluoroalkyl group-containing compound or dimethylsiloxane to the glass surface. However, if these compounds are simply applied, the bonding strength with the glass surface is weak, and the weather resistance and abrasion resistance cannot be sufficiently imparted, and it is difficult to maintain the water repellency for a long period of time. Also, regarding the drop inclination angle of the water droplet, since the surface energy is small, the water droplet having a small diameter does not roll down even if it is 90 °, and eventually the remaining water droplets are contaminated by dust and the like in the atmosphere. It also had problems.

For this reason, various attempts have been made. For example, JP-A-58-122979 discloses a water- and oil-repellent agent for the glass surface, and JP-A-58-172245 discloses a glass surface treatment agent. Each is described, it is disclosed that a polyfluoroalkyl group-containing silane compound, or a partially hydrolyzed condensate of the compound and a silane compound such as alkoxy or halogeno, particularly -CON (R ² ) -Q- or -SO ₂ N (R ² )
It is described that the presence of -Q- is necessary and the like, and the one that intends to impart water repellency, oil repellency and stain resistance to the glass surface is disclosed.

Further, for example, Japanese Unexamined Patent Publication (Kokai) No. 58-167448 describes a glass having a low reflectance, and a thin film having a thickness of 1 μm or less, which is made of a polyfluoroalkyl group-containing silane compound or a partial hydrolyzed condensate of the compound, is formed. It has been disclosed that when formed on a glass surface, it has low reflectivity and water and oil repellency without impairing transparency and the like.

Further, for example, Japanese Unexamined Patent Publication No. 1-68477 discloses a method for producing a surface-treated steel sheet having excellent water repellency and durability, and an alkoxide, monomethyl alkoxide, acetyl acetate salt of a specific metal is formed on the surface of the steel sheet. Of 0.05% by weight or more of one or more of the above and an alcohol solution containing 0.005 to 0.30 mol% of fluoroalkylsilane with respect to the total, and then heated to 100 ° C or more to give an inorganic material having a water repellent. Those trying to form an oxide film are disclosed.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, water-repellent treatment agents for glass surfaces described in JP-A-58-122979 and JP-A-58-172245, or JP-A-58-172245.
In the compound described in JP-A 58-167448, although water repellency is exhibited, the rolling property of water droplets is poor, and it is difficult to say that it can be easily commercialized by a simple coating method such as hand coating. In such a shape, uniform coating may be difficult in some cases, optical properties may be changed, and scratch resistance is not necessarily strong. Further, for example, with the surface treatment agent described in JP-A-1-68477, basically the same things as described above can be said.
In particular, it is not intended to make it as close as possible to the scratch resistance of the glass surface, the coating method is also limited, and it is not always easy to adopt it for glass products etc. with a simple coating method such as hand coating. It is hard to say that you can do it.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and a mixed solution of the specified fluoroalkylsilane compound and boric acid or alkoxide of boron is added in a specified ratio. Since it is diluted and partially hydrolyzed, it can be applied by a simple coating method, and it is easy to apply even in complicated shapes without uneven coating, and does not change the optical characteristics. Is a monolayer film or a significantly thin film similar to a monolayer film, and while making the most of the surface characteristics of the glass that is the substrate, the scratch resistance and the like are close to those of the glass itself, which may cause scratches. It is possible to obtain a water-repellent treated glass that is resistant to haze even if it is expressed and easily retains transparency, has water repellency and weather resistance, and is resistant to stains due to a small drop inclination angle of water droplets. Useful glass surface water repellent and the treating agent is to provide a water-repellent treatment method applied on a glass substrate.

That is, according to the present invention, in a water repellent treatment agent obtained by partially hydrolyzing a mixed solution of a fluoroalkylsilane compound and boric acid or a boron alkoxide, boric acid or a boron alkoxide is added to 1 mol of the fluoroalkylsilane compound. A mixed solution of a fluoroalkylsilane compound of 0.055 mol and boric acid or an alkoxide of boron is diluted with a diluting solvent to a concentration of 0.5 to 10 w.
A water repellent treatment for a glass surface, which is prepared by diluting to t% and adding water or / and an acid catalyst in an amount 10 to 10 times mol of the total mol of the fluoroalkylsilane compound and boric acid or alkoxide of boron. Agent.

Further, a mixed solution of the fluoroalkylsilane compound and boric acid or an alkoxide of boron,
The above-mentioned water repellent treatment agent for glass surface, characterized in that boric acid or boron alkoxide is 0.1 to 4 mol per mol of the fluoroalkylsilane compound.

Further, fluoroalkylsilane compound 1
A mixed solution of a fluoroalkylsilane compound in which boric acid or boron alkoxide is 0.05 to 5 mol with respect to mol and boric acid or boron alkoxide is diluted with a diluting solvent to a dilution concentration of 0.5 to 10 wt%, The total mol of the fluoroalkylsilane compound and boric acid or boron alkoxide to be added is from the same mol to 10 times m
of water or / and an acid catalyst of 1 to 10 C. P. A water-repellent treatment method for a glass substrate, which comprises forming a coating solution having a viscosity adjusted to, coating on a glass surface, and forming a film at a heating temperature of 100 ° C to 400 ° C.

Furthermore, each of the above-mentioned water repellent treatment methods for a glass substrate is characterized in that the water repellent treatment method for the glass substrate provides a monolayer film to a film thickness within a range of 5 nm. is there.

Here, as described above, a mixture of the fluoroalkylsilane compound and the boric acid or boron alkoxide, which is 0.05 to 5 mol of boric acid or boron alkoxide per 1 mol of the fluoroalkylsilane compound, is used. When the amount is less than 0.05 mol, as in the case of only the fluoroalkylsilane compound, the effect that the bonding force between the film and the glass surface becomes sufficiently strong gradually disappears. Film, that is, a film that does not approximate a monolayer film, and tends to be a thick film. For example, the application method is limited to dipping method or roll coating method. This is because coating unevenness and the like will occur with a simple method such as. As the preferred mixed solution, boric acid or boron alkoxide is added in an amount of 0.1 to 4 m with respect to 1 mol of the fluoroalkylsilane compound.
ol.

Further, the above-mentioned mixed solution was diluted with a diluting solvent to a dilution concentration of 0.5 to 10% by weight, because the water repellent performance cannot be sufficiently obtained with a thin dilution of less than 0.5% by weight.
This is because if the content exceeds wt%, coating unevenness or the like will appear.

Further, a fluoroalkylsilane compound and
For example, CF₃(CH₂)₂Si (OC
H₃)₃, CF₃(CH₂)₂SiCl₃, CF₃(C
F₂)_Five(CH₂)₂Si (OCH₃)₃, CF₃(C
F₂)_Five(CH₂)₂SiCl₃, CF₃(CF₂)₇
(CH₂)₂Si (OCH₃)₃, CF₃(CF₂)₇
(CH ₂)₂SiCl₃, CF₃(CF₂)₇(C
H₂)₂SiCH₃Cl₂, CF₃(CF₂)₇(CH
₂)₂SiCH₃(OCH₃)₂Etc.

Further, boric acid or alkoxide of boron to be added is, for example, H ₃ BO ₃ , (CH ₃ ).
₃ BO ₃ etc. may be used. Further, the diluent may be lower alcohols such as methanol, ethanol, butanol, isopropyl alcohol, or aromatic hydrocarbons such as xylene or toluene, as long as they can be uniformly dispersed and dissolved.

Furthermore, the reason for adding the water or / and the acid catalyst in the same mol to 10 times mol as the total mol of the fluoroalkylsilane compound and boric acid or alkoxide of boron is that water or / and less than the same mol is added. In the case of an acid catalyst, the fluoroalkylsilane compound and boric acid or an alkoxide of boron are not sufficiently hydrolyzed and the reactivity with the glass is deteriorated. Is sufficient.

Furthermore, as a method for applying the glass plate or the like, a brush coating or an impregnating cloth coating may be used.
Depending on the case, a usual dipping method, spray method, flow coating method, spin coating method, or other coating means can be appropriately employed. Further, after coating with the coating solution, the temperature is about 100 ° C. or higher, preferably about 100-40.
It is preferable to carry out drying at a temperature of about 0 ° C. for about 30 minutes, and after drying, lightly wipe with a dry cloth such as flannel. This is because if the temperature exceeds about 400 ° C, the water repellency may not be sufficient.

Further, the thickness of the monomolecular layered film to the range of 5 nm is set so that if the film thickness is less than the monomolecular layered film, uneven water repellency is exhibited and the film thickness exceeds 5 nm. This is because it is difficult to say that the mechanical strength such as scratch resistance is sufficiently excellent, and uneven coating and the like are more likely to occur. It should be noted that the film thickness, for example, as a result of elemental analysis of the surface, should be detected only by the C or F element
It is checked by the detection depth of the F component by Auger electron spectroscopy or secondary ion mass spectrometry.

Further, the glass substrate may be an inorganic transparent glass plate or an organic material,
It is not particularly limited to colorless or colored, and its kind, color tone, shape, etc., for example, a glass substrate with a film undercoating a SiO ₂ thin film, further as bent plate glass, as well as various tempered glass, strength-up glass, flat plate It goes without saying that it can be used not only as a single plate or as a single plate, but also as a multi-layer glass or a laminated glass.

[0020]

As described above, when the water repellent agent for glass surface of the present invention is used, the glass surface can be water repellent treated by a simple coating method such as brush coating or coating with an impregnated cloth. It is not an exaggeration to say that the scratch resistance is almost the same as that of glass, and the bonding strength between the glass and the water repellent treatment is increased, and the weather resistance is excellent, Since the falling angle of inclination is small, the water-repellent treated glass is provided with antifouling property.

[0021]

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

[0022]Example 1 Approximately 100mm x 100mm, thickness 2mm chestnut
A float glass plate surface was brush washed and dried
After that, wet the coated surface with acetone, wipe it with a flannel, and dry it.
It was wiped off with a wiping flannel. Next, fluoroalkyl sila
CF as a compound₃(CF₂)₇(CH₂)₂Si
(OCH₃)₃(Toshiba Silicone TSL8233) About
In 1 mol, as an alkoxide of boron (CH₃)₃
BO₃(Kishida Chemical Co., Ltd.)
Oroalkylsilane compound and (CH ₃)₃BO₃A mixture of
To obtain isopropyl alcohol.
Diluted with about 50 g of water, and about 60% nitric acid as water.
Add about 1 g of water (catalyzing) and add at room temperature
Solution prepared in advance by stirring for 45 minutes and hydrolyzing
5 to 6 drops on the glass plate surface,
It was applied manually by rubbing. Then the application
The glass plate at about 250 ° C in a muffle furnace
After heat treatment for 30 minutes, it is allowed to cool, and the glass plate is allowed to cool.
The coated surface was wiped off with a dry wiper to obtain a water-repellent treated glass.

With respect to the water-repellent treated glass thus obtained, water was placed on the treated surface of the water-repellent treated glass, and the contact angle and the drop inclination angle of water droplets were measured by Kyowa Interface Science Co., Ltd. CA-A type. Measured by D. P. W accelerated weather resistance test by Suga Test Machine, weather resistance, durability, etc. under the conditions of cycle of about 50 ° C, humidity of 100% for about 4 hours and about 75 ° C, and ultraviolet irradiation of 3.0 mW for about 8 hours. Was evaluated.

As a result, as shown in Table 1 and FIG. 1, the contact angle is about 107 °, which can be wiped cleanly, has uniform optical characteristics without coating unevenness, and the contact angle tends to decrease. Was relatively small, the water drop drop angle was small, and the weather resistance and durability were sufficient.

Example 2 In the same manner as in Example 1, only (CH ₃ ) ₃ BO ₃ (manufactured by Kishida Chemical Co., Ltd.) as an alkoxide of boron was about 1.5 m.
I changed it to ol.

As a result, as shown in Table 1, as in Example 1, the contact angle was about 108 °, and the optical characteristics were uniform, which could be wiped cleanly, and coating unevenness did not remain. The angle was less likely to decrease, the water drop drop angle was small, and the weather resistance and durability were sufficient.

Comparative Example 1 A case where only a fluoroalkylsilane compound was used in the same manner as in Example 1 described above, and about 1 mol of fluoroalkylalkoxysilane (manufactured by Toshiba Silicone) was diluted with about 50 g of isopropyl alcohol. , About 60
% Nitric acid (about 3 mol) was added, and the mixture was stirred at room temperature for about 1 hour and then used as a water repellent treatment agent to obtain a treated glass. In the same manner as in the above-mentioned Examples, the contact angle and the drop angle of water drop were measured, and D.I. P. A W accelerated weather resistance test was performed.

As a result, as shown in Table 1 and FIG. 1, although it has water repellency at the initial stage, it is hard to say that it has a large water drop drop inclination angle, and has weather resistance and durability. Met.

Comparative Example 2 In the same manner as in Comparative Example 1, a treated glass was obtained using only a fluorine silane compound (manufactured by Shin-Etsu Silicone) and evaluated in the same manner as in the above Example.

As a result, as shown in Table 1, although it has water repellency at the initial stage, it has a large drop angle of water drop and has weather resistance and durability as in Comparative Example 1. It was hard to say.

Comparative Example 3 In the same manner as in Comparative Example 1, a treated glass was obtained using only a silicone water repellent (manufactured by Shin-Etsu Silicone) and evaluated in the same manner as in the above Example.

As a result, as shown in Table 1, although it has water repellency at the initial stage, it has a large drop angle of water drop and has weather resistance and durability as in Comparative Examples 1 and 2. It was hard to say.

[0033]

[Table 1]

[0034]

As described above, according to the present invention,
Even with a simple coating method, uneven coating does not occur, water-repellent treated glass can be obtained inexpensively and efficiently, and water drop properties, adhesion, weather resistance, and scratch resistance can be obtained without impairing optical characteristics. A water repellent agent and a water repellent agent for a glass substrate, which has a high utility value and can be widely adopted for various coating films such as architectural or automobile window materials, various glass articles, etc. It provides a treatment method.

[Brief description of drawings]

FIG. 1 is a graph showing D.I. in Example 1 and Comparative Example 1. P. W
It is a figure which shows the water-repellent treatment agent evaluation result by an accelerated weathering test.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C23C 18/12 (72) Inventor Osamu Takahashi 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center (72) Inventor Hiroaki Arai 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center (72) Inventor Shigeo Hamaguchi 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center

Claims (4)

[Claims] 1. A water repellent treatment agent obtained by partially hydrolyzing a mixed solution of a fluoroalkylsilane compound and boric acid or an alkoxide of boron, wherein a metal salt or a metal alkoxide of 0.1 mol is added to 1 mol of the fluoroalkylsilane compound.
A mixed solution of a fluoroalkylsilane compound and boric acid or an alkoxide of boron, which is 05 to 5 mol, is diluted to a dilution concentration of 0.5 to 10 wt% with a diluting solvent, and the fluoroalkylsilane compound and a metal salt or a metal alkoxide to be added are diluted. A water-repellent agent for glass substrates, which is obtained by adding 10 to 10 times mol of water or / and an acid catalyst as the total mol. 2. The mixed solution of the fluoroalkylsilane compound and boric acid or alkoxide of boron is 0.1 to 4 mol of boric acid or alkoxide of boron with respect to 1 mol of the fluoroalkylsilane compound. Item 2. A water repellent treatment agent for glass substrates according to item 1. 3. A fluoroalkylsilane compound 1 mol
To boric acid or boron alkoxide 0.05
A mixture of a fluoroalkylsilane compound and boric acid or a alkoxide of boron, which is ˜5 mol, is diluted to a dilution concentration of 0.5 to 10 wt% with a diluent solvent, and the fluoroalkylsilane compound and boric acid or boron alkoxide are added. A water-repellent treatment agent for a glass substrate, which is obtained by adding water and / or an acid catalyst in the same mol to 10 times mol as the total mol, is used in an amount of 1-10 C. P. The viscosity of the coating solution is adjusted to 100%, and the coating solution is coated on the glass surface.
A water repellent treatment method for a glass substrate, which is characterized by forming a film at a temperature of from ° C to 400 ° C. 4. A water repellent treatment method for the glass substrate,
The water repellent treatment method for a glass substrate according to claim 1, wherein the monomolecular layered film to a film thickness within a range of 5 nm is obtained.