JP3473833B2 - Automotive partially water-repellent glass and method of manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a partially water-repellent glass for an automobile, which is partially provided with a portion having no water repellency.

[0002]

2. Description of the Related Art As a water-repellent treated glass for automobiles, various highly durable water-repellent glasses have been proposed. For example,
Japanese Unexamined Patent Publication No. 5-238781 describes an article made of a glass substrate treated with perfluoroalkylsilane, which is a water repellent, on the surface of an underlayer made of silica. In Japanese Unexamined Patent Publication No. 7-138050, micropits are disclosed. A water-repellent oxide film is described in which an underlayer composed of an upper surface layer or an uneven surface layer is formed and a water-repellent film is formed on the surface thereof.

Regarding the partially water-repellent treated glass, for example, in Japanese Unexamined Patent Publication No. 9-142888, characters, patterns and / or patterns are patterned on the surface of a glass substrate,
Forming a transparent water-repellent coating on the patterned portion,
There is described a decorative glass in which the patterned portion is raised due to a difference in light scattering intensity when water such as water droplets or raindrops adheres. In JP-A-7-157336, a transparent substrate surface is not formed with a water-repellent film forming portion. And a method for forming a water-repellent coating in which a solvent is applied to a non-forming portion at the time of application so as to partially overlap the coating liquid for forming the water-repellent coating,
Japanese Patent Application Laid-Open No. 10-297939 discloses a partially water-repellent treated glass in which a water-repellent film is applied only to a wiper-wiping part of a window glass for an automobile, and no water-repellent film is applied to the other parts.

[0004]

However, the one described in JP-A-5-238781 or JP-A-7-138050 forms an underlayer under the water-repellent layer, but has a high hardness. Even if a simple underlayer is formed, the sliding part and other parts will be used as the usage period becomes longer for severe sliding such as windshield wiper sliding or door glass door lifting. Differences in water repellency, optical properties, appearance, etc. become apparent and unfavorable as a product.

Further, JP-A-9-
The object described in Japanese Patent No. 142888 is a decorative glass, and the object described in Japanese Patent Application Laid-Open No. 7-157336 is, for example, a non-water-repellent film part at a part to be adhered to the molding on the periphery of the glass. The purpose is to improve the decrease in adhesive strength, and the purpose of the invention described in Japanese Patent Application No. 10-297939 is to improve the region of poor visibility due to the chandelier phenomenon. None of these aims to prevent various problems caused by performance deterioration due to sliding action of automobile door glass as a preventive measure.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a partially water repellent glass for an automobile door glass in which a water repellent coating is not formed on a portion which is slid by a stabilizer, and has a particularly strong sliding action. By not forming a water-repellent coating on the part, partial deterioration of the water-repellent coating does not become apparent even for a long-term sliding action due to the lifting and lowering of the door glass, and the optical performance and the appearance are maintained for a long time. It is possible to obtain a glass that is excellent in safety and aesthetics with little change with time.

That is, the partially water-repellent glass for automobiles of the present invention is a water-repellent glass having a water-repellent coating formed on the outer surface of the door glass for automobiles, and is subjected to sliding by a stabilizer relating to the elevating mechanism of the glass. It is characterized in that a water-repellent coating is formed except for the portion.

The partially water-repellent glass for automobiles of the present invention is characterized in that a water-repellent coating is not formed on a portion to which a holder for supporting the glass is adhered.
The contact angle θ of the water-repellent coating with respect to water droplets is preferably 70 ° or more.

Further, in the method for producing a partially water-repellent glass for automobiles of the present invention, a masking material is applied to a portion where a water-repellent coating is not formed, a water-repellent liquid is applied to the glass surface, and then heat treatment is performed. After the water-repellent coating is formed, the masking material is removed.

Further, in the method for producing a partially water-repellent glass for an automobile of the present invention, a water-repellent liquid is applied to the entire surface of an automobile door glass, heat treatment is performed to form the water-repellent film, and then the water-repellent film is formed. It is characterized in that a masking material is attached to the portion, and the portion other than the portion to which the masking material is attached is polished with an abrasive to remove the water-repellent coating.

Furthermore, in the method for producing a partially water-repellent glass for an automobile of the present invention, a water-repellent liquid is applied to the entire surface of an automobile door glass, followed by heat treatment to form a water-repellent film, and then a water-repellent film is formed. It is characterized in that a masking material is attached to the portion to be covered, and the portion other than the portion to which the masking material is attached is treated with an alkaline aqueous solution to remove the water-repellent coating.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The door glass for an automobile of the present invention comprises:
The present invention relates to a partially water-repellent glass for automobiles in which a water-repellent coating is not formed on a portion which is slid by a stabilizer relating to an elevating mechanism, which is a portion having a very strong sliding action.

The stabilizer is arranged in a panel below the door glass and holds the glass from both sides when the glass is moved up and down and slides it while pressing it so that the glass does not shake especially when the glass is moved up and down. , A device for guiding a smooth vertical movement of glass.

This stabilizer has a mechanism for exerting a vigorous sliding action on the outer surface of the glass when the glass is moved up and down, and the sliding portion has various mechanisms such as rolls, flocking, and balls (for example, actual opening). 60-23413, JP-A-56-131419, JP-A-61-16122.
However, the present invention is not limited to this mechanism, and the number of installed units or installed locations is not limited.

As the portion where the water-repellent coating is not formed, for example, when only one pair of stabilizers is arranged on the glass, as shown in FIG. 1, a strip-shaped region (black-painted portion) including the stabilizers. Is a part where the water-repellent coating is not formed, and when two pairs of stabilizers are arranged, as shown in FIG. 2, one thick strip (black coating part) including sliding parts by two stabilizers is provided. ) May be provided, and the method is not limited and can be appropriately performed depending on the purpose, but it is preferable that the front part of the door glass where the driver sees the door mirror is made of a water-repellent coating.

It is to be noted that, in addition to the portion that is slid by the stabilizer, a portion that strongly receives sliding or a holder portion for supporting glass as shown in FIG. 1 or 2 is prevented from being deteriorated in adhesiveness. Therefore, it is preferable not to form the water-repellent coating on the portion including the holder adhesive portion.

If a water-repellent coating is formed on the entire surface including the portion which is slid by the stabilizer, the coating of the sliding portion is worn faster than other portions, and the contact angle of the portion which is slid by the stabilizer is greatly increased. In particular, in rainy weather, that portion floats up in a streak pattern, and the water-repellent coating is liable to peel off, which is not preferable in appearance.

The door glass for automobiles is not particularly limited, and is not particularly limited in its colorlessness or coloring, its kind, color tone, shape, etc., and it is not limited to bent plate glass, but also various tempered glass and strength. It goes without saying that it can be used as a laminated glass, as well as a up glass, a flat plate or a single plate. Further, various coatings such as an ultraviolet shielding film, a heat ray shielding film, and a conductive film may be formed on the inner surface of the glass wheel.

The water-repellent liquid for forming the water-repellent coating is prepared, for example, by mixing a water-repellent agent composed of a fluoroalkyl group-containing silane compound, a solvent for dilution, and a predetermined amount of an acidic aqueous solution, followed by a predetermined time. It can be obtained by stirring to terminate the hydrolysis reaction, then adding a dehydrating agent to the solution, and performing a dehydration treatment for a predetermined period of time to cause polycondensation.

The starting material is a fluoroalkylalkoxysilane-based compound or a fluoroalkylhalogenated silane-based compound as a water repellent, and the compound is, for example, CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si.
(OR) ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (O
R) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OR) ₃ , C
F ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OR) ₃ , CF ₃ (C
F ₂ ) ₁₁ CH ₂ CH ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₉
CH ₂ CH ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ C
H ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si
R (OR) ₂ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF
₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂
SiRCl ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCl ₃ ,
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiRCl ₂ or the like can be used. In the above chemical formula, R is CH ₃ , C ₂ H
₅ and C ₃ H ₇ are shown.

As the diluent solvent, isopropyl alcohol
(Hereinafter, abbreviated as “i-PA”), methanol,
A lower alcohol solvent having a carbon number of 5 or less such as ethanol may be used, and ethers and ketones can be used in addition to the alcohol, and especially alcohol having isopropyl alcohol as a main component is used. It is preferable as a diluting solvent in the preparation of the coating liquid.

As the acidic aqueous solution as a catalyst, it is preferable to use an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid or an organic acid such as acetic acid or citric acid having a concentration of 0.01 N or more, preferably about 0.1 N to 13 N. it can. The water repellent: diluting solvent: acidic aqueous solution is in a weight ratio of 1: 5 to 50: 0.09.
The range of to 1.0 is preferable, but the range is not limited to these.

As the dehydrating agent, silica gel, synthetic zeolite, activated alumina and the like can be used, but the dehydrating agent is not limited thereto. Further, the present invention is not particularly limited, for example, when polycondensation is carried out after completion of hydrolysis or when polycondensation is started in the middle of hydrolysis.

The water repellent liquid is not limited to the above-mentioned method, and a dimethyl silicone water repellent, a mixed water repellent of the water repellent and dimethyl silicone, and a fluororesin are hybridized with silica sol. It is also possible to use other methods such as forming a water repellent film.

In order for the water-repellent coating film to exhibit excellent water repellency, an appropriate contact angle θ (°) and falling property δ (μl) are required.
It is essential to combine both, and generally, for example, when the contact angle increases, the falling property tends to decrease, and the contact angle θ is preferably 70 ° or more.

The conditions under which the water repellent liquid is applied to the surface of the glass substrate are usually at an atmospheric humidity of about 75 in order to activate the reaction between the silanol groups of the water repellent component and the hydroxyl groups on the surface of the substrate.
% RH or less is preferable, but not limited thereto. It is preferable that the surface of the glass substrate to which the water repellent liquid is applied is subjected to a surface treatment in advance to improve the strength of the film.

Further, it is particularly preferable to form an uneven underlayer on the surface of the glass substrate because the durability is further improved. As a method therefor, for example, at least one selected from metal alkoxide compounds or metal acetylacetonate compounds is used. The selected two or more compounds are tetrafunctional and trifunctional alkoxides, the two or more compounds are mixed with a solvent to form a coating solution, and the solution is coated / heated to form a micropit. A method for forming a flat surface layer can be adopted, but the method is not limited to this.

In manufacturing a partially water-repellent glass for automobiles, for example, a masking material is applied to a portion where a water-repellent coating is not formed, a water-repellent liquid is applied to the entire surface of the door glass, and then heat treatment is performed. After forming the, a method of removing the masking material, or after applying a water-repellent liquid to the surface of the door glass, after heat treatment to form a water-repellent coating, a masking material is attached to the portion where the water-repellent coating is formed, The portion other than the portion where the masking material is attached is polished with an abrasive, washed with UV ozone, exposed to strong UV light, exposed to corona discharge, or treated with an alkaline aqueous solution to remove the water-repellent coating. The partially water-repellent glass can be produced by a method or the like.

As described above, the water-repellent glass for automobiles of the present invention has both water-repellent treated water-repellent coating portions and non-water-repellent coating portions, and the water-repellent coating forming portion in rainy weather. Has a contact angle with water of about 70 ° or more, and the non-water repellent coating part has a contact angle of about 50-60 ° or less, which is the same as a normal glass surface. However, in rainy weather, a normal driver can see the exterior view of the door mirror or the outside of the vehicle clearly through the part with a large contact angle where the water-repellent coating is formed, which improves safety. .

As the method for applying the water-repellent liquid to the glass, hand coating (rubbing method), nozzle flow coating method, dipping method, spraying method, reverse coating method, flexo method, printing method, Various coating methods such as a flow coating method or a spin coating method, and known coating means such as a combination thereof can be appropriately adopted.

Further, the viscosity of the coating solution is preferably adjusted to 1 to 10 centipoise, and when it is less than 1 centipoise, the viscosity is too low to form a film, and when it exceeds 10 centipoise, the coating film is excessively coated. This is because cracks and the like occur in the film during the heating and drying process.

Furthermore, the solid content concentration of oxide of the coating solution is 0.2 to 20 wt%. If it is less than 0.2 wt%, it is too dilute and it is difficult to form a film.
%, The concentration will be too high and the film thickness will become thick, resulting in cracks in the film or turbidity during film formation, making it impossible to obtain a good quality thin film or increasing the material cost. It is connected.

[0033]

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

[0034]

[Example 1] The surface of the glass on the outer side of an automobile door glass was polished with 1% of a polishing liquid (Miritsu A manufactured by Mitsui Kinzoku Kogyo Co., Ltd. in water).
(Suspended to a certain extent) and then polished with a polish polisher, and then thoroughly washed with water. Then, "acid treatment" was performed by immersing in a 0.1 N sulfuric acid aqueous solution at 35 ° C for 1 minute. next,
A masking material (Nitto Denko Corporation) was applied to the non-water-repellent treated portion of this glass (the right half area of the glass including the portion which is slid by the stabilizer shown in black in FIG. 3 and the lower glass area including the holder portion). Made by SPV-362X-2)
Pasted. The shaded part in the black-painted part of the right half of the glass shows the part on which the stabilizer slides, and the black-painted part on the lower side is the part to which a holder or the like for supporting the door glass is adhered. It is better not to perform water repellent treatment so as not to reduce the adhesive strength between the holder and the glass.

For the water repellent treatment, a water repellent liquid is applied (at 23 ° C., 45 ° C.).
In an environment of% RH, about 2 ml / pc of a water-repellent liquid was dropped on a glass substrate, a cotton cloth (trade name: Bemcot) was sufficiently stretched over the glass surface, and air-dried for 5 minutes. The water-repellent liquid uses heptadecafluorodecyltrimethoxysilane (CF ₃
(CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ : KBM manufactured by Shin-Etsu Chemical
-7803, hereinafter referred to as FAS), isopropyl alcohol (i-PA) as a diluting solvent, and 0.1N nitric acid as an acid catalyst.
(HNO ₃ ) was mixed at a weight ratio of 1: 25: 0.3 and stirred at room temperature for 2 hours, and then the mixed sol was mixed with 5 times (by weight) FAS of a dehydrating agent (equivalent to molecular sieve 4A). It was obtained by filtering for about 16 hours and finally filtering with filter paper.

After that, heat treatment (hereinafter referred to as curing) is performed in a muffle furnace so that the glass temperature reaches 140 ° C. in 5 minutes, and the excess water repellent remaining cloudy is wiped off with iPA, and finally, The non-water repellent treated portion of the masking material was removed to obtain a partially water repellent and water repellent treated glass.

The results of measuring the in-plane contact angle of the obtained partially water-repellent glass are shown in FIG. 107-in the water repellent area
Although a high contact angle of 110 ° was obtained, the effect of the adhesive of the masking material was slightly recognized in the masking portion, but a contact angle of 50 to 68 °, which is a low level that does not cause a problem compared with ordinary glass, was observed. Indicated. The contact angle was measured under the following conditions.

“Contact angle measurement conditions” Equipment: Kyowa Interface Science CA-X type Environment: In the air (about 25 ° C) Droplet: pure water (2 μl).

[0039]

Example 2 A water repellent door glass was produced in the same manner as in Example 1. However, in Example 2, the non-water-repellent treated portion was not provided before the water-repellent treatment, and the entire exterior surface of the door glass was subjected to water-repellent treatment.
Next, the portion requiring water repellent treatment shown in FIG. 3 was covered with a masking material (SPV-A-303S manufactured by Nitto Denko). Then
Abrasive liquid (Mitsui Kinzoku Kogyo Millake A etc. in water 5-10
The glass surface other than the masking portion was sufficiently polished with a plastic polisher.
Then, after sufficiently washing with water and drying, the masking material was removed to obtain a partially water-repellent glass.

As a result of measuring the in-plane contact angle of the obtained partial water-repellent glass, a high contact angle of 107 to 110 ° was maintained in the water repellent treated portion, but 10 to 20 in the polished portion.
It showed a very low contact angle (°) and a value similar to that of ordinary glass.

[0041]

Example 3 After producing a water-repellent door glass in the same manner as in Example 2, a portion requiring water-repellent treatment was covered with a masking material (SPV-A-303S manufactured by Nitto Denko). Then glass 65
After being immersed in a 1N sodium hydroxide solution at a temperature of 10 ° C. for 10 minutes, it was thoroughly washed with water and dried, and then the masking material was removed to obtain a partially water-repellent glass.

As a result of measuring the in-plane contact angle of the obtained partial water-repellent glass, a high contact angle of 107 to 110 ° was maintained in the water repellent treated portion, but 30 to 40 ° in the alkali treated portion. Shows a low contact angle, which is almost the same as that of ordinary glass.

[0043]

Example 4 After producing a water-repellent treated door glass in the same manner as in Example 2, a portion requiring water-repellent treatment was covered with a black masking material (SPV-A-303S manufactured by Nitto Denko). Then
Using a UV ozone cleaning device (OC-4010, 40W10 lamp type, manufactured by Eyegraphics) on the glass surface, the portion from which the water-repellent coating was removed was cleaned with UV ozone for about 10 minutes. Then, the masking material was removed to obtain a partially water-repellent glass.

The in-plane contact angle of the obtained partially water-repellent treated glass was measured. As a result, the water-repellent treated portion was 107 to 110 °.
Although the high contact angle was maintained, the UV ozone washed part showed a very low contact angle of 6 to 35 °, and it was confirmed that the water-repellent coating was removed.

[0045]

Example 5 After manufacturing a water-repellent door glass in the same manner as in Example 2, a portion requiring water-repellent treatment was covered with a black masking material (SPV-A-303S manufactured by Nitto Denko). Next, a metal halide lamp (made by Eye Graphics) on the glass surface
Intense UV light (about 250 mW / cm ² ) obtained from M075-L312) was irradiated for about 15 minutes. Next, after washing with water and drying, the masking material was removed to obtain a partially water-repellent glass.

As a result of measuring the in-plane contact angle of the obtained partial water-repellent glass, a high contact angle of 107 to 110 ° was maintained in the water-repellent treated portion, but 3 in the UV-irradiated portion.
It showed a very low contact angle of 6 °, which was comparable to that of ordinary glass.

[0047]

Example 6 A water-repellent treated door glass was produced in the same manner as in Example 2. Next, using a corona discharge device CT-0212 manufactured by Sink Engineering Co., Ltd., corona discharge was exposed to the glass surface to be non-water repellent. The corona discharge output was 0.4 KW, and the glass substrate was conveyed at about 200 to 500 mm / min while the distance from the discharge wire line to the exposed glass surface was kept at 2 to 2.5 mm. In this way, the water-repellent coating was selectively removed only on the glass surface through which the discharge wire line passed, and a partially water-repellent treated glass was obtained.

As a result of measuring the in-plane contact angle of the partially water repellent glass, a high contact angle of 107 to 110 ° was maintained in the water repellent treated portion (the portion where the corona discharge wire line did not pass), The contact angle of the corona discharge wire was very low at about 10 °, and it was confirmed that the water-repellent coating was efficiently removed.

Next, using the partially water-repellent glass obtained in Examples 1 to 6, an actual vehicle door up / down test (up / down of 20,000 times) was performed. As a result, even after the test, the contact angle of the water-repellent treated portion was 100 to 105 ° and no large decrease was observed.
No difference from the initial state was observed in the sliding parts such as the stabilizer, the sliding deterioration part did not rise even in rainy weather, it did not impair the appearance quality of the product, and the effect of the partially water repellent glass Admitted. It should be noted that this effect was similarly observed in the partially water-repellent glass obtained by the method of any of Examples 1 to 6 above.

[0050]

Comparative Example 1 A water repellent door glass was produced in the same manner as in Example 1 or 2. However, in the water repellent treatment, the entire outside surface of the door glass was treated.

The in-plane contact angle of the obtained water-repellent glass was 1
The contact angle was as high as 07 to 110 °. Using this glass, an actual vehicle door up / down test (up / down of 20,000 times) was performed. Figure 5
Shows the in-plane contact angle of the glass after the test. The contact angle of the part that is slid by the stabilizer is drastically reduced, and especially when it rains, the part floats up in a streak pattern and peeling of the water-repellent film is observed, which is not desirable in appearance. It was confirmed that it is better to process.

[0052]

INDUSTRIAL APPLICABILITY The present invention is a partially water-repellent glass for an automobile door glass in which a water-repellent coating is not formed on a portion which is slid by a stabilizer, and is particularly effective on a portion having a large sliding action. By not forming the water-based film, the water-repellent film is not deteriorated even for a long-term sliding action due to the raising and lowering of the door glass, and the optical performance and the appearance are uniform for a long period of time. Excellent glass can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a partial water-repellent glass when there is one stabilizer.

[Fig.2] Two stabilizers (one non-water repellent part)
It is a figure which shows the partial water-repellent glass in the case of.

FIG. 3 is a diagram showing a masking state of a door glass.

FIG. 4 is a diagram showing a contact angle on a door glass surface.

FIG. 5 is a diagram showing a contact angle of a water-repellent door glass after an actual vehicle door test.

Continuation of front page (56) Reference JP-A-7-157336 (JP, A) JP-A-10-297939 (JP, A) JP-A-4-338137 (JP, A) JP-A-4-359086 (JP , A) JP-A-10-324545 (JP, A) Actually developed 62-26717 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) B60J 1/17 B60J 1/00 C03C 17/28 C09K 3/18 101 E06B 3/54

Claims (6)

(57) [Claims] 1. A water-repellent glass having a water-repellent coating formed on the exterior surface of an automobile door glass, wherein the water-repellent coating is formed except at least a portion of the glass which is slid by a stabilizer relating to a lifting mechanism. Partial water repellent glass for automobiles characterized by 2. The partially water-repellent glass for automobiles according to claim 1, wherein a water-repellent coating is not formed on a portion to which a holder for supporting the glass is adhered. 3. The contact angle θ of the water-repellent coating with respect to water droplets is 70.
3. The partially water-repellent glass for automobiles according to claim 1 or 2, wherein the glass is at least °. 4. A process for producing a partially water-repellent glass for an automobile according to claim 1, wherein a masking material is applied to a portion where a water-repellent coating is not formed, a water-repellent liquid is applied to the glass surface, and then heat treatment is performed. The method for producing a partially water-repellent glass for automobiles, which comprises: 5. A process for producing a partially water-repellent glass for an automobile according to claim 1, wherein a water-repellent liquid is applied on the entire surface of the door glass for an automobile, and then heat treatment is carried out to form a water-repellent film. A masking material is attached to the portion to be formed, and the portion other than the portion to which the masking material is attached is polished with an abrasive.
A method for producing a partially water-repellent glass for automobiles, which comprises polishing to remove the water-repellent coating. 6. A process for producing a partially water-repellent glass for an automobile according to claim 1, wherein a water-repellent liquid is applied to the entire surface of the door glass for an automobile, and then heat treatment is performed to form a water-repellent film, and then the water-repellent film. A method for producing a partially water-repellent glass for automobiles, which comprises applying a masking material to a portion where the mask is formed, and treating the portion other than the area where the masking material is applied with an alkaline aqueous solution to remove the water-repellent coating.