JP2002155272A - Water-repelling treatment agent and water-repelling treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repelling treatment agent effectively coatable on the surface of glass without wastefulness through preventing itself from being moved and/or repelled when coated and affording uniform water repellency and favorable water droplet mobility as a result of uniformly setting the water-repelling component on the glass surface, and to provide a water-repelling treatment method by the use of the agent. SOLUTION: This water-repelling treatment agent comprises a dimethylpolysiloxane with a dynamic viscosity at 25 deg.C of 1-20 mm2/s, a nonvolatile acid, insoluble fine powder and a solvent. This agent is coated and spread with a felt to obtain a water-repelling-treated surface. The thus obtained surface affords uniform water repellency and excellent water droplet mobility, therefore, when the above agent is coated on the surface of a glass of an automobile or the like, rainwater droplets rapidly move by the aid of wind velocity in automobile running, thus securing good visibility.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying water repellency to a surface of a glass such as a window glass, a window glass, a mirror or a mirror of an automobile, a vehicle, an aircraft or a ship. The present invention relates to a water-repellent treatment agent and a water-repellent treatment method using the water-repellent treatment agent.

[0002]

2. Description of the Related Art Conventionally, many water-repellent agents for water-repellent treatment of a windshield surface or the like have been commercially available in order to secure a view when the vehicle or the like travels in rainy weather. Examples of such a water repellent treatment agent include, for example,
Water-repellent agents containing an alkylpolysiloxane and an acid, as disclosed in JP-A No. 0-15473 and JP-B-63-67828, are known.

[0003] In recent years, WO 98/59012, a republished patent, has proposed a water-repellent agent containing an alkyl group-containing polyorganosiloxane, a fluororesin or paraffin wax in addition to these components.

[0004] Such a water-repellent agent containing an alkylpolysiloxane as a water-repellent component is a simple method in which a water-repellent agent is applied to the surface of a windshield, dried, and then wiped off with a wet cloth moistened with water. A clear glass surface excellent in water repellency can be obtained only by work, and rain can be scattered as water droplets by a running wind of an automobile or the like, and a good visibility can be secured.

[0005]

However, when such a water-repellent treatment agent is applied to a glass surface, a distinction is made between a treated portion to which the water-repellent treatment agent is applied and an untreated portion to which the water-repellent treatment agent is not applied. The water-repellent treatment agent itself may be repelled, and the water-repellent treatment agent itself may be repelled, thereby failing to obtain the excellent water repellency and water droplet mobility originally possessed by the water-repellent treatment agent. In addition, even when felt is used as a coating method, the water-repellent agent is repelled to form a polka dot and is often dried.

[0006] As described above, when the treatment of the glass surface is incomplete, a portion having low water repellency is partially generated, the mobility of the water droplet on the glass surface is reduced, and a strong wind pressure, that is, If the vehicle is not running at high speed, water droplets will remain and a problem that good visibility cannot be secured will occur.

Therefore, in order for water droplets to move on the glass surface even at low speed and low wind pressure, there must be no weak water-repellent portion on the glass surface. Therefore, the water-repellent treatment liquid is uniformly applied to the glass surface. It is preferable that the water-repellent component be uniformly applied to the glass when applied.

The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent movement and repelling during application of a water-repellent treatment agent and effectively prevent waste on the glass surface. And a water-repellent treatment using the water-repellent treatment agent, which can uniformly apply the water-repellent component and can obtain uniform water repellency and good water droplet mobility. It is to provide a method.

[0009]

In order to achieve the above object, the water repellent agent of the present invention has a kinematic viscosity at 25 ° C of 1 to 20.
It is characterized by containing dimethylpolysiloxane in the range of mm ² / s, nonvolatile acid, insoluble fine powder and solvent.

The water-repellent treating agent of the present invention comprises 1.0 to 20.0% by weight of dimethylpolysiloxane, 0.1 to 5.0% by weight of a non-volatile acid, and 0.1 to 5.0% by weight of an insoluble fine powder. ~ 1
It is preferable that the solvent is contained in the range of 0.0 wt% and the solvent is in the range of 65.0 to 98.8 wt%.

The present invention also includes a water-repellent treatment method for applying the above-described water-repellent treatment agent to a water-repellent treatment surface by spreading it using a felt. Is preferably at least one selected from polyester, polypropylene and acrylic.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The water-repellent agent of the present invention contains dimethylpolysiloxane having a kinematic viscosity at 25 ° C. of 1 to ²⁰ mm ² / s, a nonvolatile acid, an insoluble fine powder and a solvent. I have.

In the present invention, dimethylpolysiloxane is contained as a water-repellent component and contains-(Si (CH ₃ ) _2-
It is a polymer compound having a unit structure of O)-. Such _{dimethylpolysiloxane, - (Si (CH 3)} 2
-O) - strand linear dimethylpolysiloxane is linear _{and,, - (Si (CH 3} ) 2 -O) - strand include any cyclic dimethyl polysiloxane is cyclic. The degree of polymerization may be appropriately selected depending on the purpose and application. In the present invention, the kinematic viscosity at 25 ° C. is 1 to ²⁰ mm ² / s, preferably 3 to 9 mm ² / s.
Dimethylpolysiloxane in the range of mm ² / s is used. If the kinematic viscosity is greater than 20 mm ² / s, the mobility of water droplets is reduced, and the solubility in a solvent is reduced, so that separation becomes easier. On the other hand, if the kinematic viscosity is less than 1 mm ² / s, the volatility during the operation increases, making it difficult to adhere to the surface of the substrate, and the water repellency is reduced.

More specifically, such a dimethylpolysiloxane is a linear dimethylpolysiloxane,
For example, KF96L (manufactured by Shin-Etsu Chemical Co., Ltd.), SH2
00 (manufactured by Dow Corning Toray Co., Ltd.). Examples of the cyclic dimethylpolysiloxane include KF994 (manufactured by Shin-Etsu Chemical Co., Ltd.) and SH244
Octamethylcyclotetrasiloxane such as (manufactured by Dow Corning Toray) or decamethylcyclopentasiloxane such as KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and SH245 (manufactured by Dow Corning Toray) And the like. These dimethylpolysiloxanes
One type may be used alone, or two or more types may be used in combination. For example, a linear dimethylpolysiloxane and a cyclic dimethylpolysiloxane may be used in combination.

The amount of dimethylpolysiloxane is preferably from 1.0 to 20.0% by weight, more preferably from 5.0 to 18.0% by weight, based on the total amount of the water-repellent agent.
If the amount of dimethylpolysiloxane is less than 1.0% by weight, the water repellency may decrease. On the other hand, if the content is more than 20% by weight, wiping becomes difficult and the cost may be increased.

In the present invention, the non-volatile acid is an acid which does not volatilize during operation at normal temperature and normal pressure, and is, for example, an inorganic acid such as sulfuric acid or phosphoric acid, for example, sulfonic acid,
Organic acids such as methanesulfonic acid are exemplified. Preferably, sulfuric acid is used. Note that volatile acids such as hydrochloric acid and nitric acid volatilize during the operation, and it is difficult to obtain a good water repellent effect. These non-volatile acids may be used alone or in combination of two or more. The compounding amount is 0.1 to 5.0% by weight, more preferably 0.5 to 0.5% by weight in the total amount of the water repellent.
Preferably, it is about 3.0% by weight. If the amount of the non-volatile acid is less than 0.1% by weight, the water repellency may decrease. On the other hand, if the content is more than 5.0% by weight, an excess acid may remain to lower the water repellency.

In the present invention, the insoluble fine powder is a fine powder that is not dissolved in a solvent but is dispersed in a water-repellent agent in the form of a fine powder. included. As the organic fine powder, for example, polyethylene, silicone resin, tetrafluoroethylene,
Ethylene-vinyl acetate copolymer, polypropylene, cellulose acetate butyrate, silicone rubber, microcrystalline cellulose, nylon, chitosan, polystyrene,
Resin powders such as benzoguanamine / melamine condensate, acrylic resin, and phenol resin are exemplified. Among these organic fine powders, polyethylene fine powder is preferably used.

Examples of the inorganic fine powder include alumina, silica, aluminum silicate, zeolite, bentonite, talc, montmorillonite, diatomaceous earth, smectite, cerium oxide, zirconium oxide, zirconium silicate, silicon carbide, titanium oxide and tripoly. Examples include inorganic powders such as aluminum phosphate, aluminum hydroxide, barium sulfate, and calcium silicate. Among these inorganic fine powders, silica fine powder is preferably used.

The particle size of the insoluble fine powder may be 100 μm or less, but is 45 μm or less.
Those having a size of 0 μm or less, particularly 0.01 to 20 μm, are preferably used. When it is 20 μm or less, the water-repellent treatment agent is hardly repelled and can be uniformly attached.

Such insoluble fine particles may be used alone or in combination of two or more. The compounding amount is 0.1 to 10.0% by weight, more preferably 0.1 to 10.0% by weight, based on the total amount of the water-repellent treating agent.
It is preferably 5 to 5% by weight. If the compounding amount of the insoluble fine particles is less than 0.1% by weight, the effect of preventing repellency of the water repellent agent may be reduced. Also, 10.
If the amount is more than 0% by weight, the excessive fine powder may hinder the bond between the water repellent and the substrate. By blending such an insoluble fine powder, repelling of the water repellent agent can be effectively prevented.

In the present invention, the solvent is not particularly limited as long as it dissolves the above-mentioned dimethylpolysiloxane and the non-volatile acid uniformly and does not dissolve the insoluble fine particles. Solvents as main components are exemplified. Examples of the alcohols include alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. Preferably, ethanol and isopropanol are used, and more preferably, isopropanol is used. In addition, if dimethylpolysiloxane or non-volatile acid is dissolved, and the insoluble fine particles are not dissolved, such alcohols include, for example, esters such as methyl acetate and ethyl acetate, for example, hexane, xylene, An aliphatic or aromatic petroleum solvent such as kerosene may be appropriately blended.

These solvents may be used alone or in combination of two or more. The amount of the solvent is 65.0 to 98.8% by weight, and more preferably 80.0% by weight, based on the total amount of the water repellent. ~
It is preferably 98.0% by weight.

In the water-repellent treating agent of the present invention, in addition to the above-mentioned dimethylpolysiloxane, non-volatile acid, insoluble fine powder and solvent, for example, silicone oil, spindle oil, etc. Liquid oils such as isoparaffinic hydrocarbon oils and fluorine oils may be appropriately blended.

The water-repellent agent of the present invention can be prepared by, for example, dissolving dimethylpolysiloxane and a non-volatile acid in a solvent, then mixing and dispersing an insoluble fine powder.

The water-repellent treating agent of the present invention thus obtained is applied to the surface of a substrate,
A uniform transparent film (water-repellent surface) having water repellency can be formed. The surface of the substrate to which the water repellent treatment agent of the present invention is applied includes a surface of an inorganic substrate such as a glass surface.

As a treatment method for applying the water repellent treatment agent of the present invention to the surface of a substrate, for example, after impregnating the felt with the water repellent treatment agent of the present invention, After spreading and drying, the excess may be wiped off with a clean cloth, a cloth dampened with water, or flushed with water. By spreading with a felt in this way, the work efficiency is good, and the coating can be uniformly and evenly applied to the surface of the base material.

The felt can be used without any limitation as long as it is made of a material which is not attacked by the acid component of the remaining water repellent, but is made of polyester, polypropylene or acrylic which has acid resistance. It is preferable to use a felt made of such a material.

The substrate treated with the water-repellent agent of the present invention does not cause repellency of the water-repellent agent, and the water-repellent component is uniformly bonded to the substrate. In addition, good water droplet mobility can be obtained. for that reason,
In particular, if it is applied to glass surfaces such as window glass, window glass, mirrors and mirrors of automobiles, vehicles, aircraft, ships, etc., excellent water repellency is imparted to the surface, and rainwater drops due to the wind speed during traveling It can move quickly to ensure good visibility even at low speeds.

Further, even when the water-repellent agent of the present invention is applied twice on the surface of a substrate, the water-repellent agent can be applied uniformly without being repelled.

[0030]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

Water-repellent agents were prepared by blending the components shown in Examples 1 to 9 and Comparative Examples 1 to 8 below.

Example 1 Dimethylpolysiloxane (trade name: SH200-3.
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
3.0 mm ² / s) 10.0% by weight Decamethylcyclopentasiloxane (trade name: KF9)
95, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C.) 4.0
mm ² / s) 5.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.0% by weight ・ Polyethylene powder (trade name: Flowsen UF, manufactured by Sumitomo Seika Co., particle size 10-20 μm) 1.5% by weight ・Isopropyl alcohol 82.5% by weight Example 2 Dimethyl polysiloxane (trade name: KF96L-5,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 5.0mm ²
/ S) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Polyethylene powder (trade name: Flocene UF, manufactured by Sumitomo Seika Co., Ltd., particle size 10-20 μm) 1.0% by weight ・ Isopropyl alcohol 82.5% by weight Example 3 Dimethylpolysiloxane (trade name: KF96L-5,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 5.0mm ²
/ S) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Nylon powder (trade name: Olgasol 2022,
1.0% by weight-Isopropyl alcohol 82.5% by weight Example 4-Dimethyl polysiloxane (trade name: KF96L-5, manufactured by Nippon Rilsan Co., Ltd.)
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 5.0mm ²
/ S) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Titanium oxide fine powder (trade name: R-580, manufactured by Ishihara Sangyo Co., average particle size 0.28 μm) 1.0% by weight -Isopropyl alcohol 82.5% by weight Example 5-Dimethyl polysiloxane (trade name: KF96L-5,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 5.0mm ²
/ S) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Diatomaceous earth fine powder (trade name: Celite 545, manufactured by Manvl Co., particle size 10-100 μm) 1.0% by weight ・ Isopropyl alcohol 82 Example 6 Decamethylcyclopentasiloxane (trade name: KF9)
95, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C.) 4.0
mm ² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Acrylic powder (trade name: Techpolymer MB-1)
2. Sekisui Chemical Co., Ltd., average particle size 12 μm)
1.0 wt%-Isopropyl alcohol 82.5 wt% Example 7-Dimethylpolysiloxane (trade name: KF96-10,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 10.0mm
² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Polyethylene powder (trade name: Florsen UF, manufactured by Sumitomo Seika Co., particle size 10-20 μm) 1.0% by weight ・ Ethyl 82.5% by weight of alcohol Example 8 Dimethylpolysiloxane (trade name: KF96-10,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 10.0mm
² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Polyethylene powder (trade name: Flowsen UF, manufactured by Sumitomo Seika Co., particle size 10-20 μm) 1.0% by weight ・ Isopropyl 82.5% by weight of alcohol Example 9 Dimethylpolysiloxane (trade name: KF96-10,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 10.0mm
² / s) 15.0% by weight-1.5% by weight of methanesulfonic acid-1.0% by weight of polyethylene powder (trade name: Florsen UF, manufactured by Sumitomo Seika Co., Ltd., particle size: 10 to ²⁰ m)-82.5% of isopropyl alcohol % By weight Comparative Example 1 Dimethylpolysiloxane (trade name: KF96-10,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 10.0mm
² / s) 10.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.0% by weight ・ Isopropyl alcohol 89.0% by weight Comparative Example 2 ・ Dimethylpolysiloxane (trade name: SH200-3.
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
3.0 mm ² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Isopropyl alcohol 83.5% by weight Comparative Example 3 ・ Dimethylpolysiloxane (trade name: KF96L-5,
Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C) 5.0mm ²
/ S) 5.0% by weight ・ Decamethylcyclopentasiloxane (trade name: KF9
95, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C.) 4.0
mm ² / s) 10.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 2.5% by weight ・ Isopropyl alcohol 82.5% by weight Comparative Example 4 ・ Dimethylpolysiloxane (trade name: SH200-2.
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
2.0 mm ² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.0% by weight ・ Isopropyl alcohol 84.0% by weight Comparative Example 5 ・ Dimethylpolysiloxane (trade name: SH200-5)
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
50.0 mm ² / s) 10.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 2.0% by weight ・ Paraffin wax (trade name: 140, manufactured by Nippon Seiwa Co., Ltd., melting point 61 ° C.) 1.0% by weight Ethyl alcohol 87.0% by weight Comparative Example 6 Dimethyl polysiloxane (trade name: SH200-5)
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
50.0 mm ² / s) 15.0% by weight ・ Sulfuric acid (97% by weight aqueous solution) 1.5% by weight ・ Polyethylene powder (trade name: Flowsen UF, manufactured by Sumitomo Seika Co., particle size 10-20 μm) 1.0% by weight % Isopropyl alcohol 82.5% by weight Comparative Example 7 Dimethyl polysiloxane (trade name: KF96L-0.
65, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25 ° C.) 0.6
5mm ² / s) 15.0% by weight ・ Nitric acid (61% by weight aqueous solution) 1.5% by weight ・ Polyethylene powder (trade name: Flowsen UF, manufactured by Sumitomo Seika Co., particle size 10-20 μm) 1.0% by weight Isopropyl alcohol 82.5% by weight Comparative Example 8 Dimethyl polysiloxane (trade name: SH200-3.
0, manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity (25 ° C)
3.0mm ² / s) 15.0% by weight ・ Hydrochloric acid (35% by weight aqueous solution) 1.5% by weight ・ Isopropyl alcohol 83.5% by weight Evaluation A 25 cm × 40 cm glass plate is subjected to an oil film root cleaning cleaner (software). The glass surface was wetted with water, and the surface of the glass was wiped off with a clean towel. Next, each of the water-repellent treatment agents of Examples and Comparative Examples was soaked in felt (manufactured by Nippon Felt Industry Co., Ltd.), spread over the glass surface, and allowed to dry at room temperature for 10 minutes. At this time, the repelling state of the water repellent agent was evaluated. Table 1 shows the results.

Next, the glass surface was wiped with a cloth that had been squeezed into water and squeezed until the glass surface became transparent. The glass plate is tilted at an inclination of about 35 degrees, and fine water droplets are sprayed with a hand spray.
(Equivalent to 5 km) was blown to evaluate the mobility of water droplets. Table 1 shows the results.

[0034]

[Table 1]

When the surface of the substrate is treated with the water-repellent agent of the present invention, the water-repellent component can be uniformly bonded to the surface of the substrate without causing repelling of the water-repellent agent. Therefore, the water-repellent component can be applied effectively without waste, and the water-repellent component is uniformly fixed on the surface of the base material, and uniform water repellency without unevenness can be obtained. Furthermore, when the surface of the base material is treated with the water repellent treatment agent of the present invention, excellent water droplet mobility can be obtained on the surface of the base material. If applied to glass surfaces such as glass, window glass, mirrors and mirrors, raindrops can quickly move due to the wind speed during traveling, and a good view can be secured.

Further, if the water-repellent treatment agent of the present invention is applied so as to obtain a water-repellent treated surface by spreading it using a felt, the working efficiency is improved, and the surface of the base material is evenly and unevenly coated. It can be applied without.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 F term (Reference) 4G059 AA01 AC22 FA05 FA22 FA28 FA29 FB05 4H020 BA32 4J002 AB012 AB022 AB052 BB032 BB062 BB122 BC032 BG052 CC032 CC192 CL002 CP031 CP032 DE047 DE137 DE147 DG036 DG047 DH026 DH057 DJ007 DJ017 DJ047 EC038 EV236 FA082 FA087 FD202 FD206 FD207 FD208 GT00

Claims (4)

[Claims] 1. A water-repellent agent comprising dimethylpolysiloxane having a kinematic viscosity at 25 ° C. in the range of 1 to ²⁰ mm ² / s, a nonvolatile acid, an insoluble fine powder and a solvent. 2. A dimethylpolysiloxane containing 1.0 to 2 dimethylpolysiloxane.
0.0% by weight, non-volatile acid is 0.1-5.0% by weight,
0.1 to 10.0% by weight of an insoluble fine powder and 65.
The water-repellent treatment agent according to claim 1, which is contained in a range of 0 to 98.8% by weight. 3. A water-repellent treatment method comprising applying the water-repellent treatment agent according to claim 1 by using a felt to obtain a water-repellent treatment surface. 4. The method according to claim 3, wherein the felt is made of at least one material selected from polyester, polypropylene and acrylic.