KR20010046317A - Ambient temperature-hardening glass-coating composition as water-retardant - Google Patents

Abstract

PURPOSE: A water-repellent coating composition for treating glass surface is provided which hardens at room temperature and gives corrosion-resistance, weather-resistance and chemical-resistance to the glass by simply being coated to the surface of the glass. CONSTITUTION: The composition comprises: (i) 1.00-10.00 wt.% of a mixture of at least two kinds of low molecular weight water-repellent silicone represented by the formula (A); (ii) 60.00-90.0 wt.% of a mixture of at least one kind solvent of (B), (C) and (D), which dissolve the low molecular weight water-repellent silicone and volatilize at room temperature; (iii) 0.50-5.00 wt.% of volatile silicone (E) or (F) or a mixture thereof, which control volatility and give lubrication when being coated; (iv) 0.01-3.00 wt.% of reactive silane (G), (H), (I) or mixture thereof, which make the reaction easy and decrease critical angle of inclination; and (v) 0.01-3.00 wt.% of inorganic acid (J), (K), (L) or mixtures thereof, where (B) is selected from ethanol, methanol, isopropyl alcohol or diisopropyl alcohol; (C) is cyclohexane or methyl ethyl ketone; (D) is ethylene glycol ethyl ether; (E) is hexamethyldisiloxane; (F) is octamethylcyclotetrasiloxane in case of n being 4 or decamethylcyclopentasiloxane in case of n being 5; (G) is trimethylchlorosilane or dimethylchlorosilane; (H) is octadecyltrichlorosilane or octadecyltrimethoxysilane; (I) is phenyldimethylethoxysilane; (J) is diethylsulfate; (K) is ethylsulfate; and (L) is sulfuric acid or hydrochloric acid. In the formula (A), R1 or R2 are organic group of CyH2y+1(where y is an integer of 0-10) containing hydroxyalkyl group, aminoalkyl group and epoxy group, R3 or R4 are CxH2x+1(where x is an integer of 0-10), C6H5, (CH3)3SiO, and m is an integer of not more than 100.

Description

Ambient temperature-hardening glass-coating composition as water-retardant

The present invention relates to room temperature curable and water repellent glass coating compositions.

The composition that imparts water repellency by forming a transparent water-repellent coating at room temperature with simple application to ordinary glass or mirrors, especially automobile glass, prevents damage caused by rain because it is not easy to secure the field of vision despite the wiper in driving the vehicle in rainy weather. It is used for the purpose of safe driving through better visibility, protection of glass surface, and prevention of contamination. Although water-repellent glass may be used for this purpose, water-repellent glass has excellent durability and water repellency, but is not used for general automotive glass due to its limited use due to excessive manufacturing cost and difficult process.

Accordingly, various water-repellent glass coating compositions that can be cured at room temperature have been used to meet these demands of the general consumer.

However, the existing water-repellent glass coating compositions have a disadvantage in that the water repellency is poor and the durability is weak and uniform film formation is not easy to apply, and there are defects such as night diffuse reflection and wire shaking due to staining.

The purpose of the present invention is to solve these shortcomings and to be selectively used on the part to be applied with water repellency. The composition can be selectively used for water repellency and durability, acid resistance, alkali resistance, heat resistance, cold resistance and weather resistance and uniform film formation. It is made to provide a composition that significantly improves the stain, night diffuse reflection, wiper shaking phenomenon.

The present invention relates to a water-repellent glass coating composition, and more particularly, to a composition which provides excellent water repellency, wear resistance, weather resistance, and chemical resistance by forming a transparent water repellent coating through chemical and physical bonding with a glass surface by simple application at room temperature. It is about.

Generally, glass for transportation devices such as automobiles, ships, and aircraft, household glass, and building glass, which are used in the state of being exposed to the outside, is a hydroxyl group at the end of the silicate which is the main component of glass when it is contaminated with rain and various contaminants on its surface. Since (-OH) and external moisture (HOH) are hydrogen-bonded, the visual field is poor, and a technique of providing a water-repellent function to the glass surface is used to prevent this.

As a method of imparting water repellency to the glass surface, generally, a method of forming a hydrocarbon compound, a silicon compound, and a fluorine compound layer on the glass surface is performed for producing water repellent glass.

Such water-repellent glass is excellent in durability, but due to the high cost and difficulty of the manufacturing process due to the manufacturing of the water-repellent glass, such as glass for transportation devices such as automobiles, ships, aircrafts, general household, construction glass, especially automobile or general household glass It is not widely used.

With this in mind, water-repellent glass coating compositions have been released mainly in the United States and Japan. Its weakness is that it has a weakness and does not have good wiping property when applied, so that stains are generated on the glass surface, resulting in diffuse reflection at night driving, which hinders the driver's vision.

The present invention solves the above-described problems, and by using a low molecular weight water-repellent silicone that can be cured at room temperature by simple application at room temperature and forms a strong chemical and physical bond to the glass surface, the surface tension is small and easy to penetrate. A uniform film is formed on the treated surface to improve durability, and to maintain the contact angle between the surface of the coating film, which is a measure of water repellency, and water droplets as large as possible, to improve durability, water repellency, and smoothness during application. It needs to be applied.

In addition, to give a water-repellent effect to a specific surface of the general glass or the automobile glass, especially the windshield, and to improve the visibility of the driver while driving in rainy weather, the critical inclination angle of the water droplets is small, so that the water droplets do not adhere well to the external force such as wind pressure even when attached. There is a need to use reactive silins to impart a property that is easily removed by.

By using the composition of the present invention, it is possible to exhibit excellent durability and water repellency at the same time by arranging a functional group capable of making a strong chemical bond with the inner glass surface and imparting hydrophobicity to water on the outer side, and also smoothness and wiping during application It improves the castle and makes it difficult to attach water droplets in rainy weather by reducing the critical inclination angle of water droplets. Therefore, it is possible to easily remove various contaminants attached by securing a clear view of the driver in rainy weather.

In order to achieve the above object of the present invention, the present invention provides a water-repellent coating composition for glass surface treatment consisting of the following components:

1.00-10.00 weight of 2 or more types of mixtures of the low molecular weight water-repellent silicones which consist of following (A) structural formula for providing room temperature hardenability and water repellency;

60.0 to 90.0 weight of one or more of the solvents (B), (C) and (D) which can dissolve the low molecular weight water-repellent silicone mixture and are room temperature volatile;

0.50 to 5.00 weight of the following volatile silicones (E), (F) alone or mixture for application of volatile control and lubricity upon application;

0.01 to 3.00 weight of the following reactive silanes (G), (H), (I) alone or a mixture of two or more to facilitate the reaction and reduce the critical tilt angle; And

0.01 to 3.00 weight of the following inorganic acid (J), (K), (L) alone or in mixture of two or more

(A)

Wherein R ₁ or R ₂ is a hydroxyalkyl group, an aminoalkyl group, an organic group containing an epoxy group: CyH _{2y + 1} (y = 0,1,2,3, ... 10),

R ₃ or R ₄ is C _x H _{2x + 1} (x = 0,1,2,3, ... 10), C ₆ H ₅ , (CH ₃ ) ₃ SiO,

m is an integer of 100 or less.

(B) ethanol (C ₂ H ₅ OH), methanol (CH ₃ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH) or diisopropyl alcohol;

(C) cyclohexane (C ₆ H ₁₂ ), methyl ethyl ketone (MEK) or mineral spirit

(D) Ethylene glycol ethyl ether (C ₂ H ₅ OCH ₂ CH ₂ OH)

(E) (Hexamethyldisiloxane)

(F)

Where n = 4: octamethylcyclotetrasiloxane

when n = 5: decamethylcyclopentasiloxane

(G) trimethylchlorosilane ((CH ₃ ) ₃ SiCl) or dimethylchlorosilane ((CH ₃ ) ₂ SiCl ₂ );

(H) octadecyltrichlorosilane (CH ₃ (CH ₂ ) ₁₇ SiCl ₃ ) or octadecyltrimethoxysilane (CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ );

(I) phenyldimethylethoxysilane;

(J) diethylsulfate (C ₄ H ₁₀ O ₄ S);

(K) ethylsulfate (C ₂ H ₅ (SO ₃ ) OH);

(L) H ₂ SO ₄ or HCl.

According to a preferred embodiment of the composition of the present invention, a mixture of two or more kinds of the water-repellent silicone (A) for imparting room temperature curing resistance, durability and water repellency to the glass surface is preferably contained in a content of 3.00 to 7.50, and upon application It is preferable that the above-mentioned (E), (F) alone or a mixture thereof as volatile silicone for imparting control and lubrication of volatile is contained in 1.00 to 3.00 by weight, and as a reactive silane for facilitating reactivity and reducing critical tilt angle It is preferable to contain 0.50-2.00 weight of said (G), (H), (I) single or 2 or more types of mixtures.

According to a preferred embodiment of the present invention in more detail the components of the present invention are as follows:

1. Mixture of at least two or more of the following (A) silicones in order to provide room temperature curing on the glass surface and to give excellent water repellency:

(A)

Wherein R ₁ or R ₂ = hydroxyalkyl group, aminoalkyl group, epoxy group-containing organic group, C _y H _{2y + 1} (y = 0,1,2,3, ..., 10),

R ₃ or R ₄ = C _x H _{2x + 1} (x = 0,1,2,3, ... 10), C ₆ H ₅ , (CH ₃ ) ₃ SiO,

m is less than 100.

2. As the solvent capable of dissolving the polysiloxane mixture and easily volatilizing to room temperature, single or two or more compounds of (B), (C) and (D):

(B) ethanol (C ₂ H ₅ OH), methanol (CH ₃ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH) or diisopropyl alcohol (Diisopropyl alcohol)

(C) cyclohexane (C ₆ H ₁₂ ), methyl ethyl ketone (MEK) or mineral spirit

(D) ethylene glycol ethyl ether (C ₂ H ₅ OCH ₂ CH ₂ OH),

3. Includes one or a mixture of the following volatile silicones (E) and (F) for imparting lubrication control and lubrication upon application;

(E) (Hexamethyldisiloxane)

(F)

When n = 4: Octamethylcyclotetrasiloxane

When n = 5: Decamethylcyclopentasiloxane

4. In order to facilitate the reactivity and to reduce the critical inclination angle, one or a mixture of two or more of the following reactive silins (G), (H) and (I) and the following inorganic acids (J), (K) and (L) At least one of includes:

(G) trimethylchlorosilane ((CH ₃ ) ₃ SiCl) or dimethylchlorosilane ((CH ₃ ) ₂ SiCl ₂ ),

(H) octadecyltrichlorosilane (CH ₃ (CH ₂ ) ₁₇ SiCl ₃ ) or octadecyltrimethoxysilane (CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ )

(I) Phenyldimethylethoxysilane

(J) Diethyl Sulfate (C ₄ H ₁₀ O ₄ S)

(K) ethyl sulfate (C ₂ H ₅ (SO ₃ ) OH)

(L) H ₂ SO ₄ or HCl

The low molecular weight water-repellent silicone mixture included in the composition of the present invention contains 1.00 to 10.00 weight of at least two or more mixtures of the above (A), and when the glass surface is coated at room temperature, the inside of the glass surface has a uniform chemical bond in a short time. It forms a strong film, and serves to exhibit water repellency by orienting hydrophobic functional groups on the outside.

At this time, when the silicone mixture is used at 1.00 weight or less, it is difficult to apply uniformly to the part to give water repellency, and the water repellency and durability are remarkably weak. In the present invention, preferably 3.00 to 7.50 weight is appropriate because it causes diffuse reflection.

In addition, if the volatilization alone or two or more of the solvents (B), (C) and (D), which are easily volatilized after application, are not excessively polysiloxane, the coating property and the wiping property are poor. Application of the volatile silicones (E) and (F) alone or a mixture of the volatile silicone (E), (F) was used to give a smoothness to the control of the volatilization and wiping. The volatile silicone alone or mixture contains 0.50 to 5.00 weight and preferably 1.00 to 3.00 weight in a range that does not affect the low molecular weight water repellent silicone mixture imparting the water repellency.

In addition, the content of the reactive silane (G), (H), (I) alone or a mixture of two or more kinds of 0.01 to 3.00 weight, in order to reduce the critical inclination angle to the water droplets, preferably 0.50 to 2.00 weight Do.

The following examples are intended to illustrate the present invention in more detail, and are not intended to limit the present invention to these examples.

Example 1

The composition of the present invention was prepared by the following method.

First, in a reactor equipped with a mechanical stirrer, 2.5 g of amine-modified silicone and polymethylsiloxane in an 8: 2 weight ratio as a low molecular weight water-repellent silicone mixture and 85.0 g of solvent isopropyl alcohol and 4.25 g of ethylene glycol ethyl ether, which can dissolve it After stirring for 1 hour at 200rpm with a mechanical stirrer, 1.5g of sulfuric acid, 1.0g of dimethyl sulfate, 4.7g of low molecular weight amine-modified silicone and polymethylsiloxane in an 8: 2 weight ratio were added and the temperature of the reactor was 40 Keep at. Subsequently, 1.0 g of octamethylcyclotetrasiloxane and 0.05 g of trimethylchlorosilane were gradually added to the reactor, followed by stirring at 300 rpm for 3 hours to form the composition of the present invention.

Example 2

The water repellency test of the composition is as follows.

The glass specimens are washed with acetone and hexane and dried to apply the composition to a nonwoven fabric and then wiped off with a dry cloth. The glass specimens treated with the composition were measured using a face contact angle measuring device (FACE CONTACT ANGLEMETER, manufactured by Kyowa Interface Science Co. Ltd., Japan) at room temperature (inert temp.) And measured the contact angle based on the droplet size of 2 mm. As a result of measuring the rolling angle on the basis of 3 mm, the results obtained in Example 1 showed superior contact angles and rolling angles compared to Comparative Examples 1 to 4 for commercial products.

<Test result>

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Contact angle (。) 102.0 99.6 98.4 96. 98.8 Rolling angle (。) 10.0 12.6 18.4 24.0 16.2

Example 3

The acid / alkali resistance test of the composition is as follows.

After applying the composition to the glass specimen with a non-woven fabric, wipe it off with a dry cloth to form a water repellent coating, and then immerse it in an acidic solution and an alkaline solution at 25 ° C for 24 hours, and then wash it. It did not occur remarkably compared with Comparative Examples 1-4.

<Test result>

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Contact angle (。) Acid resistance Initial value 101.8 99.6 98.4 96.0 98.8 Test value 99.2 97.0 94.2 93.2 95.4 Lowered value 2.6 2.6 4.2 2.8 3.4 Alkali resistance Initial value 102.0 99.4 98.6 95.6 98.6 Test value 99.5 96.2 92.4 92.5 96.0 Lowered value 2.5 3.2 6.2 3.1 2.6 Rolling angle (。) Acid resistance Initial value 10.0 12.6 18.4 24.0 16.2 Test value 11.8 18.4 34.4 32.2 28.4 Lowered value 1.8 5.8 16.0 8.2 12.2 Alkali resistance Initial value 10.2 12.4 18.4 23.8 16.2 Test value 12.2 19.2 36.2 33.4 28.4 Lowered value 2.0 6.8 17.8 9.6 12.2

Example 4

The weathering test of the composition is as follows.

After applying the composition to the glass specimen with a non-woven fabric, wipe it off with a dry cloth to form a water repellent coating, and then repeat the distilled water cleaning process every week and expose it for 30 days to expose it to external contact. It was remarkably less compared with Comparative Examples 1-4.

<Test result>

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Initial value 102.0 99.6 98.4 96.2 98.8 Test value 97.8 90.4 86.0 82.2 89.4 Lowered value 4.2 9.2 12.4 14.4 9.4

Example 5

The heat resistance / cold resistance test of the composition is as follows.

After applying the composition to the glass specimen with a non-woven fabric, wipe it with a dry cloth to form a water-repellent coating.Then, the heat resistance is repeated 24 times at 150 ° C and 24 hours at minus 15 ° C. In view of the water repellency did not occur.

<Test result>

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Contact angle (。C) Cold resistance Initial value 101.4 99.6 98.8 96.0 98.4 Test value 100.0 98.2 97.1 94.0 96.4 Lowered angle 1.4 1.4 1.7 2.0 2.4 Heat resistance Initial value 102.0 99.4 98.6 95.8 98.8 Test value 99.8 95.6 92.0 93.0 94.4 Lowered value 2.2 3.8 6.6 2.8 4.4

Example 6

The wear resistance test of the composition is as follows.

After applying the composition to the windshield was reproduced in rainy weather to operate the wiper 45 times per minute as a result of a total of 8 hours, that is, water repellency remained 21600 times wiper operation.

<Test result>

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Wiper Run Time 8 hours 7 hours 6 hours 7 hours 7 hours Number of wiper continuous operations 21600 times Episode 18900 16200 times Episode 18900 Episode 18900

Example 7

The advantages of using a car are as follows.

As a result of applying 10 times to the windshield of the car, Example 1 had no occurrence of spots and diffuse reflections compared to Comparative Examples 1 to 4, and the frequency of wiper vibration was small.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Presence of stain none Episode 2 Episode 2 3rd time Episode 2 Occurrence of diffuse reflection none Episode 2 3rd time Episode 2 Episode 2 Wiper Tremor 1 time Episode 2 4 times 3rd time Episode 2

Example 8

The advantages of using a car are as follows.

When applied to the windshield of the windshield Example 1 in the rain at 60Km / h in rainy weather to reduce the critical inclination angle of the rain droplets can be easily blown off by the wind, so the intermittent use of the wiper makes it easy to secure visibility in the rainy weather and more speed Clear vision is achieved without the wiper operating.

The performance test of the formulation of the composition of the present invention measures the contact angle and the rolling angle to determine the water repellency of the composition, and the contact angle after the acid resistance, alkali resistance, cold resistance, heat resistance and weather resistance test to determine the persistence of the effect Rolling angle was measured and compared.

According to the present invention, ordinary glass or mirror can be given excellent water repellency, acid resistance, alkali resistance, cold resistance, heat resistance and weather resistance, and abrasion resistance by simple application. Can be.

<Test and evaluation method>

1. Contact angle measuring instrument and test method

1) Measuring device: CONTACT ANGLEMETER MODEL CA-DA · A

(KYOWA INTERFACE SCIENCE CO., LTD)

2) How to measure:

(1) The glass specimen is washed and dried.

(2) Wet a certain amount of the composition on the nonwoven fabric and apply it to the glass specimen.

(3) Wipe the remaining amount with a dry cloth.

(4) Measure contact angle when the diameter of droplet is 2mm by using CONTACT ANGLEMETER.

(5) Measure the measured value 5 times and record the average value.

2. Each measuring instrument and test method rolling

(1) Measuring device: CONTACT ANGLEMETER MODEL CA-DA · A

(KYOWA INTERFACE SCIENCE CO., LTD)

2) How to measure:

(1) The glass specimen is washed and dried.

(2) Wet a certain amount of the composition on the nonwoven fabric and apply it to the glass specimen.

(3) Wipe the remaining amount with a dry cloth.

(4) The rolling angle in case the diameter of the droplet is 3mm is measured by CONTACT ANGLEMETER and the rolling angle is measured every 2 ° and the rolling angle is subtracted by 2 °.

(5) Measure the measured value 5 times and record the average value.

3. Measurement method of acid resistance / alkali resistance

(1) After cleaning and drying the glass specimen, measure the initial contact angle and the rolling angle.

(2) Soak in acidic solution (1N hydrochloric acid solution) and alkaline solution (1N sodium hydroxide solution), and leave it for 12 hours at room temperature.

4. How to measure weather resistance

(1) The glass specimen is washed and dried.

(2) Wet a certain amount of the composition on the nonwoven fabric and apply it to the glass specimen.

(3) Wipe the remaining amount with a dry cloth and measure the initial contact angle.

(4) The contact angle is measured for 2 months every week after leaving the house.

5. How to measure heat resistance and cold resistance

(1) Apply the composition to a glass specimen with a nonwoven fabric and wipe it off with a dry cloth to form a water repellent coating. Measure the initial contact angle and the rolling angle.

(2) Heat resistance is allowed to stand for 24 hours at 150 ° C and cold resistance for 24 hours at minus 15 ° C.

(3) Repeat (2) 10 times and measure each contact angle and rolling angle.

6. Wear resistance test method

After coating on the vehicle, the weather test was performed by abrasion resistance test according to the number of operation of the wiper.

(1) After cleaning the windshield of the given test vehicle, take a photograph by reproducing rainy weather using the sprayer.

(2) Apply coating after drying.

(3) Reproduce rainy weather using the sprayer and operate the wiper about 45 times per minute.

(4) Take a picture by time and take the picture until the state before the coating is secured to the extent that the field of view falls with time.

Claims (4)

As a water-repellent coating composition for glass surface treatment, 1.00-10.00 weight of 2 or more types of mixtures of the low molecular weight water-repellent silicones which consist of following (A) structural formula for providing room temperature hardenability and water repellency; 60.0 to 90.0 weight of one or more of the solvents (B), (C) and (D) which can dissolve the low molecular weight water-repellent silicone mixture and are room temperature volatile; 0.50 to 5.00 weight of the following volatile silicones (E), (F) alone or mixture for application of volatile control and lubricity upon application; 0.01 to 3.00 weight of the following reactive silanes (G), (H), (I) alone or a mixture of two or more to facilitate the reaction and reduce the critical tilt angle; And 0.01 to 3.00 weight of the following inorganic acid (J), (K), (L) alone or in mixture of two or more A water repellent coating composition for glass surface treatment comprising: (A) Wherein R ₁ or R ₂ is a hydroxyalkyl group, an aminoalkyl group, an organic group containing an epoxy group: CyH _{2y + 1} (y = 0,1,2,3, ... 10), R ₃ or R ₄ is C _x H _{2x + 1} (x = 0,1,2,3, ... 10), C ₆ H ₅ , (CH ₃ ) ₃ SiO, m is an integer of 100 or less. (B) ethanol (C ₂ H ₅ OH), methanol (CH ₃ OH), isopropyl alcohol ((CH ₃ ) ₂ CHOH) or diisopropyl alcohol; (C) cyclohexane (C ₆ H ₁₂ ), methyl ethyl ketone (MEK) or mineral spirit (D) Ethylene glycol ethyl ether (C ₂ H ₅ OCH ₂ CH ₂ OH) (E) (Hexamethyldisiloxane) (F) Where n = 4: octamethylcyclotetrasiloxane when n = 5: decamethylcyclopentasiloxane (G) trimethylchlorosilane ((CH ₃ ) ₃ SiCl) or dimethylchlorosilane ((CH ₃ ) ₂ SiCl ₂ ); (H) octadecyltrichlorosilane (CH ₃ (CH ₂ ) ₁₇ SiCl ₃ ) or octadecyltrimethoxysilane (CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ ); (I) phenyldimethylethoxysilane; (J) diethylsulfate (C ₄ H ₁₀ O ₄ S); (K) ethylsulfate (C ₂ H ₅ (SO ₃ ) OH); (L) H ₂ SO ₄ or HCl. The composition according to claim 1, wherein the composition contains 3.00 to 7.50 by weight of a mixture of two or more kinds of the water-repellent silicone (A) in order to impart room temperature curing resistance, durability and water repellency to the glass surface. The composition according to claim 1, wherein the composition contains 1.00 to 3.00 wt% of (E), (F) alone or a mixture thereof as volatile silicone for imparting lubrication and control of volatility during application. The composition according to claim 1, wherein the composition comprises 0.50 to 2.00 wt% of (G), (H), (I) alone or a mixture of two or more kinds as a reactive silane for facilitating reactivity and reducing a critical tilt angle. .