Glass antibacterial coating liquid and preparation method thereof

Abstract

The invention discloses a glass antibacterial coating liquid, and relates to the technical field of glass coating treatment liquids, and the antibacterial coating liquid is prepared from vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, a cationic additive, a tackifier and vinyl MQ resin. According to the antibacterial coating liquid, the cationic additive is used for adsorbing bacteria with negative charges and invading cell walls of the bacteria, so that the effect of killing the bacteria is achieved, the tackifier and the vinyl MQ resin are added into the antibacterial coating liquid, the adhesion between a film layer and a glass base material is improved through the addition of the tackifier, the film layer is not prone to stripping and falling off, and the service life of the film layer is prolonged. And the vinyl MQ resin is added, so that the strength of the film layer is improved, the film layer is not easy to scratch, and the service life of the film layer is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of glass coating treatment liquid, and in particular to an antibacterial glass coating liquid and a preparation method thereof. Background Art

[0002] Antibacterial coated glass is a kind of glass that has been treated with a special antibacterial process. It is widely used in medical equipment glass and touch screens. It can eliminate or kill most bacteria and reduce the adhesion of bacteria on the glass surface. At present, the main methods used to achieve the purpose of sterilization are nano-silver coating or titanium oxide coating. Since the nano-silver in the nano-silver coating is easily oxidized and discolored and migrates over time, and the titanium oxide coating uses ultraviolet radiation to stimulate its strong oxidation ability to decompose bacteria and other organic matter to achieve antibacterial function, it generally cannot play its antibacterial role indoors or in an environment without direct sunlight. Therefore, there are glass antibacterial coating liquids that use cationic additives as antibacterial agents. For example, the Chinese invention patent with patent announcement number CN 113149457A discloses a glass antibacterial coating liquid and its preparation method, as well as a preparation method for antibacterial coated glass. The antibacterial coating liquid is prepared from vinyl silicone resin, hydrogen-containing silicone resin, catalyst, and cationic additive. After baking, the cationic additive will form "intercalation modification" on the silicone resin, so that the glass coating layer structure has the characteristic of positive charges facing outward, and the effect of killing bacteria is achieved by adsorbing negatively charged bacteria and invading their cell walls. However, since the antibacterial coating liquid belongs to addition-type organic silica gel, a cross-linked network structure is formed by a silane addition reaction of vinyl-containing organic polysiloxane and low-polymerization degree hydrogen-containing silicone oil under platinum catalysis. It does not contain polar groups itself, has poor adhesion to the surface of the substrate, and the film layer is easy to fall off. Secondly, the strength of the film layer is insufficient, and the surface is easily scratched, which affects its service life. Summary of the invention

[0003] In view of the above problems, the technical problem to be solved by the present invention is to provide a glass antibacterial coating liquid to improve the adhesion performance and strength of the film layer.

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0005]

[0006]

[0007] The tackifier is a hydrolysis condensation reaction product of 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane and dimethyl(ethyl)vinylmethyl(ethyl)oxysilane.

[0008] Furthermore, the preparation method of the tackifier is: 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane organic solvent is added into a reaction vessel at a mass ratio of 1:1-1.5 and mixed evenly, deionized water and concentrated hydrochloric acid are added, and the reaction is carried out at a temperature of 50°C-55°C for 2h-3h, and then dimethyl(ethyl)vinylmethyl(ethyl)oxysilane is added, and the reaction is continued for 1-2h, the mixture is allowed to stand for stratification, the lower layer of liquid is taken, and it is washed with deionized water until it is neutral, and the low-boiling substances are removed from the mixture at a temperature of 80°C and a vacuum degree of 0.1MPa to obtain a tackifier.

[0009] Furthermore, the molar ratio of the 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane to dimethyl(ethyl)vinylmethyl(ethyl)oxysilane is 3-5:1.

[0010] Furthermore, the molar ratio of the sum of the 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane and dimethyl(ethyl)vinylmethyl(ethyl)oxysilane to the deionized water is 1:4-6.

[0011] Furthermore, the added amount of the concentrated hydrochloric acid is 1-2wt%.

[0012] Furthermore, the viscosity of the vinyl silicone oil is 300-1000 mPa·s, and the vinyl content is 1.2-5%.

[0013] Furthermore, the viscosity of the hydrogen-containing silicone oil is 300-500 mPa·s, and the hydrogen content is 0.32-0.5%.

[0014] Furthermore, the vinyl content of the vinyl MQ silicone resin is 2-5%, and the M / Q value is 0.6-1.

[0015] Furthermore, vinyl silicone oil, hydrogenated silicone oil, vinyl MQ resin and tackifier are mixed and stirred at room temperature, and then platinum catalyst is added and stirred evenly, and finally cationic additive is added and stirred evenly, and vacuum degassing is performed to obtain glass antibacterial coating liquid.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention improves the adhesion between the film layer and the glass substrate by adding a tackifier. Since the tackifier is a hydrolysis product obtained by hydrolyzing 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane and dimethyl(ethyl)vinylmethyl(ethyl)oxysilane, the side groups in the molecular chain contain polar groups such as epoxy groups and ether groups, which provide high adhesion. The vinyl groups at the ends of the molecular chains can form a cross-linked network when the film layer is cured, and the compatibility with the substrate is good. Since the tackifier is hydrolyzed by 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane, condensed, and finally capped by dimethyl(ethyl)vinylmethyl(ethyl)oxysilane, no excess Si-OH is generated, the tackifier has high stability, and is not easy to gel over time.

[0018] The present invention improves the strength of the film layer by adding vinyl MQ resin, making the film layer less likely to be scratched and increasing the service life of the film layer. Since the vinyl groups in the vinyl MQ resin form a cross-linked network with the substrate, the ability of the addition-type organic silicon film layer to resist external forces is enhanced, and the strength is improved. Moreover, the addition of the vinyl MQ resin has little effect on the light transmittance of the glass with the antibacterial coating. DETAILED DESCRIPTION

[0019] The specific implementation modes of the present invention are further described below in conjunction with examples.

[0020] Example 1

[0021] 74.5g of 3-glycidyloxypropylmethyldiethoxysilane and 74.5g of toluene were mixed evenly and added to a reaction container, 30g of deionized water and 3g of concentrated hydrochloric acid were added, and the reaction was carried out at a temperature of 50℃-55℃ for 2h, and then 13g of dimethylvinylethoxysilane was added, and the reaction was continued for 1h. The mixture was allowed to stand for stratification, the lower layer of liquid was taken, and washed with deionized water until neutral, and the mixture was removed at a temperature of 80℃ and a vacuum degree of 0.1MPa to remove low-boiling substances to obtain a tackifier. The tackifier was sealed and stored at room temperature, and no gelation occurred for 6 months.

[0022] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 13.5g of hydrogen-containing silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, 24.5g of vinyl MQ resin with a viscosity of 500mPa·s, a vinyl content of 2.5% and an M / Q value of 0.65, and 1.8g of a thickener are mixed and stirred at room temperature, 0.42g of platinum catalyst chloroplatinic acid is added and stirred evenly, and finally 2g of a cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0023] Example 2

[0024] The tackifier of this embodiment is prepared in the same manner as in Example 1;

[0025] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 13.5g of hydrogen-containing silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, 24.5g of vinyl MQ resin with a viscosity of 500mPa·s, a vinyl content of 2.5% and an M / Q value of 0.65, and 3g of a tackifier are mixed and stirred at room temperature, 0.42g of platinum catalyst chloroplatinic acid is added and stirred evenly, and finally 4g of a cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0026] Example 3

[0027] 124.2g of 3-glycidyloxypropylmethyldiethoxysilane and 155g of toluene were mixed evenly and added to a reaction container, 45g of deionized water and 5g of concentrated hydrochloric acid were added, and the reaction was carried out at a temperature of 50℃-55℃ for 3h, and then 13g of dimethylvinylethoxysilane was added, and the reaction was continued for 2h. The mixture was allowed to stand for stratification, the lower layer of liquid was taken, and washed with deionized water until neutral, and the mixture was removed at a temperature of 80℃ and a vacuum degree of 0.1MPa to remove low-boiling substances to obtain a tackifier. The tackifier was sealed and stored at room temperature, and no gelation occurred for 6 months.

[0028] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 14.8g of hydrogenated silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, 24.5g of vinyl MQ resin with a viscosity of 500mPa·s, a vinyl content of 2.5% and an M / Q value of 0.65, and 3g of a tackifier are mixed and stirred at room temperature, 0.42g of platinum catalyst chloroplatinic acid is added and stirred evenly, and finally 6g of a cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0029] Example 4

[0030] The tackifier of this embodiment is prepared in the same manner as in embodiment 3;

[0031] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 18.5g of hydrogen-containing silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, 45g of vinyl MQ resin with a viscosity of 500mPa·s, a vinyl content of 2.5% and an M / Q value of 0.65, and 5g of a thickener are mixed and stirred at room temperature, and then 0.56g of platinum catalyst chloroplatinic acid is added and stirred evenly, and finally 6g of a cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0032] Comparative Example 1

[0033] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 13.5g of hydrogen-containing silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, and 24.5g of vinyl MQ resin with a viscosity of 500mPa·s, a vinyl content of 2.5% and an M / Q value of 0.65 are mixed and stirred at room temperature, and then 0.42g of platinum catalyst chloroplatinic acid is added and stirred evenly. Finally, 2g of cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0034] Comparative Example 2

[0035] 100g of vinyl silicone oil with a viscosity of 500mPa·s and a vinyl content of 1.2%, 13.5g of hydrogenated silicone oil with a viscosity of 300mPa·s and a hydrogen content of 0.35%, and 1.8g of a thickener are mixed and stirred at room temperature, and then 0.42g of platinum catalyst chloroplatinic acid is added and stirred evenly. Finally, 2g of a cationic additive hexadecyltrimethylammonium chloride is added and continued to be stirred evenly, and vacuum degassing is performed to obtain a glass antibacterial coating liquid.

[0036] The glass antibacterial coating liquid obtained in Examples 1-4 and Comparative Examples 1-2 was spin-coated on the glass surface to prepare samples, and their performance was tested respectively. The test results are shown in Table 1:

[0037] Adhesion: Using GB / T 9286 as the reference standard, use a knife to scratch the surface of the glass sample with an antibacterial coating layer, with a grid spacing of 2mm; adhere the tape to the sample for 5 minutes and tear it off at 60°; the adhesion level is usually divided into six levels, from 0 to 5, where 0 represents the highest adhesion and 5 represents the worst adhesion.

[0038] Light transmittance: The light transmittance of the antibacterial coated glass sample in the visible light band of 400-800nm ​​was tested using a UV-spectrophotometer;

[0039] Hardness: According to GB / T6739-1996, the hardness of the glass antibacterial coating layer was tested using a portable pencil scratch tester.

[0040] Antibacterial properties: The ability of glass coated with antibacterial film to inhibit Escherichia coli was tested.

[0041] Table 1 Test results of Examples 1-4 and Comparative Examples 1-2

[0042]

[0043]

[0044] It can be seen from the test results that the glass antibacterial coating liquid of the present invention has good adhesion to the glass substrate, and the film layer is not easy to peel off, which means that the side groups in the molecular chain contain polar groups such as epoxy groups and ether groups, which provide high adhesion and enhance the adhesion between the film layer and the glass substrate. Since the ends of the tackifier molecular chains contain vinyl groups, a cross-linked network can be formed when the film layer is cured, and it has good compatibility with the substrate.

[0045] The vinyl MQ resin is added to the glass antibacterial coating liquid of the present invention to enhance the hardness of the film layer, making the film layer not easy to be scratched, and the vinyl group is used to form a cross-linked network, so that the ability of the addition-type organic silicon film layer to resist external forces is enhanced and the strength is improved. The light transmittance test shows that compared with other inorganic additives, the addition of the vinyl MQ resin does not affect the light transmittance of the antibacterial coated glass.

[0046] The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modified changes completed under the technical spirit suggested by the present invention should belong to the patents covered by the present invention.

Claims

1. A glass antibacterial coating liquid, characterized in that: The composition includes the following weight percentages: 100 parts of vinyl silicone oil 10-20 parts of hydrogen silicone oil Platinum catalyst 0.5-0.8 parts Cationic additives 2-6 parts 1.5-5 parts of tackifier Vinyl MQ resin 20-50 parts The tackifier is a hydrolysis condensation reaction product of 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane and dimethyl(ethyl)vinylmethyl(ethyl)oxysilane.

2. The glass antibacterial coating liquid according to claim 1, characterized in that: The preparation method of the tackifier comprises the following steps: adding 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane organic solvent into a reaction container at a mass ratio of 1:1-1.5 and mixing evenly, adding deionized water and concentrated hydrochloric acid, reacting at a temperature of 50°C-55°C for 2h-3h, then adding dimethyl(ethyl)vinylmethyl(ethyl)oxysilane, continuing the reaction for 1-2h, allowing the mixture to stand for stratification, taking the lower layer of liquid, washing with deionized water until neutral, removing low-boiling substances from the mixture at a temperature of 80°C and a vacuum degree of 0.1MPa, and obtaining the tackifier.

3. The glass antibacterial coating liquid according to claim 2, characterized in that: The molar ratio of the 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane to dimethyl(ethyl)vinylmethyl(ethyl)oxysilane is 3-5:

1.

4. The glass antibacterial coating liquid according to claim 2, characterized in that: The molar ratio of the total of the 3-glycidyloxypropylmethyl(ethyl)dimethyl(ethyl)oxysilane and dimethyl(ethyl)vinylmethyl(ethyl)oxysilane to the deionized water is 1:4-6.

5. The glass antibacterial coating liquid according to claim 2, characterized in that: The added amount of the concentrated hydrochloric acid is 1-2 wt %.

6. The glass antibacterial coating liquid according to claim 1, characterized in that: The viscosity of the vinyl silicone oil is 300-1000 mPa·s, and the vinyl content is 1.2-5%.

7. The glass antibacterial coating liquid according to claim 1, characterized in that: The viscosity of the hydrogen-containing silicone oil is 300-500 mPa·s, and the hydrogen content is 0.32-0.5%.

8. The glass antibacterial coating liquid according to claim 1, characterized in that: The vinyl content of the vinyl MQ silicone resin is 2-5%, and the M / Q value is 0.6-1.

9. A method for preparing an antibacterial glass coating liquid according to any one of claims 1 to 8, characterized in that: Vinyl silicone oil, hydrogen-containing silicone oil, vinyl MQ resin and tackifier are mixed and stirred at room temperature, and then platinum catalyst is added and stirred evenly, and finally cationic additive is added and stirred evenly, and vacuum degassing is performed to obtain glass antibacterial coating liquid.

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