Fluoride-free coated glass and manufacturing process thereof

Abstract

The invention relates to the technical field of coated glass, in particular to fluoride-free coated glass and a manufacturing process thereof.The manufacturing process comprises the steps that deionized water and ethyl alcohol are sequentially used for cleaning a glass substrate, and the glass substrate is dried; uniformly spin-coating the basic coating on the surface of a glass substrate, drying and curing, taking out and cooling to room temperature to obtain single-coating glass containing a basic coating; grinding the basic coating to form a micro-rough structural surface, spin-coating the micro-rough structural surface with a heat-insulating and hydrophobic coating, and curing at room temperature to prepare double-coating glass containing the basic coating and the heat-insulating and hydrophobic coating, namely the fluoride-free coating glass. The base coating and the heat-insulating hydrophobic coating are sequentially attached to the glass substrate to form the double-coating glass, so that the long-acting hydrophobic performance and heat-insulating performance of the glass coating are ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of coated glass, and particularly to a fluorine-free coated glass and its manufacturing process. Background Art

[0002] Glass is an important building material. With the continuous improvement of the decorative requirements for buildings, the usage of glass in the construction industry is also increasing. However, when people choose glass doors and windows for buildings today, in addition to considering their aesthetic and appearance features, they pay more attention to issues such as self-cleaning, heat insulation, and environmental protection, and thus coated glass has emerged.

[0003] Ordinary glass can be processed by special physical or chemical methods to obtain hydrophobic glass with unique physical properties on its surface. Usually, it is also vividly called self-cleaning glass in commerce and belongs to the ecological and environmentally friendly "green glass". It generally refers to that after applying a special coating on the glass surface, dust or dirty liquids are difficult to adhere to the glass, or are relatively easily washed away by water, so that the glass surface can naturally remain clean. However, the current fluorine-free self-cleaning glass usually does not have good heat insulation effect and is difficult to maintain the hydrophobic effect for a long time. Based on this, a fluorine-free coated glass and its manufacturing process are proposed. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides a fluorine-free coated glass and its manufacturing process. By sequentially attaching a base coating and a heat-insulating and hydrophobic coating on a glass substrate, a double-coated glass is formed, ensuring the long-term hydrophobic performance and heat insulation performance of the glass coating.

[0005] To achieve the above object, the present invention provides the following technical solution: A fluorine-free coated glass, comprising a glass substrate and a functional coating attached to the glass substrate;

[0006] The functional coating includes a base coating attached to the surface of the glass substrate and a heat-insulating and hydrophobic coating attached to the surface of the base coating.

[0007] Preferably, the preparation method of the base paint used for the base coating is as follows: Add bisphenol A epoxy resin, polyoxypropylene triamine, silane coupling agent, and imidazole to diacetone alcohol, and stir at room temperature for 1 - 2 h to obtain the base paint.

[0008] Preferably, in terms of mass percentage, the proportion of each component in the base paint is: bisphenol A epoxy resin 3 - 6%, polyoxypropylene triamine 1 - 2%, silane coupling agent 0.5 - 1%, imidazole 1 - 2%, and diacetone alcohol 85 - 95%.

[0009] Preferably, the silane coupling agent is selected from KH-550, KH-560, and KH-570.

[0010] Preferably, the preparation method of the heat-insulating and hydrophobic coating material used for the heat-insulating and hydrophobic coating is as follows: Dissolve polydimethylsiloxane in n-hexane, add tetraethyl orthosilicate and dibutyl dilaurate, after ultrasonic treatment, add antimony tin oxide nanoparticles and hollow glass microspheres, and continue ultrasonic treatment to obtain the heat-insulating and hydrophobic coating material.

[0011] Preferably, the material ratio of polydimethylsiloxane to n-hexane is 1:(35 - 45) g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyl dilaurate is 10:(0.5 - 1):(0.5 - 1); the mass ratio of polydimethylsiloxane, antimony tin oxide nanoparticles and hollow glass microspheres is 5:1:0.5.

[0012] Preferably, the size of the antimony tin oxide nanoparticles is selected to be 80 - 120 nm, and the size of the hollow glass microspheres is selected to be 40 - 60 μm.

[0013] The present invention also provides a manufacturing process for fluorine-free coated glass, including the following steps:

[0014] (1) Clean the glass substrate with deionized water and ethanol in sequence, and dry it.

[0015] (2) Spin-coat the base coating evenly on the surface of the glass substrate, after drying and curing, take it out and cool it to room temperature to obtain a single-coated glass with a base coating.

[0016] (3) Perform frosting treatment on the base coating to form a micro-rough structure surface, spin-coat the heat-insulating and hydrophobic coating material on the micro-rough structure surface, and after curing at room temperature, obtain a double-coated glass with a base coating and a heat-insulating and hydrophobic coating, which is the fluorine-free coated glass.

[0017] Preferably, in step (2), it is dried and cured at 90 - 100 °C for 1 - 1.5 h.

[0018] Preferably, in step (3), the curing time at room temperature is 1 - 1.5 h.

[0019] The present invention provides a fluorine-free coated glass and its manufacturing process, which have the following beneficial effects compared with the prior art:

[0020] By successively attaching a base coating and a heat-insulating and hydrophobic coating on the glass substrate to form a double-coated glass, the present invention ensures the long-term hydrophobic performance and heat-insulating performance of the glass coating. Specifically, the base coating can be well combined with the glass surface and is not easily peeled off. By spin-coating the heat-insulating and hydrophobic coating material on the surface of the base coating, the formed heat-insulating and hydrophobic coating can be tightly combined with the base coating, enabling the double coating to be stably combined on the glass.

[0021] In the heat-insulating and hydrophobic coating of the present invention, polydimethylsiloxane is used as a low surface energy modifier and binder, in combination with nano-antimony tin oxide and hollow glass microspheres, to form a micro-rough structure on the surface of the coating, improving the hydrophobic and heat-insulating properties of the coating; moreover, without using fluorides, it is more environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings described herein are used to provide a further understanding of the present application and form a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation to the present application. In the drawings:

[0023] Figure 1 It is a schematic diagram of the structure of the fluoride-free coated glass of the present invention;

[0024] Figure 2 It is a schematic diagram of a simple test device for the heat-insulating performance of the fluoride-free coated glass of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] The following embodiments are used to illustrate in detail the implementation manners of the present application, so as to fully understand how the present application uses technical means to solve technical problems and achieve the realization process of technical effects and implement accordingly.

[0026] Example 1

[0027] The preparation method of the base coating is as follows: Add bisphenol A epoxy resin, polyoxypropylene triamine, silane coupling agent and imidazole to diacetone alcohol, and stir at room temperature for 1-2 h to obtain the base coating.

[0028] The mass percentage of each component in the above base coating is: bisphenol A epoxy resin 3%, polyoxypropylene triamine 1%, silane coupling agent KH-560 0.5%, imidazole 1%, and diacetone alcohol 94.5%.

[0029] Example 2

[0030] The preparation method of the base coating is as follows: Add bisphenol A epoxy resin, polyoxypropylene triamine, silane coupling agent and imidazole to diacetone alcohol, and stir at room temperature for 1-2 h to obtain the base coating.

[0031] The mass percentage of each component in the above base coating is: bisphenol A epoxy resin 6%, polyoxypropylene triamine 2%, silane coupling agent KH-550 1%, imidazole 2%, and diacetone alcohol 89%.

[0032] Example 3

[0033] The preparation method of the heat-insulating and water-repellent coating is as follows: Dissolve polydimethylsiloxane in n-hexane, add tetraethyl orthosilicate and dibutyltin dilaurate, after ultrasonic treatment, add antimony tin oxide nanoparticles (the size is selected as 80 - 120 nm) and hollow glass microspheres (the size is selected as 40 - 60 μm), and continue ultrasonic treatment to obtain the heat-insulating and water-repellent coating.

[0034] The material liquid ratio of the above-mentioned polydimethylsiloxane and n-hexane is 1:35 g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyltin dilaurate is 10:0.5:0.5; the mass ratio of polydimethylsiloxane, antimony tin oxide nanoparticles and hollow glass microspheres is 5:1:0.5.

[0035] Example 4

[0036] The preparation method of the heat-insulating and water-repellent coating is as follows: Dissolve polydimethylsiloxane in n-hexane, add tetraethyl orthosilicate and dibutyltin dilaurate, after ultrasonic treatment, add antimony tin oxide nanoparticles (the size is selected as 80 - 120 nm) and hollow glass microspheres (the size is selected as 40 - 60 μm), and continue ultrasonic treatment to obtain the heat-insulating and water-repellent coating.

[0037] The material liquid ratio of the above-mentioned polydimethylsiloxane and n-hexane is 1:45 g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyltin dilaurate is 10:1:1; the mass ratio of polydimethylsiloxane, antimony tin oxide nanoparticles and hollow glass microspheres is 5:1:0.5.

[0038] Example 5

[0039] A manufacturing process of a fluorine-free coated glass includes the following steps:

[0040] (1) Clean the glass substrate with deionized water and ethanol in sequence, and dry it.

[0041] (2) Spin-coat the base coating evenly on the surface of the glass substrate, after drying and curing at 100 °C for 1 h, take it out and cool it to room temperature to obtain a single-coated glass with a base coating.

[0042] (3) Conduct a frosting treatment on the base coating to form a micro-rough structural surface, spin-coat the heat-insulating and water-repellent coating on the micro-rough structural surface, and after curing at room temperature for 1 h, obtain a double-coated glass with a base coating and a heat-insulating and water-repellent coating, which is the fluorine-free coated glass.

[0043] In this example, the base coating in Example 1 and the heat-insulating and water-repellent coating in Example 3 are adopted. The obtained fluorine-free coated glass, from bottom to top, is successively a glass substrate, a base coating, and a heat-insulating and water-repellent coating.

[0044] Example 6

[0045] A manufacturing process for fluorine-free coated glass, comprising the following steps:

[0046] (1) Clean the glass substrate successively with deionized water and ethanol, and then dry it;

[0047] (2) Spin-coat the base coating evenly on the surface of the glass substrate. After drying and curing at 90 °C for 1 - 1.5 h, take it out and cool it to room temperature to obtain a single-coated glass with a base coating;

[0048] (3) Conduct a frosting treatment on the base coating to form a micro-rough structural surface. Spin-coat the heat-insulating and hydrophobic coating on the micro-rough structural surface. After curing at room temperature for 1.5 h, a double-coated glass with a base coating and a heat-insulating and hydrophobic coating is prepared, which is the fluorine-free coated glass.

[0049] In this example, the base coating in Example 2 and the heat-insulating and hydrophobic coating in Example 4 are used. The obtained fluorine-free coated glass from bottom to top is successively a glass substrate, a base coating, and a heat-insulating and hydrophobic coating.

[0050] Comparative Example 1

[0051] A manufacturing process for fluorine-free coated glass, comprising the following steps:

[0052] (1) Clean the glass substrate successively with deionized water and ethanol, and then dry it;

[0053] (2) Spin-coat the heat-insulating and hydrophobic coating on the surface of the glass substrate. After curing at room temperature for 1 h, a double-coated glass with a heat-insulating and hydrophobic coating is prepared, which is the fluorine-free coated glass.

[0054] In this comparative example, the heat-insulating and hydrophobic coating in Example 3 is used. The obtained fluorine-free coated glass from bottom to top is successively a glass substrate and a heat-insulating and hydrophobic coating.

[0055] Comparative Example 2

[0056] A manufacturing process for fluorine-free coated glass, comprising the following steps:

[0057] (1) Clean the glass substrate successively with deionized water and ethanol, and then dry it;

[0058] (2) Spin-coat the base coating evenly on the surface of the glass substrate. After drying and curing at 100 °C for 1 h, take it out and cool it to room temperature to obtain a single-coated glass with a base coating;

[0059] (3) Spin-coat the heat-insulating and hydrophobic coating on the base coating. After curing at room temperature for 1 h, a double-coated glass with a base coating and a heat-insulating and hydrophobic coating is prepared, which is the fluorine-free coated glass.

[0060] In this comparative example, the base coating in Example 1 and the heat-insulating and hydrophobic coating in Example 3 were used. The obtained fluorine-free coated glass from bottom to top was successively a glass substrate, a base coating, and a heat-insulating and hydrophobic coating.

[0061] Comparative Example 3

[0062] A manufacturing process of fluorine-free coated glass was basically the same as that in Example 5, except that:

[0063] The preparation method of the heat-insulating and hydrophobic coating was as follows: Polydimethylsiloxane was dissolved in n-hexane, tetraethyl orthosilicate and dibutyl dilaurate were added, and after ultrasonic treatment, antimony tin oxide nanoparticles (with a size selected from 80 - 120 nm) were added, and ultrasonic treatment was continued to obtain the heat-insulating and hydrophobic coating.

[0064] The material ratio of the above-mentioned polydimethylsiloxane and n-hexane was 1:35 g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyl dilaurate was 10:0.5:0.5; the mass ratio of polydimethylsiloxane and antimony tin oxide nanoparticles was 5:1.

[0065] In this comparative example, the base coating in Example 1 was used. The obtained fluorine-free coated glass from bottom to top was successively a glass substrate, a base coating, and a heat-insulating and hydrophobic coating.

[0066] Comparative Example 4

[0067] A manufacturing process of fluorine-free coated glass was basically the same as that in Example 5, except that:

[0068] The preparation method of the heat-insulating and hydrophobic coating was as follows: Polydimethylsiloxane was dissolved in n-hexane, tetraethyl orthosilicate and dibutyl dilaurate were added, and after ultrasonic treatment, hollow glass microspheres (with a size selected from 40 - 60 μm) were added, and ultrasonic treatment was continued to obtain the heat-insulating and hydrophobic coating.

[0069] The material ratio of the above-mentioned polydimethylsiloxane and n-hexane was 1:35 g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyl dilaurate was 10:0.5:0.5; the mass ratio of polydimethylsiloxane and hollow glass microspheres was 5:1.

[0070] In this comparative example, the base coating in Example 1 was used. The obtained fluorine-free coated glass from bottom to top was successively a glass substrate, a base coating, and a heat-insulating and hydrophobic coating.

[0071] Performance Detection

[0072] 1. The contact angles of the fluorine-free coated glass in Examples 5 - 6 and Comparative Examples 1 - 3 before and after tape peeling were measured with a contact angle measuring instrument (SDC-100S). A 200 g weight was used to press the tape on the outer coating of the fluorine-free coated glass, and then peeling was carried out. The specific results are shown in the following table.

[0073] Table 1 Hydrophobicity and Stability

[0074]

[0075] As can be seen from the above table:

[0076] (1) Compared with Example 5, the fluorine-free coated glass in Comparative Example 1 lacks a base coating, and as the number of tape peeling increases, the hydrophobic performance of its coating decreases significantly;

[0077] (2) Compared with Example 5, the heat-insulating and hydrophobic coating of the fluorine-free coated glass in Comparative Example 3 does not add hollow glass microspheres and cannot form a micro-rough surface with antimony tin oxide nanoparticles, affecting its hydrophobic performance.

[0078] (3) The fluorine-free coated glasses in Examples 5 and 6 have excellent hydrophobic performance and hydrophobic stability.

[0079] 2. Referring to the standard of JG / T235-2008, a simple test device for the heat-insulating performance of fluorine-free coated glass was made, as shown in Figure 2 . Among them, an iodine-tungsten lamp with 275W was used to simulate the solar light source for heating, and the temperature difference inside and outside was measured. The specific results are shown in the following table.

[0080] Table 2 Heat Insulation

[0081]

[0082]

[0083] As can be seen from the above table: Compared with Example 6, the heat-insulating and hydrophobic coatings in Comparative Examples 3 and 4 do not use antimony tin oxide nanoparticles and hollow glass microspheres in combination, resulting in a decrease in heat-insulating performance.

[0084] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A fluorine-free coated glass, characterized in that: including a glass substrate and a functional coating attached to the glass substrate; The functional coating comprises a base coating attached to the surface of the glass substrate and a heat-insulating and hydrophobic coating attached to the surface of the base coating.

2. The fluorine-free coated glass according to claim 1, characterized in that: The preparation method of the base coating used for the base coating is as follows: add bisphenol A epoxy resin, polyoxypropylene triamine, silane coupling agent and imidazole into diacetone alcohol, stir at room temperature for 1-2 hours, and prepare the base coating.

3. The fluorine-free coated glass according to claim 2, characterized in that: In terms of mass percentage, the components in the base coating are as follows: 3-6% of bisphenol A epoxy resin, 1-2% of polyoxypropylene triamine, 0.5-1% of silane coupling agent, 1-2% of imidazole, and 85-95% of diacetone alcohol.

4. The fluorine-free coated glass according to claim 2, characterized in that: The silane coupling agent is selected from KH-550, KH-560 and KH-570.

5. The fluorine-free coated glass according to claim 1, characterized in that: The preparation method of the thermal insulation hydrophobic coating used in the thermal insulation hydrophobic coating is as follows: polydimethylsiloxane is dissolved in n-hexane, tetraethyl orthosilicate and dibutyl dilaurate are added, nano antimony tin oxide and hollow glass microspheres are added after ultrasonic treatment, and ultrasonic treatment is continued to obtain the thermal insulation hydrophobic coating.

6. The fluorine-free coated glass according to claim 5, characterized in that: The material-liquid ratio of polydimethylsiloxane and n-hexane is 1:(35-45) g / mL; the mass ratio of polydimethylsiloxane, tetraethyl orthosilicate and dibutyl dilaurate is 10:(0.5-1):(0.5-1); and the mass ratio of polydimethylsiloxane, nano antimony tin oxide and hollow glass microspheres is 5:1:0.

5.

7. The fluorine-free coated glass according to claim 5, characterized in that: The size of the nano antimony tin oxide is selected to be 80-120 nm, and the size of the hollow glass microsphere is selected to be 40-60 μm.

8. The manufacturing process of fluorine-free coating glass according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Cleaning the glass substrate with deionized water and ethanol in turn, and drying it; (2) evenly spin-coating the base coating onto the surface of the glass substrate, drying and curing it, taking it out and cooling it to room temperature to obtain a single-coated glass containing the base coating; (3) The base coating is frosted to form a micro-rough structure surface, and a heat-insulating hydrophobic coating is spin-coated on the micro-rough structure surface. After curing at room temperature, a double-coated glass containing a base coating and a heat-insulating hydrophobic coating is obtained, that is, a fluorine-free coated glass.

9. The process for manufacturing fluorine-free coated glass according to claim 8, characterized in that: In step (2), the mixture is dried and cured at 90-100° C. for 1-1.5 hours.

10. The process for manufacturing fluorine-free coated glass according to claim 8, characterized in that: In step (3), the room temperature curing time is 1-1.5h.

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