High-temperature-resistant scratch-resistant easy-to-clean glass product and preparation method thereof

Abstract

The invention belongs to the technical field of glass product processing, and particularly relates to a high-temperature-resistant scratch-resistant easy-to-clean glass product and a preparation method thereof. The glass product comprises a glass substrate and an easy-to-clean film layer attached to the glass substrate, the easy-to-clean film layer is formed by curing the following coating composition in percentage by mass: 30-40% of polysiloxane containing a coupling group; 20%-40% of D3F; 10%-20% of nano silicon dioxide filler; 0.01%-0.1% of a silicon alkoxide catalyst; and 10%-30% of an anhydrous diluting solvent. The easy-to-clean film layer of the glass product adopts a specific fluorosilicone material to replace a fluorocarbon material, so that the high-temperature-resistant durability of the easy-to-clean film layer can be remarkably improved. By utilizing the coupling and cross-linking curing effects of the specific polysiloxane containing the coupling group, the glass substrate, the nano silicon dioxide filler and the fluorine-containing polysiloxane precursor, the high temperature resistance, scratch resistance, easiness in cleaning and durability of the glass product are remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of glass product processing, and in particular relates to a high-temperature resistant, scratch-resistant and easy-to-clean glass product and a preparation method thereof. Background Art

[0002] Glass products are widely used in building materials, high-end kitchenware, bathroom, household appliances and other products. At the same time, due to their application environment, they have high requirements for the easy-to-clean properties of glass products and their long-lasting performance of high temperature resistance and scratch resistance.

[0003] Hydrophobic and oleophobic treatment of glass products is the main method to improve their anti-pollution and easy-to-clean properties. CN118307212 A discloses a hydrophobic and oleophobic easy-to-clean glass and a preparation method thereof, wherein the easy-to-clean glass comprises a glass substrate layer and an easy-to-clean film layer attached to the glass substrate layer, wherein the easy-to-clean film layer is formed by spraying a configured coating composition on the glass surface and curing, wherein the components of the coating composition include 26% to 30% of methyl nonafluorobutyl ether, 62% to 68% of ethyl nonafluorobutyl ether, 2% to 3% of fluorine-modified silane coupling agent, 1.0% to 1.2% of surfactant, 1% to 2% of leveling agent, and 0.2% to 0.7% of substrate wetting agent. The obtained glass has the advantages of good hydrophobic and oleophobic properties, high light transmittance, and low haze. However, it uses small molecular fluorocarbon materials as the main component, has poor high temperature resistance and weak bonding with the glass substrate. CN 113045212 A discloses a method for preparing oleophobic and hydrophobic stove glass, using a silicifying agent SiO2 and 2,2-trifluoro-1,1,2-trichloroethane (F113) and a fluorine-containing mixture as a nano-level oleophobic and hydrophobic coating to treat the glass surface, making the glass easy to clean. However, the preparation process of the nano-level oleophobic and hydrophobic coating is relatively complicated, and the high temperature resistance and durability of the fluorocarbon material needs to be further improved.

[0004] Organopolysiloxane has the advantages of high temperature resistance, hydrophobic and oleophobic properties, and fluorine-containing materials have low surface energy properties, so that fluorine-containing organopolysiloxane has both advantages. CN 110791199 A discloses a fluorine-containing organopolysiloxane self-cleaning coating, including 5-50wt% of fluorine-containing siloxane precursor and 50-95wt% of siloxane prepolymer; its preparation method is as follows: under normal temperature environment, the fluorine-containing siloxane precursor and the siloxane prepolymer are mixed and stirred, and after stirring evenly, a film is sprayed on the substrate; placed in a constant temperature and humidity environment containing an ammonia atmosphere and allowed to stand for a preset time to obtain a fluorine-containing organopolysiloxane self-cleaning coating. This self-cleaning coating has strong hydrophobicity, good self-cleaning effect, high wear resistance, and a wide range of uses. However, the fluorine-containing siloxane precursor used is easy to self-condense and cross-link, and has poor compatibility with the siloxane prepolymer. At the same time, the reactive sites of the siloxane prepolymer are too few, resulting in poor controllability of the copolymerization effect of the two. Summary of the invention

[0005] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a high temperature resistant, scratch resistant and easy to clean glass product.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned high temperature resistant, scratch resistant and easy-to-clean glass product.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A high temperature resistant, scratch resistant and easy-to-clean glass product comprises a glass substrate and an easy-to-clean film layer attached to the glass substrate; the easy-to-clean film layer is formed by curing a coating composition having the following mass percentage:

[0009]

[0010] The polysiloxane containing coupling groups is prepared by the following method:

[0011] The vinyl silane coupling agent and hydrogen-containing silicone oil are mixed evenly under nitrogen protection conditions, the temperature is raised to 60-90° C., and a platinum catalyst is added to carry out an addition reaction to obtain polysiloxane containing a coupling group.

[0012] The preparation of the polysiloxane containing coupling groups involves a reaction route such as Figure 1 The polysiloxane containing coupling groups of the present invention has a high content of coupling active sites, which can significantly improve the binding force with the glass substrate and the nano-silica filler, and can also participate in the subsequent cross-linking curing (dealcoholization condensation) reaction of the D3F ring-opening reaction product, thereby improving the easy-to-clean property and durability of the coating.

[0013] Furthermore, the vinyl silane coupling agent is selected from vinyl trimethoxy silane or vinyl triethoxy silane.

[0014] Furthermore, the hydrogen-containing silicone oil is selected from terminal and / or side group hydrogen-containing silicone oils having a hydrogen content of 0.2% to 1.2% (wt%) and an average molecular weight of 2000 to 10000 g / mol.

[0015] Furthermore, the mass ratio of the added amount of the vinyl silane coupling agent to the hydrogen-containing silicone oil is 0.2 to 1:1.

[0016] Furthermore, the platinum catalyst is chloroplatinic acid or Custer's catalyst (bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum).

[0017] Furthermore, the addition reaction time is 2 to 6 hours.

[0018] Furthermore, the siliconate catalyst is potassium trimethylsiliconate.

[0019] Furthermore, the anhydrous dilution solvent is acetone, ethanol or isopropanol.

[0020] The method for preparing the above-mentioned high temperature resistant, scratch resistant and easy-to-clean glass product comprises the following preparation steps:

[0021] The coating composition is applied to the surface of the glass substrate, dried at 60-90° C. to form a film, and then heated to 110-150° C. to perform copolymerization, cross-linking and curing reaction to obtain a high-temperature resistant, scratch-resistant and easy-to-clean glass product.

[0022] The principle of the present invention is as follows: the coating composition of the present invention is mainly composed of polysiloxane containing coupling groups, D3F and nano-silica filler, wherein the polysiloxane containing coupling groups reacts with the glass substrate and the nano-silica filler to initially form a film after drying to remove the solvent, and then the temperature is raised to 110-150°C for copolymerization, cross-linking and curing reaction, D3F undergoes ring-opening polymerization under silicon alkoxide catalyst conditions to generate a fluorine-containing polysiloxane precursor, and further undergoes dealcoholization, cross-linking and curing with the remaining coupling groups under catalytic conditions to obtain an easy-to-clean film layer with strong adhesion to glass products.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The easy-to-clean film layer of the glass product of the present invention uses high-temperature resistant fluorosilicone material instead of fluorocarbon material, which can significantly improve the high-temperature resistance and durability of the easy-to-clean film layer.

[0025] (2) The polysiloxane containing coupling groups used in the present invention has low surface tension and a long Si-O-Si molecular main chain that is resistant to high temperatures. The coupling groups have a low tendency to self-condense, and can significantly enhance the coupling and cross-linking curing effect of the coupling groups with the glass substrate, nano-silica filler and fluorine-containing polysiloxane precursor, thereby significantly improving the hydrophobic and oleophobic properties of the easy-to-clean coating on glass products and the high temperature resistance, scratch resistance and easy-to-clean durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention provides a reaction scheme for preparing the polysiloxane containing coupling groups. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0028] Example 1

[0029] A method for preparing a high temperature resistant, scratch resistant and easy-to-clean glass product, comprising the following preparation steps:

[0030] The coating composition was coated on the surface of the glass substrate with a designed thickness of 50 μm, dried at 85° C. for 15 minutes to form a film, and then heated to 130° C. for copolymerization, cross-linking and curing reaction for 150 minutes to obtain a high-temperature resistant, scratch-resistant and easy-to-clean glass product.

[0031] The coating composition comprises the following components in percentage by weight:

[0032]

[0033] The polysiloxane containing coupling groups is prepared by the following method:

[0034] Vinyl triethoxysilane and side-group hydrogenated silicone oil with a hydrogen content of 0.72% (wt%) and an average molecular weight of 7500 g / mol are mixed evenly under nitrogen protection conditions, the mass ratio of the added amount of vinyl triethoxysilane to the hydrogenated silicone oil is 0.6:1, the temperature is raised to 85°C, and a Custer catalyst with a mass concentration of 0.01% is added to carry out an addition reaction for 3 hours until the vinyl reaction is complete to obtain a polysiloxane containing a coupling group.

[0035] The easy-to-clean glass products obtained in this embodiment are subjected to oleophobic and hydrophobic performance tests (contact angle tests are performed using hexadecane droplets and water droplets, respectively). The results show that the surface contact angle of the hexadecane droplets is 113°, and the surface contact angle of the water droplets is 135°; after high-temperature treatment at 240°C for 2h, the surface contact angle of the hexadecane droplets is 108°, and the surface contact angle of the water droplets is 126°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of the hexadecane droplets is 104°, and the surface contact angle of the water droplets is 127°. It can be seen from the above results that the glass products obtained by the present invention have excellent oleophobic and hydrophobic properties, and still have good oleophobic and hydrophobic properties after high-temperature treatment and steel wool friction treatment, and the easy-to-clean effect has good long-lasting performance.

[0036] Example 2

[0037] A method for preparing a high temperature resistant, scratch resistant and easy-to-clean glass product, comprising the following preparation steps:

[0038] The coating composition was coated on the surface of the glass substrate with a designed thickness of 50 μm, dried at 70° C. for 15 minutes to form a film, and then heated to 140° C. for copolymerization, cross-linking and curing reaction for 150 minutes to obtain a high-temperature resistant, scratch-resistant and easy-to-clean glass product.

[0039] The coating composition comprises the following components in percentage by weight:

[0040]

[0041] The polysiloxane containing coupling groups is prepared by the following method:

[0042] Vinyltriethoxysilane and side-group hydrogenated silicone oil with a hydrogen content of 0.9% (wt%) and an average molecular weight of 4000 g / mol are mixed evenly under nitrogen protection conditions, the mass ratio of the added amount of vinyltriethoxysilane to the hydrogenated silicone oil is 0.8:1, the temperature is raised to 90°C, and a chloroplatinic acid catalyst with a mass concentration of 0.02% is added to carry out an addition reaction for 4 hours until the vinyl reaction is complete to obtain a polysiloxane containing a coupling group.

[0043] The test results of the oleophobic and hydrophobic properties of the easy-to-clean glass products obtained in this embodiment show that the surface contact angle of the hexadecane droplet is 116°, and the surface contact angle of the water droplet is 138°; after high-temperature treatment at 240°C for 2h, the surface contact angle of the hexadecane droplet is 105°, and the surface contact angle of the water droplet is 124°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of the hexadecane droplet is 99°, and the surface contact angle of the water droplet is 122°. It can be seen from the above results that the glass products obtained by the present invention have excellent oleophobic and hydrophobic properties, and still have good oleophobic and hydrophobic properties after high-temperature treatment and steel wool friction treatment, and the easy-to-clean effect has good lasting performance.

[0044] Example 3

[0045] A method for preparing a high temperature resistant, scratch resistant and easy-to-clean glass product, comprising the following preparation steps:

[0046] The coating composition was coated on the surface of the glass substrate with a designed thickness of 50 μm, dried at 80° C. for 15 minutes to form a film, and then heated to 120° C. for copolymerization, cross-linking and curing reaction for 150 minutes to obtain a high-temperature resistant, scratch-resistant and easy-to-clean glass product.

[0047] The coating composition comprises the following components in percentage by weight:

[0048]

[0049] The polysiloxane containing coupling groups is prepared by the following method:

[0050] Vinyltrimethoxysilane and terminal side-group hydrogenated silicone oil with a hydrogen content of 0.5% (wt%) and an average molecular weight of 9600g / mol are mixed evenly under nitrogen protection conditions, the mass ratio of the added amount of vinyltrimethoxysilane to the hydrogenated silicone oil is 0.4:1, the temperature is raised to 80°C, and a Custer catalyst with a mass concentration of 0.01% is added to carry out an addition reaction for 4 hours until the vinyl reaction is complete to obtain a polysiloxane containing a coupling group.

[0051] The test results of the oleophobic and hydrophobic properties of the easy-to-clean glass products obtained in this embodiment show that the surface contact angle of the hexadecane droplet is 108°, and the surface contact angle of the water droplet is 132°; after high-temperature treatment at 240°C for 2h, the surface contact angle of the hexadecane droplet is 97°, and the surface contact angle of the water droplet is 119°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of the hexadecane droplet is 100°, and the surface contact angle of the water droplet is 118°. It can be seen from the above results that the glass products obtained by the present invention have excellent oleophobic and hydrophobic properties, and still have good oleophobic and hydrophobic properties after high-temperature treatment and steel wool friction treatment, and the easy-to-clean effect has good long-lasting performance.

[0052] Comparative Example 1

[0053] A method for preparing a high-temperature resistant, scratch-resistant and easy-to-clean glass product. Compared with Example 1, the coating composition does not contain a polysiloxane component containing a coupling group, the D3F content is increased to 66%, and the rest is the same.

[0054] The oleophobic and hydrophobic performance test results of the easy-to-clean glass products obtained in this comparative example showed that the surface contact angle of hexadecane droplets was 125°, and the surface contact angle of water droplets was 146°; after high-temperature treatment at 240°C for 2h, the surface contact angle of hexadecane droplets was 116°, and the surface contact angle of water droplets was 135°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of hexadecane droplets was 62°, and the surface contact angle of water droplets was 79°.

[0055] By comparing the results of this comparative example with Example 1, it can be seen that without adding the polysiloxane component containing the coupling group into the coating composition, the initial oleophobic and hydrophobic properties of the obtained easy-to-clean coating are improved to a certain extent, but the scratch resistance is obviously insufficient, and the easy-to-clean effect and the scratch resistance durability are poor.

[0056] Comparative Example 2

[0057] A method for preparing a high-temperature resistant, scratch-resistant and easy-to-clean glass product. Compared with Example 1, an equal amount of fluorosilane coupling agent 1H, 1H, 2H, 2H-perfluorodeoxytriethoxysilane is used in the coating composition to replace the D3F component, and the rest is the same.

[0058] The oleophobic and hydrophobic performance test results of the easy-to-clean glass products obtained in this comparative example showed that the surface contact angle of hexadecane droplets was 102°, and the surface contact angle of water droplets was 121°; after high-temperature treatment at 240°C for 2h, the surface contact angle of hexadecane droplets was 99°, and the surface contact angle of water droplets was 118°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of hexadecane droplets was 90°, and the surface contact angle of water droplets was 103°.

[0059] By comparing the results of this comparative example with Example 1, it can be seen that after the fluorosilane coupling agent is used to replace the D3F component, the initial oleophobic and hydrophobic properties and the scratch resistance durability of the obtained easy-to-clean coating are significantly reduced. The reason is that the self-condensation cross-linking of the fluorosilane coupling agent and the cross-linking activity with the polysiloxane containing the coupling group are too strong, resulting in excessive cross-linking density and embedding of fluorine-containing chains, while reducing the coupling reaction with the glass substrate, resulting in a reduction in oleophobic and hydrophobic properties and scratch resistance durability.

[0060] Comparative Example 3

[0061] A method for preparing a high-temperature resistant, scratch-resistant and easy-to-clean glass product. Compared with Example 1, an equal amount of fluorosilane coupling agent 1H, 1H, 2H, 2H-perfluorodeoxytriethoxysilane is used in the coating composition to replace the polysiloxane component containing a coupling group, and the rest is the same.

[0062] The oleophobic and hydrophobic performance test results of the easy-to-clean glass products obtained in this comparative example showed that the surface contact angle of hexadecane droplets was 116°, and the surface contact angle of water droplets was 141°; after high-temperature treatment at 240°C for 2h, the surface contact angle of hexadecane droplets was 110°, and the surface contact angle of water droplets was 129°; after rubbing back and forth with 0# steel wool with a load of 1kg for 7500 times, the surface contact angle of hexadecane droplets was 83°, and the surface contact angle of water droplets was 96°.

[0063] By comparing the results of this comparative example with Example 1, it can be seen that after the fluorosilane coupling agent is used to replace the polysiloxane component containing a coupling group, the scratch resistance and durability of the obtained easy-to-clean coating are significantly reduced. The reason is that the self-condensation cross-linking activity of the fluorosilane coupling agent under the catalyst condition is too strong and the wetting effect is poor, resulting in poor coupling effect with the glass substrate and nano-silica filler, and the combination effect with the subsequent fluorinated polysiloxane is poor, resulting in a reduction in scratch resistance and durability.

[0064] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A high temperature resistant, scratch resistant and easy to clean glass product, characterized in that: The invention comprises a glass substrate and an easy-to-clean film layer attached to the glass substrate; the easy-to-clean film layer is formed by curing a coating composition having the following mass percentage: The polysiloxane containing coupling groups is prepared by the following method: The vinyl silane coupling agent and hydrogen-containing silicone oil are mixed evenly under nitrogen protection conditions, the temperature is raised to 60-90° C., and a platinum catalyst is added to carry out an addition reaction to obtain polysiloxane containing a coupling group.

2. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The vinyl silane coupling agent is selected from vinyl trimethoxy silane or vinyl triethoxy silane.

3. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The hydrogen-containing silicone oil is selected from terminal and / or side group hydrogen-containing silicone oils with a hydrogen content of 0.2% to 1.2% and an average molecular weight of 2000 to 10000 g / mol.

4. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The mass ratio of the added amount of the vinyl silane coupling agent to the hydrogen-containing silicone oil is 0.2 to 1:

1.

5. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The platinum catalyst is chloroplatinic acid or a Custer catalyst.

6. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The addition reaction time is 2 to 6 hours.

7. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The siliconate catalyst is potassium trimethylsiliconate.

8. The high temperature resistant, scratch resistant and easy to clean glass product according to claim 1, characterized in that: The anhydrous dilution solvent is acetone, ethanol or isopropanol.

9. The method for preparing a high temperature resistant, scratch resistant and easy to clean glass product according to any one of claims 1 to 8, characterized in that: The method comprises the following preparation steps: The coating composition is applied to the surface of the glass substrate, dried at 60-90° C. to form a film, and then heated to 110-150° C. to perform copolymerization, cross-linking and curing reaction to obtain a high-temperature resistant, scratch-resistant and easy-to-clean glass product.

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