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

Abstract

The present invention belongs to the technical field of glass product processing, and specifically relates to a high-temperature resistant, scratch-resistant, and easy-to-clean glass product and its preparation method. 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 a coating composition comprising the following percentages by weight: 30% to 40% polysiloxane containing coupling groups; 20% to 40% D3F; 10% to 20% nano-silica filler; 0.01% to 0.1% silicon alkoxide catalyst; and 10% to 30% anhydrous dilution solvent. The easy-to-clean film layer of the glass product of the present invention uses a specific fluorosilicone material instead of a fluorocarbon material, which can significantly improve the high-temperature resistance and durability of the easy-to-clean film layer. By utilizing the coupling and cross-linking curing effect of the specific polysiloxane containing coupling groups with the glass substrate, nano-silica filler, and fluorine-containing polysiloxane precursor, the high-temperature resistance, scratch resistance, and easy-to-clean durability of the glass product are significantly improved.

Description

Technical Field

[0001] The present 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 fixtures, household appliances, and other products. At the same time, their application environments place high demands on glass products for their easy-to-clean properties and long-lasting performance in terms of high temperature and scratch resistance.

[0003] Performing hydrophobic and oleophobic treatment on 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 its preparation method. The easy-to-clean glass includes a glass substrate layer and an easy-to-clean film layer attached to the glass substrate layer. The easy-to-clean film layer is formed by spraying a prepared coating composition on the glass surface and curing. The components of the coating composition include 26% to 30% methyl nonafluorobutyl ether, 62% to 68% ethyl nonafluorobutyl ether, 2% to 3% fluorine-modified silane coupling agent, 1.0% to 1.2% surfactant, 1% to 2% leveling agent and 0.2% to 0.7% 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 molecule 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. The method uses a silicifying agent, SiO2, 2,2-trifluoro-1,1,2-trichloroethane (F113), and a fluorine-containing mixture as a nanoscale oleophobic and hydrophobic coating to treat the glass surface, making it easier to clean. However, the preparation process for this nanoscale oleophobic and hydrophobic coating is relatively complex, and the high-temperature resistance and durability of the fluorocarbon material used need to be further improved.

[0004] Organopolysiloxanes have the advantages of high temperature resistance, hydrophobicity and oleophobicity, and fluorine-containing materials have low surface energy, making them combine the advantages of both. CN 110791199 A discloses a fluorine-containing organopolysiloxane self-cleaning coating, comprising 5-50wt% of a fluorine-containing siloxane precursor and 50-95wt% of a siloxane prepolymer; the preparation method is as follows: under a room temperature environment, the fluorine-containing siloxane precursor and the siloxane prepolymer are mixed and stirred, and after stirring evenly, a film is sprayed on a substrate; the mixture is 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 applications. However, the fluorine-containing siloxane precursor used is prone to self-condensation and cross-linking, and has poor compatibility with the siloxane prepolymer. At the same time, the siloxane prepolymer has too few reactive sites, 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 percentages:

[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, the temperature is raised to 60-90° C., and a platinum catalyst is added to carry out an addition reaction to obtain polysiloxane containing coupling groups.

[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 nano-silica filler. At the same time, it can participate in the subsequent cross-linking and curing (dealcoholization condensation) reaction of the D3F ring-opening reaction product, thereby improving the easy-to-clean properties 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 with 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 preparation method of 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 a 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 reactions to obtain a high-temperature, 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 comprises polysiloxane containing coupling groups, D3F and nano-silica filler as main components, wherein the polysiloxane containing coupling groups undergoes coupling reaction with the glass substrate and the nano-silica filler after drying to remove the solvent, thereby initially forming a film, and then the temperature is raised to 110-150°C for copolymerization, cross-linking and curing reaction, and D3F undergoes ring-opening polymerization under silicon alkoxide catalyst conditions to generate a fluorine-containing polysiloxane precursor, which is further dealcoholized and cross-linked and cured 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 a high-temperature resistant fluorosilicone material instead of a 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-chain Si-O-Si molecular main chain that is resistant to high temperatures. The coupling groups have a low tendency to self-condense, which can significantly enhance the coupling and cross-linking curing effect between the coupling groups and 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 following is a reaction scheme for the preparation of the polysiloxane containing coupling groups according to the present invention. DETAILED DESCRIPTION

[0027] The present invention will be further described in detail below with reference to 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 comprises the following steps:

[0030] The coating composition was applied to 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] Vinyltriethoxysilane and side-group hydrogenated silicone oil with a hydrogen content of 0.72% (wt%) and an average molecular weight of 7500 g / mol were mixed evenly under nitrogen protection conditions. The mass ratio of vinyltriethoxysilane to hydrogenated silicone oil was 0.6:1. The temperature was raised to 85°C, and a Custer catalyst with a mass concentration of 0.01% was added to carry out an addition reaction for 3 hours until the vinyl reaction was complete to obtain a polysiloxane containing a coupling group.

[0035] The oleophobic and hydrophobic properties of the easy-to-clean glass product obtained in this embodiment were tested (contact angle tests were performed using hexadecane droplets and water droplets, respectively). The results showed that the surface contact angle of the hexadecane droplet was 113°, and the surface contact angle of the water droplet was 135°. After high-temperature treatment at 240°C for 2 hours, the surface contact angle of the hexadecane droplet was 108°, and the surface contact angle of the water droplet was 126°. After rubbing 7500 times with 0# steel wool with a load of 1kg, the surface contact angle of the hexadecane droplet was 104°, and the surface contact angle of the water droplet was 127°. The above results show that the glass product obtained by the present invention has excellent oleophobic and hydrophobic properties, and still has good oleophobic and hydrophobic properties after high-temperature treatment and steel wool friction treatment, and has a good long-lasting easy-to-clean effect.

[0036] Example 2

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

[0038] The coating composition was applied to 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 were mixed evenly under nitrogen protection conditions. The mass ratio of vinyltriethoxysilane to hydrogenated silicone oil was 0.8:1. The temperature was raised to 90°C, and chloroplatinic acid catalyst with a mass concentration of 0.02% was added to carry out addition reaction for 4 hours until the vinyl reaction was complete to obtain polysiloxane containing coupling groups.

[0043] The oleophobic and hydrophobic properties of the easy-to-clean glass product obtained in this embodiment were tested. The surface contact angle of a hexadecane droplet was 116°, and the surface contact angle of a water droplet was 138°. After high-temperature treatment at 240°C for 2 hours, the surface contact angle of a hexadecane droplet was 105°, and the surface contact angle of a water droplet was 124°. After rubbing 7500 times with 0# steel wool with a load of 1kg, the surface contact angle of a hexadecane droplet was 99°, and the surface contact angle of a water droplet was 122°. These results indicate that the glass product obtained by the present invention has excellent oleophobic and hydrophobic properties, and maintains good oleophobic and hydrophobic properties even after high-temperature treatment and steel wool friction treatment, with good long-lasting easy-to-clean performance.

[0044] Example 3

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

[0046] The coating composition was applied to 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 hydrogenated silicone oil with a hydrogen content of 0.5% (wt%) and an average molecular weight of 9600 g / mol were mixed evenly under nitrogen protection conditions. The mass ratio of vinyltrimethoxysilane to hydrogenated silicone oil was 0.4:1. The temperature was raised to 80°C, and a Custer catalyst with a mass concentration of 0.01% was added to carry out an addition reaction for 4 hours until the vinyl reaction was complete to obtain a polysiloxane containing a coupling group.

[0051] The oleophobic and hydrophobic properties of the easy-to-clean glass product obtained in this embodiment were tested. The surface contact angle of a hexadecane droplet was 108°, and the surface contact angle of a water droplet was 132°. After high-temperature treatment at 240°C for 2 hours, the surface contact angle of a hexadecane droplet was 97°, and the surface contact angle of a water droplet was 119°. After rubbing 7500 times with 0# steel wool with a load of 1kg, the surface contact angle of a hexadecane droplet was 100°, and the surface contact angle of a water droplet was 118°. These results indicate that the glass product obtained by the present invention has excellent oleophobic and hydrophobic properties, and maintains good oleophobic and hydrophobic properties after high-temperature treatment and steel wool friction treatment, with good long-lasting easy-to-clean 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 product obtained in this comparative example showed that the surface contact angle of the hexadecane droplet was 125°, and the surface contact angle of the water droplet was 146°; after high-temperature treatment at 240°C for 2h, the surface contact angle of the hexadecane droplet was 116°, and the surface contact angle of the water droplet was 135°; after rubbing back and forth 7500 times with 0# steel wool with a load of 1kg, the surface contact angle of the hexadecane droplet was 62°, and the surface contact angle of the water droplet was 79°.

[0055] From the comparison results of this comparative example and 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 and 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 a fluorosilane coupling agent 1H,1H,2H,2H-perfluorodeoxysilane is used in the coating composition to replace the D3F component, and the rest of the components are the same.

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

[0059] Comparison of this comparative example with Example 1 reveals that replacing the D3F component with a fluorosilane coupling agent significantly reduces the initial oleophobic and hydrophobic properties and the scratch resistance of the resulting easy-to-clean coating. This is due to the fluorosilane coupling agent's excessive activity in self-condensation crosslinking and crosslinking with the coupling-group-containing polysiloxane, resulting in excessive crosslinking density and entrapment of fluorine-containing chains. This also reduces the coupling reaction with the glass substrate, resulting in reduced oleophobic and hydrophobic properties and scratch resistance.

[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 a fluorosilane coupling agent 1H,1H,2H,2H-perfluorodeoxysilane is used in the coating composition to replace the polysiloxane component containing a coupling group, and the rest of the composition is the same.

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

[0063] Comparison of this comparative example with Example 1 reveals that replacing the coupling-group-containing polysiloxane component with a fluorosilane coupling agent significantly reduces the scratch resistance and durability of the resulting easy-to-clean coating. This is due to the fluorosilane coupling agent's excessively strong self-condensation crosslinking activity and poor wetting properties under catalytic conditions, resulting in poor coupling with the glass substrate and nano-silica filler. This also weakens its binding with the subsequent fluoropolysiloxane, leading to reduced scratch resistance and durability.

[0064] The above embodiments are preferred implementations of the present invention, but the implementations 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 considered as equivalent replacement methods and are included in the scope of protection 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 percentages: The polysiloxane containing coupling groups is prepared by the following method: The vinyl silane coupling agent and hydrogenated silicone oil are mixed evenly under nitrogen protection, the temperature is raised to 60-90° C., and a platinum catalyst is added to carry out an addition reaction to obtain a polysiloxane containing a coupling group; The silicon alkoxide catalyst is potassium trimethylsilanol; The high-temperature-resistant, scratch-resistant, and easy-to-clean glass product is prepared by the following method: The coating composition is applied to the surface of a 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 reactions to obtain a high-temperature, scratch-resistant, and easy-to-clean glass product.

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 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 anhydrous dilution solvent is acetone, ethanol or isopropanol.

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