An impact-resistant self-cleaning tempered glass and its preparation method

Abstract

This invention belongs to the field of tempered glass preparation technology, and particularly relates to an impact-resistant self-cleaning tempered glass and its preparation method. Using epoxy acrylate, a repair agent, an oil-phase solvent, a photoinitiator, polyvinyl alcohol, and an acrylamide sulfonic acid derivative as raw materials, self-healing microcapsules are obtained through mixing, emulsification, and UV polymerization. These microcapsules are then modified with aluminum phosphate and low surface energy substances to obtain hydrophobic modified microcapsules. These microcapsules are mixed with aqueous epoxy resin to obtain a coating mixture, which is then coated onto the glass surface. After drying and cooling, coated tempered glass with excellent impact resistance, self-healing, and self-cleaning properties is obtained.

Description

Technical Field

[0001] This invention belongs to the field of tempered glass preparation technology, specifically relating to an impact-resistant self-cleaning tempered glass and its preparation method. Background Technology

[0002] In the construction industry, tempered glass has become an indispensable material in modern architecture. With its excellent high strength and impact resistance, it effectively withstands strong winds, heavy rain, and accidental impacts, providing reliable safety for buildings. Its good thermal stability also allows it to remain stable even under drastic temperature changes, greatly enhancing the safety and durability of buildings. Currently, tempered glass production technologies mainly include two methods: physical tempering and chemical tempering. Physical tempering involves heating the glass to near its softening point and then rapidly cooling it, creating compressive stress on the glass surface and tensile stress internally, thereby improving the glass's strength and impact resistance. Chemical tempering, on the other hand, uses particle exchange to exchange ions on the glass surface with ions in the solution, forming a compressive stress layer on the glass surface to strengthen it. With the rapid expansion of the market, the performance requirements for glass are constantly increasing. In addition to traditional requirements for high strength and safety, tempered glass with emerging characteristics such as good light transmission, heat insulation, and self-cleaning properties has become a new opportunity for industry development.

[0003] Chinese patent CN116554749B discloses a method for preparing a self-healing, highly hydrophobic, and highly transparent acrylic film. First, the acrylic surface is treated with polysiloxane and cured into a film. Then, nanodiamonds prepared by detonation are ground, dispersed, oxidized to remove impurities, and centrifuged to extract the nanodiamond particles. Ag@TiO2 nanoparticles are dispersed in an ethanol solution of water and polyvinylpyrrolidone (PVP) to form a PVP dispersion, which is then sprayed onto the acrylic surface and dried to cure into a film. By coating the acrylic surface with polysiloxane, the silane functional groups can react with the glass surface through hydroxylation, generating a strong bond. The hydrophobic alkane groups have low surface energy, forming a hydrophobic film. Simultaneously, the nanodiamond particles in the film increase both light transmittance and hydrophobicity. However, this method suffers from poor adhesion to the glass coating and difficulty in synergistically optimizing impact resistance and self-cleaning properties. Therefore, developing a preparation method that can synergistically improve the impact resistance, self-healing, and self-cleaning properties of tempered glass has become a pressing technical challenge in this field. Summary of the Invention

[0004] To address at least one of the above problems, the present invention provides a method for preparing impact-resistant self-cleaning tempered glass, comprising the following steps:

[0005] S100 uses epoxy acrylate, repair agent, oil phase solvent, photoinitiator, polyvinyl alcohol, and acrylamide sulfonic acid derivative as raw materials, which are mixed, emulsified, and UV polymerized to obtain self-healing microcapsules;

[0006] S200. Using self-healing microcapsules and aluminum phosphate as raw materials, aluminum phosphate-modified self-healing microcapsules are prepared.

[0007] S300. By combining aluminum phosphate-modified self-healing microcapsules with low surface energy materials, hydrophobic modified microcapsules are obtained.

[0008] S400, a coating mixture was prepared using hydrophobically modified microcapsules and waterborne epoxy resin as raw materials;

[0009] S500. After pretreatment and tempering composite treatment of the glass substrate, the coating mixture is applied to the glass surface, and after drying and cooling, the impact-resistant self-cleaning tempered glass is obtained.

[0010] Furthermore, step S100 specifically includes:

[0011] S110. Add epoxy acrylate, linseed oil, and dichloromethane to the reactor and stir at 25-30℃ for 15-20 min. Then add photoinitiator and continue stirring for 15-20 min to obtain the oil phase. Mix polyvinyl alcohol and deionized water and stir at 80-85℃ for 40-60 min. Allow to cool naturally to room temperature to obtain the aqueous phase.

[0012] S120. The oil phase is added dropwise to the aqueous phase. After emulsification and solvent removal, an acrylamide sulfonic acid derivative is added. The mixture is stirred until dissolved, and the pH of the system is adjusted to 4-5. Under an inert atmosphere, the mixture is polymerized by UV irradiation, centrifuged, washed, and dried to obtain the self-healing microcapsules.

[0013] Furthermore, step S200 specifically includes:

[0014] S210. Add sodium hexametaphosphate to deionized water, stir to dissolve, then add aluminum phosphate, heat to 50-60℃, stir for 20-40 min to obtain aluminum phosphate suspension.

[0015] S220. Add self-healing microcapsules to deionized water, sonicate for 10-20 min, then add aluminum phosphate suspension dropwise, heat to 40-50℃, stir for 2-3 h, adjust the pH of the system to 5.5-6.5, and obtain aluminum phosphate modified self-healing microcapsules after centrifugation, washing and drying.

[0016] Furthermore, step S300 specifically includes:

[0017] S310. Add aluminum phosphate-modified self-healing microcapsules to anhydrous ethanol and ultrasonically stir for 10-20 min to obtain a stable microcapsule ethanol dispersion.

[0018] S320. Add a low surface energy substance to anhydrous ethanol, raise the temperature to 45-55℃, stir until dissolved, cool to room temperature, and then add it dropwise to the microcapsule ethanol dispersion. Raise the temperature to 60-70℃, stir for 3-4 hours, and obtain hydrophobic modified microcapsules after centrifugation, washing, and drying.

[0019] Furthermore, the low surface energy substance is a saturated straight-chain fatty acid with 12-18 carbon atoms.

[0020] Further, step S400 specifically involves: adding waterborne epoxy resin, polycarboxylate dispersant and organosilicon defoamer to the reactor, stirring for 10-20 minutes, then adding waterborne polyamide curing agent, continuing to stir for 20-30 minutes, then adding hydrophobic modified microcapsules, and dispersing at high speed for 10-20 minutes to obtain the coating mixture.

[0021] Furthermore, step S500 specifically includes:

[0022] S510. After cleaning the glass sample, it is subjected to plasma treatment and tempering composite treatment to obtain a pretreated glass sample. After tempering composite treatment, a pretreated tempered glass sample is obtained.

[0023] S520. The coating mixture is applied to the surface of the pretreated tempered glass sample by spraying, and the impact-resistant self-cleaning tempered glass is obtained after drying and curing.

[0024] Furthermore, during spraying, the air pressure is controlled at 0.3-0.5MPa, the nozzle distance from the surface of the pretreated tempered glass sample is 20-30cm, and the coating thickness is controlled at 100-150μm.

[0025] An impact-resistant self-cleaning tempered glass is prepared using a method for preparing impact-resistant self-cleaning tempered glass as described in any of the above technical solutions.

[0026] The present invention has the following beneficial effects:

[0027] Self-healing microcapsules were prepared by using epoxy acrylate as the microcapsule wall material, linseed oil as the core material, dichloromethane as the oil phase solvent, and polyvinyl alcohol as the emulsifying stabilizer in the aqueous phase, with the addition of an acrylamide sulfonic acid derivative. The microcapsule surface was further modified with aluminum phosphate, an inorganic rigid particle that effectively enhances the mechanical strength of the microcapsules. To enable the prepared coating to have self-cleaning properties, a low surface energy substance was modified on the aluminum phosphate surface. Finally, this mixture was combined with an aqueous epoxy resin to obtain a coating mixture with self-healing and self-cleaning properties. This mixture was sprayed onto pretreated tempered glass samples to obtain tempered glass with impact resistance, self-healing, and self-cleaning properties. Detailed Implementation

[0028] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0029] Tempered glass is widely used in construction, transportation, and other fields due to its advantages such as high strength, thermal shock resistance, and lack of sharp edges after breakage. With increasing application demands, the requirements for additional functions of tempered glass are gradually increasing. Traditional methods to improve the impact resistance of tempered glass mainly involve coating it with abrasion-resistant coatings; however, existing abrasion-resistant coatings are brittle and lack sufficient impact toughness. Therefore, this application provides a method for preparing impact-resistant self-cleaning tempered glass, specifically including the following steps:

[0030] S100 uses epoxy acrylate, repair agent, oil phase solvent, photoinitiator, polyvinyl alcohol, and acrylamide sulfonic acid derivative as raw materials, which are mixed, emulsified, and UV polymerized to obtain self-healing microcapsules;

[0031] S200. Using self-healing microcapsules and aluminum phosphate as raw materials, aluminum phosphate-modified self-healing microcapsules are prepared.

[0032] S300. By combining aluminum phosphate-modified self-healing microcapsules with low surface energy materials, hydrophobic modified microcapsules are obtained.

[0033] S400, a coating mixture was prepared using hydrophobically modified microcapsules and waterborne epoxy resin as raw materials;

[0034] S500. After pretreatment and tempering composite treatment of the glass substrate, the coating mixture is applied to the glass surface, and after drying and cooling, the impact-resistant self-cleaning tempered glass is obtained.

[0035] Specifically, step S100 is as follows:

[0036] S110. Add epoxy acrylate, linseed oil, and dichloromethane to the reactor and stir at 25-30℃ for 15-20 min. Then add photoinitiator and continue stirring for 15-20 min to obtain the oil phase. Mix polyvinyl alcohol and deionized water and stir at 80-85℃ for 40-60 min. Allow to cool naturally to room temperature to obtain the aqueous phase.

[0037] S120. The oil phase is added dropwise to the aqueous phase. After emulsification and solvent removal, an acrylamide sulfonic acid derivative is added. The mixture is stirred until dissolved, and the pH of the system is adjusted to 4-5. Under an inert atmosphere, the mixture is polymerized by UV irradiation, centrifuged, washed, and dried to obtain the self-healing microcapsules.

[0038] In this step, the mass ratio of epoxy acrylate, linseed oil, dichloromethane, photoinitiator, polyvinyl alcohol, and acrylamide sulfonic acid derivative is 100:20-40:150-250:3-8:5-12:8-15; the photoinitiator is trimethylbenzoyl-diphenylphosphine oxide; the acrylamide sulfonic acid derivative is 2-acrylamide-2-methylpropanesulfonic acid; the emulsification process uses a high-speed shear emulsifier with a rotation speed of 8000-12000 r / min and an emulsification time of 20-30 min; the UV irradiation conditions are: wavelength 365 nm, power 80-120 W, and irradiation time 15-30 min; the centrifugation conditions are: 6000-8000 r / min and time 10-15 min; the washing conditions are: washing with deionized water 3-5 times; the drying conditions are: temperature 60-80℃ and drying time 12-18 h.

[0039] In this step, epoxy acrylate is used as the microcapsule wall material, linseed oil as the core material, dichloromethane as the oil phase solvent, and polyvinyl alcohol as the emulsifying stabilizer in the aqueous phase. After emulsification and removal of the dichloromethane solvent, the epoxy acrylate migrates to the oil-water interface. An acrylamide sulfonic acid derivative is then added, and UV irradiation initiates the polymerization of the epoxy acrylate and acrylamide sulfonic acid derivative into a shell. The linseed oil core material is encapsulated within the wall material. When the coating is damaged, the microcapsules embedded in the coating rupture and release the linseed oil. Upon exposure to the atmosphere, the oil reacts with oxygen and automatically cures into a thin film, enabling the coating to self-heal.

[0040] Specifically, step S200 is as follows:

[0041] S210. Add sodium hexametaphosphate to deionized water, stir to dissolve, then add aluminum phosphate, heat to 50-60℃, stir for 20-40 min to obtain aluminum phosphate suspension.

[0042] S220. Add self-healing microcapsules to deionized water, sonicate for 10-20 min, then add aluminum phosphate suspension dropwise, heat to 40-50℃, stir for 2-3 h, adjust the pH of the system to 5.5-6.5, and obtain aluminum phosphate modified self-healing microcapsules after centrifugation, washing and drying.

[0043] In step S210, the mass ratio of sodium hexametaphosphate to aluminum phosphate is 0.5-1.5:100, where sodium hexametaphosphate acts as a dispersant to prevent the agglomeration of aluminum phosphate particles. In step S220, the mass ratio of self-healing microcapsules to aluminum phosphate is 100:15-30; the ultrasonic power is 150-250W; the dropping rate of the aluminum phosphate suspension is 0.5-1mL / min, and the dropping method can avoid uneven coating caused by excessively high local concentrations; the centrifugation conditions are 6000-8000r / min for 10-15min; the washing conditions are 3-5 washes with deionized water; and the drying conditions are 70-90℃ for 8-12h.

[0044] In step S210, sodium hexametaphosphate adsorbs onto the surface of aluminum phosphate particles, forming an electrostatic repulsion layer that promotes uniform dispersion of aluminum phosphate and forms a stable suspension. In step S220, the sulfonic acid groups on the surface of the self-healing microcapsules are negatively charged; aluminum phosphate undergoes weak degradation in aqueous solution to generate Al. 3+ and PO4 3- Al 3+ Electrostatic attraction with sulfonic acid groups causes aluminum phosphate particles to gradually deposit on the surface of microcapsules. Furthermore, as an inorganic rigid particle, aluminum phosphate effectively enhances the mechanical strength of the microcapsules.

[0045] Specifically, step S300 is as follows:

[0046] S310. Add aluminum phosphate-modified self-healing microcapsules to anhydrous ethanol and ultrasonically stir for 10-20 min to obtain a stable microcapsule ethanol dispersion.

[0047] S320. Add a low surface energy substance to anhydrous ethanol, raise the temperature to 45-55℃, stir until dissolved, cool to room temperature, and then add it dropwise to the microcapsule ethanol dispersion. Raise the temperature to 60-70℃, stir for 3-4 hours, and obtain hydrophobic modified microcapsules after centrifugation, washing, and drying.

[0048] In this step, the mass ratio of the aluminum phosphate-modified self-healing microcapsules to the low surface energy material is 100:5-12; the ultrasonic power is 100-200W; the centrifugation conditions are 6000-8000 r / min for 10-15 min; the washing conditions are 3-5 washes with anhydrous ethanol; and the drying conditions are 50-70℃ for 6-10 h. The low surface energy material is a saturated straight-chain fatty acid with 12-18 carbon atoms, preferably stearic acid, myristic acid, palmitic acid, or lauric acid. When the carbon chain length is less than 12, the alkyl chain is too short, resulting in insufficient hydrophobicity. When the carbon chain length is greater than 18, the fatty acid molecular chain is too long, resulting in large steric hindrance, making it difficult to fully react with the aluminum phosphate modification layer and easily leading to microcapsule aggregation. In step S320, fatty acid molecules interact with the aluminum phosphate modification layer, grafting long-chain alkyl groups onto the surface of the microcapsule. The long-chain alkyl groups have strong hydrophobic effects, and the straight-chain structure facilitates the orientation of fatty acid molecules on the surface of the microcapsule, forming a regular hydrophobic layer, which improves the self-cleaning effect of the coating. The saturated structure avoids the oxidative degradation of unsaturated bonds, thus improving the durability of the hydrophobic properties.

[0049] Specifically, step S400 involves adding waterborne epoxy resin, polycarboxylate dispersant, and silicone defoamer to a reactor, stirring for 10-20 minutes, adding waterborne polyamide curing agent, continuing stirring for 20-30 minutes, then adding hydrophobic modified microcapsules, and dispersing at high speed for 10-20 minutes to obtain the coating mixture.

[0050] In this step, the mass ratio of waterborne epoxy resin, polycarboxylate dispersant, silicone defoamer, waterborne polyamide curing agent, and hydrophobic modified microcapsules is 100:1-3:0.5-1.5:40-60:10-25; the polycarboxylate dispersant is preferably sodium polycarboxylate, and the silicone defoamer is preferably a polyether-modified silicone defoamer.

[0051] In this step, waterborne epoxy resin serves as the coating matrix. The epoxy groups in its molecular chain undergo a ring-opening crosslinking reaction with the amino groups in the waterborne polyamide curing agent to form a three-dimensional network structure, which fixes the hydrophobic modified microcapsules in the coating, giving the coating good adhesion, hardness, and toughness. The addition of polycarboxylate dispersants can uniformly disperse the hydrophobic modified microcapsules in the epoxy resin system through electrostatic repulsion and steric hindrance effects, avoiding microcapsule aggregation. The addition of silicone defoamers can reduce the surface tension of the system and eliminate bubbles generated during stirring, thus preventing defects such as pinholes and bubbles from appearing after the coating has cured.

[0052] Specifically, step S500 is as follows:

[0053] S510. After cleaning the tempered glass sample, it is subjected to plasma treatment and tempering composite treatment to obtain a pretreated tempered glass sample.

[0054] S520. The coating mixture is applied to the surface of the pretreated tempered glass sample by spraying, and the impact-resistant self-cleaning tempered glass is obtained after drying and curing.

[0055] In step S510, the glass sample is first ultrasonically cleaned in deionized water for 20-30 minutes to remove surface dust. Then, the surface is wiped with anhydrous ethanol to remove oil stains. Next, it is transferred to a plasma treatment device for plasma treatment in a mixed atmosphere of oxygen and argon to obtain a pretreated glass sample. During plasma treatment, the volume ratio of oxygen to argon is 0.4-0.5:1, the plasma treatment frequency is 8-10 kHz, the output voltage is 30-32 kV, and the plasma treatment time is 2-5 minutes. The tempering composite treatment process is as follows: the pretreated glass sample is transferred to a tempering furnace, heated to 650-700℃, held for tempering, and then quenched to obtain the pretreated tempered glass sample. An air-cooled tempering process is used, with a cooling wind speed of 30-40 m / s and a cooling time of 5-10 minutes.

[0056] In step S520, the air pressure is controlled at 0.3-0.5MPa during spraying, the nozzle is 20-30cm away from the surface of the pretreated tempered glass sample, and the coating thickness is controlled at 100-150μm. The drying and curing conditions are as follows: first dry at 80-90℃ for 30-40min, and then increase the temperature to 100-120℃ for curing for 2-4h.

[0057] In this step, plasma treatment is used to etch the glass surface to form a rough structure and introduce hydroxyl groups, which improves the adhesion between the coating and the glass substrate. The coating is then uniformly applied to the glass surface using a spraying process. When impacted, the microcapsule wall material ruptures, releasing the repair agent linseed oil. The repair agent flows and fills the cracks, while the aluminum phosphate particles, as rigid particles, prevent crack propagation. The long-chain alkyl groups on the coating surface form a hydrophobic layer, giving the glass surface a self-cleaning function.

[0058] The epoxy acrylate used in this invention is bisphenol A epoxy acrylate (RY, 1101, industrial grade), purchased from Kailin Ruiyang Chemical Co., Ltd.; flaxseed oil (industrial grade), purchased from Guoguang Fragrance Factory; and waterborne epoxy resin (LN109, industrial grade), purchased from Jiangsu Lanling Chemical Group Co., Ltd. All reagents used in this invention are commercially available.

[0059] The pretreated tempered glass sample processing procedure used in this invention is as follows: After cleaning, the glass sample undergoes plasma treatment and tempering composite treatment to obtain a pretreated tempered glass sample. Specifically, the glass sample is first ultrasonically cleaned in deionized water for 30 minutes to remove surface dust, then wiped with anhydrous ethanol to remove oil stains, and then transferred to a plasma treatment device for plasma treatment in a mixed atmosphere of oxygen and argon. In the plasma treatment, the volume ratio of oxygen to argon is 0.5:1, the plasma treatment frequency is 8 kHz, the output voltage is 30 kV, and the plasma treatment time is 3 minutes. The tempering composite treatment procedure is as follows: The pretreated glass sample is transferred to a tempering furnace, and the temperature is increased to 660°C at a heating rate of 5°C / min. After holding the temperature for tempering for 30 minutes, it is quenched to obtain the pretreated tempered glass sample. An air-cooled tempering process is used, with a cooling wind speed of 40 m / s and a cooling time of 8 minutes.

[0060] Example 1

[0061] S1. Add 100 parts by weight of epoxy acrylate, 35 parts by weight of linseed oil, and 220 parts by weight of dichloromethane to the reactor. Stir at 30°C for 20 min, then add 6 parts by weight of photoinitiator trimethylbenzoyl-diphenylphosphine oxide and continue stirring for 20 min to obtain the oil phase. Mix 10 parts by weight of polyvinyl alcohol and 120 parts by weight of deionized water and stir at 85°C for 50 min. Allow to cool naturally to room temperature to obtain the aqueous phase. Add the oil phase dropwise to the aqueous phase at a rate of 1.5 mL / min using high-speed shear. After emulsifying at 10,000 r / min for 25 min, dichloromethane was removed by vacuum distillation. Then, 12 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid were added and stirred until dissolved. The pH of the system was adjusted to 4.5 with dilute hydrochloric acid. Polymerization was carried out under a nitrogen atmosphere and a 100W UV lamp with a wavelength of 365 nm for 25 min. After polymerization, the mixture was centrifuged at 8,000 r / min for 12 min, washed 4 times with deionized water, and dried in a vacuum drying oven at 70℃ for 16 h to obtain self-healing microcapsules.

[0062] S2. Add 0.3 parts by weight of sodium hexametaphosphate to 180 parts by weight of deionized water, stir to dissolve, then add 20 parts by weight of aluminum phosphate, heat to 55℃, stir for 30 min to obtain aluminum phosphate suspension; add 100 parts by weight of self-healing microcapsules to 170 parts by weight of deionized water, sonicate at 200W for 15 min, then add aluminum phosphate suspension dropwise at a rate of 0.8 mL / min, heat to 45℃, stir for 2.5 h, adjust the pH of the system to 6.0 with sodium hydroxide solution, centrifuge at 7000 r / min for 12 min, wash 4 times with deionized water, and dry in an 80℃ vacuum drying oven for 10 h to obtain aluminum phosphate modified self-healing microcapsules;

[0063] S3. Add 100 parts by weight of aluminum phosphate-modified self-healing microcapsules to 450 parts by weight of anhydrous ethanol, and sonicate at 150W for 15 min to obtain a stable microcapsule ethanol dispersion; add 10 parts by weight of myristic acid to 250 parts by weight of anhydrous ethanol, raise the temperature to 50℃, stir until dissolved, cool to room temperature, and add it dropwise to the microcapsule ethanol dispersion at a rate of 0.8 mL / min; raise the temperature to 65℃, stir for 3.5 h, centrifuge at 8000 r / min for 12 min, wash 4 times with anhydrous ethanol, and dry in a vacuum drying oven at 60℃ for 8 h to obtain hydrophobic modified microcapsules;

[0064] S4. Add 100 parts by weight of waterborne epoxy resin, 2.5 parts by weight of dispersant 731A and 1.2 parts by weight of defoamer WT-355 to the reactor, stir for 15 min, then add 52 parts by weight of curing agent Basonat HI2000 NG, continue stirring for 25 min, then add 22 parts by weight of hydrophobic modified microcapsules, disperse at 1200 r / min for 15 min to obtain coating mixture;

[0065] S5. The coating mixture is sprayed onto the surface of the pretreated tempered glass sample by spraying. The air pressure is controlled at 0.4MPa and the nozzle is 25cm away from the surface of the pretreated tempered glass sample. The coating thickness is controlled at 120μm. The sprayed sample is placed at 90℃ to dry for 40min, and then the temperature is increased to 120℃ to cure for 3h. It is then naturally cooled to room temperature to obtain impact-resistant self-cleaning tempered glass.

[0066] Example 2

[0067] This embodiment differs from Embodiment 1 in the following ways:

[0068] In step S1, 100 parts by weight of epoxy acrylate, 20 parts by weight of linseed oil, and 150 parts by weight of dichloromethane were added to the reactor and stirred at 25°C for 15 min. Then, 3 parts by weight of photoinitiator trimethylbenzoyl-diphenylphosphine oxide were added and stirred for another 15 min to obtain the oil phase. 5 parts by weight of polyvinyl alcohol and 100 parts by weight of deionized water were mixed and stirred at 80°C for 40 min, then naturally cooled to room temperature to obtain the aqueous phase. The oil phase was added dropwise to the aqueous phase, and after emulsification and solvent removal, 8 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid were added. The UV irradiation conditions were: wavelength 365 nm, power 80 W, irradiation time 15 min; centrifugation conditions were 6000 r / min, time 10 min; and drying conditions were: temperature 60°C, drying time 12 h.

[0069] In step S2, 0.08 parts by weight of sodium hexametaphosphate were added to 120 parts by weight of deionized water, stirred and dissolved, and then 15 parts by weight of aluminum phosphate were added. The mixture was heated to 50°C and stirred for 20 min to obtain an aluminum phosphate suspension. 100 parts by weight of self-healing microcapsules were added to 150 parts by weight of deionized water, and the mixture was ultrasonically stirred at 150W for 10 min. The aluminum phosphate suspension was then added dropwise at a rate of 0.5 mL / min. The mixture was heated to 40°C and stirred for 2 h. The pH of the system was adjusted to 6.0 with sodium hydroxide solution. The mixture was centrifuged at 6000 r / min for 10 min and then dried in a vacuum drying oven at 80°C for 10 h to obtain aluminum phosphate-modified self-healing microcapsules.

[0070] In step S3, 100 parts by weight of aluminum phosphate-modified self-healing microcapsules were added to 400 parts by weight of anhydrous ethanol and ultrasonically stirred at 100W for 10 min to obtain a stable microcapsule ethanol dispersion. 5 parts by weight of myristic acid were added to 200 parts by weight of anhydrous ethanol, the temperature was raised to 45℃, and the mixture was stirred until dissolved. After cooling to room temperature, the mixture was added dropwise to the microcapsule ethanol dispersion, the temperature was raised to 60℃, and the mixture was stirred for 3 h. After centrifugation at 6000 r / min for 10 min, the mixture was washed and dried in a vacuum drying oven at 50℃ for 6 h to obtain hydrophobically modified microcapsules.

[0071] In step S4, 100 parts by weight of waterborne epoxy resin, 1 part by weight of dispersant 731A and 0.5 parts by weight of defoamer WT-355 are added to the reactor. After stirring for 10 minutes, 40 parts by weight of curing agent Basonat HI2000 NG are added and stirring is continued for 25 minutes. Then, 10 parts by weight of hydrophobic modified microcapsules are added and dispersed at high speed for 10 minutes to obtain the coating mixture.

[0072] In step S5, the air pressure is controlled at 0.3 MPa during spraying, the nozzle is 20 cm away from the surface of the pretreated tempered glass sample, and the coating thickness is controlled at 100 μm. The drying and curing conditions are as follows: first dry at 80℃ for 30 min, and then increase the temperature to 100℃ for 2 h of curing.

[0073] Example 3

[0074] This embodiment differs from Embodiment 1 in the following ways:

[0075] In step S1, 100 parts by weight of epoxy acrylate, 40 parts by weight of linseed oil, and 250 parts by weight of dichloromethane were added to the reactor and stirred at 30°C for 20 min. Then, 8 parts by weight of photoinitiator trimethylbenzoyl-diphenylphosphine oxide were added, and stirring was continued for another 20 min to obtain the oil phase. 12 parts by weight of polyvinyl alcohol and 150 parts by weight of deionized water were mixed and stirred at 85°C for 60 min, and then naturally cooled to room temperature to obtain the aqueous phase. The oil phase was added dropwise to the aqueous phase, and after emulsification and solvent removal, 15 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid were added. The UV irradiation conditions were: wavelength 365 nm, power 120 W, irradiation time 30 min; centrifugation conditions were 8000 r / min, time 15 min; and drying conditions were: temperature 80°C, drying time 18 h.

[0076] In step S2, 0.5 parts by weight of sodium hexametaphosphate were added to 200 parts by weight of deionized water and stirred until dissolved. Then, 30 parts by weight of aluminum phosphate were added, heated to 60°C, and stirred for 40 min to obtain an aluminum phosphate suspension. 100 parts by weight of self-healing microcapsules were added to 200 parts by weight of deionized water and stirred ultrasonically at 250W for 20 min. The aluminum phosphate suspension was then added dropwise at a rate of 1 mL / min. The mixture was heated to 50°C and stirred for 3 h. The pH of the system was adjusted to 6.0 with sodium hydroxide solution, centrifuged at 8000 r / min for 15 min, and dried in a vacuum drying oven at 90°C for 12 h to obtain aluminum phosphate-modified self-healing microcapsules.

[0077] In step S3, 100 parts by weight of aluminum phosphate-modified self-healing microcapsules were added to 480 parts by weight of anhydrous ethanol and ultrasonically stirred at 200W for 20 min to obtain a stable microcapsule ethanol dispersion. 12 parts by weight of myristic acid were added to 300 parts by weight of anhydrous ethanol, the temperature was raised to 55℃, and the mixture was stirred until dissolved. After cooling to room temperature, the mixture was added dropwise to the microcapsule ethanol dispersion, the temperature was raised to 70℃, and the mixture was stirred for 4 h. After centrifugation at 8000 r / min for 15 min, the mixture was washed and dried in a vacuum drying oven at 70℃ for 10 h to obtain hydrophobically modified microcapsules.

[0078] In step S4, 100 parts by weight of waterborne epoxy resin, 3 parts by weight of dispersant 731A and 1.5 parts by weight of defoamer WT-355 are added to the reactor. After stirring for 20 minutes, 60 parts by weight of curing agent Basonat HI2000 NG are added and stirring is continued for 30 minutes. Then, 25 parts by weight of hydrophobic modified microcapsules are added and dispersed at high speed for 20 minutes to obtain the coating mixture.

[0079] In step S5, the air pressure is controlled at 0.5 MPa during spraying, the nozzle is 30 cm away from the surface of the pretreated tempered glass sample, and the coating thickness is controlled at 150 μm. The drying and curing conditions are as follows: first dry at 90℃ for 40 min, and then increase the temperature to 120℃ for curing for 4 h.

[0080] Example 4

[0081] This embodiment differs from Embodiment 1 in the following ways:

[0082] In step S1, 100 parts by weight of epoxy acrylate, 28 parts by weight of linseed oil, and 180 parts by weight of dichloromethane were added to the reactor and stirred at 30°C for 20 min. Then, 4 parts by weight of photoinitiator trimethylbenzoyl-diphenylphosphine oxide were added, and stirring was continued for another 20 min to obtain the oil phase. 8 parts by weight of polyvinyl alcohol and 110 parts by weight of deionized water were mixed and stirred at 85°C for 50 min, then naturally cooled to room temperature to obtain the aqueous phase. The oil phase was added dropwise to the aqueous phase, and after emulsification and solvent removal, 10 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid were added. The UV irradiation conditions were: wavelength 365 nm, power 100 W, irradiation time 20 min; centrifugation conditions were 7000 r / min, time 12 min; and drying conditions were: temperature 70°C, drying time 15 h.

[0083] In step S2, 0.2 parts by weight of sodium hexametaphosphate were added to 150 parts by weight of deionized water and stirred until dissolved. Then, 16.5 parts by weight of aluminum phosphate were added, heated to 55°C, and stirred for 30 min to obtain an aluminum phosphate suspension. 100 parts by weight of self-healing microcapsules were added to 150 parts by weight of deionized water and stirred ultrasonically at 200W for 15 min. The aluminum phosphate suspension was then added dropwise at a rate of 0.8 mL / min. The mixture was heated to 45°C and stirred for 2.5 h. The pH of the system was adjusted to 6.0 with sodium hydroxide solution. The mixture was centrifuged at 7000 r / min for 12 min and dried in a vacuum drying oven at 75°C for 10 h to obtain aluminum phosphate-modified self-healing microcapsules.

[0084] In step S3, 100 parts by weight of aluminum phosphate-modified self-healing microcapsules were added to 420 parts by weight of anhydrous ethanol and ultrasonically stirred at 150W for 15 min to obtain a stable microcapsule ethanol dispersion. 8 parts by weight of myristic acid were added to 220 parts by weight of anhydrous ethanol, the temperature was raised to 50℃, and the mixture was stirred until dissolved. After cooling to room temperature, the mixture was added dropwise to the microcapsule ethanol dispersion, the temperature was raised to 65℃, and the mixture was stirred for 3.5 h. After centrifugation at 7000 r / min for 12 min, the mixture was washed and dried in a vacuum drying oven at 60℃ for 8 h to obtain hydrophobically modified microcapsules.

[0085] In step S4, 100 parts by weight of waterborne epoxy resin, 1.5 parts by weight of dispersant 731A and 0.8 parts by weight of defoamer WT-355 are added to the reactor. After stirring for 15 minutes, 48 ​​parts by weight of curing agent Basonat HI2000 NG are added and stirring is continued for 30 minutes. Then, 18 parts by weight of hydrophobic modified microcapsules are added and dispersed at high speed for 15 minutes to obtain the coating mixture.

[0086] In step S5, the air pressure is controlled at 0.4 MPa during spraying, the nozzle is 22 cm away from the surface of the pretreated tempered glass sample, and the coating thickness is controlled at 110 μm. The drying and curing conditions are as follows: first dry at 85°C for 30 min, and then increase the temperature to 110°C for 3 h for curing.

[0087] Comparative Example 1

[0088] Compared with Example 1, this comparative example does not undergo aluminum phosphate modification, but otherwise follows the same procedure as Example 1. Specifically:

[0089] S1. Preparation of self-healing microcapsules according to step S1 in Example 1;

[0090] S2. Referring to step S3 in Example 1: Add 100 parts by weight of self-healing microcapsules to 450 parts by weight of anhydrous ethanol, and sonicate at 150W for 15 min to obtain a stable microcapsule ethanol dispersion; add myristic acid to 250 parts by weight of anhydrous ethanol, raise the temperature to 50°C, stir until dissolved, cool to room temperature, and add it dropwise to the microcapsule ethanol dispersion at a rate of 0.8 mL / min; raise the temperature to 65°C, stir for 3.5 h, centrifuge at 8000 r / min for 12 min, wash 4 times with anhydrous ethanol, and dry in a vacuum drying oven at 60°C for 8 h to obtain hydrophobic modified microcapsules;

[0091] S3. Preparation of the coating mixture according to step S4 in Example 1;

[0092] S4. Preparation of tempered glass according to step S5 in Example 1.

[0093] Comparative Example 2

[0094] Compared with Example 1, this comparative example does not undergo hydrophobic modification, and all other aspects are the same as in Example 1, specifically:

[0095] S1. Preparation of self-healing microcapsules according to step S1 in Example 1;

[0096] S2. Preparation of aluminum phosphate-modified self-healing microcapsules as described in step S2 of Example 1;

[0097] S3. Referring to the preparation method of the coating mixture in step S4 of Example 1, wherein the aluminum phosphate-modified self-healing microcapsules are directly used for coating preparation, specifically: 100 parts by weight of aqueous epoxy resin, 2.5 parts by weight of dispersant 731A and 1.2 parts by weight of defoamer WT-355 are added to the reactor, and after stirring for 15 min, 52 parts by weight of curing agent Basonat HI2000 NG are added, and stirring is continued for 25 min. Then, 22 parts by weight of aluminum phosphate-modified self-healing microcapsules are added, and the mixture is dispersed at 1200 r / min for 15 min to obtain the coating mixture.

[0098] S4. Preparation of tempered glass according to step S5 in Example 1.

[0099] Comparative Example 3

[0100] Compared with Example 1, in the preparation process of step S3, the low surface energy substance myristic acid was replaced with hexanoic acid, and the rest was the same as in Example 1.

[0101] Comparative Example 4

[0102] Compared with Example 1, this comparative example uses only water-based epoxy resin as the coating, specifically:

[0103] S1. Add 100 parts by weight of waterborne epoxy resin, 2.5 parts by weight of dispersant 731A and 1.2 parts by weight of defoamer WT-355 to the reactor, stir for 15 minutes, then add 52 parts by weight of curing agent Basonat HI2000 NG, and continue stirring for 25 minutes to obtain the coating mixture.

[0104] S2. Preparation of tempered glass according to step S5 in Example 1.

[0105] Comparative Example 5

[0106] Compared with Example 1, this comparative example does not involve plasma treatment of the glass sample during pretreatment, while the remaining processes are the same as in Example 1.

[0107] Related tests:

[0108] Impact resistance: Tested in accordance with the relevant provisions of GB15763.2-2005 "Safety Glass for Building - Part 2: Tempered Glass";

[0109] Fragmentation condition: Tested in accordance with the relevant provisions of GB15763.2-2005 "Safety Glass for Building - Part 2: Tempered Glass";

[0110] Adhesion test: The test shall be conducted in accordance with the relevant provisions of GB / T9286-1998 "Cross-cut test of paint and varnish film";

[0111] Antifouling test: After conducting a 10-minute droplet continuous rolling test (glycerol 45%) and a mud pouring test (mud 45%) on the samples prepared in each embodiment and comparative example, the water contact angle and mud contact angle were measured using a contact angle meter.

[0112] Repair performance test: The samples prepared in each example and comparative example were scratched on the coating surface with a scalpel (about 30 μm). After 12 hours of repair, the scratch morphology was observed to characterize the self-healing effect of the coating.

[0113] The test results are shown in Table 1.

[0114] Table 1. Relevant performance test results by group

[0115]

[0116] The test results show that without aluminum phosphate modification (Comparative Example 1), impact resistance and adhesion decrease. Surface aluminum phosphate modification improves the compatibility between microcapsules and the substrate, enhancing mechanical properties. In anhydrous hydrophobic modification (Comparative Examples 2 and 4), the water contact angle is small, and there is no self-cleaning function, indicating that hydrophobic modification helps achieve self-cleaning. However, when the carbon chain is too short (Comparative Example 3), insufficient hydrophobicity occurs, indicating that carbon chain length has a significant impact on hydrophobicity. Without microcapsule modification (Comparative Example 4), the impact strength decreases significantly, and the coating lacks self-healing properties when damaged, indicating that the addition of microcapsules improves impact resistance and imparts self-healing properties to the coating. During the pretreatment of the glass substrate, without plasma treatment, the coating adhesion decreases significantly, indicating that plasma treatment significantly improves the bonding force between the coating and the glass substrate.

[0117] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0118] Although embodiments of this application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing impact-resistant self-cleaning tempered glass, characterized in that, Includes the following steps: S110. Add epoxy acrylate, linseed oil, and dichloromethane to the reactor and stir at 25-30℃ for 15-20 min. Then add photoinitiator and continue stirring for 15-20 min to obtain the oil phase. Mix polyvinyl alcohol and deionized water and stir at 80-85℃ for 40-60 min. Allow to cool naturally to room temperature to obtain the aqueous phase. S120. The oil phase is added dropwise to the aqueous phase. After emulsification and solvent removal, an acrylamide sulfonic acid derivative is added. After stirring until dissolved, the pH of the system is adjusted to 4-5. Under an inert atmosphere, the self-healing microcapsules are obtained by UV irradiation polymerization, centrifugation, washing, and drying. S210. Add sodium hexametaphosphate to deionized water, stir to dissolve, then add aluminum phosphate, heat to 50-60℃, stir for 20-40 min to obtain aluminum phosphate suspension. S220. Add self-healing microcapsules to deionized water, stir ultrasonically for 10-20 min, then add aluminum phosphate suspension dropwise, heat to 40-50℃, stir for 2-3 h, adjust the pH of the system to 5.5-6.5, and obtain aluminum phosphate modified self-healing microcapsules after centrifugation, washing and drying. S310. Add aluminum phosphate-modified self-healing microcapsules to anhydrous ethanol and ultrasonically stir for 10-20 min to obtain a stable microcapsule ethanol dispersion. S320. Add a low surface energy substance to anhydrous ethanol, raise the temperature to 45-55℃, stir until dissolved, cool to room temperature, and then dropwise add it to the microcapsule ethanol dispersion. Raise the temperature to 60-70℃, stir for 3-4 hours, and obtain hydrophobic modified microcapsules after centrifugation, washing, and drying. S400: Add waterborne epoxy resin, polycarboxylate dispersant and silicone defoamer to the reactor, stir for 10-20 min, then add waterborne polyamide curing agent, continue stirring for 20-30 min, then add hydrophobic modified microcapsules, disperse at high speed for 10-20 min to obtain coating mixture. S500. After pretreatment and tempering composite treatment of the glass substrate, the coating mixture is applied to the glass surface, and after drying and cooling, the impact-resistant self-cleaning tempered glass is obtained.

2. The method for preparing impact-resistant self-cleaning tempered glass according to claim 1, characterized in that, The low surface energy substance is a saturated straight-chain fatty acid with 12-18 carbon atoms.

3. The method for preparing impact-resistant self-cleaning tempered glass according to claim 1, characterized in that, Step S500 is as follows: S510. After cleaning the glass sample, it is subjected to plasma treatment and tempering composite treatment to obtain a pretreated glass sample. After tempering composite treatment, a pretreated tempered glass sample is obtained. S520. The coating mixture is applied to the surface of the pretreated tempered glass sample by spraying, and the impact-resistant self-cleaning tempered glass is obtained after drying and curing.

4. The method for preparing impact-resistant self-cleaning tempered glass according to claim 3, characterized in that, During spraying, control the air pressure to 0.3-0.5MPa, keep the nozzle 20-30cm away from the surface of the pretreated tempered glass sample, and control the coating thickness to 100-150μm.

5. An impact-resistant, self-cleaning tempered glass, characterized in that, It is prepared by the method for preparing impact-resistant self-cleaning tempered glass as described in any one of claims 1-4.

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