An anti-microwave-radiation and anti-blue-light spectacle lens and a preparation method thereof

Abstract

The application discloses a kind of microwave radiation and blue light prevention spectacle lens and preparation method thereof, belong to optical lens technical field, from structure is divided into three layers, from bottom to top in turn is blue light prevention layer, water-resistant and dirt-proof layer and microwave radiation prevention layer, by the special synergy between three layers make its interface well combined, not easy to peel off, and have good microwave radiation and blue light prevention effect, and can prevent oil dirt, when using in rainy day, can avoid the adhesion of rainwater, avoid affecting sight;Pyridine group is contained in the dirt-proof layer prepared by the application, easy to form coordination bond with the cobalt metal ion of ZIF-8 / iron oxide composite fiber in microwave radiation prevention layer, form pyridine group doping, the dielectric loss tangent of ZIF-8 is lower, the energy consumption efficiency of microwave electric field is limited.Pyridine group doping coordination can promote the formation of active site, enhance dipole polarization and interface polarization, improve the microwave radiation prevention performance of microwave radiation prevention layer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of optical lenses, and particularly relates to an eyeglass lens with microwave radiation prevention and blue light prevention and a preparation method thereof. BACKGROUND

[0002] With the rapid development of electronic information technology, various electronic devices (such as smart phones, computers, 5G communication base stations, microwave ovens, etc.) have been widely integrated into daily work and life, and the potential harm of the blue light and microwave radiation generated by the electronic devices to the eye health of human body is increasingly highlighted. Long-term irradiation of blue light can cause eye fatigue and dryness, and can even damage the macular area of the retina in severe cases. Long-term exposure to microwave radiation can affect the physiological functions of the eye tissue, especially for people who frequently contact communication devices and medical instruments. At the same time, as a key appliance for daily wear, the eyeglass lens is prone to be contaminated by oil and dust, and rainwater adhered to the surface of the eyeglass lens during rainy days can form a water film, which seriously affects the clarity of vision and even causes safety hazards. Therefore, water resistance and stain resistance have become important practical needs of the eyeglass lens.

[0003] To meet the above protection needs, single-function eyeglass lens products have appeared in the prior art: for example, anti-blue light eyeglass lenses are prepared by adding metal oxides, MOF materials, etc., or microwave radiation prevention eyeglass lenses are prepared by using magnetic particles and dielectric materials in combination. Meanwhile, some products achieve basic stain resistance effect by surface coating of a hydrophobic coating. However, the prior art has obvious limitations: on the one hand, single-function products cannot simultaneously cope with the dual threats of blue light and microwave radiation, and a few products that attempt to integrate microwave radiation prevention and blue light prevention functions mostly use a simple layering and compounding method, lack of design of the interface synergy of each functional layer, and thus the interlayer bonding force is weak, and peeling is prone to occur after long-term wear or wiping, which seriously affects the service life of the product; on the other hand, the existing multifunctional eyeglass lenses often fail to balance the core protection performance and water resistance and stain resistance — some products strengthen the protection effect while ignoring the stain resistance design, or the stain resistance coating and the protection layer have poor compatibility, which leads to attenuation of the protection performance and the stain resistance effect is not durable, and the problems of rainwater adhesion and oil stain cleaning are still not effectively solved. Therefore, it is an urgent need in the current industry to develop an integrated eyeglass lens that has stable microwave radiation prevention and blue light prevention functions, and has firm interlayer bonding and excellent water resistance and stain resistance.

[0004] The existing eyeglass lenses that integrate microwave radiation prevention and blue light prevention functions mostly use a simple layering and compounding method of the functional layers, lack of design of the interface synergy, and thus the interlayer bonding force is insufficient, and peeling is prone to occur during long-term use, which not only affects the protection effect, but also shortens the service life of the product. SUMMARY

[0005] The present application aims to provide a kind of glasses with microwave radiation and blue light prevention and its preparation method, from structure is divided into three layers, from bottom to top in turn is blue light prevention layer, water-resistant and dirt-resistant layer and microwave radiation prevention layer, by the special synergy between three layers makes its interface well combined, not easy to peel off, and have good microwave radiation and blue light prevention effect, and can prevent oil dirt, when using in rainy day, can avoid the adhesion of rain, avoid affecting sight.

[0006] The object of the present application can be achieved by the following technical solutions:

[0007] A kind of glasses with microwave radiation and blue light prevention and its preparation method, comprising the following steps:

[0008] Step one: with cetyltrimethylammonium bromide as surfactant, under ammonia, form micellar template, tetraethyl orthosilicate is used as silicon source, after hydrolysis condensation reaction, then using isopropanol and ammonium nitrate to remove template to obtain silica particles;By silica particles as core, cetyltrimethylammonium bromide forms local micellar template, urea is assisted under tetraethyl orthosilicate hydrolysis condensation to form spiculate silicon layer to obtain spiculate silica powder.

[0009] Step two: by 5-hydroxyisophthalic acid as ligand, hydrothermal coordination with chromium nitrate, in-situ growth of chromium-based metal organic framework on the surface of spiculate silica, to obtain chromium MOF / spiculate silica powder;Chromium MOF / spiculate silica powder is sprayed on glasses substrate to obtain glasses containing blue light prevention layer.

[0010] Step three: with polymethyl methacrylate-b-4-vinylpyridine, vinyl POSS, methyl methacrylate and double bond in methacrylic acid structure to initiate polymerization network, then immerse glasses containing blue light prevention layer in polymerization network to form water-resistant and dirt-resistant layer.

[0011] Step four: by ferrous chloride, after redox reaction with sodium thiosulfate in alkaline to generate ferrous oxide, then coordinate with 2-methylimidazole and cobalt nitrate hexahydrate to form ZIF-8, then electrospun after using polyacrylonitrile as fiber forming matrix to obtain ZIF-8 / iron oxide composite fiber, spray ZIF-8 / iron oxide composite fiber on water-resistant and dirt-resistant layer to form microwave radiation prevention layer, to obtain glasses with microwave radiation and blue light prevention.

[0012] Further, the specific preparation steps of silica particles are as follows:

[0013] The cetyltrimethylammonium bromide and ammonia water were added into a reaction kettle, stirred at 20-25°C and 500-600 r / min for 30-40 min, then tetraethyl orthosilicate was added, and the reaction was continued for 6-7 h, centrifuged at 8000-9000 r / min for 5-8 min, and the filter cake was transferred to isopropanol and ammonium nitrate, reacted at 80-90°C for 24-26 h, vacuum freeze-dried at -20°C for 12-14 h to obtain silica particles.

[0014] Further, the amount ratio of cetyltrimethylammonium bromide, ammonia water, tetraethyl orthosilicate, isopropanol and ammonium nitrate was 30-35 g: 2-3 L: 170-180 mL: 1.5-2 L: 14-16 g.

[0015] Further, the specific preparation steps of the burr-shaped silica powder were as follows:

[0016] The cetyltrimethylammonium bromide, urea, silica particles and deionized water were added into a reaction kettle, stirred at 20-25°C and 500-600 r / min for 30-40 min, then isopropanol and tetraethyl orthosilicate were added, and the stirring was continued for 30-40 min, heated to 70-80°C, and the reaction was continued for 16-18 h, filtered, the filter cake was washed with deionized water for 2-4 times, vacuum dried at 60-80°C for 1-2 h, transferred to a muffle furnace, heated to 550-600°C and calcined for 6-8 h to obtain burr-shaped silica powder.

[0017] Further, the amount ratio of cetyltrimethylammonium bromide, urea, silica particles, deionized water, isopropanol and tetraethyl orthosilicate was 20-22 g: 12-20 g: 8-10 g: 450-500 mL: 16-20 mL: 4-8 mL.

[0018] Further, the specific preparation steps of the chromium MOF / burr-shaped silica powder were as follows:

[0019] The burr-shaped silica powder, 5-hydroxyisophthalic acid and deionized water were added into a reaction kettle, cetyl sodium sulfate was dissolved in 50-60 wt% ethanol solution and then added into the reaction kettle, stirred at 100-110°C and 400-500 r / min for 1-2 h, then chromium nitrate was added, and the stirring reaction was continued for 24-26 h, suction filtered, the filter cake was washed with deionized water and anhydrous ethanol for 2-4 times respectively, vacuum dried at 60-80°C for 1-2 h to obtain chromium MOF / burr-shaped silica powder.

[0020] Further, the amount ratio of the needle-shaped silicon dioxide powder, 5-hydroxyisophthalic acid, deionized water, sodium dodecyl sulfate, ethanol solution and chromium nitrate is 15-20 g:20-25 g:800-900 mL:2-3 g:120-140 mL:10-11 g.

[0021] Further, the specific preparation steps of the anti-blue light layer of the spectacle lens are as follows:

[0022] The spectacle substrate is ultrasonically cleaned in deionized water for 40-60 min, vacuum dried at 60-80℃ for 1-2 h, then the chromium MOF / needle-shaped silicon dioxide powder is sprayed on the spectacle substrate to obtain the spectacle lens containing the anti-blue light layer with a thickness of 500-600 nm.

[0023] Further, the specific preparation steps of the water-resistant and stain-resistant layer are as follows:

[0024] Methyl methacrylate, polymethyl methacrylate-b-4-vinylpyridine, methacrylic acid, vinyl POSS and deionized water are added to a reaction kettle, stirred at 20-25℃ and 500-600 r / min for 30-40 min, then sodium dodecyl sulfate and ammonium persulfate are added, heated to 80-90℃ to obtain a mixed solution, then the spectacle lens containing the anti-blue light layer is immersed in the mixed solution and continues to react for 1-2 h, the spectacle lens is taken out and vacuum dried at 60-80℃ for 1-2 h to form the water-resistant and stain-resistant layer with a thickness of 100-200 nm.

[0025] Further, the amount ratio of methyl methacrylate, polymethyl methacrylate-b-4-vinylpyridine, methacrylic acid, vinyl POSS, deionized water, sodium dodecyl sulfate and ammonium persulfate is 15-20 g:17-19 g:16-17 g:5-7 g:250-300 mL:3-4 g:1-2 g.

[0026] Further, the specific preparation steps of the ZIF-8 / iron oxide composite fiber are as follows:

[0027] Sodium thiosulfate, ferrous chloride, sodium hydroxide and deionized water are added to a reaction kettle, stirred at 200-220℃ and 500-600 r / min for 5-6 h to obtain ferrous oxide, then the ferrous oxide, 2-methylimidazole, cobalt nitrate hexahydrate, polyacrylonitrile and N,N-dimethylformamide are added to the reaction kettle, stirred at 20-25℃ and 500-600 r / min for 30-40 min, transferred to a syringe, and electrospun under the experimental conditions of an external voltage of 20-22 kV, a propulsion speed of 3-4 mm / h and a receiving distance of 18-20 cm to obtain the ZIF-8 / iron oxide composite fiber.

[0028] Further, the amount ratio of sodium thiosulfate, ferrous chloride, sodium hydroxide and deionized water is 3-4g: 10-12g: 4-6g: 120-140mL.

[0029] Further, the amount ratio of ferrous oxide, 2-methylimidazole, cobalt nitrate hexahydrate, polyacrylonitrile and N,N-dimethylformamide is 2-4g: 2-3g: 3-5g: 18-25g: 250-300mL.

[0030] Further, the specific preparation steps of the spectacle lens with microwave radiation prevention and blue light prevention are as follows:

[0031] The ZIF-8 / iron oxide composite fiber is sprayed on the water-resistant and stain-resistant layer to form a microwave radiation prevention layer with a thickness of 200-300nm, and the spectacle lens with microwave radiation prevention and blue light prevention is obtained.

[0032] The beneficial effects of the present application are:

[0033] 1. The microwave radiation prevention and blue light prevention spectacle lens prepared by the present application is divided into three layers from the bottom to the top, namely the blue light prevention layer, the water-resistant and stain-resistant layer and the microwave radiation prevention layer, and the interface between the three layers is well combined through the special synergistic relationship, and is not easy to peel off, and has good microwave radiation prevention and blue light prevention effects, and can prevent oil stains, and can avoid the adhesion of rainwater in rainy days, and can avoid affecting the line of sight.

[0034] 2. The blue light prevention layer prepared by the present application is a chromium MOF structure hydrothermally synthesized on the surface of the burr-shaped silicon dioxide powder, the rare earth ion chromium has a characteristic absorption harmful to blue light, and the Mie scattering effect of the burr-shaped silicon dioxide is used to realize the double protection effect of absorption and scattering, and avoid the decrease of light transmittance caused by single scattering; as the bottom layer, the burr-shaped structure can significantly improve the mechanical interlocking effect with the second layer, and improve the interface bonding force.

[0035] 3. The water-resistant and stain-resistant layer prepared by the present application is a polymerization network initiated by polymethyl methacrylate-b-4-vinylpyridine, vinyl POSS, methyl methacrylate and methyl methacrylate, which has good hydrophobic effect, and as the middle layer, it can increase the adhesion between the blue light prevention layer and the microwave radiation prevention layer, and avoid the peeling of the coating.

[0036] 4. The microwave radiation prevention layer prepared by the present application is formed by spraying ZIF-8 / iron oxide composite fiber on the water-resistant and stain-resistant layer, and a three-dimensional network structure is formed by polyacrylonitrile as a fiber matrix, iron oxide as a magnetic semiconductor material and ZIF-8, which constructs a continuous magnetic and electric conduction path, strengthens the eddy current loss and hysteresis loss, and the special design of this layer is beneficial to the close combination with the water-resistant and stain-resistant layer.

[0037] 5. The anti-pollution layer prepared by the present application contains pyridine groups, which can act as strong ligands for transition metal ions and as Lewis base groups, easily forming coordination bonds with the cobalt metal ions of the ZIF-8 / iron oxide composite fibers in the anti-microwave radiation layer, resulting in pyridine group doping and a low dielectric loss tangent of ZIF-8, limiting the efficiency of microwave electric field energy consumption. The doping coordination of pyridine groups can promote the formation of active sites, enhance dipole polarization and interfacial polarization, and improve the anti-microwave radiation performance of the anti-microwave radiation layer. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 Transmission electron microscope image of the hair-like silica powder of Example 3.

[0039] Figure 2 Scanning electron microscope image of the ZIF-8 / iron oxide composite fiber of Example 3.

[0040] Figure 3 N2 adsorption-desorption curves of the chromium MOF / hair-like silica powder and the hair-like silica powder of Example 3.

[0041] Figure 4 Pore size distribution graph of the chromium MOF / hair-like silica powder and the hair-like silica powder of Example 3. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0043] Example 1: A preparation method of a pair of glasses with anti-microwave radiation and anti-blue light, comprising the following steps:

[0044] S1: 30 g of cetyltrimethylammonium bromide and 2 L of ammonia water were added to a reaction kettle, stirred at 20℃ and 500 r / min for 30 min, then 170 mL of tetraethyl orthosilicate was added and the reaction was continued for 6 h, centrifuged at 8000 r / min for 5 min, and the filter cake was transferred to 1.5 L of isopropanol and 14 g of ammonium nitrate, reacted at 80℃ for 24 h, and vacuum freeze-dried at -20℃ for 12 h to obtain silica particles.

[0045] S2: 20 g of cetyltrimethylammonium bromide, 12 g of urea, 8 g of silica particles, and 450 mL of deionized water were added to a reaction kettle, stirred at 20 °C and 500 r / min for 30 min, then 16 mL of isopropyl alcohol and 4 mL of tetraethyl orthosilicate were added, and stirring was continued for 30 min, heated to 70 °C, and the reaction was continued for 16 h, filtered, the filter cake was washed with deionized water twice, vacuum dried at 60 °C for 1 h, transferred to a muffle furnace, heated to 550 °C and calcined for 6 h to obtain a burr-shaped silica powder.

[0046] S3: 15 g of burr-shaped silica powder, 20 g of 5-hydroxyisophthalic acid, and 800 mL of deionized water were added to a reaction kettle, 2 g of cetyl sodium sulfate was dissolved in 120 mL of a 50 wt% ethanol solution and added to the reaction kettle, stirred at 100 °C and 400 r / min for 1 h, then 10 g of chromium nitrate was added, and the reaction was continued for 24 h, suction filtered, the filter cake was washed with deionized water and anhydrous ethanol twice, vacuum dried at 60 °C for 1 h, and a chromium MOF / burr-shaped silica powder was obtained.

[0047] S4: The spectacle substrate was ultrasonically cleaned in deionized water for 40 min, vacuum dried at 60 °C for 1 h, then the chromium MOF / burr-shaped silica powder was sprayed onto the spectacle substrate to obtain a spectacle lens containing a 500 nm thick blue light blocking layer.

[0048] S5: 15 g of methyl methacrylate, 17 g of polymethyl methacrylate-b-4-vinylpyridine, 16 g of methacrylic acid, 5 g of vinyl POSS, and 250 mL of deionized water were added to a reaction kettle, stirred at 20 °C and 500 r / min for 30 min, then 3 g of sodium dodecyl sulfate and 1 g of ammonium persulfate were added, heated to 80 °C to obtain a mixed solution, the spectacle lens containing the blue light blocking layer was immersed in the mixed solution, and the reaction was continued for 1 h, the spectacle lens was removed, vacuum dried at 60 °C for 1 h, and a 100 nm thick water-resistant and stain-resistant layer was formed.

[0049] S6: 3 g of sodium thiosulfate, 10 g of ferrous chloride, 4 g of sodium hydroxide and 120 mL of deionized water were added into a reaction kettle, and stirring was carried out at 200℃ and 500 r / min for 5 h to obtain ferrous oxide, and then 2 g of ferrous oxide, 2 g of 2-methylimidazole, 3 g of cobalt nitrate hexahydrate, 18 g of polyacrylonitrile and 250 mL of N,N-dimethylformamide were added into the reaction kettle, and stirring was carried out at 20℃ and 500 r / min for 30 min, and then the mixture was transferred into a syringe, and electrospinning was carried out under the conditions that the applied voltage was 20 kV, the advancing speed was 3 mm / h and the receiving distance was 18 cm to obtain ZIF-8 / iron oxide composite fibers, and the ZIF-8 / iron oxide composite fibers were sprayed on the water-resistant and stain-resistant layer to form a microwave radiation-proof layer with a thickness of 200 nm, and thus an eyeglass sheet with microwave radiation-proof and blue light-proof functions was obtained.

[0050] Embodiment 2: A preparation method of an eyeglass sheet with microwave radiation-proof and blue light-proof functions, comprising the following steps:

[0051] S1: 32.5 g of cetyltrimethylammonium bromide and 2.5 L of aqueous ammonia were added into a reaction kettle, and stirring was carried out at 22.5℃ and 550 r / min for 35 min, and then 175 mL of tetraethyl orthosilicate was added, and the reaction was continued for 6.5 h, and then centrifugation was carried out at 8500 r / min for 6.5 min, and then the filter cake was transferred into 1.75 L of isopropanol and 15 g of ammonium nitrate, and the reaction was carried out at 85℃ for 25 h, and then vacuum freeze-drying was carried out at -20℃ for 13 h to obtain silica particles.

[0052] S2: 21 g of cetyltrimethylammonium bromide, 16 g of urea, 9 g of silica particles and 475 mL of deionized water were added into a reaction kettle, and stirring was carried out at 22.5℃ and 550 r / min for 35 min, and then 18 mL of isopropanol and 6 mL of tetraethyl orthosilicate were added, and stirring was continued for 35 min, and then heating was carried out to 75℃, and the reaction was continued for 17 h, and then filtration was carried out, and then the filter cake was washed with deionized water for 3 times, and then vacuum drying was carried out at 70℃ for 1.5 h, and then the filter cake was transferred into a muffle furnace, and heating was carried out to 575℃ for calcination for 7 h to obtain a bristled silica powder.

[0053] S3: 17.5 g of the bristled silica powder, 22.5 g of 5-hydroxyisophthalic acid and 850 mL of deionized water were added into a reaction kettle, and then 2.5 g of cetyl sodium sulfate was dissolved in 130 mL of an ethanol solution with a concentration of 55 wt% and then added into the reaction kettle, and stirring was carried out at 105℃ and 450 r / min for 1.5 h, and then 10.5 g of chromium nitrate was added, and the reaction was continued for 25 h under stirring, and then suction filtration was carried out, and then the filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and then vacuum drying was carried out at 70℃ for 1.5 h to obtain a chromium MOF / bristled silica powder.

[0054] S4: The eyeglass substrate was placed in deionized water for ultrasonic cleaning for 50 min, vacuum drying at 70℃ for 1.5 h, then the chromium MOF / bristle-like silicon dioxide powder was sprayed on the eyeglass substrate to obtain an eyeglass lens containing a blue light-proof layer with a thickness of 550 nm.

[0055] S5: 17.5 g of methyl methacrylate, 18 g of poly(methyl methacrylate)-b-4-vinylpyridine, 16.5 g of methacrylic acid, 6 g of vinyl POSS and 275 mL of deionized water were added to the reaction kettle, stirred at 22.5℃ and 550 r / min for 35 min, then 3.5 g of sodium dodecyl sulfate and 1.5 g of ammonium persulfate were added, heated to 85℃ to obtain a mixed solution, then the eyeglass lens containing the blue light-proof layer was immersed in the mixed solution and the reaction was continued for 1.5 h, the eyeglass lens was taken out and vacuum dried at 70℃ for 1.5 h to form a water-resistant and stain-resistant layer with a thickness of 150 nm.

[0056] S6: 3.5 g of sodium thiosulfate, 11 g of ferrous chloride, 5 g of sodium hydroxide and 130 mL of deionized water were added to the reaction kettle, stirred at 210℃ and 550 r / min for 5.5 h to obtain ferrous oxide, then 3 g of ferrous oxide, 2.5 g of 2-methylimidazole, 4 g of cobalt nitrate hexahydrate, 21.5 g of polyacrylonitrile and 275 mL of N,N-dimethylformamide were added to the reaction kettle, stirred at 22.5℃ and 550 r / min for 35 min, transferred to a syringe, and electrospun under the following conditions: an external voltage of 21 kV, a propulsion speed of 3.5 mm / h, and a receiving distance of 19 cm to obtain ZIF-8 / iron oxide composite fibers, which were sprayed on the water-resistant and stain-resistant layer to form a microwave radiation-proof layer with a thickness of 250 nm, thereby obtaining an eyeglass lens with microwave radiation-proof and blue light-proof properties.

[0057] Example 3: A method for preparing an eyeglass lens with microwave radiation-proof and blue light-proof properties, comprising the following steps:

[0058] S1: 35 g of cetyltrimethylammonium bromide and 3 L of ammonia water were added to the reaction kettle, stirred at 25℃ and 600 r / min for 40 min, then 180 mL of tetraethyl orthosilicate was added and the reaction was continued for 7 h, centrifuged at 9000 r / min for 8 min, and the filter cake was transferred to 2 L of isopropanol and 16 g of ammonium nitrate, reacted at 90℃ for 26 h, and vacuum freeze-dried at -20℃ for 14 h to obtain silica particles.

[0059] S2: 22 g of cetyltrimethylammonium bromide, 20 g of urea, 10 g of silica particles, and 500 mL of deionized water were added to a reaction kettle, stirred at 25°C and 600 r / min for 40 min, then 20 mL of isopropyl alcohol and 8 mL of tetraethyl orthosilicate were added, and stirring was continued for 40 min, heated to 80°C, and the reaction was continued for 18 h. The filter cake was washed with deionized water 4 times, vacuum dried at 80°C for 2 h, transferred to a muffle furnace, heated to 600°C, and calcined for 8 h to obtain a burr-shaped silica powder.

[0060] S3: 20 g of burr-shaped silica powder, 25 g of 5-hydroxyisophthalic acid, and 900 mL of deionized water were added to a reaction kettle, 3 g of cetyl sodium sulfate was dissolved in 140 mL of a 60 wt% ethanol solution and added to the reaction kettle, stirred at 110°C and 500 r / min for 2 h, then 11 g of chromium nitrate was added, and the stirring reaction was continued for 26 h. The filter cake was washed with deionized water and anhydrous ethanol 4 times, respectively, vacuum dried at 80°C for 2 h, and a chromium MOF / burr-shaped silica powder was obtained.

[0061] S4: The spectacle substrate was ultrasonically cleaned in deionized water for 60 min, vacuum dried at 80°C for 2 h, then the chromium MOF / burr-shaped silica powder was sprayed onto the spectacle substrate to obtain a spectacle lens containing a 600 nm thick blue light blocking layer.

[0062] S5: 20 g of methyl methacrylate, 19 g of poly(methyl methacrylate)-b-4-vinylpyridine, 17 g of methacrylic acid, 7 g of vinyl POSS, and 300 mL of deionized water were added to a reaction kettle, stirred at 25°C and 600 r / min for 40 min, then 4 g of sodium dodecyl sulfate and 2 g of ammonium persulfate were added, heated to 90°C to obtain a mixed solution, the spectacle lens containing the blue light blocking layer was immersed in the mixed solution, and the reaction was continued for 2 h. The spectacle lens was removed and vacuum dried at 80°C for 2 h to form a 200 nm thick water-resistant and stain-resistant layer.

[0063] S6: 4 g of sodium thiosulfate, 12 g of ferrous chloride, 6 g of sodium hydroxide and 140 mL of deionized water were added to the reaction kettle, stirred at 220℃ and 600 r / min for 6 h to obtain ferrous oxide, then 4 g of ferrous oxide, 3 g of 2-methylimidazole, 5 g of cobalt nitrate hexahydrate, 25 g of polyacrylonitrile and 300 mL of N,N-dimethylformamide were added to the reaction kettle, stirred at 25℃ and 600 r / min for 40 min, transferred to a syringe, and electrospun under the experimental conditions of an applied voltage of 22 kV, a propelling speed of 4 mm / h and a receiving distance of 20 cm to obtain ZIF-8 / iron oxide composite fibers. The ZIF-8 / iron oxide composite fibers were sprayed on the water-resistant and stain-resistant layer to form a microwave radiation-resistant layer with a thickness of 300 nm, thereby obtaining a spectacle lens with microwave radiation resistance and blue light resistance.

[0064] In the examples and comparative examples:

[0065] The poly(methyl methacrylate)-b-4-vinylpyridine was purchased from Xi'an Qiyue Biology, and the item number was Q-0004638.

[0066] The vinyl POSS was purchased from Shanghai Maikelin Biochemical Technology Co., Ltd., and the CAS number was 69655-76-1.

[0067] Comparative Example 1: On the basis of Example 3, the burr-shaped silica powder in step S3 was replaced with the silica particles prepared in step S1.

[0068] Comparative Example 2: On the basis of Example 3, the poly(methyl methacrylate)-b-4-vinylpyridine in step S5 was omitted.

[0069] Comparative Example 3: On the basis of Example 3, the cobalt nitrate hexahydrate in step S6 was omitted.

[0070] The spectacle lenses with microwave radiation resistance and blue light resistance prepared in Examples 1-3 and Comparative Examples 1-3 were tested for performance, and the results are shown in Table 1:

[0071] 1. The ultraviolet transmittance was tested according to the standard of GB 10810.3-2006 “Spectacle lenses and related spectacle products Part 3: Transmittance specification and measurement method”.

[0072] 2. The blue light transmittance was tested according to the standard of GB / T 38120-2019 “Light health and light safety application technical requirements for blue light protection film”.

[0073] 3. The 100 keV γ-ray shielding rate was tested according to the standard of GB / T 23466-2009 “Glass plate for radiation protection”, and the 100 keV γ-ray shielding rate = (1-γ-ray dose rate after passing through the lens / incident γ-ray dose rate) x 100%.

[0074]

[0075] As can be seen from Table 1, Comparative Example 1 replaces the burr-shaped silicon dioxide powder in step S3 with the silicon dioxide particles prepared in step S1. The burr protrusions of the burr-shaped silicon dioxide can increase the specific surface area, allowing the chromium MOF to be uniformly loaded and forming a dense absorption and scattering network. The surface of the ordinary silicon dioxide particles is smooth, the chromium MOF load is reduced and unevenly distributed, resulting in an increase in the transmittance of harmful blue light at 400 nm and an increase in the transmittance of ultraviolet light. The scattering of the burr-shaped structure has wavelength selectivity, the scattering of the ordinary silicon dioxide particles has no selectivity, the burr-shaped structure can form mechanical interlocking with the intermediate water-resistant and stain-resistant layer, and the ordinary silicon dioxide particles are combined only by intermolecular forces. After long-term wear and wiping, the anti-blue light layer and the water-resistant and stain-resistant layer are prone to peeling.

[0076] In Comparative Example 2, the polymethyl methacrylate-b-4-vinylpyridine in step S5 is omitted. The polymethyl methacrylate-b-4-vinylpyridine is a block copolymer, in which the polymethyl methacrylate segment is compatible with the chromium MOF / silicon dioxide of the anti-blue light layer, and the 4-vinylpyridine segment has a coordination effect with the ZIF-8 / iron oxide of the anti-microwave radiation layer, acting as a bridging effect. After the omission, the water-resistant and stain-resistant layer is only an ordinary acrylate polymer network, and the interfacial force with the upper and lower layers is only van der Waals force, resulting in a significant decrease in adhesion strength and easy peeling of the coating. The pyridine group can form a coordination bond with the cobalt ions of ZIF-8, achieving pyridine doping and strengthening the dipole polarization and interfacial polarization of ZIF-8. After the omission, there is no pyridine doping, the dielectric loss tangent of ZIF-8 cannot be improved, the microwave energy consumption efficiency is reduced, and the amphiphilic structure of polymethyl methacrylate-b-4-vinylpyridine can optimize the surface energy of the water-resistant and stain-resistant layer and improve the hydrophobic effect. After the omission, the hydrophilic and hydrophobic levels of the polymer network are destroyed, rainwater adhesion and oil stain residue problems are obvious, and the visibility in rainy weather is affected.

[0077] In Comparative Example 3, based on Example 3, the cobalt nitrate hexahydrate in step S6 is omitted. The formation of ZIF-8 depends on the coordination reaction between 2-methylimidazole and cobalt ions. After the omission of cobalt nitrate hexahydrate, only iron oxide / polyacrylonitrile composite fibers can be obtained, losing the porous scattering and polarization loss effect of ZIF-8. Only iron oxide cannot achieve dual microwave protection by absorption and scattering, and the microwave transmittance increases significantly. The porous framework of ZIF-8 can fix the iron oxide particles, preventing their agglomeration. Without ZIF-8, the iron oxide particles are prone to agglomeration during electrospinning, resulting in uneven distribution of active sites in the anti-microwave radiation layer. Without cobalt ions, there is no ZIF-8, and the pyridine groups in the water-resistant and stain-resistant layer lack coordination objects, and are only combined with the anti-microwave radiation layer by physical adsorption, resulting in a decrease in interfacial adhesion. After long-term use, the anti-microwave radiation layer is prone to peeling off.

[0078] While embodiments of the present application have been shown and described, it is to be understood that the embodiments described are merely divergences of the principles and spirit of the present application and that numerous modifications, changes, substitutions, and alterations can be made thereto without departing from the principles and spirit of the present application.

Claims

1. A method for preparing a spectacle lens that protects against microwave radiation and blue light, characterized in that, Includes the following steps: Step 1: Using hexadecyltrimethylammonium bromide to form a micelle template in ammonia water, tetraethyl orthosilicate is used as the silicon source. After hydrolysis and condensation reaction, isopropanol and ammonium nitrate are used to remove the template to obtain silica particles. Using silica particles as the core, tetraethyl orthosilicate is hydrolyzed and condensed with urea to form a burr-like silicon layer to obtain burr-like silica powder. Step 2: Using 5-hydroxyisophthalic acid as a ligand, chromium nitrate is hydrothermally coordinated to grow a chromium-based metal-organic framework in situ on the surface of burred silica to obtain chromium MOF / burred silica powder; the chromium MOF / burred silica powder is then sprayed onto an eyeglass lens to obtain an eyeglass lens containing a blue light blocking layer. Step 3: Add methyl methacrylate, polymethyl methacrylate-b-4-vinylpyridine, methacrylic acid, vinyl POSS and deionized water to a reaction vessel and stir for 30-40 minutes at 20-25℃ and 500-600 r / min. Then add sodium dodecyl sulfate and ammonium persulfate and heat to 80-90℃ to obtain a mixed solution. Immerse the eyeglass lens containing the blue light blocking layer in the mixed solution and continue the reaction for 1-2 hours. Remove the eyeglass lens and vacuum dry it at 60-80℃ for 1-2 hours to form a water-resistant and anti-fouling layer with a thickness of 100-200 nm. Step 4: Ferrous chloride reacts with sodium thiosulfate to generate ferrous oxide, which then coordinates with 2-methylimidazole and cobalt nitrate hexahydrate to form ZIF-8. After electrospinning with polyacrylonitrile, ZIF-8 / ferrous oxide composite fiber is obtained. The ZIF-8 / ferrous oxide composite fiber is then sprayed onto a water-resistant and stain-resistant layer to form a microwave radiation protection layer, resulting in eyeglass lenses that protect against microwave radiation and blue light.

2. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific preparation steps for the silica particles are as follows: Hexadecyltrimethylammonium bromide and ammonia were added to a reaction vessel and stirred for 30-40 min at 20-25℃ and 500-600 r / min. Then tetraethyl orthosilicate was added and the reaction was continued for 6-7 h. After centrifugation at 8000-9000 r / min for 5-8 min, the filter cake was transferred to isopropanol and ammonium nitrate and reacted at 80-90℃ for 24-26 h. After vacuum freeze-drying at -20℃ for 12-14 h, silica particles were obtained. The ratio of hexadecyltrimethylammonium bromide, ammonia, tetraethyl orthosilicate, isopropanol, and ammonium nitrate is 30-35g: 2-3L: 170-180mL: 1.5-2L: 14-16g.

3. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific preparation steps for the burr-like silica powder are as follows: Hexadecyltrimethylammonium bromide, urea, silica particles, and deionized water were added to a reaction vessel and stirred for 30-40 minutes at 20-25°C and 500-600 r / min. Then, isopropanol and tetraethyl orthosilicate were added, and stirring was continued for another 30-40 minutes. The mixture was then heated to 70-80°C and reacted for 16-18 hours. The mixture was filtered, and the filter cake was washed 2-4 times with deionized water. It was then vacuum dried at 60-80°C for 1-2 hours and transferred to a muffle furnace. The mixture was then calcined at 550-600°C for 6-8 hours to obtain burr-like silica powder. The ratio of hexadecyltrimethylammonium bromide, urea, silica particles, deionized water, isopropanol and tetraethyl orthosilicate is 20-22g: 12-20g: 8-10g: 450-500mL: 16-20mL: 4-8mL.

4. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific preparation steps for the chromium MOF / burred silica powder are as follows: Add spiky silica powder, 5-hydroxyisophthalic acid and deionized water to a reaction vessel. Dissolve sodium hexadecyl sulfate in 50-60 wt% ethanol solution and add it to the reaction vessel. Stir at 100-110℃ and 400-500 r / min for 1-2 h. Then add chromium nitrate and continue stirring for 24-26 h. Filter the mixture and wash the filter cake 2-4 times with deionized water and anhydrous ethanol, respectively. Dry it under vacuum at 60-80℃ for 1-2 h to obtain chromium MOF / spiky silica powder. The ratio of the amount of the burr-like silica powder, 5-hydroxyisophthalic acid, deionized water, sodium hexadecyl sulfate, ethanol solution and chromium nitrate is 15-20g: 20-25g: 800-900mL: 2-3g: 120-140mL: 10-11g.

5. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific preparation steps for the blue light blocking layer on the eyeglass lens are as follows: The lens substrate is ultrasonically cleaned in deionized water for 40-60 minutes and vacuum dried at 60-80℃ for 1-2 hours. Then, chromium MOF / burred silica powder is sprayed onto the lens substrate to obtain a lens containing a blue light blocking layer with a thickness of 500-600nm.

6. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The ratio of methyl methacrylate, polymethyl methacrylate-b-4-vinylpyridine, methacrylic acid, vinyl POSS, deionized water, sodium dodecyl sulfate, and ammonium persulfate is 15-20g: 17-19g: 16-17g: 5-7g: 250-300mL: 3-4g: 1-2g.

7. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific preparation steps of the ZIF-8 / iron oxide composite fiber are as follows: Sodium thiosulfate, ferrous chloride, sodium hydroxide, and deionized water were added to a reaction vessel and stirred for 5-6 hours at 200-220℃ and 500-600 r / min to obtain ferrous oxide. Then, ferrous oxide, 2-methylimidazole, cobalt nitrate hexahydrate, polyacrylonitrile, and N,N-dimethylformamide were added to the reaction vessel and stirred for 30-40 minutes at 20-25℃ and 500-600 r / min. The mixture was then transferred to a syringe and electrospun under experimental conditions of an applied voltage of 20-22 kV, a feed rate of 3-4 mm / h, and a receiving distance of 18-20 cm to obtain ZIF-8 / ferrous oxide composite fiber. The ratio of sodium thiosulfate, ferrous chloride, sodium hydroxide, and deionized water is 3-4g:10-12g:4-6g:120-140mL; the ratio of ferrous oxide, 2-methylimidazole, cobalt nitrate hexahydrate, polyacrylonitrile, and N,N-dimethylformamide is 2-4g:2-3g:3-5g:18-25g:250-300mL.

8. The method for preparing a spectacle lens with microwave radiation protection and blue light protection according to claim 1, characterized in that, The specific manufacturing steps for the eyeglass lens with microwave radiation protection and blue light protection are as follows: ZIF-8 / iron oxide composite fiber is sprayed onto a water-resistant and stain-resistant layer to form a microwave radiation protection layer with a thickness of 200-300nm, resulting in eyeglass lenses that protect against microwave radiation and blue light.

9. A pair of eyeglass lenses that protect against microwave radiation and blue light, characterized in that, It is prepared by the preparation method described in any one of claims 1-8.

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