Preparation method of antifouling and antibacterial spectacle lens coating

Abstract

The invention relates to the field of optical lens coatings, and particularly discloses a preparation method of an antifouling and antibacterial spectacle lens coating. The preparation method of the antifouling and antibacterial spectacle lens coating comprises the following steps: depositing a silicon dioxide substrate on the surface of a lens through plasma enhanced chemical vapor deposition treatment; the preparation method comprises the following steps: dispersing nano-graphene and nano-silver particles in an ethanol solvent, adding a silane coupling agent to form a homogeneous suspension, loading the suspension on the surface of a silicon dioxide substrate through a spin-coating method, and carrying out heat treatment curing to form an antibacterial layer, with the loading amount of nano-silver being less than or equal to 0.5 wt%; and etching the surface of the antibacterial layer by adopting a reactive ion etching method, and then grafting perfluorooctyltriethoxysilane on the etched surface at 80-100 DEG C by adopting a vapor deposition method to form the hydrophobic layer. The preparation method of the antifouling and antibacterial spectacle lens coating has the advantages of being antibacterial, antifouling and high in durability.

Description

Technical Field

[0001] The present application relates to the field of optical lens coatings, and more specifically, it relates to a preparation method for an anti-fouling and antibacterial coating for spectacle lenses. Background Art

[0002] Modern spectacle lens coating technology covers multiple functional thin films on the lens surface through nanoscale processes, significantly enhancing the visual experience and lens durability. Common coating types include anti-reflection films (reducing reflective interference), anti-fouling and hydrophobic films (resisting fingerprints and oil stains), anti-blue light films (filtering harmful light), and anti-static films (reducing dust adsorption). These coatings not only optimize the light transmittance but also achieve comprehensive protection such as scratch resistance and ultraviolet protection through composite stacking, becoming an important barrier for spectacle wearers to confront daily environmental challenges.

[0003] Despite the continuous progress of coating technology, the persistence of its antibacterial and anti-fouling capabilities remains a pain point in the industry. During daily use, sebum, sweat, and air pollutants are likely to remain on the lens surface. The hydrophobic effect of traditional anti-fouling films gradually decays with friction and cleaning, resulting in the adsorption of oil to form stubborn stains. More seriously, the coating layer lacks long-lasting antibacterial components and is prone to bacterial growth in a humid environment, which may cause eye infections or skin sensitivity problems. Summary of the Invention

[0004] In order to enable the coating of spectacle lenses to maintain long-lasting antibacterial and anti-fouling properties, the present application provides a preparation method for an anti-fouling and antibacterial coating for spectacle lenses.

[0005] The preparation method for an anti-fouling and antibacterial coating for spectacle lenses provided by the present application adopts the following technical solutions: A preparation method for an anti-fouling and antibacterial coating for spectacle lenses, comprising the following steps: Depositing a silicon dioxide substrate with a thickness of 50 - 100 nm on the lens surface through plasma-enhanced chemical vapor deposition treatment; Dispersing nano-graphene and nano-silver particles in an ethanol solvent at a mass ratio of (1 - 3):1, then adding a silane coupling agent to form a homogeneous suspension, and loading the suspension on the surface of the silicon dioxide substrate by spin coating, and curing it by heat treatment at 120 - 150 °C to form an antibacterial layer, where the nano-silver loading amount ≤ 0.5 wt%; Performing etching treatment on the surface of the antibacterial layer by reactive ion etching, with an etching power of 80 - 120 W and an etching depth of 100 - 200 nm, and then grafting perfluorooctyltriethoxysilane on the etched surface at 80 - 100 °C by chemical vapor deposition to form a hydrophobic layer.

[0006] By adopting the above technical solution, a dense silica substrate is formed by plasma-enhanced chemical vapor deposition (PECVD), providing excellent adhesion and optical transparency; nano-graphene and nano-silver particles are fixed by covalent bonds to form a synergistic antibacterial layer, and the nano-silver loading ≤ 0.5 wt% achieves efficient antibacterial while ensuring safety; reactive ion etching combined with fluoro-silane modification constructs a biomimetic hydrophobic structure, significantly improving the anti-fouling ability and reducing fingerprint and grease adsorption. The overall process takes into account long-term antibacterial, self-cleaning and mechanical durability, meeting the daily use requirements.

[0007] Optionally, the radio frequency power supply frequency of the plasma-enhanced chemical vapor deposition treatment is 13.56 MHz, the power density is 0.5 - 1.5 W / cm², and the deposition rate is 5 - 10 nm / min.

[0008] By adopting the above technical solution, by defining the radio frequency power supply frequency, power density and deposition rate, the plasma energy distribution and reaction uniformity are optimized, ensuring uniform thickness of the silica substrate and significantly reduced surface roughness, effectively avoiding substrate defects, enhancing the bonding strength between the coating and the lens body, and maintaining high light transmittance at the same time.

[0009] Optionally, the etching gas used in the reactive ion etching is CF 4 / O 2 mixed gas, and the gas flow ratio of the reactive ion etching is CF 4 :O 2 =(2 - 4):1.

[0010] By adopting the above technical solution, CF 4 / O 2 mixed gas is used for reactive ion etching. Through the chemical oxidation of O 2 and the physical bombardment of CF 4 , the etching directionality is synergistically controlled to form a honeycomb-like micro-nano structure with steep sidewalls and uniform pore diameters on the surface of the antibacterial layer. The optimization of the CF 4 / O 2 ratio can balance the etching rate and structural fidelity, avoid the loss of antibacterial agents caused by over-etching, and provide an ideal morphological substrate for subsequent fluoro-silane modification at the same time.

[0011] Optionally, an alternating magnetic field with an intensity of 0.1 - 0.5 T is applied to the etching area during the reactive ion etching process.

[0012] By adopting the above technical solution, the paramagnetism of nano-silver particles is utilized to induce their directional arrangement along the magnetic field direction to form a continuous conductive network. The magnetic field-assisted etching synchronously optimizes the anisotropic distribution of the honeycomb structure, enables the antibacterial agents to be enriched on the surface of the micro-columns / holes, increases the antibacterial active area, and the antistatic performance inhibits dust adsorption.

[0013] Optionally, after the etching treatment on the surface of the antibacterial layer, a secondary etching is required. The power of the secondary etching is 20 - 40 W, and the etching depth is 40 - 80 nm.

[0014] By adopting the above technical solution, a secondary nano - scale texture can be further constructed on the surface of the 100 - 200 nm main groove structure formed by the first etching. Through the size gradient design of double etching, the surface roughness presents a multi - level nested feature, further increasing the water contact angle and reducing the rolling angle. At the same time, the micro - nano structure formed by the secondary etching can also increase the grafting surface area of the subsequent hydrophobic layer, enabling perfluorosilane molecules to form a denser low - surface - energy coverage layer on the surface, and enhancing the repelling ability of the coating to pollutants such as oils and dust.

[0015] Optionally, nitrogen - doped titanium dioxide with a particle size of 5 - 15 nm is also added to the suspension, and the addition amount of nitrogen - doped titanium dioxide is 10 - 30% of the mass of nano - silver.

[0016] By adopting the above technical solution, after adding nitrogen - doped titanium dioxide, the antibacterial layer generates reactive oxygen under visible light excitation of 400 - 550 nm, and attacks the bacterial cell membrane synergistically with nano - silver ions, further enhancing the antibacterial and bacteriostatic effects.

[0017] Optionally, the preparation method of the nitrogen - doped titanium dioxide is as follows: Mix tetrabutyl titanate and absolute ethanol at a volume ratio of 1:(3 - 5), and add citric acid. The molar ratio of citric acid to tetrabutyl titanate is 1:(10 - 20) to obtain solution A; Dissolve urea in deionized water to prepare solution B with a concentration of 0.5 - 1.5 mol / L; Dropwise add solution B into solution A. The volume ratio of solution A to solution B added is (5 - 3):1, and use microwave with a power of 300 - 500 W, a temperature of 80 - 100 °C, and a reaction time of 20 - 40 minutes to obtain a gel; The gel is subjected to the following three - stage heat treatment in sequence: The first stage: Keep warm in an air atmosphere at 200 - 250 °C for 1 - 1.2 hours; The second stage: Keep warm in a nitrogen atmosphere at 350 - 400 °C for 2 - 2.2 hours; The third stage: Anneal in an argon atmosphere at 500 - 550 °C and keep warm for 30 - 40 minutes; Ball - mill and sieve the annealed product to obtain nitrogen - doped titanium dioxide with a particle size of 5 - 15 nm.

[0018] By adopting the above technical solution, nitrogen - doped TiO is prepared by microwave - assisted sol - gel method combined with a three - stage annealing process 2, microwave field accelerates hydrolysis and in-situ doping of nitrogen atoms, and the decomposition of urea provides a uniform nitrogen source; three-stage heat treatment can regulate the crystal phase and nitrogen doping amount, shift the light absorption edge to 550 nm, significantly improve the visible light catalytic efficiency compared with the traditional method, and the particle dispersibility is excellent.

[0019] Optionally, 5-10% by volume of hydrogen is introduced into argon during the third-stage annealing process.

[0020] By adopting the above technical solution, 5-10% hydrogen is introduced during the third-stage annealing to form a weakly reducing atmosphere, inducing oxygen vacancy defects in the TiO 2 lattice. Oxygen vacancies act as electron traps to inhibit the recombination of photo-generated carriers, increase the photocurrent density, and enhance the adsorption and activation ability of organic substances at the same time. Hydrogen-assisted annealing synchronously inhibits the excessive growth of grains and ensures the compatibility between nanoparticles and the coating.

[0021] In summary, the present application has the following beneficial effects: 1. Since the present application enhances the adhesion through a dense silica bottom layer, then realizes efficient and safe antibacterial by a graphene / silver synergistic antibacterial layer, constructs a micro-nano rough structure by reactive ion etching + grafts fluorosilane to form a low surface energy hydrophobic layer, this multi-layer functional design enables the coating to have long-term antibacterial, superhydrophobic anti-fouling, high light transmittance and coating durability, meeting the long-term use requirements of spectacle lenses in daily complex environments.

[0022] 2. In the present application, preferably through the hierarchical rough structure design of "main grooves + secondary textures", a multi-level nested roughness gradient is formed on the coating surface, significantly improving the air interception ability and the grafting efficiency of hydrophobic layer molecules, achieving an increase in contact angle and a decrease in rolling angle.

[0023] 3. The method of the present application expands the light absorption edge to 550 nm through nitrogen atom doping and oxygen vacancy defect regulation, improves the visible light catalytic efficiency, generates reactive oxygen species under light irradiation, forms a dual antibacterial mechanism with nano silver ions, introduces a weakly reducing atmosphere of 5-10% hydrogen during the third stage of heat treatment, further inhibits the recombination of photo-generated carriers, and ensures the uniform dispersion of nanoparticles in the coating, avoiding the decrease in light transmittance and functional attenuation caused by agglomeration. Specific Embodiments

[0024] The following further elaborates on the present application with reference to embodiments. It should be specifically noted that: for those conditions not specified in the following embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from ordinary commercial sources.

[0025] Preparation Example 1 A preparation method of nitrogen-doped titanium dioxide is as follows: Prepare the following raw materials: Tetrabutyl titanate (TBT, purity ≥ 99%), absolute ethanol (analytical pure), citric acid (analytical pure), urea (analytical pure), deionized water (resistivity ≥ 18 MΩ·cm), argon (purity ≥ 99%), nitrogen (purity ≥ 99%), hydrogen (purity ≥ 99%).

[0026] Measure 20 mL of tetrabutyl titanate and add 80 mL of absolute ethanol. Stir magnetically for 5 minutes until evenly mixed.

[0027] Weigh 0.88 g of citric acid with a molar ratio of TBT:citric acid = 1:15. Slowly add it to the above mixture and continue stirring for 30 minutes to form a transparent pale yellow solution A.

[0028] Weigh 12.0 g of urea and dissolve it in 100 mL of deionized water to prepare solution B with a concentration of 1.0 mol / L. Sonicate for 10 minutes until completely dissolved.

[0029] Add solution B dropwise to solution A at a rate of 2 mL / min with a total volume ratio of solution A:solution B = 4:1. Continuously stir magnetically to obtain a mixture. Transfer the mixture to a microwave reactor and set the parameters: microwave power 400 W, temperature 90 °C, reaction time 30 minutes. Apply ultrasonic assistance synchronously with a power density of 80 W / L. After the reaction, a light blue translucent gel is obtained and left to age for 12 hours.

[0030] First stage: Place the gel in an alumina crucible, put it into a tube furnace, and introduce air with a flow rate of 200 mL / min. Heat it to 220 °C at a rate of 5 °C / min and hold for 1 hour to remove residual organic matter.

[0031] Second stage: Switch to a nitrogen atmosphere with a flow rate of 150 mL / min. Heat it to 375 °C at a rate of 5 °C / min and hold for 2 hours to promote the substitution of nitrogen atoms for lattice oxygen.

[0032] Third stage: Switch to a mixture of argon - hydrogen with an argon:hydrogen ratio of 92.5:7.5 (volume fraction) and a flow rate of 100 mL / min. Heat it to 525 °C at a rate of 10 °C / min and hold for 35 minutes, then naturally cool to room temperature.

[0033] Crush the heat-treated bulk material and put it into a ball mill jar with zirconia grinding balls at a ball-to-material ratio of 10:1. Set the rotation speed to 300 rpm and the time to 3 hours. Pause for 10 minutes every 30 minutes to prevent overheating. Screen the ball-milled product through a 400-mesh sieve and collect N-TiO 2 nanoparticles with a particle size of 5 - 15 nm.

[0034] Preparation Example 2 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the molar ratio of citric acid to tetrabutyl titanate is 1:10.

[0035] Preparation Example 3 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the molar ratio of citric acid to tetrabutyl titanate is 1:20.

[0036] Preparation Example 4 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the concentration of Solution B is 0.5 mol / L.

[0037] Preparation Example 5 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the concentration of Solution B is 1.5 mol / L.

[0038] Preparation Example 6 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the volume ratio of Solution A to Solution B added is 5:1.

[0039] Preparation Example 7 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that the volume ratio of Solution A to Solution B added is 3:1.

[0040] Preparation Example 8 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that hydrogen is not introduced into argon during the annealing process in the third stage.

[0041] Preparation Example 9 A preparation method of nitrogen-doped titanium dioxide is as follows: The difference from Preparation Example 1 is that instead of three-step heat treatment, conventional heat treatment as shown in the following table is adopted.

[0042] Table 1 Heat treatment parameters of Preparation Example 9 Temperature range Atmosphere Time Pre-drying 120℃ Air 1 hour Main annealing 450℃ Nitrogen 3 hours Example 1 A preparation method of an anti-fouling and antibacterial coating for spectacle lenses: Prepare the following raw materials: CR-39 resin lens substrate, silane (SiH 4, purity ≥ 99.99%), oxygen (purity ≥ 99.9%), nano-graphene (sheet diameter 50 - 100 nm, thickness ≤ 5 nm), nano-silver particles (particle size 10 - 20 nm, purity ≥ 99.9%), nitrogen-doped titanium dioxide (particle size 5 - 15 nm, prepared by Preparation Example 1), perfluorooctyltriethoxysilane (FOTS, purity ≥ 98%), absolute ethanol (analytical grade), silane coupling agent (KH-550, purity ≥ 95%).

[0044] Place the lens substrate in the PECVD reaction chamber and evacuate to a base pressure ≤ 1×10 -3 Pa. Introduce silane and oxygen with a flow ratio of 1:2 and maintain the total gas pressure at 20 Pa. Turn on the radio frequency power supply with a frequency of 13.56 MHz and a power density of 1.0 W / cm², and heat the substrate to 250 °C. Control the deposition rate at 8 nm / min and continue for 12.5 minutes to form a silica substrate with a thickness of 100 nm.

[0045] Weigh 0.2 g of nano-graphene and 0.1 g of nano-silver particles, and add them to 50 mL of absolute ethanol. Add 0.2 g of silane coupling agent and 0.02 g of nitrogen-doped titanium dioxide, and ultrasonically disperse for 60 minutes at 40 kHz and a power of 150 W to obtain a homogeneous suspension. Drop the suspension onto the surface of the silica substrate and spin-coat at 2000 rpm for 30 seconds. Cure on a hot plate at 140 °C for 1 hour to form an antibacterial layer.

[0046] Use a reactive ion etching (RIE) device to etch the surface of the antibacterial layer. The etching gas is selected as CF 4 / O 2 mixed gas with a flow ratio of 3:1 and a total flow rate of 40 sccm. Set the power of the reactive ion etching (RIE) device to 100 W, the chamber pressure to 15 Pa, the etching depth to 150 nm, and form honeycomb-shaped fractal grooves. Apply an alternating magnetic field of 0.3 T synchronously during the etching process to induce the directional arrangement of nano-silver.

[0047] The reactive ion etching (RIE) device reduces the power to 30 W for secondary etching, maintaining the CF 4 / O 2 flow ratio of 3:1 to form columnar grooves with a depth of 60 nm.

[0048] Place the etched lens in a vapor deposition furnace and raise the furnace temperature to 90 °C. Introduce perfluorooctyltriethoxysilane vapor with argon as the carrier gas at a flow rate of 50 mL / min and deposit for 2 hours to obtain a hydrophobic layer with a thickness of 20 - 30 nm.

[0049] Example 2 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that nano-graphene and nano-silver particles are dispersed in an ethanol solvent at a mass ratio of 1:1.

[0050] Example 3 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that nano-graphene and nano-silver particles are dispersed in an ethanol solvent at a mass ratio of 3:1.

[0051] Example 4 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the power density in plasma-enhanced chemical vapor deposition treatment is 0.5 W / cm².

[0052] Example 5 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the power density in plasma-enhanced chemical vapor deposition treatment is 1.5 W / cm².

[0053] Example 6 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the gas flow ratio in reactive ion etching is CF 4 :O 2 =2:1.

[0054] Example 7 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the gas flow ratio in reactive ion etching is CF 4 :O 2 =4:1.

[0055] Example 8 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the etching gas used in reactive ion etching is CF 4。

[0056] Example 9 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the etching gas used in reactive ion etching is O 2 .

[0057] Example 10 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that an alternating magnetic field with an intensity of 0.1 T is applied to the etching area during reactive ion etching.

[0058] Example 11 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that an alternating magnetic field with a strength of 0.5 T is applied to the etching area during the reactive ion etching process.

[0059] Example 12 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that no alternating magnetic field is applied to the etching area during the reactive ion etching process.

[0060] Example 13 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that no secondary etching is performed.

[0061] Example 14 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the addition amount of nitrogen-doped titanium dioxide is 0.01 g.

[0062] Example 15 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the addition amount of nitrogen-doped titanium dioxide is 0.03 g.

[0063] Examples 16 - 24 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that the nitrogen-doped titanium dioxide is sequentially prepared from Preparation Examples 2 - 9.

[0064] Comparative Example 1 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that no silicon dioxide substrate deposition is performed on the coating.

[0065] Comparative Example 2 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that 0.3 g of nano silver particles are weighed and added to 50 mL of absolute ethanol. 0.2 g of silane coupling agent and 0.02 g of nitrogen-doped titanium dioxide are added, and ultrasonic dispersion is carried out at 40 kHz and a power of 150 W for 60 minutes to obtain a homogeneous suspension. The suspension is dropped onto the surface of the silicon dioxide substrate and spin-coated at 2000 rpm for 30 seconds. It is cured on a hot plate at 140 °C for 1 hour to form an antibacterial layer.

[0066] Comparative Example 3 A preparation method of an anti-fouling and antibacterial glasses lens coating: The difference from Example 1 is that no etching treatment is performed, and perfluorooctyltriethoxysilane is directly surface-grafted by chemical vapor deposition.

[0067] Performance detection test

[0068] Antibacterial rate: According to the ISO22196 standard, the 24-hour antibacterial rate against Staphylococcus aureus (ATCC6538) and Escherichia coli (ATCC25922) was tested.

[0069] Water contact angle: According to the ISO27448 standard, a contact angle measuring instrument was used to measure the static contact angle and the rolling angle.

[0070] Light transmittance: The light transmittance of the coating was tested using an ultraviolet-visible spectrophotometer (wavelength 550 nm).

[0071] After 90 days of simulated daily use, the antibacterial property and water contact angle were re-measured. Simulated daily use included placing it in a natural exposed environment and wiping it once every 6 hours with Yijiexin disposable anti-fog lens wipes (composition: all-wood pulp wet-strength paper, non-ionic surfactant, deionized water). When wiping, wipe in a spiral shape from the center outwards.

[0072] Table 2 Detection data 24h antibacterial rate 90-day antibacterial rate Initial contact angle 90-day contact angle Light transmittance Staphylococcus aureus / Escherichia coli Staphylococcus aureus / Escherichia coli (°) (°) (%) Example 1 99.9% / 99.8% 98.5% / 98.2% 165 162 98 Example 2 99.7% / 99.6% 97.8% / 97.5% 160 157 97 Example 3 99.5% / 99.3% 97.2% / 96.8% 163 160 97.5 Example 4 99.2% / 99.0% 95.0% / 94.5% 158 153 96 Example 5 98.8% / 98.5% 94.2% / 93.8% 155 150 95.5 Example 6 99.0% / 98.8% 96.0% / 95.5% 162 158 97.8 Example 7 98.5% / 98.3% 95.5% / 95.0% 159 155 97.2 Example 8 97.5% / 97.0% 90.2% / 89.5% 148 142 94 Example 9 96.0% / 95.5% 88.0% / 87.0% 140 135 93.5 Example 10 99.3% / 99.1% 97.0% / 96.5% 163 159 97.5 Example 11 99.6% / 99.4% 97.5% / 97.0% 164 161 97.8 Example 12 98.0% / 97.8% 93.5% / 93.0% 156 150 96.5 Example 13 98.5% / 98.2% 94.0% / 93.5% 152 146 96 Example 14 99.1% / 98.9% 96.5% / 96.0% 161 157 97.5 Example 15 99.4% / 99.2% 97.2% / 96.8% 164 160 97.8 Example 16 99.7% / 99.5% 97.8% / 97.3% 164 160 97.8 Example 17 99.6% / 99.4% 97.5% / 97.0% 163 159 97.5 Example 18 99.3% / 99.1% 97.0% / 96.5% 162 158 97.2 Example 19 99.0% / 98.8% 96.5% / 96.0% 161 156 97 Example 20 98.8% / 98.5% 96.0% / 95.5% 160 155 96.8 Example 21 98.5% / 98.2% 95.5% / 95.0% 159 154 96.5 Example 22 98.0% / 97.8% 94.5% / 94.0% 157 152 96 Example 23 97.5% / 97.0% 93.0% / 92.5% 155 150 95.5 Example 24 96.5% / 96.0% 89.0% / 88.5% 150 143 94.5 Comparative Example 1 85.0% / 83.0% 70.0% / 68.0% 130 115 97 Comparative Example 2 99.9% / 99.8% 85.0% / 83.0% 145 130 94 Comparative Example 3 92.0% / 90.5% 80.0% / 78.0% 115 100 95 Combining Example 1 and Comparative Example 1 and referring to Table 2, it can be seen that in Comparative Example 1, no silica substrate was deposited, and its initial antibacterial rate was significantly lower than that of Example 1. Moreover, after 90 days, the antibacterial performance decreased significantly to below 70%. This indicates that the dense structure formed by PECVD of the silica substrate enhances the adhesion between the antibacterial layer and the lens body, thereby ensuring the mechanical stability of the coating. The absence of the base layer causes the antibacterial agent to directly contact the resin surface, resulting in poor interfacial compatibility and easy peeling due to stress concentration.

[0073] Combining Example 1 and Comparative Example 2 and referring to Table 2, it can be seen that in Comparative Example 2, only nano-silver was added, and its 90-day antibacterial rate decreased significantly compared to Example 1. This shows that although increasing the silver content improves the antibacterial property in the short term, excessive silver particles are more likely to agglomerate or migrate and lose during long-term wiping, resulting in functional decay.

[0074] Combining Example 1 and Comparative Example 3 and referring to Table 2, it can be seen that in Comparative Example 3, no etching treatment was carried out, and both its initial contact angle and the contact angle after 90 days were much lower than those of Example 1, and the antibacterial rate decreased significantly. This indicates that the micro-nano rough structure constructed by reactive ion etching is the key to the efficient grafting of the hydrophobic layer: the honeycomb-like grooves formed by etching increase the specific surface area and the air interception effect, enabling the perfluorosilane molecules to form a continuous low surface energy coverage layer to achieve superhydrophobicity; at the same time, the structure exposes more antibacterial active sites, enhancing the contact efficiency between the antibacterial agent and bacteria.

[0075] Combining Examples 1-3 and Table 2, it can be seen that when the ratio of nanographene to silver increases from 1:1 to 3:1, the initial antibacterial rate slightly decreases from 99.7% / 99.6% to 99.5% / 99.3%, but the light transmittance remains above 97%. This shows that the two-dimensional structure of graphene can synergistically inhibit the excessive release of silver ions through physical barrier and chemical adsorption, thereby prolonging the antibacterial timeliness. The design of mass ratio (1-3): 1 strikes a balance between antibacterial efficiency and long-term effectiveness.

[0076] Combining Example 1 and Example 4-5 with Table 2, it can be seen that low power leads to insufficient plasma energy, SiO 2 The density of the substrate layer decreases and surface defects increase; high power causes excessive etching, increases substrate roughness, and intensifies light scattering. Limiting the power density to 0.5-1.5W / cm² can optimize the deposition rate and film quality.

[0077] Combining Example 1 and Examples 6-9 with Table 2, it can be seen that CF4 / O 2 In the mixed gas, O 2 Chemical oxidation can soften the etching interface, while physical bombardment of CF4 can enhance anisotropic etching. The flow ratio (2-4):1 can balance the etching directionality and structural fidelity, avoiding over-etching or structural collapse caused by pure gas.

[0078] Combining Example 1 and Examples 10-12 with Table 2, it can be seen that when a 0.3T magnetic field is applied, the antibacterial rate and contact angle are better than when no magnetic field is applied. The magnetic field induces the nanosilver to be oriented along the magnetic lines to form a conductive network, inhibiting the electrostatic adsorption of dust; at the same time, the anisotropic distribution of the honeycomb structure is optimized, so that the antibacterial agent is enriched on the surface of the microcolumns and the active area is increased. However, the magnetic field strength exceeding 0.5T will aggravate particle migration, resulting in a slight decrease in light transmittance.

[0079] Combining Example 1 and Example 13 with Table 2, it can be seen that Example 13 did not undergo secondary etching, and its contact angle was 13° lower than that of Example 1, and the 90-day antibacterial rate decreased by 4.5%. This shows that the secondary nanotexture formed by the secondary etching further increases the grafting density of the hydrophobic layer through the multi-level roughness design, enhances the stability of the Cassie-Baxter state, and reduces the penetration of pollutants; at the same time, the nano-scale grooves can fix more antibacterial agents and delay loss.

[0080] Combining Example 1 and Examples 14-15 with Table 2, it can be seen that an appropriate amount of TiO 2 Reactive oxygen species (ROS) are generated under visible light, which work together with silver ions to destroy bacterial membranes. However, excessive addition will cause light scattering due to particle agglomeration, which will reduce light transmittance. The preferred addition amount of 10-30% can take into account both photocatalytic activity and optical performance.

[0081] Combined with Example 1 and Examples 16 - 24 and Table 2, it can be seen that the N-TiO prepared in Preparation Example 1 2 exhibits the best performance, while the antibacterial rates and contact angles of Preparation Examples 8 and 9 decrease significantly. This indicates that hydrogen-assisted reduction during three-stage annealing can generate oxygen vacancies, inhibit the recombination of photo-generated carriers, and improve the photocatalytic efficiency; while conventional annealing leads to uneven nitrogen doping, grain coarsening, and weakened visible light response. Optimizing the nitrogen doping process is crucial for the long-term antibacterial property of the coating.

[0082] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A method for preparing an antifouling and antibacterial eyeglass lens coating, characterized in that: The following steps are involved: A silicon dioxide substrate with a thickness of 50-100 nm is deposited on the surface of the lens by plasma enhanced chemical vapor deposition; Nanographene and nanosilver particles are dispersed in an ethanol solvent in a mass ratio of (1-3):1, and a silane coupling agent is added to form a homogeneous suspension. The suspension is loaded on the surface of a silicon dioxide substrate by spin coating, and cured by heat treatment at 120-150°C to form an antibacterial layer, wherein the nanosilver loading is ≤0.5wt%; The surface of the antibacterial layer is etched by reactive ion etching, with an etching power of 80-120 W and an etching depth of 100-200 nm. Perfluorooctyltriethoxysilane is then grafted on the etched surface by vapor deposition at 80-100° C. to form a hydrophobic layer.

2. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 1, characterized in that: The radio frequency power supply frequency of the plasma enhanced chemical vapor deposition process is 13.56 MHz, the power density is 0.5-1.5 W / cm², and the deposition rate is 5-10 nm / min.

3. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 1, characterized in that: The etching gas used in the reactive ion etching is a CF4 / O2 mixed gas, and the gas flow ratio of the reactive ion etching is CF4:O2=(2-4):

1.

4. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 1, characterized in that: During the reactive ion etching process, an alternating magnetic field with a strength of 0.1-0.5T is applied to the etching area.

5. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 1, characterized in that: After the etching treatment is performed on the surface of the antibacterial layer, a secondary etching is required, wherein the power of the secondary etching is 20-40W and the etching depth is 40-80nm.

6. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 1, characterized in that: Nitrogen-doped titanium dioxide with a particle size of 5-15 nm is also added to the suspension, and the amount of the nitrogen-doped titanium dioxide added is 10-30% of the mass of the nano-silver.

7. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 6, characterized in that: The preparation method of the nitrogen-doped titanium dioxide is: Tetrabutyl titanate and anhydrous ethanol are mixed in a volume ratio of 1:(3-5), and citric acid is added, and the molar ratio of citric acid to tetrabutyl titanate is 1:(10-20), to obtain solution A; Dissolve urea in deionized water to prepare solution B with a concentration of 0.5-1.5 mol / L; Add solution B dropwise into solution A, the volume ratio of solution A to solution B is (5-3):1, microwave at 300-500W power, temperature 80-100°C, reaction time 20-40 minutes, to obtain a gel; The gel was subjected to the following three heat treatments in sequence: The first stage: keep warm for 1-1.2 hours in air atmosphere at 200-250℃; The second stage: keep warm at 350-400℃ in nitrogen atmosphere for 2-2.2 hours; The third stage: annealing at 500-550℃ in argon atmosphere for 30-40 minutes; The annealed product is ball-milled and sieved to obtain nitrogen-doped titanium dioxide with a particle size of 5-15 nm.

8. The method for preparing the antifouling and antibacterial eyeglass lens coating according to claim 7, characterized in that: During the third stage annealing, 5-10% by volume of hydrogen is introduced into the argon gas.