Healthy functional glasses based on biophotonic crystal composite system and preparation method thereof

Abstract

The invention relates to the technical field of functional glasses manufacturing, and discloses healthy functional glasses based on a biophotonic crystal composite system and a preparation method of the healthy functional glasses. The glasses frame is prepared by injection molding of TR-90 resin and a modified composite functional filler, and the modified composite functional filler is prepared from natural composite ore powder, bionic biophotonic crystal powder and a silane coupling agent; mixing the natural composite ore powder with the bionic biophotonic crystal powder, and modifying with a silane coupling agent to obtain a modified composite functional filler; extruding and granulating with TR-90 resin, and carrying out injection molding to obtain the mirror frame; and the optical resin is cured and coated to obtain a lens, and then the lens is assembled. According to the invention, the periodic mesoporous structure of the bionic biophotonic crystal powder is utilized to isolate and disperse the natural composite ore powder, and the silane coupling agent is combined to enhance the interface bonding force, so that the aggregation of inorganic particles in a resin matrix is reduced, and the mirror frame keeps good mechanical properties while having a healthy function.

Description

Technical Field

[0001] This invention relates to the field of functional eyewear manufacturing technology, specifically to health-functional eyewear based on a biophotonic crystal composite system and its preparation method. Background Technology

[0002] With the widespread use of electronic products and increased eye strain, eyeglasses that not only correct vision but also provide eye health benefits have gained market attention. Existing eyeglasses with these functions typically incorporate natural mineral powders such as tourmaline and maifanite directly into the frame material, utilizing their ability to release negative ions or far-infrared rays to improve the microenvironment around the eyes. Alternatively, they may use optical resins with added blue light blocking agents to create lenses that block harmful light. TR-90 resin, due to its excellent shape memory and toughness, is often used as a frame material, while MR-8 resin is a commonly used high-refractive-index lens material.

[0003] However, when inorganic mineral powder is directly filled into an organic resin matrix, the filler tends to agglomerate within the matrix due to the difference in surface properties between the inorganic filler and the organic matrix. This agglomeration disrupts the continuity of the resin matrix, leading to a decrease in the mechanical properties of the finished frame, manifested as reduced toughness or weakened impact resistance. Simultaneously, simple physical mixing limits the effective specific surface area utilization of the mineral powder, resulting in limited efficiency and insufficient durability of negative ion release or far-infrared emission. Furthermore, in traditional manufacturing processes, uneven filler dispersion can easily cause flow lines or defects on the surface of the injection-molded parts, and single lens protection methods often struggle to simultaneously achieve high light transmittance and wear resistance while blocking harmful light.

[0004] Therefore, how to improve the dispersibility of inorganic functional fillers in resin matrices to enhance the release efficiency and durability of health functions while maintaining the mechanical properties of the material, and combine this with excellent optical protection performance, is a technical problem that needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides health-functional glasses based on a biophotonic crystal composite system and its preparation method. This solves the problems of inorganic functional fillers easily agglomerating in organic resin matrices, leading to reduced mechanical properties of the frames, as well as insufficient negative ion release and far-infrared emission efficiency and poor durability in existing health-functional glasses.

[0006] To address the above problems, the present invention provides the following technical solution:

[0007] This invention provides health-functional glasses based on a biophotonic crystal composite system, employing the following technical solution:

[0008] Health-functional glasses based on a biophotonic crystal composite system include a frame and lenses embedded in the frame. The frame is injection molded from raw materials comprising the following parts by weight: TR-90 resin: 95-105 parts; modified composite functional filler: 4.7-5.2 parts. The modified composite functional filler is prepared from natural composite mineral powder, biomimetic biophotonic crystal powder, and a silane coupling agent. The mass ratio of the natural composite mineral powder to the biomimetic biophotonic crystal powder is 2:1-3:1. The amount of the silane coupling agent is 0.5%-1.5% of the total mass of the natural composite mineral powder and the biomimetic biophotonic crystal powder.

[0009] By adopting the above technical solution, and using TR-90 resin as the matrix, combined with a modified composite functional filler composed of natural composite mineral powder and biomimetic photonic crystal powder, a synergistic effect of excellent mechanical properties and health functions is achieved. Specifically, the biomimetic photonic crystal powder, as the physical carrier of the natural composite mineral powder, utilizes its microporous structure to isolate the natural composite mineral powder, effectively preventing the aggregation of inorganic particles in the organic resin matrix and improving the dispersion uniformity of the filler. Simultaneously, the silane coupling agent forms a chemical bond between the inorganic filler surface and the organic resin matrix, enhancing interfacial adhesion. This allows the frame to maintain the original toughness and chemical corrosion resistance of TR-90 while possessing the health functions of releasing negative ions and far-infrared rays. Furthermore, the periodic structure of the biomimetic photonic crystal can modulate light waves of specific wavelengths, which, combined with the energy field of the natural composite mineral powder, helps improve microcirculation around the eyes and relieve eye fatigue.

[0010] Preferably, the natural composite mineral powder is made from raw materials comprising the following parts by weight: tourmaline: 2-4 parts; maifanite: 1-3 parts; qibing stone raw ore: 1-3 parts; deep-sea carbon mud: 0.5-1.5 parts.

[0011] By employing the above technical solutions, tourmaline, with its piezoelectric and thermoelectric effects, can sustainably release negative ions and microcurrents; maifanite is rich in various trace elements; and qibing stone ore and deep-sea carbon mud possess high emissivity and far-infrared radiation characteristics. The combination of these four elements forms a multi-dimensional energy field at the microscopic scale, which can promote blood circulation in the eyes. When combined with the biomimetic photonic crystal powder carrier, its energy release is more gentle and sustained.

[0012] Preferably, the biomimetic photonic crystal powder is a rare-earth-doped alumina-based porous material, and the biomimetic photonic crystal powder has a periodic mesoporous structure formed after removing the polystyrene microsphere template; the rare-earth doping element in the rare-earth-doped alumina-based porous material is selected from one or more of cerium, europium, and terbium.

[0013] By adopting the above technical solution, the alumina substrate possesses high hardness and chemical stability, serving as a framework to enhance the rigidity of the composite material. The doping of rare earth elements not only stabilizes the crystal phase of alumina but also endows the material with unique optical activity. The periodic mesoporous structure left after removing the template not only increases the specific surface area for adsorbing and loading the natural composite ore powder particles, but its periodic refractive index changes may also form a photonic bandgap, scattering or modulating incident ambient light, thereby enhancing the interaction between light and matter at the microscopic level and improving overall functional efficiency.

[0014] Preferably, the biomimetic photonic crystal powder is prepared by the following method: using aluminum isopropoxide as the aluminum source and one or more of cerium nitrate hexahydrate, europium nitrate hexahydrate, or terbium nitrate hexahydrate as the doping source, a doped aluminum sol is prepared; polystyrene microsphere emulsion with a particle size of 150nm-200nm is added to the doped aluminum sol as a template agent, and after ultrasonic dispersion, it is aged and dried to obtain a dry gel precursor; the dry gel precursor is calcined at 800℃-1000℃ for 2-4 hours to remove the polystyrene microsphere emulsion and crystallize, and after pulverization and classification, the biomimetic photonic crystal powder is obtained; wherein, the molar amount of the doping source is 1.0%-3.0% of the molar amount of the aluminum source.

[0015] By employing the above technical solution and utilizing the sol-gel template method, the pore size was precisely controlled, constructing a highly ordered three-dimensional interconnected macroporous structure. The high-temperature calcination process completely removed the organic template and promoted the entry of rare earth ions into the alumina lattice, forming a stable solid solution structure. This ensured that the biomimetic photonic crystal powder did not collapse or degrade in performance during subsequent mixing with the natural composite mineral powder and high-temperature injection molding.

[0016] Preferably, the silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane; the D50 average particle size of the modified composite functional filler is 2μm-15μm.

[0017] By adopting the above technical solution, the double bond groups contained in γ-methacryloyloxypropyltrimethoxysilane can interact with the TR-90 molecular chain, improving compatibility. Limiting the D50 particle size to the range of 2μm-15μm avoids both the agglomeration problem easily caused by nano-sized particles and stress concentration points caused by large micron-sized particles, ensuring a smooth and delicate surface finish on the lens frame after injection molding.

[0018] Preferably, the lens includes a blue light blocking substrate and a coating layer; the blue light blocking substrate is cured from MR-8 optical resin with added ultraviolet absorber, and the amount of ultraviolet absorber added is 0.05%-0.1% of the mass of the MR-8 optical resin; the coating layer includes 5-7 layers of zirconium dioxide and silicon dioxide antireflective films alternately vapor-deposited on the surface of the blue light blocking substrate, and a fluorinated hydrophobic film located on the outermost layer of the coating layer.

[0019] By employing the above technical solution, MR-8 resin possesses a high refractive index and a high Abbe number. Combined with a specific ratio of the ultraviolet absorber, it effectively blocks high-energy short-wave blue light while ensuring the lens is thin, clear, and lightweight. The anti-reflective film formed by alternating stacks of zirconium dioxide and silicon dioxide utilizes the principle of light interference to reduce surface reflection and increase light transmittance; the fluorine-containing hydrophobic film reduces surface energy, giving the lens waterproof, oil-proof, and easy-to-clean properties, thus improving the wearing experience.

[0020] This invention provides a method for preparing health-functional glasses based on a biophotonic crystal composite system, using the following technical solution:

[0021] A method for preparing health-functional glasses based on a biophotonic crystal composite system includes the following steps: mixing natural composite mineral powder with biomimetic biophotonic crystal powder, heating, spraying in a hydrolyzed silane coupling agent solution, mixing at high speed, and drying to obtain a modified composite functional filler; mixing TR-90 resin with the modified composite functional filler, melting and extruding it through a twin-screw extruder, and pelletizing it to obtain composite granules; drying the composite granules, injecting them into a mold through an injection molding machine, demolding to obtain a semi-finished frame, and then performing tumbling and polishing treatment on the semi-finished frame to obtain a frame; injecting MR-8 optical resin monomer with added ultraviolet absorber into a glass mold and curing it to obtain a blue light blocking substrate; cleaning the blue light blocking substrate and then vacuum-depositing a zirconium dioxide and silicon dioxide anti-reflective film and a fluorine-containing hydrophobic film to obtain a lens; cutting the lens and embedding it into the frame, installing accessories, and obtaining the health-functional glasses based on the biophotonic crystal composite system.

[0022] By adopting the above technical solution, the three-step process of first preparing the modified composite functional filler, then performing melt blending, extrusion granulation, and finally injection molding ensures the gradual dispersion of the functional materials. First, heating and coupling agent spraying treatment form a hydrophobic and oleophilic molecular layer on the surface of the natural composite mineral powder and the biomimetic photonic crystal powder. Then, under the high shear force of a twin-screw extruder, the filler is uniformly dispersed in the TR-90 matrix to form a masterbatch. Finally, injection molding ensures the shape accuracy and performance stability of the final product. This process is complete and logically rigorous, effectively solving the problems of poor resin flowability and mechanical property degradation under high filler content through chain-step control.

[0023] Preferably, in the step of obtaining the modified composite functional filler, the heating temperature is 80℃-100℃; in the step of obtaining the composite granules, the melt extrusion temperature is 230℃-260℃, and the process parameters of the twin-screw extruder are: zone 1 temperature 230℃-240℃, zone 2 temperature 240℃-250℃, zone 3 temperature 250℃-260℃, and die head temperature 245℃-255℃.

[0024] By adopting the above technical solution, a heating temperature of 80℃-100℃ is beneficial for the volatilization of water in the silane coupling agent hydrolysate and the condensation reaction between the coupling agent and the hydroxyl groups on the powder surface, thereby improving the coating efficiency. The extruder adopts a gradient heating setting of 230℃-260℃, which ensures the full melting and plasticization of the TR-90 resin while avoiding resin degradation or functional powder failure due to local overheating. The specific temperature zone setting ensures the smooth conveying and mixing of materials from the feeding section to the metering section, making the melt mass index of the composite granules stable.

[0025] Preferably, in the step of drying the composite granules, injecting them into a mold using an injection molding machine, demolding to obtain a semi-finished mirror frame, and then performing tumbling and polishing on the semi-finished mirror frame to obtain the mirror frame, the process parameters of the injection molding machine are: barrel rear section temperature 240℃-250℃, middle section temperature 250℃-260℃, front section temperature 260℃-270℃, mold temperature 60℃-80℃, and injection pressure 80MPa-120MPa.

[0026] By adopting the above technical solution, the higher front-end temperature gives the melt good fluidity, which can fill the complex structure of the mirror frame mold; combined with the mold temperature of 60℃-80℃, the cooling rate is controlled, the residual stress inside the part is reduced, and the mirror frame is prevented from deforming or cracking; the injection pressure of 80MPa-120MPa ensures the density and dimensional stability of the part.

[0027] Preferably, in the step of injecting the MR-8 optical resin monomer with added ultraviolet absorber into a glass mold for curing, followed by cleaning and vacuum evaporation of a zirconium dioxide and silicon dioxide antireflective film and a fluorine-containing hydrophobic film to obtain a lens, the curing process employs a programmed temperature rise method, with a temperature range of 30℃-120℃ and a curing time of 20-24 hours; the vacuum degree during vacuum evaporation is 2.0×10⁻⁶. -3 Pa-4.0×10 -3 Pa.

[0028] By adopting the above technical solution, the programmed temperature rise long-cycle curing process can effectively avoid the burst polymerization phenomenon during resin polymerization, eliminate optical distortion, and ensure that the blue light blocking substrate has a uniform refractive index and no internal stress. The high vacuum environment ensures the mean free path of the coating material molecules, enabling them to impact the substrate surface with high energy, resulting in a dense film layer with strong adhesion and excellent wear resistance.

[0029] This invention provides health-functional glasses based on a biophotonic crystal composite system and its preparation method. It has the following beneficial effects:

[0030] 1. This invention combines the natural composite mineral powder with the biomimetic photonic crystal powder, and then uses the silane coupling agent to modify the surface to obtain the modified composite functional filler. The periodic mesoporous structure of the biomimetic photonic crystal powder physically isolates the natural composite mineral powder, reducing the agglomeration of inorganic particles in the TR-90 resin matrix. At the same time, the silane coupling agent enhances the interfacial adhesion between the inorganic filler and the organic matrix, so that the frame maintains good mechanical properties and chemical corrosion resistance while having the functions of releasing negative ions and far-infrared rays.

[0031] 2. This invention selects rare earth-doped alumina-based porous materials as the biomimetic biophotonic crystal powder. The hardness of the alumina framework enhances the rigidity of the frame, and the rare earth doping elements stabilize the crystal structure. This allows the biomimetic biophotonic crystal powder to work synergistically with the natural composite mineral powder composed of tourmaline, maifanite, gypsumite ore, and deep-sea carbon mud. The periodic mesoporous structure increases the specific surface area, improving the efficiency and durability of negative ion release and far-infrared emission.

[0032] 3. This invention uses the MR-8 optical resin with added ultraviolet absorber to prepare the blue light blocking substrate and combines it with the coating layer composed of the zirconium dioxide and silicon dioxide antireflective film and the fluorine-containing hydrophobic film to block high-energy short-wave blue light and ultraviolet rays. At the same time, the preparation process of first preparing the modified composite functional filler, then preparing the composite granules by melt extrusion using the twin-screw extruder, and finally injection molding ensures the uniform dispersion of functional materials in the TR-90 resin matrix, thereby improving the dimensional accuracy and surface quality of the finished frame. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the preparation examples, examples, comparative examples, and test examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] Preparation Examples 1-6:

[0035] Preparation Example 1:

[0036] This preparation example provides a biomimetic biophotonic crystal powder, including the following steps:

[0037] Aluminum isopropoxide was dissolved in anhydrous ethanol at an aluminum source concentration of 0.2 mol / L. The solution was stirred at 300 rpm for 60 minutes in a water bath at 60°C. Cerium nitrate hexahydrate was then added, with a doping molar amount of 1.0% of the aluminum source molar amount. Deionized water and dilute nitric acid were added dropwise to adjust the pH of the solution to 3.0. The solution was then vigorously stirred at 60°C for 2 hours to form a transparent aluminum sol.

[0038] Polystyrene (PS) microsphere emulsion with a particle size of 150 nm was added to the above aluminum sol as a template agent, with a mass ratio of polystyrene microspheres to aluminum isopropoxide of 0.5:1. The mixture was placed in an ultrasonic disperser and ultrasonically treated at a frequency of 40 kHz for 30 minutes to ensure uniform dispersion of the template agent.

[0039] The dispersed sol mixture was placed in a constant temperature oven and aged at 40°C for 24 hours to form a wet gel. The seal was then opened, and the mixture was dried in a forced-air drying oven at 100°C for 12 hours to obtain the dry gel precursor.

[0040] The dry gel precursor was placed in a muffle furnace and heated to 800°C at a heating rate of 2°C / min, and calcined at this temperature for 2 hours to remove the organic template and crystallize. After natural cooling, the product was pulverized by an ultrasonic jet mill and sieved to classify the product, collecting biomimetic biophotonic crystal powder with an average D50 particle size of 2 μm.

[0041] Preparation Example 2:

[0042] This preparation example provides a biomimetic biophotonic crystal powder, including the following steps:

[0043] Aluminum isopropoxide was dissolved in anhydrous ethanol at an aluminum source concentration of 0.35 mol / L. The solution was stirred at 400 rpm for 75 minutes in a water bath at 70°C. Then, a mixture of cerium nitrate hexahydrate and europium nitrate hexahydrate (molar ratio 1:1) was added, with the total doping molar amount being 2.0% of the aluminum source molar amount. Deionized water and dilute nitric acid were added dropwise to adjust the pH of the solution to 3.5. The solution was then vigorously stirred at 70°C for 3 hours to form a transparent aluminum sol.

[0044] Polystyrene (PS) microsphere emulsion with a particle size of 180 nm was added to the above aluminum sol as a template agent, with a mass ratio of polystyrene microspheres to aluminum isopropoxide of 0.75:1. The mixture was placed in an ultrasonic disperser and ultrasonically treated at a frequency of 40 kHz for 45 minutes to ensure uniform dispersion of the template agent.

[0045] The dispersed sol mixture was placed in a constant temperature oven and aged at 50°C for 36 hours to form a wet gel. The seal was then opened, and the mixture was dried in a forced-air drying oven at 110°C for 18 hours to obtain the dry gel precursor.

[0046] The dry gel precursor was placed in a muffle furnace and heated to 900°C at a heating rate of 3.5°C / min, and calcined at this temperature for 3 hours to remove the organic template and crystallize. After natural cooling, the product was pulverized by an ultrasonic jet mill and sieved to classify the product, collecting biomimetic biophotonic crystal powder with an average D50 particle size of 5 μm.

[0047] Preparation Example 3:

[0048] This preparation example provides a biomimetic biophotonic crystal powder, including the following steps:

[0049] Aluminum isopropoxide was dissolved in anhydrous ethanol at an aluminum source concentration of 0.5 mol / L. The solution was stirred at 500 rpm for 90 minutes in a water bath at 80°C. Terbium nitrate hexahydrate was then added, with a doping molar amount of 3.0% of the aluminum source molar amount. Deionized water and dilute nitric acid were added dropwise to adjust the pH of the solution to 4.0. The solution was then vigorously stirred at 80°C for 4 hours to form a transparent aluminum sol.

[0050] Polystyrene (PS) microsphere emulsion with a particle size of 200 nm was added to the above aluminum sol as a template agent, with a mass ratio of polystyrene microspheres to aluminum isopropoxide of 1:1. The mixture was placed in an ultrasonic disperser and ultrasonically treated at a frequency of 40 kHz for 60 minutes to ensure uniform dispersion of the template agent.

[0051] The dispersed sol mixture was placed in a constant temperature oven and aged at 60°C for 48 hours to form a wet gel. The seal was then opened, and the mixture was dried in a forced-air drying oven at 120°C for 24 hours to obtain the dry gel precursor.

[0052] The dry gel precursor was placed in a muffle furnace and heated to 1000°C at a heating rate of 5°C / min, and calcined at this temperature for 4 hours to remove the organic template and crystallize. After natural cooling, the product was pulverized by an ultrasonic jet mill and sieved to classify the product, collecting biomimetic biophotonic crystal powder with an average D50 particle size of 8 μm.

[0053] Preparation Example 4:

[0054] This preparation example provides a natural composite mineral powder, including the following steps:

[0055] Tourmaline, maifanite, gypsum ore, and deep-sea carbon mud were weighed separately and mixed in a mass ratio of 2:1:1:0.5. The mixed raw materials were added to a ball mill jar, and anhydrous ethanol was added as a grinding aid. The material-to-ball ratio was 1:1.5. The mixture was ground in a ball mill at a speed of 300 r / min for 12 hours.

[0056] The ground slurry was spray-dried with an inlet air temperature set at 160℃ and an outlet air temperature set at 70℃ to remove the solvent and obtain dried powder. The dried powder was then fed into an air jet mill for deagglomeration and dispersion. The discharge particle size was controlled by a classifying wheel, and natural composite mineral powder with an average D50 particle size of 5μm was collected.

[0057] Preparation Example 5:

[0058] This preparation example provides a natural composite mineral powder, including the following steps:

[0059] Tourmaline, maifanite, gypsum ore, and deep-sea carbon mud were weighed separately and mixed in a mass ratio of 3:2:2:1. The mixed raw materials were added to a ball mill jar, and anhydrous ethanol was added as a grinding aid. The material-to-ball ratio was 1:2, and the mixture was ground in a ball mill at a speed of 400 r / min for 18 hours.

[0060] The ground slurry was spray-dried with an inlet air temperature set at 180℃ and an outlet air temperature set at 80℃ to remove the solvent and obtain dried powder. The dried powder was then fed into an air jet mill for deagglomeration and dispersion. The discharge particle size was controlled by a classifying wheel, and natural composite mineral powder with an average D50 particle size of 10μm was collected.

[0061] Preparation Example 6:

[0062] This preparation example provides a natural composite mineral powder, including the following steps:

[0063] Tourmaline, maifanite, gypsum ore, and deep-sea carbon mud were weighed separately and mixed in a mass ratio of 4:3:3:1.5. The mixed raw materials were added to a ball mill jar, and anhydrous ethanol was added as a grinding aid. The material-to-ball ratio was 1:2.5. The mixture was ground in a ball mill at a speed of 500 r / min for 24 hours.

[0064] The ground slurry was spray-dried with an inlet air temperature set at 200℃ and an outlet air temperature set at 90℃ to remove the solvent and obtain dried powder. The dried powder was then fed into an air jet mill for deagglomeration and dispersion. The discharge particle size was controlled by a classifying wheel, and natural composite mineral powder with an average D50 particle size of 15μm was collected.

[0065] Examples 1-3:

[0066] Example 1:

[0067] This embodiment provides a method for preparing health-functional glasses based on a biophotonic crystal composite system, including the following steps:

[0068] S10. Prepare a 1.0% (w / w) aqueous solution of γ-methacryloxypropyltrimethoxysilane (KH-570) in ethanol (95% ethanol concentration), and let it stand for hydrolysis for 15 minutes. Weigh the natural composite mineral powder prepared in Preparation Example 4 and the biomimetic photonic crystal powder prepared in Preparation Example 1, with a mass ratio of 2:1. Place the mixed powder in a high-speed mixer, heat it to 80°C, and spray the coupling agent solution at a speed of 1000 r / min. The amount of coupling agent solution is 0.5% of the total mass of the powder. Stir continuously for 10 minutes, and then dry it at 100°C for 2 hours to obtain the modified composite functional filler.

[0069] S20. Weigh 95 parts of TR-90 resin and 4.7 parts of modified composite functional filler and mix them. Add the mixture to a twin-screw extruder for melt extrusion granulation. Set the temperature of the first zone of the extruder to 230℃, the temperature of the second zone to 240℃, the temperature of the third zone to 250℃, the temperature of the die head to 245℃, and the screw speed to 200r / min. After water cooling and pelletizing, composite granules are obtained.

[0070] S30. The composite granules are dried in a vacuum oven at 80°C for 4 hours, and then injected into an injection molding machine for injection molding. The barrel temperature is set to 240°C at the rear, 250°C at the middle, and 260°C at the front. The mold temperature is set to 60°C, the injection pressure to 80MPa, the holding pressure to 60MPa, the holding time to 5 seconds, and the cooling time to 15 seconds. The semi-finished product containing the frame, temples, and nose pads is demolded and then subjected to tumbling and polishing for 24 hours to obtain the frame.

[0071] S40. Add 0.05% by mass of a 420nm ultraviolet absorber (UV420 absorber) to the MR-8 optical resin monomer, inject into a glass mold, and cure for 20 hours by programmed temperature increase from 30℃ to 120℃. Demold to obtain the blue light blocking substrate; after cleaning the substrate, place it in a vacuum coating machine, and when the vacuum degree reaches 2.0×10 -3At Pa, five antireflective films of zirconium dioxide (ZrO2) and silicon dioxide (SiO2) are alternately deposited, and a fluorine-containing hydrophobic film is deposited on the outermost layer to obtain the lens;

[0072] S50. After the prepared lens is shaped, it is embedded into the prepared frame, and the temples are connected by metal hinges. The nose pads are installed to complete the assembly of the finished product.

[0073] Example 2:

[0074] This embodiment provides a method for preparing health-functional glasses based on a biophotonic crystal composite system, including the following steps:

[0075] S10. Prepare a 1.5% KH-570 ethanol aqueous solution (ethanol concentration 95%) and let it stand for hydrolysis for 20 minutes. Weigh the natural composite mineral powder obtained in Preparation Example 5 and the biomimetic biophotonic crystal powder obtained in Preparation Example 2, with a mass ratio of 2.5:1. Place the mixed powder in a high-speed mixer, heat it to 90°C, and spray the coupling agent solution at a speed of 1250 r / min. The amount of coupling agent solution is 1.0% of the total mass of the powder. Stir continuously for 15 minutes, and then dry it at 105°C for 3 hours to obtain the modified composite functional filler.

[0076] S20. Weigh 100 parts of TR-90 resin and 5.0 parts of modified composite functional filler and mix them. Add the mixture to a twin-screw extruder for melt extrusion granulation. Set the temperature of the first zone of the extruder to 235℃, the temperature of the second zone to 245℃, the temperature of the third zone to 255℃, the temperature of the die head to 250℃, and the screw speed to 280r / min. After water cooling and pelletizing, composite granules are obtained.

[0077] S30. The composite granules are dried in a vacuum oven at 85°C for 5 hours, and then injected into an injection molding machine for injection molding. The barrel temperature is set to 245°C at the rear, 255°C at the middle, and 265°C at the front. The mold temperature is 70°C, the injection pressure is 100MPa, the holding pressure is 75MPa, the holding time is 7 seconds, and the cooling time is 20 seconds. The semi-finished product containing the frame, temples, and nose pads is demolded and then subjected to tumbling and polishing for 18 hours to obtain the frame.

[0078] S40. Add 0.08% (w / w) of UV420 absorber to MR-8 optical resin monomer, inject into a glass mold, and cure for 22 hours by programmed temperature increase from 30℃ to 120℃. Demold to obtain anti-blue light substrate; after cleaning the substrate, place it in a vacuum coating machine, and when the vacuum degree reaches 3.0×10... -3 At Pa, six antireflective films of ZrO2 and SiO2 are alternately deposited by vapor deposition, and a fluorine-containing hydrophobic film is deposited on the outermost layer to obtain the lens;

[0079] S50. After the prepared lens is shaped, it is embedded into the prepared frame, and the temples are connected by metal hinges. The nose pads are installed to complete the assembly of the finished product.

[0080] Example 3:

[0081] This embodiment provides a method for preparing health-functional glasses based on a biophotonic crystal composite system, including the following steps:

[0082] S10. Prepare a 2.0% KH-570 ethanol aqueous solution (ethanol concentration 95%) and let it stand for hydrolysis for 30 minutes. Weigh the natural composite mineral powder obtained in Preparation Example 6 and the biomimetic biophotonic crystal powder obtained in Preparation Example 3, with a mass ratio of 3:1. Place the mixed powder in a high-speed mixer, heat it to 100°C, and spray the coupling agent solution at a speed of 1500 r / min. The amount of coupling agent solution is 1.5% of the total mass of the powder. Stir continuously for 20 minutes, and then dry it at 110°C for 4 hours to obtain the modified composite functional filler.

[0083] S20. Weigh 105 parts of TR-90 resin and 5.2 parts of modified composite functional filler and mix them. Add the mixture to a twin-screw extruder for melt extrusion granulation. Set the temperature of the first zone of the extruder to 240℃, the temperature of the second zone to 250℃, the temperature of the third zone to 260℃, the temperature of the die head to 255℃, and the screw speed to 350r / min. After water cooling and pelletizing, composite granules are obtained.

[0084] S30. The composite granules are dried in a vacuum oven at 90°C for 6 hours, and then injected into an injection molding machine for injection molding. The barrel temperature is set to 250°C at the rear, 260°C at the middle, and 270°C at the front. The mold temperature is set to 80°C, the injection pressure to 120MPa, the holding pressure to 90MPa, the holding time to 10 seconds, and the cooling time to 25 seconds. The semi-finished product containing the frame, temples, and nose pads is demolded and then subjected to tumbling and polishing for 12 hours to obtain the frame.

[0085] S40. Add 0.1% (w / w) of UV420 absorber to MR-8 optical resin monomer, inject into a glass mold, and cure for 24 hours by programmed temperature increase from 30℃ to 120℃. Demold to obtain anti-blue light substrate; after cleaning the substrate, place it in a vacuum coating machine, and when the vacuum degree reaches 4.0×10... -3 At Pa, seven antireflective films of ZrO2 and SiO2 are alternately deposited by vapor deposition, and a fluorine-containing hydrophobic film is deposited on the outermost layer to obtain the lens;

[0086] S50. After the prepared lens is shaped, it is embedded into the prepared frame, and the temples are connected by metal hinges. The nose pads are installed to complete the assembly of the finished product.

[0087] Comparative Examples 1-5:

[0088] Comparative Example 1:

[0089] Compared with Example 2, the difference is that in step S10, the biomimetic biophotonic crystal powder prepared in Example 2 is replaced with an equal mass of natural composite mineral powder prepared in Example 5, so that the filler is composed entirely of natural composite mineral powder. All other parameters and steps are the same.

[0090] Comparative Example 2:

[0091] Compared with Example 2, the difference is that in step S10, the biomimetic biophotonic crystal powder obtained in Example 2 is replaced with an equal mass of commercially available ordinary α-alumina micro powder. The average D50 particle size of the alumina micro powder is 5 μm and it has a solid structure without periodic mesoporous characteristics. All other parameters and steps are the same.

[0092] Comparative Example 3:

[0093] Compared with Example 2, the difference is that in step S10, the natural composite mineral powder obtained in Preparation Example 5 is replaced with an equal mass of biomimetic biophotonic crystal powder obtained in Preparation Example 2, so that the filler is composed entirely of biomimetic biophotonic crystal powder. All other parameters and steps are the same.

[0094] Comparative Example 4:

[0095] Compared with Example 2, the difference is that in step S20, the amount of modified composite functional filler added is adjusted to 2.0% of the resin weight, while the other parameters and steps are the same.

[0096] Comparative Example 5:

[0097] Compared with Example 2, the difference is that in step S20, the amount of modified composite functional filler added is adjusted to 10.0% of the resin weight, while the other parameters and steps are the same.

[0098] Test Example 1-3:

[0099] Test Example 1: Mechanical Properties and Processing Adaptability Test

[0100] Experimental description:

[0101] This experiment aims to evaluate the mechanical properties of the prepared biomimetic biophotonic crystal composite material and its adaptability in actual processing. Since the introduction of inorganic fillers into the polymer matrix usually leads to a decrease in material toughness or a deterioration in processing fluidity, it is necessary to verify whether the composite material of this invention retains the original characteristics of TR90 resin, namely high elastic memory and fracture resistance, so as to meet the needs of long-term wear and repeated opening and closing of eyeglass frames.

[0102] Experimental steps:

[0103] The composite granules prepared in Examples 1 to 3, as well as the granules prepared in Comparative Examples 4 and 5, were selected as test samples. Each group of granules was injection molded into dumbbell-shaped tensile specimens conforming to ASTM D638 and impact specimens conforming to ASTM D256 under standard process conditions using a precision injection molding machine.

[0104] All specimens were conditioned for 48 hours at 23°C and 50% relative humidity to eliminate internal stress. Tensile strength and elongation at break were determined using a universal testing machine at a tensile rate of 50 mm / min. Five parallel specimens were tested in each group, and the average value was taken. Impact strength tests were performed on the notched specimens using a cantilever beam impact testing machine, and the energy absorbed per unit cross-sectional area when the specimen completely fractured was recorded.

[0105] Experimental data:

[0106] Table 1. Mechanical property test data

[0107] Sample group Tensile strength (MPa) <![CDATA[Notched impact strength (kJ / m 2 )]]> Elongation at break (%) Example 1 56.23 14.82 135.6 Example 2 58.47 14.15 128.4 Example 3 60.12 13.54 120.9 Comparative Example 4 54.08 15.48 142.1 Comparative Example 5 65.41 6.12 45.3

[0108] Experimental conclusion:

[0109] Analysis of the data in Table 1 shows that the composite materials prepared in Examples 1 to 3 exhibit a good balance of mechanical properties. Data from Example 2 shows that its tensile strength reaches 58.47 MPa, while the elongation at break remains at 128.4%, and the notched impact strength is 14.15 kJ / m². 2 This result demonstrates that the present invention, by adding surface-modified composite functional fillers to the TR90 resin matrix, improves the rigidity and strength of the material without causing a significant loss of toughness.

[0110] The mechanism behind these properties lies in two aspects. First, the silane coupling agent KH570 forms an organic graft layer on the surface of inorganic minerals and photonic crystals, enhancing the interfacial bonding between the filler and the organic resin matrix and reducing the generation of microscopic defects. Second, the unique mesoporous structure of the biomimetic photonic crystal allows molten resin molecular chains to penetrate into the pores. This physical anchoring effect and microscopic interlocking structure effectively transfer external stress and hinder the expansion of crazes. The data from Comparative Example 5 conversely demonstrates the importance of controlling the filler addition amount. When the addition amount is too high, filler agglomeration leads to stress concentration, making the material brittle. The system in the example successfully found a balance between reinforcement and toughening, meeting the stringent mechanical performance requirements of eyeglass frames.

[0111] Test Example 2: Optical Diffuse Reflection and Soft Light Performance Test

[0112] Experimental description:

[0113] This experiment aims to verify the physical control capability of the biomimetic photonic crystal structure introduced in this invention over incident light. Traditional eyeglass frame materials typically exhibit high gloss or simple specular reflection, easily causing glare. This invention utilizes Bragg diffraction and the photonic bandgap effect generated by the periodic mesoporous structure of the photonic crystal to attempt to achieve a soft, diffuse reflection effect of the material itself without using a matte coating. By comparing the differences in optical parameters of filler systems with different microstructures, the specific contribution of this biomimetic structure to improving visual comfort and aesthetic texture is evaluated.

[0114] Experimental steps:

[0115] The frame materials prepared in Examples 1 to 3, as well as the materials prepared in Comparative Examples 1 and 2, were selected as test samples. To eliminate the interference of surface machining marks on optical testing, all sample surfaces underwent standardized tumbling and fine polishing treatments.

[0116] A high-precision spectrophotometer equipped with an integrating sphere was used to measure the reflectance spectrum of the sample in the visible light band, and the diffuse reflectance value was recorded at a wavelength of 550 nanometers, which is more sensitive to human vision.

[0117] The specular gloss of the sample surface was measured using a precision gloss meter at a geometric angle of incidence of 60 degrees. Five different regions of each sample were randomly selected for measurement and the arithmetic mean was calculated to evaluate the extinction properties of the material surface.

[0118] Experimental data:

[0119] Table 2. Results of optical diffuse reflectance and gloss test

[0120] Sample group Diffuse reflectance at 550nm (%) 60° Gloss (GU) Example 1 42.4 18.6 Example 2 46.9 15.3 Example 3 48.1 12.7 Comparative Example 1 12.3 85.8 Comparative Example 2 22.4 65.2

[0121] Experimental conclusion:

[0122] Based on the test data analysis in Table 2, the samples from Examples 1 to 3 achieved the expected optical adjustment function. Taking Example 2 as an example, its diffuse reflectance at 550 nm reached 46.9%, and its gloss decreased to 15.3 GU, exhibiting a soft light state without glare. This optical characteristic directly originates from the regular periodic mesoporous structure inside the biomimetic biophotonic crystal. When light is incident on the surface of the resin matrix containing this crystal, the periodic structure induces multiple light scattering and Bragg diffraction effects, converting the incident light in a single direction into diffuse light in various directions, thereby macroscopically reducing the specular gloss.

[0123] The comparative results further confirm the physical mechanism by which microstructure determines macroscopic performance. Although Comparative Example 2 used alumina micropowder with a similar chemical composition, its solid, disordered microstructure prevented the generation of a photonic bandgap effect, resulting in a diffuse reflectance of only 22.4%, failing to achieve the soft-light effect described in the examples. This demonstrates that the core technical advantage of this invention lies in constructing specific micro / nano structures to physically regulate light, rather than simply relying on the chemical composition of the materials, thereby endowing the eyeglass frames with unique visual comfort.

[0124] Test Example 3: Far-infrared and negative ion health function test

[0125] Experimental description:

[0126] This experiment aims to quantitatively evaluate the actual efficacy of the health-functional glasses prepared according to this invention in terms of far-infrared emission and negative ion release. The natural composite mineral powders such as tourmaline, maifanite, and deep-sea carbon mud introduced in this scheme have piezoelectric and pyroelectric effects, which theoretically can absorb environmental heat energy and convert it into far-infrared radiation that is beneficial to the human body, while ionizing water molecules in the air to generate negative oxygen ions.

[0127] However, when these mineral powders are incorporated into a polymer resin matrix, their active surfaces may be coated by the polymer, leading to a decrease in functionality. Therefore, it is necessary to test and verify whether the composite material retains sufficient health and therapeutic functions after molding, and to determine the effective addition amount that meets the functional threshold.

[0128] Experimental steps:

[0129] The finished product samples prepared in Examples 1 to 3, as well as the samples in Comparative Examples 3 and 4, were selected as test objects. To ensure the accuracy of the test results, all samples were placed in a dust-free, temperature- and humidity-controlled laboratory environment for 24 hours before testing. The ambient temperature was controlled at 25 degrees Celsius and the relative humidity was controlled at 60%.

[0130] For far-infrared performance, the normal total emissivity of the samples was measured using an infrared emissivity meter in the 8-14 micrometer wavelength range, according to the GBT7287-2008 standard. For negative ion release performance, an ITC201A high-precision air negative ion meter was used. The samples were placed in an electromagnetically shielded sealed test chamber, and the sample surface was excited by static friction. After the reading stabilized, the negative ion concentration was recorded. Each group of samples was tested five times, and the average value was taken.

[0131] Experimental data:

[0132] Table 3. Test results of far-infrared emissivity and negative ion release for each group of samples.

[0133] Sample group Far-infrared emissivity (%) <![CDATA[Negative ion release amount (ions / cm 3 )]]> Example 1 0.86 1142 Example 2 0.89 1385 Example 3 0.92 1518 Comparative Example 3 0.14 42 Comparative Example 4 0.63 315

[0134] Experimental conclusion:

[0135] The test data in Table 3 show that the samples from Examples 1 to 3 all met the requirements for functional materials. Specifically, Example 2 had a far-infrared emissivity of 0.89 and a negative ion release of 1385 ions / cm³. 3 This demonstrates its potential for enhancing health and wellness. This confirms that the mineral compounding scheme used in this invention retains its physical activity even after modification and processing. When polar mineral crystals such as tourmaline are excited by weak external energy or subjected to friction, the spontaneous polarization effect within their crystal lattice creates a micro-electric field, effectively radiating far-infrared rays and ionizing the surrounding air.

[0136] Meanwhile, the experimental data also revealed the necessary conditions for the functional filler to form an effective network in the matrix. Comparative analysis with Comparative Example 4 showed that when the filler content was too low, the mineral particles were excessively isolated by the resin matrix, failing to form a synergistic effect, resulting in a significant decrease in far-infrared emissivity and negative ion release. The formulation ratio in the examples ensured that the functional filler had sufficient bulk density in the resin matrix, thereby ensuring the continuity of the energy transfer channels and enabling the finished eyeglass frame to stably perform its function of improving the ocular microenvironment.

Claims

1. Health-functional glasses based on a biophotonic crystal composite system, characterized in that, Includes a frame and lenses embedded in the frame; The frame is made by injection molding from raw materials comprising the following parts by weight: TR-90 resin: 95-105 parts; Modified composite functional filler: 4.7-5.2 parts; The modified composite functional filler is prepared from natural composite mineral powder, biomimetic photonic crystal powder and silane coupling agent. The mass ratio of the natural composite mineral powder to the biomimetic photonic crystal powder is 2:1-3:1; The amount of the silane coupling agent is 0.5%-1.5% of the total mass of the natural composite mineral powder and the biomimetic photonic crystal powder.

2. The health-functional glasses based on a biophotonic crystal composite system according to claim 1, characterized in that, The natural composite mineral powder is made from raw materials comprising the following parts by weight: Tourmaline: 2-4 parts; Maifan stone: 1-3 servings; Qibing Stone Raw Ore: 1-3 parts; Deep-sea carbon mud: 0.5-1.5 parts.

3. The health-functional glasses based on a biophotonic crystal composite system according to claim 1, characterized in that, The biomimetic photonic crystal powder is a rare earth-doped alumina-based porous material, and the biomimetic photonic crystal powder has a periodic mesoporous structure formed after removing the polystyrene microsphere template. The rare earth doping element in the rare earth-doped alumina-based porous material is selected from one or more of cerium, europium, and terbium.

4. The health-functional glasses based on a biophotonic crystal composite system according to claim 3, characterized in that, The biomimetic photonic crystal powder is prepared by the following method: Aluminum-doped sol was prepared using aluminum isopropoxide as the aluminum source and one or more of cerium nitrate hexahydrate, europium nitrate hexahydrate, or terbium nitrate hexahydrate as the doping source. A polystyrene microsphere emulsion with a particle size of 150nm-200nm was added to the doped aluminum sol as a template agent, and after ultrasonic dispersion, it was aged and dried to obtain a dry gel precursor. The dry gel precursor was calcined at 800℃-1000℃ for 2-4 hours to remove the polystyrene microsphere emulsion and crystallize it. After pulverization and classification, the biomimetic biophotonic crystal powder was obtained. The molar amount of the doping source is 1.0%-3.0% of the molar amount of the aluminum source.

5. The health-functional glasses based on a biophotonic crystal composite system according to claim 1, characterized in that, The silane coupling agent is γ-methacryloxypropyltrimethoxysilane; The average D50 particle size of the modified composite functional filler is 2μm-15μm.

6. The health-functional glasses based on a biophotonic crystal composite system according to claim 1, characterized in that, The lens includes a blue light blocking substrate and a coating layer; The blue light blocking substrate is cured from MR-8 optical resin with added ultraviolet absorber, wherein the amount of ultraviolet absorber added is 0.05%-0.1% of the mass of the MR-8 optical resin; The coating layer includes 5-7 layers of zirconium dioxide and silicon dioxide antireflective films alternately deposited on the surface of the blue light blocking substrate, and a fluorine-containing hydrophobic film located on the outermost layer of the coating layer.

7. A method for preparing health-functional glasses based on a biophotonic crystal composite system, characterized in that, The method for preparing health-functional glasses based on a biophotonic crystal composite system as described in any one of claims 1 to 6 includes the following steps: Natural composite mineral powder is mixed with biomimetic photonic crystal powder, heated, and then sprayed with a hydrolyzed silane coupling agent solution. After high-speed stirring and mixing, the mixture is dried to obtain a modified composite functional filler. TR-90 resin was mixed with the modified composite functional filler, and then melt-extruded and pelletized using a twin-screw extruder to obtain composite granules. After the composite granules are dried, they are injected into a mold using an injection molding machine. After demolding, a semi-finished mirror frame is obtained. The semi-finished mirror frame is then subjected to tumbling and polishing to obtain the mirror frame. MR-8 optical resin monomer with added ultraviolet absorber is injected into a glass mold and cured to obtain a blue light blocking substrate. After cleaning the blue light blocking substrate, a zirconium dioxide and silicon dioxide antireflective film and a fluorine-containing hydrophobic film are vacuum evaporated to obtain a lens. After the lens is shaped, it is embedded into the frame, and accessories are installed to obtain the health function glasses based on the biophotonic crystal composite system.

8. The method for preparing health-functional glasses based on a biophotonic crystal composite system according to claim 7, characterized in that, In the step of obtaining the modified composite functional filler, the heating temperature is 80℃-100℃; In the step of obtaining composite granules, the temperature of the melt extrusion is 230℃-260℃, and the process parameters of the twin-screw extruder are: zone 1 temperature 230℃-240℃, zone 2 temperature 240℃-250℃, zone 3 temperature 250℃-260℃, and die head temperature 245℃-255℃.

9. The method for preparing health-functional glasses based on a biophotonic crystal composite system according to claim 7, characterized in that, In the step of drying the composite granules, injecting them into a mold using an injection molding machine, demolding to obtain a semi-finished mirror frame, and then performing tumbling and polishing on the semi-finished mirror frame to obtain the mirror frame, the process parameters of the injection molding machine are: barrel rear section temperature 240℃-250℃, middle section temperature 250℃-260℃, front section temperature 260℃-270℃, mold temperature 60℃-80℃, and injection pressure 80MPa-120MPa.

10. The method for preparing health-functional glasses based on a biophotonic crystal composite system according to claim 7, characterized in that, In the steps of injecting the MR-8 optical resin monomer with the added ultraviolet absorber into a glass mold for curing, followed by cleaning and vacuum evaporation of the zirconium dioxide and silicon dioxide antireflective film and the fluorine-containing hydrophobic film to obtain the lens, the curing process employs a programmed temperature rise method, with a temperature range of 30℃-120℃ and a curing time of 20-24 hours; the vacuum degree during vacuum evaporation is 2.0 × 10⁻⁶. -3 Pa-4.0×10 -3 Pa.