A method for manufacturing a finished oxygen permeable contact lens

Abstract

The application discloses a preparation method of a light-oxygen contact lens, and belongs to the technical field of contact lenses and flexible wearable devices. A certain amount of a silicon-based hydrogel base is first injected into a contact lens mold for ultraviolet curing to form a central visual optical area of the contact lens, then a zero-dimensional heterojunction photocatalytic material after surface modification is mixed with the silicon-based hydrogel base, and then the mixture is injected into the contact lens mold for ultraviolet curing to form an outer ring photocatalytic functional area, and after demolding, soaking and edge grinding, the light-oxygen contact lens is obtained. The zero-dimensional heterojunction photocatalytic material is selected, the structure and appearance of the light-oxygen contact lens are optimized, the excellent self-oxygen performance of the light-oxygen contact lens is ensured, and the visual function of the central optical area of the contact lens is not affected by the placement of the heterojunction photocatalytic material, and the appearance is more beautiful and easier to accept. The application significantly improves the beauty, convenience, comfort and safety of wearing of the light-oxygen contact lens.

Description

Technical Field

[0001] This invention relates to the field of contact lenses and flexible wearable technology, specifically to a method for preparing a photo-oxygen-generating contact lens. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] There is no magic bullet for myopia prevention. Once you become nearsighted, you'll be stuck with eyeglasses for life. While convenient, eyeglasses have drawbacks such as being bulky and potentially causing nasal bridge collapse and deformation. Contact lenses (also known as corneal contact lenses) are lightweight, offer excellent visual results, and are aesthetically pleasing. With the continuous development and application of contact lenses, they will be able to replace eyeglasses and be widely used in vision correction, myopia treatment, artificial intelligence, wearable technology, and other fields.

[0004] The cornea is avascular, and its epithelial cells are metabolically active, deriving 80% of its oxygen from the air. Wearing contact lenses prevents oxygen from directly reaching the cornea, leading to corneal hypoxia and potentially causing eye diseases. Photo-oxygenating contact lenses (Chinese patent ZL201911333162.6) absorb light and convert water into oxygen, offering ample light energy, extremely low water consumption, and no impact on the cornea's normal metabolic water requirements. This completely solves the problem of corneal hypoxia caused by contact lens wear, significantly improving the comfort and safety of contact lens wear. However, to achieve these complex functions, it is necessary to encapsulate flexible photocatalytic materials (electrodes) within the contact lens. While the application of flexible thin-film photocatalytic materials (electrodes) has facilitated the realization of photo-oxygenating contact lenses, a suitable production method is lacking. Directly encapsulating flexible thin-film photocatalytic materials (electrodes) presents challenges in determining their position and shape during the transition from a planar to a spherical surface, leading to misalignment issues that affect visual function and result in poor device consistency. Secondly, the embedded flexible thin-film photocatalytic material (electrode) does not match the mechanical modulus of the contact lens, which significantly affects the stability of the lens and wearing comfort (such as foreign body sensation, congestion, fatigue, and secretions). Using a zero-dimensional heterojunction photocatalytic material can avoid these problems.

[0005] Photocatalytic oxygen-generating contact lenses are composed of photocatalytic materials (electrodes) and hydrogel. Compared with traditional contact lenses, they have a more complex structure, involving a large variety and number of materials. Since they are in prolonged contact with the eye during use, the comfort, convenience, and safety of photocatalytic oxygen-generating contact lenses are key factors in their acceptance by consumers. In particular, wearing safety is directly related to the user's health and life, and therefore receives significant attention. Therefore, providing a new method for manufacturing photocatalytic oxygen-generating contact lenses is crucial, forming the basis for aesthetics, convenience, comfort, and safety. This patent addresses the complex structure of existing photocatalytic oxygen-generating contact lenses by inventing a novel manufacturing method. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for preparing photo-oxygen-generating contact lenses. This method utilizes a zero-dimensional heterojunction photocatalytic material, avoiding the problems of difficult-to-determine position and shape, misalignment, and poor device consistency that often occur when flexible thin-film photocatalytic materials transition from a planar to a spherical surface. This method is suitable for contact lenses made of polymethyl methacrylate hydrogels, silicone-based hydrogels, etc., and features simple equipment, convenient operation, low cost, and high reliability. The resulting photo-oxygen-generating contact lenses are aesthetically pleasing and readily accepted. The zero-dimensional heterojunction photocatalytic material exhibits excellent mechanical modulus matching with the contact lens matrix, ensuring comfortable, convenient, and safe wear. The photo-oxygen-generating contact lenses constructed using this invention allow for precise control of both the visual optical region and the photocatalytic functional region, particularly the color control of the photocatalytic functional region, thus meeting personalized needs.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A method for preparing photo-oxygen-generating contact lenses involves first preparing a zero-dimensional heterojunction photocatalytic material and surface modification using a silane coupling agent; weighing and mixing end-capped polydimethylsiloxane monomer (10.0–30.0 wt%), hydrophilic monomer (45.0–80.0 wt%), crosslinking agent (1.0–6.0 wt%), and initiator (0.5–2.0 wt%) according to their weight percentages to obtain a silicone-based hydrogel matrix; dripping 1–4 μL of the silicone-based hydrogel matrix into an outer mold of the contact lens, placing an inner mold inside, and curing under ultraviolet light for 10–30 minutes. Separate the inner and outer molds; mix the surface-modified zero-dimensional heterojunction photocatalytic material with the silicon-based hydrogel matrix at a ratio of 0.2–5.0 wt% to form a composite silicon-based hydrogel matrix; drop 5–15 μL of the composite silicon-based hydrogel matrix into the outer mold of the contact lens, place the inner mold inside, and cure under ultraviolet light for 10–30 minutes, then separate the inner and outer molds; remove the cured contact lens from the inner mold, and soak it in ethanol and deionized water in sequence to extract and remove unpolymerized monomers and oligomers from the lens; after edge grinding, immerse it in physiological saline for equilibration to obtain the photo-oxygen-generating contact lens.

[0009] Preferably, the zero-dimensional heterojunction photocatalytic material is constructed from photocatalytic materials with excellent biocompatibility, such as gold, platinum, iron oxide, copper oxide, copper aluminate, zinc oxide, titanium dioxide, carbon nitride, etc.

[0010] Furthermore, the end-capped polysiloxane monomer includes one or any combination of monomethyl methacrylate end-capped polysiloxane monomer, dimethyl methacrylate end-capped polysiloxane monomer, and vinyl end-capped dimethyl polysiloxane, in a mass ratio of 10.0 to 30.0 wt%.

[0011] Furthermore, the hydrophilic monomer is one or any combination of methyl methacrylate, N-vinyl-N-methylacetamide, N,N-dimethylacrylamide, and N-vinylpyrrolidone, in a mass ratio of 45.0 to 80.0 wt%.

[0012] Preferably, the methyl methacrylate contains at least 50 wt% of the hydrophilic monomer.

[0013] Furthermore, the crosslinking agent includes one or any combination of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triallyl isocyanurate, and vinyl methacrylate, in a mass ratio of 1.0 to 6.0 wt%.

[0014] Preferably, the proportion of ethylene glycol dimethacrylate is not less than 40 wt%.

[0015] Further, the initiator is one or any combination of azobisisobutyronitrile, benzoyl peroxide, azobisisobutyronitrile, and 2-hydroxy-2-methyl-1-phenyl-1-propanone, with a mass ratio of 0.5 to 2.0 wt%.

[0016] The beneficial effects obtained by this invention are as follows:

[0017] 1. This invention involves incorporating a zero-dimensional heterojunction photocatalytic material into a silicon-based hydrogel matrix and effectively separating the visual optical region and the photocatalytic functional region through a two-step polymerization method, ultimately obtaining a photo-oxygen-generating contact lens that does not affect visual function. Using the above technical solution, the preparation method of the photo-oxygen-generating contact lens has advantages such as simple equipment, convenient operation, and low cost. The constructed photo-oxygen-generating contact lens allows for precise control of the visual optical region and the photocatalytic functional region, especially the color control of the photocatalytic functional region, which can meet personalized needs.

[0018] 2. This invention is suitable for various contact lens matrix materials such as polymethyl methacrylate hydrogel and silicone-based hydrogel. The equipment is simple, easy to operate, low in cost, and highly reliable.

[0019] 3. This invention can adjust the size of the opto-optical region and the photocatalytic functional region of the photo-oxygen-generating contact lens by adjusting the amount of matrix injection, and can also adjust the color of the photocatalytic functional region by selecting zero-dimensional heterojunction photocatalytic materials. The constructed photo-oxygen-generating contact lenses are aesthetically pleasing, easy to accept, and meet personalized needs.

[0020] 4. The zero-dimensional heterojunction photocatalytic material selected in this invention has excellent mechanical matching with the contact lens matrix, making the photo-oxygen-generating contact lenses comfortable, convenient, and safe to wear.

[0021] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, the following describes the preferred embodiment in detail with reference to the accompanying drawings. Attached Figure Description

[0022] Figure 1 Schematic diagram of the fabrication process for photo-oxygen-generating contact lenses.

[0023] Figure 2 Scanning electron microscope (SEM) images of gold-loaded iron oxide nanoparticles (a), cured photo-oxygen-generating contact lenses (b), and soaked photo-oxygen-generating contact lenses (c).

[0024] Figure 3 UV-Vis diffuse reflectance spectrum of gold-loaded iron oxide nanoparticles

[0025] Figure 4 Visible light absorption spectra of the visual optical region and photocatalytic functional region of the photo-oxygen-generating contact lens loaded with gold nanoparticles and iron oxide nanoparticles.

[0026] Figure 5 Tensile stress-strain diagrams of silicon-based hydrogels composed of different zero-dimensional heterojunction photocatalytic materials

[0027] Figure 6 Visible transmittance diagrams of photocatalytic functional regions in different light-generating oxygen contact lenses

[0028] Figure 7 Visible light absorption spectra of visual optical regions and photocatalytic functional regions of different photo-oxygen-generating contact lenses

[0029] Figure 8 Photos of photo-oxygen-generating contact lenses prepared with different zero-dimensional heterojunction photocatalytic materials after curing and immersion. Detailed Implementation Plan

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0031] Example 1:

[0032] First, iron oxide nanoparticles with gold nanoparticles loaded on the surface were prepared [material preparation can be found in Q. Lin, et al. Mater. Chem. Phy. 307 (2023) 128173], which is a zero-dimensional heterojunction photocatalytic material, and the surface was modified with silane coupling agent (KH550);

[0033] Methyl methacrylate-terminated polysiloxane monomer was selected as the terminator for polydimethylsiloxane monomer; methyl methacrylate (70 wt%), N,N-dimethylacrylamide (10 wt%), and N-vinylpyrrolidone (20 wt%) were uniformly mixed to form a hydrophilic monomer; ethylene glycol dimethacrylate (80 wt%) and polyethylene glycol dimethacrylate (20 wt%) were mixed to form a crosslinking agent; and azobisisobutyronitrile (75 wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (25 wt%) were mixed to form an initiator.

[0034] Weigh the above-mentioned end-capped polydimethylsiloxane monomer (16.0 wt%), hydrophilic monomer (79.0 wt%), crosslinking agent (4.0 wt%), and initiator (1.0 wt%) according to their weight, mix them evenly, and obtain a silicone-based hydrogel matrix; drop 3 μL of the silicone-based hydrogel matrix into the outer mold of the contact lens, and place it into the inner mold (e.g., Figure 1 As shown, the photocatalyst material was cured by UV light (365nm, 30W) for 12 minutes, and the inner and outer molds were separated. The surface-modified zero-dimensional heterojunction photocatalyst material was mixed with the silicon-based hydrogel matrix at a ratio of 2.0wt% to form a composite silicon-based hydrogel matrix. 12μL of the composite was dropped into the outer mold of the contact lens, and the inner mold was placed in it. The lens was then irradiated with UV light for 25 minutes, and the inner and outer molds were separated. The contact lens was removed from the inner mold and soaked in ethanol and deionized water in sequence to extract and remove unpolymerized monomers and oligomers from the lens. After edge grinding, the lens was immersed in physiological saline for equilibration to obtain the photo-oxygen-generating contact lens.

[0035] The surface morphology of gold-loaded iron oxide nanoparticles was observed using scanning electron microscopy. Figure 2 a) Gold nanoparticles were successfully loaded onto the surface of the nano-iron oxide particles. The surface plasmon resonance effect of the gold nanoparticles can enhance the visible light absorption performance of the photocatalytic material and improve its photo-oxygen generation capacity. Furthermore, compared to fiber (one-dimensional) or sheet-like (two-dimensional) photocatalytic materials, being zero-dimensional materials (nanoparticles), they will not puncture the silicon-based hydrogel matrix under external force, exhibiting better mechanical stability and mechanical adaptability. The nano-iron oxide particles are red, and the central optical region of the cured photo-oxygen generation contact lenses is transparent. Figure 2 (b) The photocatalytic functional area appears red. After soaking, the water absorption volume of the photo-oxygen-generating contact lenses increases ( Figure 2c) The central visual optical region is transparent, allowing the JIT (applicant's initials) logo on the back to be clearly seen without affecting visual function; the color of the photocatalytic functional region can enrich the true eye color, producing different appearance effects, making the eyes appear larger or changing the eye color. This embodiment successfully prepared a photo-oxygen-generating contact lens according to the method of the present invention.

[0036] Example 2:

[0037] First, iron oxide nanoparticles with gold nanoparticles loaded on their surface were prepared, i.e., zero-dimensional heterojunction photocatalytic materials, and their surfaces were modified with a silane coupling agent (KH550). Methyl methacrylate-terminated polysiloxane monomer (60 wt%) and vinyl-terminated dimethyl polysiloxane (40 wt%) were uniformly mixed to form a terminated polydimethyl siloxane monomer. Methyl methacrylate (60 wt%), N,N-dimethylacrylamide (20 wt%), and N-vinylpyrrolidone (20 wt%) were uniformly mixed to form a hydrophilic monomer. Ethylene glycol dimethacrylate (80 wt%) and polyethylene glycol dimethacrylate (20 wt%) were mixed to form a crosslinking agent. Azobisisobutyronitrile (80 wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (20 wt%) were mixed to form an initiator.

[0038] The capped polydimethylsiloxane monomer (18.0 wt%), hydrophilic monomer (76.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed and mixed evenly to obtain a silicone-based hydrogel matrix. 3 μL of the silicone-based hydrogel matrix was dropped into the outer mold of the contact lens, and the inner mold was placed in. The mixture was cured by UV light (365 nm, 30 W) for 10 minutes, and the inner and outer molds were separated. The surface-modified zero-dimensional heterojunction photocatalyst material was mixed evenly with the silicone-based hydrogel matrix at a ratio of 3.0 wt% to form a composite silicone-based hydrogel matrix. 12 μL of the composite was dropped into the outer mold of the contact lens, and the inner mold was placed in. The mixture was cured by UV light for 25 minutes, and the inner and outer molds were separated. The contact lens was removed from the inner mold and soaked in ethanol and deionized water in sequence to extract and remove unpolymerized monomers and oligomers from the lens. After edge grinding, the lens was immersed in physiological saline for equilibration to obtain a photo-oxygen-generating contact lens.

[0039] The UV-Vis diffuse reflectance spectrum of gold-loaded iron oxide nanoparticles is as follows: Figure 3 As shown, the gold-loaded iron oxide nanoparticles exhibit strong absorption in the visible light region, and the surface plasmon resonance effect of the gold nanoparticles causes a new absorption peak at 556 nm. Figure 4 The visible light absorption spectra of the visual optical region and photocatalytic functional region of this photo-oxygen-generating contact lens are shown. The visible light transmittance of the visual optical region is above 95%, and the curve is smooth, indicating good visual performance in the visual optical region. This is due to the light absorption characteristics of the iron oxide nanoparticles loaded with gold nanoparticles. Figure 3 The visible light transmittance of the photocatalytic functional region decreases (to approximately 70%), with a significant drop in visible light transmittance at 500–700 nm. If the photocatalytic material enters the visual optical region, it will severely affect the visual effect, potentially causing discoloration of observed objects. This invention effectively constructs both the visual optical region and the photocatalytic functional region through a two-step curing method, ensuring the visual effect of the photo-oxygen-generating contact lenses and making them more aesthetically pleasing.

[0040] Example 3:

[0041] First, nano-iron oxide (Au@α-Fe2O3), nano-zinc oxide / titanium dioxide (ZnO / TiO2), nano-graphitic carbon nitride (Au@g-C3N4), nano-zinc oxide / copper aluminate (ZnO / CuAl2O4), and nano-iron oxide / copper aluminate (α-Fe2O3 / CuAl2O4) loaded with gold nanoparticles were prepared, which are zero-dimensional heterojunction photocatalytic materials. The surfaces were then modified with a silane coupling agent (KH550).

[0042] A methyl methacrylate-terminated polysiloxane monomer (50 wt%) and a vinyl-terminated dimethyl polysiloxane monomer (50 wt%) were uniformly mixed to form a terminated polydimethyl siloxane monomer; a methyl methacrylate monomer (60 wt%), an N,N-dimethylacrylamide monomer (20 wt%), and an N-vinylpyrrolidone monomer (20 wt%) were uniformly mixed to form a hydrophilic monomer; an ethylene glycol dimethacrylate monomer (80 wt%) and a polyethylene glycol dimethacrylate monomer (20 wt%) were mixed to form a crosslinking agent; and an azobisisobutyronitrile monomer (80 wt%) and a 2-hydroxy-2-methyl-1-phenyl-1-propanone monomer (20 wt%) were mixed to form an initiator.

[0043] The end-capped polydimethylsiloxane monomer (20.0 wt%), hydrophilic monomer (74.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed and mixed evenly to obtain a silicone-based hydrogel matrix. 2 μL of the silicone-based hydrogel matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was cured by UV light (365 nm, 30 W) for 10 minutes, and the inner and outer molds were separated. A surface-modified zero-dimensional heterojunction photocatalyst material was mixed evenly with the silicone-based hydrogel matrix at a ratio of 1.0 wt% to form a composite silicone-based hydrogel matrix. 10 μL of this composite matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was irradiated by UV light for 25 minutes, and the inner and outer molds were separated. The contact lens was removed from the inner mold and successively soaked in ethanol and deionized water to extract and remove unpolymerized monomers and oligomers from the lens. After edge grinding, the lens was immersed in physiological saline for equilibration to obtain a photo-oxygen-generating contact lens.

[0044] The average thickness of the photo-oxygen-generating contact lenses was measured to be 86 μm. The oxygen permeability of photo-oxygen-generating contact lenses prepared with different zero-dimensional heterojunction photocatalytic materials was tested using an oxygen permeability meter. The results are shown in Table 1. The pure silicon-based hydrogel contact lens (No. 1) exhibited excellent oxygen permeability, with an oxygen permeability of approximately 116 Barrer / cm, but this still did not meet the requirements for long-term wear (Dk / t > 125 Barrer / cm). Under dark conditions, the oxygen permeability of different photo-oxygen-generating contact lenses was similar to that of the pure silicon-based hydrogel contact lens, indicating that the addition of 1.0 wt% zero-dimensional heterojunction photocatalytic material did not block the oxygen permeability channels of the silicon-based hydrogel. Under illumination, the oxygen permeability of the photo-oxygen-generating contact lenses significantly improved, meeting the requirements for long-term wear. This demonstrates that the present invention can effectively prepare photo-oxygen-generating contact lenses, significantly improving their oxygen permeability.

[0045] Table 1. Oxygen permeability of contact lenses with different light-generating oxygen systems.

[0046]

[0047] Example 4:

[0048] First, nano-graphite phase carbon nitride (Au@α-Fe2O3) loaded with gold nanoparticles, i.e., zero-dimensional heterojunction photocatalytic material, was prepared and its surface was modified with silane coupling agent (KH550). Methyl methacrylate-terminated polysiloxane monomer (50 wt%) and vinyl-terminated dimethyl polysiloxane (50 wt%) were uniformly mixed to form a terminated polydimethyl siloxane monomer. Methyl methacrylate (60 wt%), N,N-dimethylacrylamide (20 wt%) and N-vinylpyrrolidone (20 wt%) were uniformly mixed to form a hydrophilic monomer. Ethylene glycol dimethacrylate (80 wt%) and polyethylene glycol dimethacrylate (20 wt%) were mixed to form a crosslinking agent. Azobisisobutyronitrile (80 wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (20 wt%) were mixed to form an initiator. End-capped polydimethylsiloxane monomer (20.0 wt%), hydrophilic monomer (74.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed and mixed evenly to obtain a silicon-based hydrogel matrix. Surface-modified zero-dimensional heterojunction photocatalytic material (nanographitic carbon nitride loaded with gold nanoparticles, Au@α-Fe2O3) was mixed evenly with the silicon-based hydrogel matrix at ratios of 2.0 wt%, 5.0 wt%, and 10.0 wt% to form a composite silicon-based hydrogel matrix.

[0049] The silicone-based hydrogel matrix and the composite silicone-based hydrogel matrix were placed in a mechanical testing mold (20*10*1mm) and irradiated with ultraviolet light for 25 minutes. After removal from the mold, they were successively immersed in ethanol and deionized water to extract and remove unpolymerized monomers and oligomers from the lens. The mechanical properties of the silicone-based hydrogel and the composite silicone-based hydrogel were tested using a mechanical testing machine. The results are as follows: Figure 5 As shown, compared to silicon-based hydrogels, the silicon-based hydrogels composited with 2.0 wt% and 5.0 wt% of zero-dimensional heterojunction photocatalyst material exhibit consistent low tensile stress-strain curves. The tensile strength only begins to increase after the deformation reaches 15%, indicating that the composite of 2.0 wt% zero-dimensional heterojunction photocatalyst material does not affect the flexibility of contact lenses and makes them convenient to use. As the content of zero-dimensional heterojunction photocatalyst material increases to 10.0 wt%, the strength of the composite silicon-based hydrogel continuously improves, and a sudden change occurs in the low tensile stress-strain region, leading to a significant decrease in the flexibility of the composite silicon-based hydrogel. The results demonstrate that the composite of 5.0 wt% zero-dimensional heterojunction photocatalyst material in this invention does not affect the flexibility of contact lenses.

[0050] Example 5:

[0051] First, surface-loaded gold nanoparticles were prepared, including gold-coated iron oxide nanoparticles (Au@α-Fe2O3), zinc oxide / titanium dioxide nanoparticles (ZnO / TiO2), gold-coated graphitic carbon nitride nanoparticles (Au@g-C3N4), zinc oxide / copper aluminate nanoparticles (ZnO / CuAl2O4), and iron oxide / copper aluminate nanoparticles (α-Fe2O3 / CuAl2O4), i.e., zero-dimensional heterojunction photocatalytic materials. Surface modification was performed using a silane coupling agent (KH550). The polymers were then end-capped with methyl dimethacrylate. The siloxane monomer is a capped polydimethylsiloxane monomer; methyl methacrylate (65 wt%), N,N-dimethylacrylamide (20 wt%), and N-vinylpyrrolidone (15 wt%) are uniformly mixed to form a hydrophilic monomer; ethylene glycol dimethacrylate (80 wt%) and polyethylene glycol dimethacrylate (20 wt%) are mixed to form a crosslinking agent; and azobisisobutyronitrile (80 wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (20 wt%) are mixed to form an initiator. The capped polydimethylsiloxane monomer (20.0 wt%), hydrophilic monomer (74.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed and mixed evenly to obtain a silicone-based hydrogel matrix. 2 μL of the silicone-based hydrogel matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was cured by UV light (365 nm, 30 W) for 10 minutes, and the inner and outer molds were separated. A surface-modified zero-dimensional heterojunction photocatalyst material was mixed evenly with the silicone-based hydrogel matrix at a ratio of 2.0 wt% to form a composite silicone-based hydrogel matrix. 10 μL of this composite matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was irradiated by UV light for 25 minutes, and the inner and outer molds were separated. The contact lens was removed from the inner mold and successively soaked in ethanol and deionized water to extract and remove unpolymerized monomers and oligomers from the lens. After edge grinding, the lens was immersed in physiological saline for equilibration to obtain a photo-oxygen-generating contact lens.

[0052] Figure 6 The visible light absorption spectra of different photocatalytic functional regions in photo-oxygen-generating contact lenses are shown. The visible light transmittance of the silicon-based hydrogel (i.e., the visual optical region of the photo-oxygen-generating contact lens) is above 95%. However, since different zero-dimensional heterojunction photocatalytic materials have their own visible light absorption characteristics, the visible light transmittance of the zero-dimensional heterojunction photocatalytic material composite silicon-based hydrogel is significantly reduced, meaning the visible light transmittance of the photocatalytic functional region of the photo-oxygen-generating contact lens is significantly decreased. Compared to silicon-based hydrogel, the absorption rate of the zero-dimensional heterojunction photocatalytic material composite silicon-based hydrogel changes across different wavelengths, leading to changes in the light entering the eye and poor visual performance. Therefore, this invention uses pure silicon-based hydrogel as the visual optical region and zero-dimensional heterojunction photocatalytic material composite silicon-based hydrogel as the photocatalytic functional region, ensuring both the visual performance and oxygen-generating function of the photo-oxygen-generating contact lens.

[0053] Example 6:

[0054] First, gold-loaded nano-graphitic carbon nitride (Au@g-C3N4), nano-zinc oxide / titanium dioxide (ZnO / TiO2), and nano-zinc oxide / copper aluminate (ZnO / CuAl2O4), i.e., zero-dimensional heterojunction photocatalytic materials, were prepared and surface-modified with a silane coupling agent (KH550). Methyl methacrylate-terminated polysiloxane monomers were used as the end-terminated polydimethylsiloxane monomers. Methyl methacrylate (65wt%), N,N-dimethylacrylamide (20wt%), and N-vinylpyrrolidone (15wt%) were uniformly mixed to form a hydrophilic monomer. Ethylene glycol dimethacrylate (70wt%) and polyethylene glycol dimethacrylate (30wt%) were mixed to form a crosslinking agent. Azobisisobutyronitrile (75wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (25wt%) were mixed to form an initiator. End-capped polydimethylsiloxane monomer (20.0 wt%), hydrophilic monomer (74.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed and mixed evenly to obtain a silicone-based hydrogel matrix. 3 μL of the silicone-based hydrogel matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was cured by UV light (365 nm, 30 W) for 10 minutes, and the inner and outer molds were separated. A surface-modified zero-dimensional heterojunction photocatalyst material was mixed evenly with the silicone-based hydrogel matrix at a ratio of 2.0 wt% to form a composite silicone-based hydrogel matrix. 11 μL of this composite was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was cured by UV light for 25 minutes, and the inner and outer molds were separated. The final product was then photographed. Figure 7 a, b, c; Remove the contact lenses from the inner mold, and soak them sequentially in ethanol and deionized water to extract and remove unpolymerized monomers and oligomers from the lenses; after edge grinding, equilibrate them in physiological saline to obtain photo-oxygen-generating contact lenses, and then photograph them. Figure 7 d, e, f.

[0055] Different zero-dimensional heterojunction photocatalytic materials exhibit different colors. For example, gold-loaded nano-graphitic carbon nitride (Au@g-C3N4), nano-zinc oxide / titanium dioxide (ZnO / TiO2), and nano-zinc oxide / copper aluminate (ZnO / CuAl2O4) appear pale yellow, titanium white, and milky white, respectively. Au@g-C3N4 photocatalytic oxygen-generating contact lenses (…) Figure 7 a and d), ZnO / TiO2 photo-oxygen-generating contact lenses ( Figure 7 b and e) and ZnO / CuAl2O4 photo-oxygen-generating contact lenses ( Figure 7 The photocatalytic functional regions (c) and (f) exhibit different colors, while the visual optical functional region remains highly transparent. Therefore, by selectively adjusting the color of the photocatalytic functional region using zero-dimensional heterojunction photocatalytic materials, the constructed photo-oxygen-generating contact lenses are aesthetically pleasing, readily accepted, and meet individual needs.

[0056] Example 7:

[0057] First, surface-loaded gold nanoparticles of iron oxide (Au@α-Fe2O3, D=30nm) and gold-loaded copper silicate / copper aluminate nanoparticles (Au@Cu2SiO3 / CuAl2O4, D=60nm) were prepared, namely zero-dimensional heterojunction photocatalytic materials, and surface modified with silane coupling agent (KH550). Methyl methacrylate-terminated polysiloxane monomers were used as end-terminated polydimethylsiloxane monomers. Methyl methacrylate (65wt%), N,N-dimethylacrylamide (20wt%), and N-vinylpyrrolidone (15wt%) were uniformly mixed to form hydrophilic monomers. Ethylene glycol dimethacrylate (70wt%) and polyethylene glycol dimethacrylate (30wt%) were mixed to form crosslinking agents. Azobisisobutyronitrile (75wt%) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (25wt%) were mixed to form initiators. The capped polydimethylsiloxane monomer (20.0 wt%), hydrophilic monomer (74.0 wt%), crosslinking agent (5.0 wt%), and initiator (1.0 wt%) were weighed according to weight and mixed evenly to obtain a silicon-based hydrogel matrix. 3 μL of the silicon-based hydrogel matrix was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was cured by UV light (365 nm, 30 W) for 10 minutes, and the inner and outer molds were separated. A surface-modified zero-dimensional heterojunction photocatalyst material was mixed evenly with the silicon-based hydrogel matrix at a ratio of 4.0 wt% to form a composite silicon-based hydrogel matrix. 11 μL of this composite was dropped into the outer mold of a contact lens, and the inner mold was placed inside. The mixture was irradiated by UV light for 25 minutes, and the inner and outer molds were separated. The results were then photographed. Figure 8 a, b; Remove the contact lenses from the inner mold, and soak them sequentially in ethanol and deionized water to extract and remove unpolymerized monomers and oligomers from the lenses; after edge grinding, equilibrate them in physiological saline to obtain photo-oxygen-generating contact lenses, and then photograph them, etc. Figure 8 c, d.

[0058] By employing zero-dimensional heterojunction photocatalytic materials with smaller particle sizes, the color of the photocatalytic functional region becomes more delicate. Figure 8 By utilizing the inherent colors of zero-dimensional heterojunction photocatalytic materials, such as the red of iron oxide and the blue of copper silicate, photo-oxygen-generating contact lenses have been achieved. Figure 8 The color adjustment of the photocatalytic functional region of ) compared with the above colors ( Figure 7 Red and blue are more aesthetically pleasing and easier to accept, and can be adjusted to better meet individual needs.

Claims

1. A method for preparing a photo-oxygen-generating contact lens, characterized in that, Includes the following steps: (1) A zero-dimensional heterojunction photocatalytic material was prepared and its surface was modified with a silane coupling agent to obtain a surface-modified zero-dimensional heterojunction photocatalytic material; this zero-dimensional heterojunction photocatalytic material can absorb light to convert water into oxygen. (2) Weigh 10.0~30.0wt% of end-capped polydimethylsiloxane monomer, 45.0~80.0wt% of hydrophilic monomer, 1.0~6.0wt% of crosslinking agent and 0.5~2.0wt% of initiator according to the weight percentage, mix them evenly, and obtain a silicone-based hydrogel matrix; (3) Drop 1~4 μL of the silicone hydrogel matrix from step (2) into the outer mold of the contact lens, place the inner mold in it, cure it under ultraviolet light for 10~30 minutes, and separate the inner and outer molds; (4) The surface-modified zero-dimensional heterojunction photocatalytic material of step (1) is mixed with the silicon-based hydrogel matrix of step (2) at a ratio of 0.2~5.0wt% to form a composite silicon-based hydrogel matrix; (5) Drop 5~15 μL of composite silicone hydrogel matrix into the outer mold of the contact lens, place the inner mold in it, irradiate with ultraviolet light for 10~30 minutes to cure, and then separate the inner and outer molds; (6) Remove the contact lens from the inner mold and soak it in ethanol and deionized water in sequence to extract and remove unpolymerized monomers and oligomers from the lens; (7) After edge grinding, the lenses are immersed in physiological saline to balance and produce light-generating oxygen contact lenses.

2. The method for preparing photo-oxygen-generating contact lenses according to claim 1, characterized in that, The terminated polysiloxane monomers include one or any combination of monomethyl methacrylate terminated polysiloxane monomers, dimethyl methacrylate terminated polysiloxane monomers, and vinyl terminated dimethyl polysiloxanes.

3. The method for preparing photo-oxygen-generating contact lenses according to claim 1, characterized in that, The hydrophilic monomer is one or any combination of methyl methacrylate, N-vinyl-N-methylacetamide, N,N-dimethylacrylamide, and N-vinylpyrrolidone.

4. The method for preparing photo-oxygen-generating contact lenses according to claim 1, characterized in that, The crosslinking agent includes one or any combination of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triallyl isocyanurate, and vinyl methacrylate.

5. The method for preparing a photo-oxygen-generating contact lens according to claim 1, characterized in that, The initiator is one or any combination of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptanenitrile, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

6. Photo-oxygen-generating contact lenses prepared by any one of claims 1 to 5.

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