A long-acting mirror frame material and glasses capable of suppressing the deposition of metal ions

Abstract

The present application belongs to the technical field of mirror frame materials, and particularly relates to a long-acting mirror frame material for inhibiting metal ion precipitation and glasses. The present application provides a long-acting mirror frame material for inhibiting metal ion precipitation, which comprises the following components: 80-120 parts of a metal matrix, 5-15 parts of an interface bonding agent, 20-40 parts of a charge repulsion polymer, 3-8 parts of a nano-composite antibacterial agent, 10-25 parts of reinforcing fibers, and 5-10 parts of an elasticity regulator. Through the synergistic effect of the interface bonding agent, the charge repulsion polymer, the zinc-loaded zeolite, the reinforcing fibers and the functional coating, a multiple protection mechanism from the interface to the surface is synergistically constructed, so that the long-acting inhibition of metal ion precipitation is achieved, and the mechanical strength, the antibacterial durability and the comprehensive performance of the material are significantly improved.

Description

Technical Field

[0001] This invention belongs to the field of eyeglass frame material technology, specifically relating to an eyeglass frame material and eyeglasses that effectively inhibit the precipitation of metal ions. Background Technology

[0002] In practical applications within the eyewear industry, allergies caused by metal frames have long been a problem that plagues both consumers and manufacturers.

[0003] In existing technologies, manufacturers typically address this issue using surface coatings or alloy modification. Surface coatings primarily involve applying organic coatings such as epoxy resin or polyurethane to a metal substrate, reducing metal-skin contact through physical barriers. However, the frequent opening and closing and adjustment of eyeglass frames during daily use can cause microcracks in the coating due to mechanical stress, especially at stress concentration points such as temple hinges and nose pads. The coating often peels off locally within months, losing its protective function. Another alloy modification method involves adjusting the metal composition to reduce the tendency for ion precipitation, such as adding cobalt or manganese to nickel alloys. However, this often leads to decreased material processing performance, making the frames prone to cracking during stamping, significantly reducing the yield rate. Simultaneously, the material's elastic modulus is also affected, causing the temple clamping force to gradually weaken during use.

[0004] In addition, some existing technologies attempt to use antibacterial ingredients, such as adding nano-silver ions or using antibacterial coatings. However, these solutions have significant limitations. Silver ions themselves easily form silver chloride precipitates in the presence of chloride ions, which not only reduces the antibacterial effect but may also cause the coating to become cloudy, affecting the appearance of the frame. More importantly, these antibacterial ingredients have limited adhesion to the metal substrate and will gradually be lost under long-term immersion in sweat, failing to provide lasting protection.

[0005] Existing solutions often focus on improving a single problem while neglecting the interrelationships between various performance indicators. For example, adding nano-silver to improve antibacterial properties may accelerate the electrochemical corrosion of metals, while increasing the degree of cross-linking to enhance coating adhesion may reduce the material's flexibility. These mutually restrictive factors make it difficult for existing technologies to achieve a balance between suppressing ion release, maintaining mechanical properties, and ensuring long-term stability. Therefore, there is a need to design a frame material and eyeglasses that can effectively suppress metal ion release over a long period. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, a frame material and eyeglasses that effectively suppress the precipitation of metal ions are provided.

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

[0008] A long-lasting frame material that inhibits the precipitation of metal ions, comprising the following components by weight: 80-120 parts of metal matrix, 5-15 parts of interface binder, 20-40 parts of charge repulsion polymer, 3-8 parts of nanocomposite antibacterial agent, 10-25 parts of reinforcing fiber, and 5-10 parts of elasticity modifier.

[0009] The preparation method of this eyeglass frame material includes the following steps: melting a metal matrix into an ingot, hot rolling it into a strip, cold rolling it to a thickness of 0.6-0.9 mm, uniformly coating an interface binder solution onto the surface of the metal matrix, and pre-curing it at 85-95℃ for 15-25 minutes; then mixing a charge-repellent polymer, a nanocomposite antibacterial agent, reinforcing fibers, and an elastic modifier, and melt-blending them at 190-210℃ using a twin-screw extruder, granulating them to obtain composite material particles, and coating the composite material particles onto the surface of the metal matrix treated with the interface binder by injection molding, which forms the polymer layer, wherein the injection molding temperature is 195-205℃, the mold pressure is 8-12 MPa, and the holding time is 15-25 seconds; then cooling and cutting to obtain the eyeglass frame material.

[0010] The interface binder is a silane coupling agent compound system, which is a compound mixture of silane coupling agent KH560 and silane coupling agent KH792, with a mass ratio of 2-4:1.

[0011] In the actual use of eyeglasses, the first problem we need to solve is the interfacial bonding between the metal matrix and the polymer layer. This application addresses this key technical challenge by using a composite system of silane coupling agents KH560 and KH792 as the interfacial bonding agent. These two coupling agents work synergistically; the epoxy groups provided by KH560 and the amino groups provided by KH792 form an interpenetrating network structure after hydrolysis. When this composite system is hydrolyzed under weakly acidic conditions, its silanol groups form stable siloxane bonds with the hydroxyl groups on the surface of the metal matrix, while the organic functional groups at the other end form strong chemical bonds with the subsequent charge-repellent polymer layer. This dual bonding mechanism establishes a strong molecular bridge between the metal matrix and the polymer layer, effectively preventing the generation and propagation of microcracks at the interface.

[0012] The specific steps for preparing the interface binder into a solution are as follows: dissolve the interface binder in an isopropanol aqueous solution to prepare a solution with a mass concentration of 6%-12%, adjust the pH value to 5.0-6.0 with lactic acid, hydrolyze the solution at 55-65℃ for 1.5-2.5 hours, add nano-alumina accounting for 0.3%-0.8% of the total mass of the interface binder, ultrasonically disperse the solution for 40-70 minutes, and cool it to room temperature to obtain the interface binder solution.

[0013] The metal matrix is ​​a low-ion precipitation titanium alloy, and its composition by weight percentage includes: titanium 92%-96%, aluminum 2.5%-4%, vanadium 0.5%-1.5%, and zirconium 0.1%-0.5%.

[0014] The charge-repellent polymer is a modified polyelectrolyte, and its preparation method includes the following steps: dissolving polydiallyldimethylammonium chloride as a polymer in deionized water to prepare a solution with a mass concentration of 12%-18%, adding glutaraldehyde at a mass of 8%-12% of the polymer, reacting at 50-60℃ for 2-3 hours, adding hydroxyethyl acrylate at a mass of 3%-6% of the polymer, and continuing the reaction for 1.5-2.5 hours. After the reaction is completed, cooling to room temperature, precipitating with ethanol, filtering, and vacuum drying are performed to obtain the modified polyelectrolyte, i.e., the charge-repellent polymer.

[0015] After ensuring interfacial stability, we need to address the migration of metal ions within the material. Even with good interfacial bonding, trace amounts of ions may still leach from the metal matrix under prolonged immersion in sweat. If these ions are not effectively blocked, they will gradually migrate to the material surface. Existing physical barrier methods lack effective interception capabilities for ions already embedded in the polymer layer. This application addresses this problem by introducing a charge-repellent polymer with a specific structure. This charge-repellent polymer is prepared using polydiallyldimethylammonium chloride as a matrix, crosslinked with glutaraldehyde, and functionalized with hydroxyethyl acrylate. This modification process retains a high density of quaternary ammonium salt cationic groups on the polymer molecular chain while forming a moderately crosslinked network structure. When metal ions attempt to migrate within the material, they are continuously subjected to the electrostatic repulsion generated by the fixed cations on the polymer chain. This charge-repellent effect significantly reduces the ion migration rate. Simultaneously, the moderate degree of crosslinking ensures that the polymer network possesses sufficient stability while maintaining a certain degree of swelling, facilitating the directional repulsion of ions under an electric field.

[0016] The nanocomposite antibacterial agent is zinc-loaded zeolite, and its preparation method includes the following steps: zeolite powder and zinc sulfate solution are mixed at a mass ratio of 1:3, and ion exchange reaction is carried out at 70 to 80°C for 3 to 4 hours. After the reaction is completed, the mixture is centrifuged, washed with deionized water until neutral, and vacuum dried at 90°C for 8 hours to obtain zinc-loaded zeolite, i.e., the zinc nanocomposite antibacterial agent.

[0017] Meanwhile, we also need to consider the problem of microbial corrosion during the use of materials. The frames are exposed to a warm and humid environment for extended periods, making them prone to bacterial and fungal growth. The acidic substances produced by microbial metabolism accelerate material aging and may form biofilms that promote ion migration. Existing silver-based antibacterial agents have drawbacks such as easy discoloration and potential for accelerated electrochemical corrosion. This application selects zinc-loaded zeolite as a nanocomposite antibacterial agent. Zeolite has a regular porous structure and a large specific surface area, allowing zinc ions to be stably fixed within its framework through ion exchange. This unique structure enables the slow release of zinc ions at a controllable rate, ensuring a long-lasting antibacterial effect while avoiding the problem of silver ions easily precipitating with chloride ions in sweat and becoming ineffective. Zinc ions interact with negatively charged groups on the cell membranes of microorganisms, disrupting their normal metabolic functions. Simultaneously, they can form competitive adsorption at metal deposition sites, further inhibiting the dissolution of harmful metal ions.

[0018] The reinforcing fiber is a polyimide fiber with a length of 80-150 micrometers and a diameter of 8-12 micrometers; the elastic modifier is a thermoplastic polyurethane with a melt index of 8-12 g / 10 min and a Shore hardness of 75A-85A.

[0019] The next challenge is balancing the mechanical properties of the materials. Eyeglass frames need sufficient strength to maintain their shape, while also requiring a certain degree of flexibility to ensure wearing comfort. Existing technologies often struggle to simultaneously meet the requirements of high strength and high flexibility. This application achieves this goal through the synergistic effect of polyimide fibers and thermoplastic polyurethane. The polyimide fibers are uniformly dispersed within the material, forming a three-dimensional network framework that provides excellent strength and rigidity. Meanwhile, the thermoplastic polyurethane, acting as an elastic modifier, effectively absorbs and disperses stress through the soft segments of its molecular chains, endowing the material with good flexibility and impact resistance. The synergistic effect of these two components allows the material to effectively bear stress through the fiber network and buffer energy through the deformation of the elastomer when subjected to external forces, achieving a balance between strength and flexibility.

[0020] A functional coating is also provided on the surface of the frame material, which comprises, by weight: 60-80 parts of water-based acrylic resin, 5-8 parts of nano-cerium oxide, 0.6-1.2 parts of leveling agent, and 0.4-0.9 parts of defoamer;

[0021] The preparation method of the functional coating solution includes: mixing water-based acrylic resin with nano-cerium oxide, ultrasonically dispersing for 25-35 minutes, adding leveling agent and defoamer, and stirring for 20-40 minutes to obtain the functional coating solution;

[0022] The functional coating solution is applied by spraying it onto the surface of the frame material and curing it at 85-95°C for 25-35 minutes.

[0023] Finally, we need to consider the durability of the material surface. The frame surface is in direct contact with the external environment, facing multiple challenges such as wear, scratches, and chemical corrosion. This application addresses this issue by applying a functional coating to the material surface. This functional coating is composed of a water-based acrylic resin and nano-cerium oxide. The nano-cerium oxide particles possess extremely high hardness and chemical stability; they are uniformly dispersed in the resin matrix, significantly improving the coating's wear resistance and scratch resistance. Simultaneously, the unique redox properties of nano-cerium oxide enable it to effectively scavenge free radicals in the environment and decompose organic acids in sweat, thereby slowing down the aging process of the coating. This dual effect of physical reinforcement and chemical protection ensures that the functional coating maintains its complete protective function during long-term use.

[0024] A type of eyeglasses has a frame made of a frame material that effectively inhibits the release of metal ions. The frame material of the eyeglasses of this application constructs a multi-layered comprehensive protection system encompassing interfacial bonding, ion blocking, antibacterial protection, mechanical reinforcement, and surface protection. Each layer works in concert to reinforce and enhance the others, achieving long-term inhibition of metal ion release while ensuring the safety and durability of the material during use. This systematic solution overcomes the limitations of single improvement measures in existing technologies.

[0025] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0026] 1. This invention achieves a multifunctional synergistic effect through the careful formulation of its components. The interfacial binder ensures the integrity of the overall structure, the charge-repellent polymer constructs an energy barrier for ion migration, the nanocomposite antibacterial agent provides biological protection, and the reinforcing fibers and elastic modifiers ensure a balance of mechanical properties. These functions promote each other and together constitute a comprehensive solution for long-term inhibition of metal ion precipitation.

[0027] 2. The charge-repulsive polymer used in this invention constructs a stable positive electric field on the surface and inside the material through the permanent positive charge carried on its molecular chains. When metal ions attempt to migrate outward, they are electrostatically repelled by this electric field. This charge-repulsion mechanism, combined with a physical barrier, forms a dual protection. The synergistic effect of the dense barrier established by the interfacial binder and the electrostatic field constructed by the charge-repulsive polymer significantly improves the effect of inhibiting ion precipitation from both physical isolation and electrochemical interception levels. The combination of the charge-repulsive polymer and the zinc-loaded zeolite antibacterial agent not only physically blocks ion migration but also fundamentally inhibits metal ion precipitation through the charge-repulsion mechanism, while maintaining the material's excellent mechanical properties and long-lasting antibacterial effect.

[0028] 3. The nanocomposite antibacterial agent of this invention uses zinc-loaded zeolite as the active ingredient, utilizing the porous structure of zeolite to achieve stable loading and controllable release of zinc ions. While inhibiting microbial growth, zinc ions also reduce the precipitation of other harmful metal ions through competitive inhibition. This design avoids the discoloration problem that may occur when using silver ions, providing more stable antibacterial performance.

[0029] 4. This invention utilizes the synergistic effect of polyimide fibers and thermoplastic polyurethane to form a rigid-flexible three-dimensional network structure within the material. This structure not only provides excellent mechanical support, ensuring sufficient strength and shape stability for the frame, but also endows the material with good toughness, effectively buffering mechanical stress during daily use and reducing damage to the protective layer caused by deformation.

[0030] 5. The functional coating of the present invention adopts a composite system of water-based acrylic resin and nano-cerium oxide. The introduction of nano-cerium oxide not only improves the wear resistance of the coating, but its unique redox properties can also effectively decompose the organic acid components in sweat, reduce the corrosion of the material surface by these acidic substances, and thus extend the protective life of the coating.

[0031] 6. The frame material of this invention establishes a strong chemical bond between the metal substrate and the polymer layer by introducing an interfacial binder. This bond not only improves interlayer adhesion, but more importantly, it forms a dense molecular barrier at the interface, effectively blocking the penetration of corrosive media such as sweat into the metal substrate, thereby reducing the dissolution driving force of metal ions from the source.

[0032] 7. This invention introduces nano-cerium oxide into a functional coating, which works synergistically with a charge-repellent polymer layer to achieve a passive protection mechanism focused on enhancing durability. The nano-cerium oxide particles possess extremely high hardness and chemical stability. When uniformly dispersed in water-based acrylic resin, they act as a fine reinforcing phase, effectively improving the macroscopic abrasion resistance and scratch resistance of the coating. This physically reduces the risk of the coating thinning or breaking due to daily wear.

[0033] 8. In this invention, nano-cerium oxide and the charge-repellent polymer layer together construct a more robust defense system. The charge-repellent polymer mainly prevents metal ions from migrating outward through electrostatic pressure, while the surface nano-cerium oxide maintains the integrity of the coating through physicochemical processes. When combined, even if the surface layer suffers extremely minor damage due to long-term use, the underlying charge-repellent function can still operate effectively, and the presence of nano-cerium oxide limits further damage to a certain extent, forming a functional complementarity and enhancement. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] In the specific embodiments of this application, the sources of various main raw materials are briefly described as follows:

[0036] Silane coupling agent KH560: purchased from Dongguan Shanyi Plastic Chemical Co., Ltd.

[0037] Silane coupling agent KH792: purchased from Nanjing Xuanhao New Material Technology Co., Ltd.

[0038] Polydiallyl ammonium chloride: purchased from Zhangjiagang Kaibao Environmental Protection Technology Co., Ltd.

[0039] Nano-cerium oxide, zinc sulfate, and glutaraldehyde: purchased from Sinopharm Chemical Reagent Co., Ltd.

[0040] Hydroxyethyl acrylate: Purchased from Shandong Jinyueyuan New Materials Co., Ltd.

[0041] Zeolite powder: purchased from Lingshou County Leixiang Mineral Products Processing Plant

[0042] Polyimide fiber: purchased from Changchun Gaoqi Polyimide Materials Co., Ltd.

[0043] Thermoplastic polyurethane: purchased from Shanghai Xuchun Chemical Technology Co., Ltd.

[0044] Water-based acrylic resin: purchased from Guangzhou Jiaxuan Chemical Co., Ltd.

[0045] Metal matrix: Purchased from Shenzhen Tianyue Hard Alloy Co., Ltd.

[0046] Nano-alumina: Purchased from Beijing Huawirui Chemical Technology Co., Ltd.

[0047] Leveling agent: purchased from Shanghai Puhao Chemical Co., Ltd.

[0048] Defoamer: Purchased from Henan Runquan Purification Materials Co., Ltd.

[0049] The technical solution of this application is as follows:

[0050] A long-lasting frame material that inhibits the precipitation of metal ions, comprising the following components by weight: 80-120 parts of metal matrix, 5-15 parts of interface binder, 20-40 parts of charge repulsion polymer, 3-8 parts of nanocomposite antibacterial agent, 10-25 parts of reinforcing fiber, and 5-10 parts of elasticity modifier.

[0051] The preparation method of this eyeglass frame material includes the following steps: melting a metal matrix into an ingot, hot rolling it into a strip, cold rolling it to a thickness of 0.6-0.9 mm, uniformly coating an interface binder solution onto the surface of the metal matrix, and pre-curing it at 85-95℃ for 15-25 minutes; then mixing a charge-repellent polymer, a nanocomposite antibacterial agent, reinforcing fibers, and an elastic modifier, and melt-blending them at 190-210℃ using a twin-screw extruder, granulating them to obtain composite material particles, and coating the composite material particles onto the surface of the metal matrix treated with the interface binder by injection molding, which forms the polymer layer, wherein the injection molding temperature is 195-205℃, the mold pressure is 8-12 MPa, and the holding time is 15-25 seconds; then cooling and cutting to obtain the eyeglass frame material.

[0052] The interface binder is a silane coupling agent compound system, which is a compound mixture of silane coupling agent KH560 and silane coupling agent KH792, with a mass ratio of 2-4:1.

[0053] The specific steps for preparing the interface binder into a solution are as follows: dissolve the interface binder in an isopropanol aqueous solution to prepare a solution with a mass concentration of 6%-12%, adjust the pH value to 5.0-6.0 with lactic acid, hydrolyze the solution at 55-65℃ for 1.5-2.5 hours, add nano-alumina accounting for 0.3%-0.8% of the total mass of the interface binder, ultrasonically disperse the solution for 40-70 minutes, and cool it to room temperature to obtain the interface binder solution.

[0054] The metal matrix is ​​a low-ion precipitation titanium alloy, and its composition by weight percentage includes: titanium 92%-96%, aluminum 2.5%-4%, vanadium 0.5%-1.5%, and zirconium 0.1%-0.5%.

[0055] The charge-repellent polymer is a modified polyelectrolyte, and its preparation method includes the following steps: dissolving polydiallyldimethylammonium chloride as a polymer in deionized water to prepare a solution with a mass concentration of 12%-18%, adding glutaraldehyde at a mass of 8%-12% of the polymer, reacting at 50-60℃ for 2-3 hours, adding hydroxyethyl acrylate at a mass of 3%-6% of the polymer, and continuing the reaction for 1.5-2.5 hours. After the reaction is completed, cooling to room temperature, precipitating with ethanol, filtering, and vacuum drying are performed to obtain the modified polyelectrolyte, i.e., the charge-repellent polymer.

[0056] The nanocomposite antibacterial agent is zinc-loaded zeolite, and its preparation method includes the following steps: zeolite powder and zinc sulfate solution are mixed at a mass ratio of 1:3, and ion exchange reaction is carried out at 70 to 80°C for 3 to 4 hours. After the reaction is completed, the mixture is centrifuged, washed with deionized water until neutral, and vacuum dried at 90°C for 8 hours to obtain zinc-loaded zeolite, i.e., the zinc nanocomposite antibacterial agent.

[0057] The reinforcing fiber is a polyimide fiber with a length of 80-150 micrometers and a diameter of 8-12 micrometers; the elastic modifier is a thermoplastic polyurethane with a melt index of 8-12 g / 10 min and a Shore hardness of 75A-85A.

[0058] A functional coating is also provided on the surface of the frame material, which comprises, by weight: 60-80 parts of water-based acrylic resin, 5-8 parts of nano-cerium oxide, 0.6-1.2 parts of leveling agent, and 0.4-0.9 parts of defoamer;

[0059] The preparation method of the functional coating solution includes: mixing water-based acrylic resin with nano-cerium oxide, ultrasonically dispersing for 25-35 minutes, adding leveling agent and defoamer, and stirring for 20-40 minutes to obtain the functional coating solution;

[0060] The functional coating solution is applied by spraying it onto the surface of the frame material and curing it at 85-95°C for 25-35 minutes.

[0061] A type of eyeglasses whose frame is made of a frame material that effectively inhibits the release of metal ions.

[0062] This invention utilizes the synergistic effects of interface binders, charge-repellent polymers, zinc-loaded zeolites, reinforcing fibers, and functional coatings to construct a multi-layered protection mechanism from the interface to the surface. This mechanism effectively inhibits the precipitation of metal ions while significantly improving the mechanical strength, antibacterial durability, and overall performance of the material.

[0063] The present invention will be described in detail below through examples and comparative examples, but the scope of protection of the present invention is not limited to these examples. Unless otherwise specified, the chemical reagents and raw materials used in the following examples and comparative examples are all conventional commercially available products. Example

[0064] This embodiment provides a long-lasting frame material that inhibits the precipitation of metal ions. The preparation process is as follows: First, an interface binder solution is prepared. Silane coupling agent KH560 and silane coupling agent KH792 are compounded at a mass ratio of 4:1. 12g of this compound system is dissolved in 88g of isopropanol aqueous solution, with a volume ratio of isopropanol to water of 8:2. The pH value is adjusted to 5.0 with lactic acid, and the reaction is carried out at 65°C for 1.5 hours. Nano-alumina, accounting for 0.8% of the total mass of the interface binder, is added, and the mixture is ultrasonically dispersed for 40 minutes. The mixture is then cooled to room temperature for later use.

[0065] The metal substrate is melted into an ingot, hot-rolled into a strip, and cold-rolled to a thickness of 0.6 mm. The above-mentioned interface binder solution is uniformly coated on the surface of the metal substrate and pre-cured at 95°C for 15 minutes.

[0066] Next, a charge-repulsive polymer was prepared by dissolving polydiallyldimethylammonium chloride in deionized water to prepare a solution with a mass concentration of 18%. Glutaraldehyde, accounting for 12% of the polymer mass, was added, and the reaction was carried out at 50°C for 3 hours. Then, hydroxyethyl acrylate, accounting for 6% of the polymer mass, was added, and the reaction was continued for 1.5 hours. After the reaction was completed, the product was precipitated with ethanol, filtered, and vacuum dried to obtain the modified polyelectrolyte.

[0067] To prepare a nanocomposite antibacterial agent, zeolite powder and zinc sulfate solution were mixed at a mass ratio of 1:3, and an ion exchange reaction was carried out at 80°C for 3 hours. After centrifugation, the mixture was washed until neutral and then vacuum dried at 90°C for 8 hours to obtain zinc-loaded zeolite.

[0068] 120 parts of a metal matrix, 5 parts of an interfacial binder, 40 parts of a charge-repellent polymer, 3 parts of a nanocomposite antibacterial agent, 25 parts of polyimide fiber, and 5 parts of thermoplastic polyurethane were prepared. The polyimide fiber had a length of 80 micrometers and a diameter of 12 micrometers. The thermoplastic polyurethane had a melt index of 8 g / 10 min and a Shore hardness of 85A. The charge-repellent polymer, nanocomposite antibacterial agent, polyimide fiber, and thermoplastic polyurethane were mixed and melt-blended at 210°C using a twin-screw extruder, followed by granulation to obtain composite material particles. These composite material particles were then injection molded onto the surface of a metal matrix treated with the interfacial binder. The injection molding temperature was 205°C, the mold pressure was 8 MPa, and the holding time was 25 seconds. After cooling, the particles were cut into finished shapes. Finally, a functional coating is applied to the surface of the frame material. 80 parts by weight of water-based acrylic resin, 5 parts by weight of nano-cerium oxide, 1.2 parts by weight of leveling agent, and 0.4 parts by weight of defoamer are mixed and ultrasonically dispersed for 25 minutes. The leveling agent and defoamer are added and stirred for 40 minutes. The mixture is then applied to the surface of the frame material by spraying and cured at 95°C for 25 minutes. Example

[0069] In this embodiment, the similarities to those in Embodiment 1 will not be repeated, and the differences are as follows:

[0070] This embodiment provides another long-lasting frame material for inhibiting metal ion precipitation, and its preparation process is as follows: An interface binder solution is prepared by mixing silane coupling agent KH560 and silane coupling agent KH792 at a mass ratio of 2:1. 6g of this mixture is dissolved in 94g of isopropanol aqueous solution, and the pH is adjusted to 6.0 with lactic acid. The mixture is then hydrolyzed at 55°C for 2.5 hours. Nano-alumina, accounting for 0.3% of the total mass of the interface binder, is added, and the mixture is ultrasonically dispersed for 70 minutes. The mixture is then cooled to room temperature for later use.

[0071] The metal substrate is melted into an ingot, hot-rolled into a strip, and then processed into a strip with a thickness of 0.9 mm. An interface binder solution is coated onto the surface of the metal substrate and pre-cured at 85°C for 25 minutes.

[0072] To prepare a charge-repellent polymer, polydiallyldimethylammonium chloride was prepared into a 12% (w / w) solution, and glutaraldehyde (8% (w / w) of the polymer mass) was added. The mixture was reacted at 60°C for 2 hours, and then hydroxyethyl acrylate (3% (w / w) of the polymer mass) was added. The reaction was continued for 2.5 hours. The resulting modified polyelectrolyte was obtained.

[0073] To prepare a nanocomposite antibacterial agent, zeolite powder and zinc sulfate solution were mixed at a mass ratio of 1:3 and subjected to ion exchange reaction at 70°C for 4 hours to obtain zinc-loaded zeolite.

[0074] Take 80 parts of metal matrix, 15 parts of interface binder, 20 parts of charge repulsion polymer, 8 parts of nanocomposite antibacterial agent, 10 parts of polyimide fiber, and 10 parts of thermoplastic polyurethane. The polyimide fiber has a length of 150 micrometers and a diameter of 8 micrometers. The thermoplastic polyurethane has a melt index of 12 g / 10 min and a Shore hardness of 75A. Mix the components and melt-blend them at 190°C using a twin-screw extruder, then granulate to obtain composite material particles. Inject the material onto the surface of the metal matrix at an injection temperature of 195°C, a mold pressure of 12 MPa, and a holding time of 15 seconds. Finally, prepare a functional coating by taking 60 parts by weight of waterborne acrylic resin, 8 parts by weight of nano-cerium oxide, 0.6 parts by weight of leveling agent, and 0.9 parts by weight of defoamer. Spray the coating solution onto the surface of the frame and cure it at 85°C for 35 minutes. Example

[0075] In this embodiment, the similarities to those in Embodiment 1 will not be repeated, and the differences are as follows:

[0076] This embodiment provides another long-lasting frame material that inhibits the precipitation of metal ions, and its preparation process is as follows: An interface binder solution is prepared by mixing silane coupling agent KH560 and silane coupling agent KH792 at a mass ratio of 3:1. 9g of this mixture is dissolved in 91g of isopropanol aqueous solution, and the pH is adjusted to 5.5 with lactic acid. The mixture is then hydrolyzed at 60°C for 2 hours. Nano-alumina, accounting for 0.5% of the total mass of the interface binder, is added, and the mixture is ultrasonically dispersed for 55 minutes. The mixture is then cooled to room temperature for later use.

[0077] The metal substrate is processed into a strip with a thickness of 0.7 mm. An interface bonding agent solution is coated on the surface of the metal substrate and pre-cured at 90°C for 20 minutes.

[0078] To prepare a charge-repellent polymer, polydiallyldimethylammonium chloride was prepared into a 15% (w / w) solution, and glutaraldehyde (10% (w / w) of the polymer mass) was added. The mixture was reacted at 55°C for 2.5 hours, and then hydroxyethyl acrylate (4% (w / w) of the polymer mass) was added. The reaction was continued for another 2 hours. The resulting modified polyelectrolyte was obtained.

[0079] To prepare a nanocomposite antibacterial agent, zeolite powder and zinc sulfate solution were mixed at a mass ratio of 1:3 and subjected to an ion exchange reaction at 75°C for 3.5 hours to obtain zinc-loaded zeolite.

[0080] 100 parts of a metal matrix, 10 parts of an interfacial binder, 30 parts of a charge-repellent polymer, 5 parts of a nanocomposite antibacterial agent, 15 parts of polyimide fiber, and 8 parts of thermoplastic polyurethane were prepared. The polyimide fiber had a length of 120 micrometers and a diameter of 10 micrometers. The thermoplastic polyurethane had a melt index of 10 g / 10 min and a Shore hardness of 80 A. The components were mixed and melt-blended at 200°C using a twin-screw extruder, and then granulated to obtain composite material particles. This material was then injection-molded onto the surface of the metal matrix at 200°C, a mold pressure of 10 MPa, and a holding time of 20 seconds. Finally, a functional coating was prepared by taking 70 parts by weight of water-based acrylic resin, 6 parts by weight of nano-cerium oxide, 0.9 parts by weight of leveling agent, and 0.6 parts by weight of defoamer. This coating solution was then sprayed onto the surface of the frame and cured at 90°C for 30 minutes.

[0081] In this comparative example, the similarities with Example 1 will not be repeated, and the differences are as follows:

[0082] Without using any interface binder, the composite material is directly injection molded onto a metal substrate that has not undergone any surface treatment.

[0083] In this comparative example, the similarities with Example 1 will not be repeated, and the differences are as follows:

[0084] Unmodified polydiallyldimethylammonium chloride was used as the charge-repulsive polymer, i.e., without glutaraldehyde crosslinking and hydroxyethyl acrylate modification.

[0085] In this comparative example, the similarities with Example 1 will not be repeated, and the differences are as follows:

[0086] Nano-silver was used instead of zinc-loaded zeolite as an antibacterial agent, and the amount added was the same.

[0087] In this comparative example, the similarities with Example 1 will not be repeated, and the differences are as follows:

[0088] Instead of using polyimide fiber reinforcement, the amount of charge-repellent polymer is increased accordingly to maintain the overall component balance.

[0089] In this comparative example, the similarities with Example 1 will not be repeated, and the differences are as follows:

[0090] The functional coating does not use nano-cerium oxide, but only uses water-based acrylic resin with leveling agents and defoamers.

[0091] The performance of the samples obtained in the examples and comparative examples was evaluated using the following test methods: Nickel ion deposition was tested according to ISO 12894 standard, after the samples were immersed in artificial sweat for 30 days; antibacterial properties were tested according to GB / T 31402-2015 standard, using Staphylococcus aureus and Escherichia coli as test bacteria; tensile strength and elongation at break were tested according to GB / T 1040-2018 standard; coating abrasion resistance was tested according to GB / T 23988-2009 standard using a Taber abrasion tester; and aging resistance was tested according to GB / T 1865-2009 standard, with the coating condition evaluated after a 500-hour UV aging test. The specific test results are shown in Table 1.

[0092] As shown in Table 1, all three examples exhibit excellent performance across all indicators, with nickel ion deposition levels significantly lower than the comparative example. Example 1 demonstrates the best performance in suppressing ion deposition and mechanical strength, which is closely related to its higher content of charge-repellent polymers and reinforcing fibers. The parameter configuration of Example 2 favors the material's flexibility and processability, resulting in the highest elongation at break while maintaining good overall performance. Example 3 achieves the best balance across all performance indicators.

[0093] Comparative Example 1, which did not use any interfacial binder, showed a significantly higher nickel ion deposition rate than the Example, resulting in a substantial performance decline, demonstrating that the interfacial binder is fundamental. Comparative Example 2, using an unmodified charge-repellent polymer, exhibited a significantly reduced ion-blocking effect, indicating that glutaraldehyde crosslinking and hydroxyethyl acrylate modification are crucial for constructing a stable charge-repellent network, highlighting the key role of the charge-repellent structure. Comparative Example 3, using nano-silver instead of zinc-loaded zeolite, not only resulted in decreased antibacterial performance but also caused coating opacity, verifying the silver ion defect problem mentioned in the background section. Comparative Example 4, without reinforcing fibers, showed improved flexibility but a significant decrease in tensile strength, demonstrating the indispensable role of polyimide fibers in maintaining the structural stability of the frame. Comparative Example 5, lacking nano-cerium oxide in its functional coating, exhibited significantly reduced wear resistance and powdering after aging, proving the irreplaceable role of nano-cerium oxide in improving coating durability and anti-aging capabilities.

[0094] Table 1 Analysis of Test Results

[0095]

[0096] Test results show that the present invention, through the systematic combination of interface binder, charge repulsion polymer, zinc-loaded zeolite antibacterial agent, polyimide fiber, thermoplastic polyurethane and functional coating containing nano-cerium oxide, has indeed achieved long-term suppression of metal ion precipitation, while ensuring good mechanical properties and durability of the material.

[0097] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A frame material for long-term suppression of metal ion precipitation, characterized in that, By weight, the frame material comprises the following components: 80-120 parts of metal matrix, 5-15 parts of interface binder, 20-40 parts of charge repulsion polymer, 3-8 parts of nanocomposite antibacterial agent, 10-25 parts of reinforcing fiber, and 5-10 parts of elasticity modifier. The metal matrix is ​​a low-ion precipitation titanium alloy, and its composition by weight percentage includes: titanium 92%-96%, aluminum 2.5%-4%, vanadium 0.5%-1.5%, and zirconium 0.1%-0.5%. The interface binder is a silane coupling agent compound system, which is a compound mixture of silane coupling agent KH560 and silane coupling agent KH792, with a mass ratio of 2-4:

1. The charge-repellent polymer is a modified polyelectrolyte, and its preparation method includes the following steps: dissolving polydiallyldimethylammonium chloride as a polymer in deionized water to prepare a solution with a mass concentration of 12%-18%, adding glutaraldehyde at a mass of 8%-12% of the polymer, reacting at 50-60℃ for 2-3 hours, adding hydroxyethyl acrylate at a mass of 3%-6% of the polymer, and continuing the reaction for 1.5-2.5 hours. After the reaction is completed, cooling to room temperature, precipitating with ethanol, filtering, and vacuum drying are performed to obtain the modified polyelectrolyte, i.e., the charge-repellent polymer. The nanocomposite antibacterial agent is zinc-loaded zeolite; The reinforcing fiber is a polyimide fiber; The elastic modifier is thermoplastic polyurethane.

2. The frame material for long-term suppression of metal ion precipitation according to claim 1, characterized in that, The preparation method of this eyeglass frame material includes the following steps: melting a metal matrix into an ingot, hot rolling it into a strip, cold rolling it to a thickness of 0.6-0.9 mm, uniformly coating an interface binder solution onto the surface of the metal matrix, and pre-curing it at 85-95℃ for 15-25 minutes; then mixing a charge-repellent polymer, a nanocomposite antibacterial agent, reinforcing fibers, and an elastic modifier, and melt-blending them at 190-210℃ using a twin-screw extruder, granulating them to obtain composite material particles, and coating the composite material particles onto the surface of the metal matrix treated with the interface binder by injection molding, which forms the polymer layer, wherein the injection molding temperature is 195-205℃, the mold pressure is 8-12 MPa, and the holding time is 15-25 seconds; then cooling and cutting to obtain the eyeglass frame material.

3. The frame material for long-term suppression of metal ion precipitation according to claim 2, characterized in that, The specific steps for preparing the interface binder into a solution are as follows: dissolve the interface binder in an isopropanol aqueous solution to prepare a solution with a mass concentration of 6%-12%, adjust the pH value to 5.0-6.0 with lactic acid, hydrolyze the solution at 55-65℃ for 1.5-2.5 hours, add nano-alumina accounting for 0.3%-0.8% of the total mass of the interface binder, ultrasonically disperse the solution for 40-70 minutes, and cool it to room temperature to obtain the interface binder solution.

4. The frame material for long-term suppression of metal ion precipitation according to claim 1, characterized in that, The preparation method of the zinc-loaded zeolite includes the following steps: zeolite powder and zinc sulfate solution are mixed at a mass ratio of 1:3, and ion exchange reaction is carried out at 70 to 80°C for 3 to 4 hours. After the reaction is completed, the mixture is centrifuged, washed with deionized water until neutral, and vacuum dried at 90°C for 8 hours to obtain zinc-loaded zeolite, which is a nanocomposite antibacterial agent.

5. The frame material for long-term suppression of metal ion precipitation according to claim 1, characterized in that, The polyimide fiber has a length of 80-150 micrometers and a diameter of 8-12 micrometers; the thermoplastic polyurethane has a melt index of 8-12 g / 10 min and a Shore hardness of 75A-85A.

6. The frame material for long-term suppression of metal ion precipitation according to claim 1, characterized in that, A functional coating is also provided on the surface of the frame material, which comprises, by weight: 60-80 parts of water-based acrylic resin, 5-8 parts of nano-cerium oxide, 0.6-1.2 parts of leveling agent, and 0.4-0.9 parts of defoamer; The preparation method of the functional coating solution includes: mixing water-based acrylic resin with nano-cerium oxide, ultrasonically dispersing for 25-35 minutes, adding leveling agent and defoamer, and stirring for 20-40 minutes to obtain the functional coating solution; The functional coating solution is applied by spraying it onto the surface of the frame material and curing it at 85-95°C for 25-35 minutes.

7. A pair of eyeglasses, characterized in that, The frame is made of any one of the frame materials described in claims 1-6 that provides long-lasting inhibition of metal ion precipitation.

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