Glasses frame with negative ion release function

Abstract

The application provides a glasses frame with a negative ion release function, which is composed of a metal matrix layer, a transition barrier layer and a functional release layer from inside to outside; the transition barrier layer is in direct contact with the metal matrix layer, and is composed of a chelate-modified nanocomposite barrier material; the functional release layer is covered on the transition barrier layer, and is composed of a plasmonic activated rare earth doped mineral composite material. Through the synergistic effect of the three layers of functional materials, the application effectively blocks the penetration of sweat corrosive ions to the metal matrix, stably releases negative ions to neutralize the acidic substances on the contact surface, significantly inhibits the precipitation of metal ions and improves the wearing microenvironment, and at the same time guarantees the light weight and durability of the glasses frame.

Description

Technical Field

[0001] The invention belongs to the technical field of glasses manufacturing, and in particular relates to a glasses frame with a negative ion releasing function. Background Art

[0002] Modern eyeglass frames, particularly those made of metal materials such as titanium alloy, nickel alloy, and shape memory alloy, are highly popular due to their high strength and plasticity, particularly those focused on lightweight and stylish designs. Renowned brands such as RayFlex's TitanFlex series make extensive use of custom titanium alloys. However, these frames face a common and challenging issue during long-term wear: corrosion from human sweat.

[0003] Human sweat is a complex substance, containing sodium chloride, lactic acid, urea, and trace amounts of metal ions. Chloride ions are extremely penetrating and corrosive. For example, in RayFlex's TitanFlex frames, where the leg cuffs are in prolonged contact with the skin, sweat continuously erodes the frame's surface. Existing materials research indicates that even titanium alloys, known for their excellent biocompatibility, can gradually destroy their passivation film in long-term, high-concentration sweat environments, particularly in close contact areas where sweat is trapped and difficult to evaporate. This leads to the continuous but trace precipitation of alloying elements such as titanium, nickel, vanadium, and aluminum from the base metal.

[0004] These trace but continuously released metal ions can penetrate into the skin tissue they come into contact with. For wearers with sensitive skin, this can easily trigger contact allergic reactions, manifesting as localized redness, itching, papules, and even scaling. This phenomenon is common in consumer complaints and clinical dermatology reports, impacting both wearer comfort and brand reputation. Furthermore, long-term corrosion can cause localized thinning of the frame material, compromising its mechanical strength and lifespan.

[0005] The existing technology solves this problem mainly by the following ways:

[0006] Topcoat treatment: Applying polyurethane, acrylic resin, or an inert inorganic coating to the metal frame's surface can, to a certain extent, prevent sweat from coming into direct contact with the metal substrate. However, organic coatings are susceptible to wear and aging, and can affect the frame's heat dissipation and surface texture. While expensive DLC coatings offer excellent performance, their high cost limits their widespread adoption.

[0007] Completely inert material coating: Using precious metal plating such as pure gold or platinum, or entirely using medical-grade 316L stainless steel. While this solves the corrosion problem, it's extremely expensive, significantly increasing the product's price and hindering mainstream market adoption. Pure gold coatings are also too soft and easily scratched.

[0008] Isolation design: Silicone or plastic covers are placed on the temples and nose pads. This method is the most intuitive and effective, but it significantly increases the size and weight of the frame, destroying the original slim and simple aesthetic of the metal frame, and has low consumer acceptance.

[0009] All of the above existing solutions have significant limitations, including short-term effects, high costs, and compromised aesthetics and wearability. In particular, they all employ a "passive defense" approach, focusing solely on physical isolation or complete inert replacement. They fail to fundamentally improve the microenvironment at the site of sweat contact or neutralize some of the harmful components in sweat. Therefore, there is a need for eyeglass frames with negative ion release capabilities. Summary of the Invention

[0010] In order to overcome the defects in the prior art, a glasses frame with a negative ion releasing function is provided.

[0011] In order to achieve the above object, the present invention provides the following technical solutions:

[0012] A glasses frame with a negative ion release function, wherein the glasses frame material is compounded from the inside to the outside in order: a metal matrix layer, a transition barrier layer, and a functional release layer;

[0013] The transition barrier layer is in direct contact with the metal matrix layer, and the transition barrier layer is composed of a chelate-modified nanocomposite barrier material;

[0014] The function release layer covers the transition barrier layer, and the function release layer is composed of plasma-activated rare earth doped mineral composite material.

[0015] The metal base layer is any one of nickel-titanium alloy, titanium alloy, and 316L stainless steel.

[0016] The thickness of the transition barrier layer is 6-10 microns. The transition barrier layer includes a transition barrier layer matrix resin, nano-inorganic particles, and a metal ion chelating agent. Based on the total mass of the transition barrier layer, the mass percentage of the nano-inorganic particles is 5.0%-7.5%, the mass percentage of the metal ion chelating agent is 0.9%-1.1%, and the remainder is the transition barrier layer matrix resin.

[0017] The matrix resin is polyetheretherketone or modified polyaryletherketone containing carboxyl side chains, and the content of carboxyl groups in the modified polyaryletherketone containing carboxyl side chains is 1.2-1.4 mol%; the nano inorganic particles are γ-Al2O3 powder with an average particle size D50 of 20-50 nanometers; and the metal ion chelating agent is at least one of methylenediphosphonic acid and ethylenediaminetetramethylenephosphonic acid sodium salt.

[0018] Metal eyeglass frames are in close contact with the human body when worn, and the high concentration of chloride ions in sweat can penetrate the passivation film on the metal surface. This corrosion process causes the continuous precipitation of alloy elements, which can easily cause contact dermatitis in people with sensitive skin. Existing solutions use organic coatings for physical barriers, but polyurethane or acrylic resin coatings are prone to microcracks under long-term bending and friction. Sweat components penetrate along the cracks and accelerate substrate corrosion. The transition barrier layer set in this application uses a chelated modified nanocomposite barrier material. The matrix resin of this layer is modified polyaryletherketone containing carboxyl side chains. The specific carboxyl content ensures that the molecular chain segments have sufficient active sites, which can form chemical anchors with the metal matrix through coordination bonds, significantly improving the interlayer bonding strength. The high specific surface area of ​​nano-inorganic particles forms a maze-like barrier network in the resin matrix, forcing the migration path of chloride ions to be extended. Metal ion chelators such as sodium salt of ethylenediaminetetramethylenephosphonic acid, the phosphonate groups in their molecules can selectively capture nickel ions that have precipitated from the matrix, forming a stable chelate ring structure, blocking the free harmful ions from diffusing outward. The three work together to make the transition layer have the functions of interface strengthening, physical barrier and chemical capture, inhibiting the ion precipitation channel from the source.

[0019] The thickness of the functional release layer is 40-55 microns. The functional release layer includes a functional release layer matrix resin and a negative ion releasing filler. Based on the total mass of the functional release layer, the mass percentage of the negative ion releasing filler is 33%-37%; the matrix resin of the functional release layer is polyetheretherketone or a modified polyaryletherketone containing a carboxyl side chain, and the negative ion releasing filler is a rare earth-doped strontium titanate-based composite mineral powder, wherein the doped rare earth elements include cerium and samarium, and the molar ratio of cerium to samarium is 1:0.95-1.05. The average particle size D50 of the negative ion releasing filler is 1.2-1.6 microns.

[0020] The negative ion-releasing filler is pretreated as follows before use: the negative ion-releasing filler is dehydrated for 2-3 hours under vacuum conditions of less than 0.01 Pa and a temperature of 280-320°C; then placed in a mixed atmosphere of nitrogen and carbon dioxide with a volume ratio of 4:1, and treated in a plasma environment with a radio frequency power of 400-600 W and a frequency of 13.56 MHz for 5-6 minutes.

[0021] A silane coupling agent is also added to the components of the functional release layer. The silane coupling agent contains both epoxy groups and amino groups in its molecules, wherein the molar ratio of the number of epoxy groups to the number of amino groups is 2.2-2.5:1, and the added amount of the silane coupling agent accounts for 2.0%-2.2% of the total mass of the functional release layer.

[0022] However, simply blocking sweat penetration still has significant limitations. Long-term exposure to a confined sweat environment leads to continuous acidification of the skin surface microenvironment, accelerating corrosion and exacerbating skin discomfort. Existing precious metal coatings or inert stainless steel solutions can block ion exchange, but they cannot improve the chemical environment at the contact surface. This application introduces a functional release layer, which utilizes a plasma-activated rare-earth-doped mineral composite material. Its core mechanism is energy conversion and environmental regulation. The negative ion-releasing filler is a strontium titanate-based composite mineral powder co-doped with cerium and samarium. The molar ratio of cerium to samarium is strictly controlled to create oxygen vacancies and defect energy level distribution within the crystal lattice. During filler pretreatment, vacuum dehydration removes surface-adsorbed water molecules. Then, plasma treatment with a mixed atmosphere of nitrogen and carbon dioxide modifies the filler surface with active carbonyl groups. When exposed to mild body heat and mechanical stress during wear, this active surface stimulates the cleavage of water molecules in the air, preferentially releasing active substances, primarily hydroxyl anions. These anions penetrate the sweat layer and neutralize with the dissociated hydrogen ions of lactic acid to form neutral water molecules, significantly reducing the acidity of the contact interface to near the normal pH of the skin. At the same time, negative ions compete with chloride ions for adsorption, weakening the corrosive activity of chloride ions. This process continuously consumes hydrogen ions in sweat and maintains a dynamic balance, forming a self-regulating microenvironment.

[0023] In addition, multi-layer composite structures often face the problem of interlayer stress failure, especially the bending part of the temple, which is prone to peeling of the functional layer under repeated deformation. This application solves this defect by adding a special silane coupling agent to the functional release layer. The molar ratio of epoxy groups and amino groups in the silane molecule is precisely designed. The amino group preferentially combines with the carbonyl group on the surface of the plasma-activated negative ion-releasing filler to form a strong covalent bond, and the excess epoxy group undergoes a ring-opening reaction with the carboxyl group in the matrix resin of the functional release layer. Through chemical bonding bridging, the silane coupling agent constructs a continuous three-dimensional network at the filler resin interface. Its cross-linking density can effectively disperse the bending stress and avoid protection failure caused by interface debonding. This bonding strength is higher than that of traditional physical adsorption.

[0024] A transparent wear-resistant protective layer is coated on the outer surface of the functional release layer. The wear-resistant protective layer is made of fluorosilicone modified polyurethane acrylate light-curing material and has a thickness of 4.5-5.5 microns.

[0025] The fluorosilicone modified polyurethane acrylate light-curing material comprises the following components by mass percentage:

[0026] Fluorosilicone modified polyurethane acrylate prepolymer 60-65%;

[0027] Dipentaerythritol hexaacrylate 10-15%;

[0028] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide TPO 5-7%;

[0029] Polyether modified polysiloxane 0.8-1.2%;

[0030] Propylene glycol methyl ether acetate balance.

[0031] The preparation method of the fluorosilicone modified polyurethane acrylate prepolymer comprises the following steps:

[0032] (a) Prepolymerization: 35-40 parts by weight of isophorone diisocyanate and 50-55 parts by weight of polytetramethylene ether glycol were added to a reactor under nitrogen protection. After heating to 72-76°C, 0.05-0.1 parts by weight of dibutyltin dilaurate as a catalyst was added. The reaction was kept at this temperature for 2.5-3 hours, and the NCO group content was monitored to reach 8.2-8.8 wt%.

[0033] (b) Fluorosilicon modification: adding 8-10 parts by mass of a fluorine-containing silane monomer, wherein the fluorine-containing silane monomer is tridecafluorooctylalkoxypropyltrimethoxysilane, to the product obtained in step (a), and continuing the reaction at 62-68°C for 1.5-2 hours;

[0034] (c) Acrylate end-capping: Add 0.15-0.2 parts by weight of p-hydroxyanisole as a polymerization inhibitor to the product obtained in step (b), cool to 58-62°C, and dropwise add a mixture of 7-8 parts by weight of hydroxyethyl acrylate and 4-5 parts by weight of trimethylolpropane triacrylate. Keep warm and react until the NCO group content is ≤0.1wt%;

[0035] (d) Dilution and post-treatment: adding 20-25 parts by weight of tetrahydrofuran acrylate as a reactive diluent to the product obtained in step (c), stirring and mixing, cooling to below 40° C., and discharging to obtain a fluorosilicone-modified polyurethane acrylate prepolymer.

[0036] Daily cleaning and wiping or external scratching may damage the active surface of the functional release layer, and moisture penetration will also affect the negative ion release efficiency. In order to address the functional degradation caused by surface wear, the present invention provides a wear-resistant protective layer on the outermost layer. The wear-resistant protective layer of the present application adopts fluorosilicone-modified polyurethane acrylate photocuring material, in which the fluorine-containing silane monomer spontaneously migrates to the coating surface during film formation, reduces the surface energy and forms a dense fluorocarbon barrier. This barrier increases the water contact angle and effectively prevents the penetration of environmental moisture. The synergistic cross-linking of the difunctional acrylate monomer enables the polymer network to form an alternating structure of hard segment micro-regions and flexible chain segments. When subjected to mechanical scratching, the hard segment resists plastic deformation, and the flexible segment buffers stress transfer through conformational changes. The protective layer maintains an ultra-thin thickness of about 5 microns, and its surface hardness can still reach 4H level, ensuring the long-term stability of the functional layer.

[0037] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0038] 1. The eyeglass frame material described in this application utilizes a unique multi-layered design, with each functional layer synergistically forming a dynamic protective system: a transition barrier layer inhibits metal ion precipitation, a functional release layer modulates the chemical properties of the sweat microenvironment, and a wear-resistant protective layer maintains surface integrity. Through a three-stage mechanism of physical barrier, chemical chelation, and in-situ neutralization, this system maintains stable protective properties even under long-term wear conditions, demonstrating significant advantages in addressing metal substrate corrosion and skin allergies.

[0039] 2. To control metal ion release, the transition barrier layer of this application utilizes a chelated, modified nanocomposite barrier material system. Nano-γ-Al₂O₃ particles form a dense physical barrier within the matrix resin, blocking the diffusion path of chloride ions from sweat into the metal matrix. Simultaneously, the metal ion chelator captures precipitated allergenic metal ions, such as nickel ions, through molecular chelation. The active groups in the carboxyl-modified resin further strengthen the interfacial bond with the matrix. This combined mechanism significantly reduces the concentration of harmful ions migrating to the skin surface.

[0040] 3. The key to improving the wearing microenvironment of the eyeglass frame material of this application lies in the plasma-activated rare earth-doped mineral filler in the functional release layer. After vacuum dehydration to eliminate surface adsorbed water, plasma treatment with a nitrogen-carbon dioxide mixed atmosphere in a specific proportion optimizes the strontium titanate lattice defect distribution. This activation treatment makes the energy state of cerium and samarium ions in the lattice more susceptible to weak mechanical stress excitation, thereby continuously releasing negative ions such as hydroxyl protons. These negative ions react with hydrogen ions in sweat to reduce the acidity of the contact surface and weaken the activity of chloride ions, thereby improving skin contact conditions from a chemical level.

[0041] 4. The interlayer bonding stability of the eyeglass frame material of this application is achieved through a specialized silane coupling agent. The precisely controlled molar ratio of epoxy to amino groups in the silane coupling agent allows the amino groups to preferentially anchor to the inorganic filler or transition layer surface. Excess epoxy groups then undergo a ring-opening reaction with the carboxyl groups in the functional release layer resin, forming a covalent bond network at the interface. This chemical bonding mechanism effectively resists shear stress during frame bending, preventing interlayer delamination failure.

[0042] 5. The outermost wear-resistant protective layer of the eyeglass frame material of this application utilizes a fluorosilicone-modified polyurethane acrylate light-curable material. The fluorinated segments form a low-energy barrier on the coating surface, imparting hydrophobic and anti-fouling properties. The cross-linked network of the polyurethane backbone and multifunctional acrylate provides scratch resistance. This protective layer not only reduces damage to the functional layer caused by external abrasion, but its dense structure also acts as a secondary barrier to inhibit the infiltration of ambient moisture.

[0043] 6. The integrated design of the glasses frame material of this application meets the requirements of wearing comfort. While achieving ion barrier and microenvironment regulation, the ultra-thin functional structure fully retains the lightweight characteristics of the metal frame, and there is no problem of increased volume caused by additional sheaths. DETAILED DESCRIPTION

[0044] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0045] In this application, the sources of various raw materials are briefly described as follows:

[0046] Transition barrier layer matrix resin

[0047] Polyetheretherketone: purchased from Victrex, UK, with CAS number 55088-54-5 and model VICTREX 450G.

[0048] Modified polyaryletherketone containing carboxyl side chains: purchased from Jilin Zhongyan Polymer Materials Co., Ltd., CAS number is a custom-synthesized product, model number is ZYPEEK-COOH-1.3.

[0049] Nano inorganic particles

[0050] γ-Al2O3 powder: purchased from Evonik Industries AG, Germany, with CAS number 1344-28-1 and model Aeroxide AluC 805.

[0051] Metal ion chelators

[0052] Methylene diphosphonic acid: purchased from Clariant Chemicals Co., Ltd., Switzerland, with CAS number 1449-75-4 and model number DEQUEST 2010.

[0053] Ethylenediaminetetramethylenephosphonic acid sodium salt: purchased from Shandong Taihe Water Treatment Technology Co., Ltd., CAS No. 1429-50-1, model PBTCA-Na4.

[0054] Functional release layer matrix resin

[0055] Polyetheretherketone: the same as the transition barrier layer matrix resin, model VICTREX 450G.

[0056] Modified polyaryletherketone containing carboxyl side chains: the same as the transition barrier layer matrix resin, model number is ZYPEEK-COOH-1.3.

[0057] Negative ion releasing filler

[0058] Rare earth-doped strontium titanate-based composite mineral powder: purchased from Hunan Rare Earth Metal Materials Research Institute, CAS number is a custom-synthesized product, model number is HNRE-SrTiO3-Ce / Sm-1.0.

[0059] Silane coupling agent

[0060] Epoxy-amino bifunctional silane: purchased from Momentive Performance Materials Group, USA, with CAS number 3388-04-3 and model number SILQUEST A-1126.

[0061] Wear-resistant protective layer components

[0062] Isophorone diisocyanate: purchased from Covestro, Germany, with CAS No. 4098-71-9 and model Desmodur I.

[0063] Polytetramethylenetetrahydrofuran ether glycol: purchased from BASF Corporation of the United States, CAS No. 25190-06-1, model PolyTHF1000.

[0064] Tridecafluorooctyl alkoxypropyl trimethoxysilane: purchased from Daikin Fluoro Chemical Co., Ltd., CAS No. 85857-16-5, model OPTOOL DAC-HP.

[0065] Hydroxyethyl acrylate: purchased from Nippon Shokubai Co., Ltd., CAS No. 818-61-1, model HEA.

[0066] Trimethylolpropane triacrylate: purchased from Sartomer, CAS No. 15625-89-5, model SR351.

[0067] Tetrahydrofuran acrylate: purchased from Changxing Materials Industry Co., Ltd., CAS No. 2399-48-6, model EM223.

[0068] Dipentaerythritol hexaacrylate: purchased from Allnex Resins Co., Ltd., CAS No. 29570-58-9, model DPHA.

[0069] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide: purchased from Tianjin Jiuri New Materials Co., Ltd., CAS No. 75980-60-8, model TPO.

[0070] Polyether-modified polysiloxane: purchased from Evonik Industries AG, Germany, with CAS No. 67762-19-0 and model TEGOGlide 482.

[0071] Propylene glycol methyl ether acetate: purchased from Dow Chemical Company, CAS No. 108-65-6, model No. Dowanol PMA.

[0072] Dibutyltin dilaurate: purchased from Beijing Yinuokai Technology Co., Ltd., CAS No. 77-58-7, model T-12.

[0073] p-Hydroxyanisole: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 150-76-5, model MEHQ.

[0074] The technical solution of this application is:

[0075] A glasses frame with a negative ion release function, wherein the glasses frame material is compounded from the inside to the outside in order: a metal matrix layer, a transition barrier layer, and a functional release layer;

[0076] The transition barrier layer is in direct contact with the metal matrix layer, and the transition barrier layer is composed of a chelate-modified nanocomposite barrier material;

[0077] The function release layer covers the transition barrier layer, and the function release layer is composed of plasma-activated rare earth doped mineral composite material.

[0078] The metal base layer is any one of nickel-titanium alloy, titanium alloy, and 316L stainless steel.

[0079] The thickness of the transition barrier layer is 6-10 microns. The transition barrier layer includes a transition barrier layer matrix resin, nano-inorganic particles, and a metal ion chelating agent. Based on the total mass of the transition barrier layer, the mass percentage of the nano-inorganic particles is 5.0%-7.5%, the mass percentage of the metal ion chelating agent is 0.9%-1.1%, and the remainder is the transition barrier layer matrix resin.

[0080] The matrix resin is polyetheretherketone or modified polyaryletherketone containing carboxyl side chains, and the content of carboxyl groups in the modified polyaryletherketone containing carboxyl side chains is 1.2-1.4 mol%; the nano inorganic particles are γ-Al2O3 powder with an average particle size D50 of 20-50 nanometers; and the metal ion chelating agent is at least one of methylenediphosphonic acid and ethylenediaminetetramethylenephosphonic acid sodium salt.

[0081] The thickness of the functional release layer is 40-55 microns. The functional release layer includes a functional release layer matrix resin and a negative ion releasing filler. Based on the total mass of the functional release layer, the mass percentage of the negative ion releasing filler is 33%-37%; the matrix resin of the functional release layer is polyetheretherketone or a modified polyaryletherketone containing a carboxyl side chain, and the negative ion releasing filler is a rare earth-doped strontium titanate-based composite mineral powder, wherein the doped rare earth elements include cerium and samarium, and the molar ratio of cerium to samarium is 1:0.95-1.05. The average particle size D50 of the negative ion releasing filler is 1.2-1.6 microns.

[0082] The negative ion-releasing filler is pretreated as follows before use: the negative ion-releasing filler is dehydrated for 2-3 hours under vacuum conditions of less than 0.01 Pa and a temperature of 280-320°C; then placed in a mixed atmosphere of nitrogen and carbon dioxide with a volume ratio of 4:1, and treated in a plasma environment with a radio frequency power of 400-600 W and a frequency of 13.56 MHz for 5-6 minutes.

[0083] A silane coupling agent is also added to the components of the functional release layer. The silane coupling agent contains both epoxy groups and amino groups in its molecules, wherein the molar ratio of the number of epoxy groups to the number of amino groups is 2.2-2.5:1, and the added amount of the silane coupling agent accounts for 2.0%-2.2% of the total mass of the functional release layer.

[0084] A transparent wear-resistant protective layer is coated on the outer surface of the functional release layer. The wear-resistant protective layer is made of fluorosilicone modified polyurethane acrylate light-curing material and has a thickness of 4.5-5.5 microns.

[0085] The fluorosilicone modified polyurethane acrylate light-curing material comprises the following components by mass percentage:

[0086] Fluorosilicone modified polyurethane acrylate prepolymer 60-65%;

[0087] Dipentaerythritol hexaacrylate 10-15%;

[0088] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide TPO 5-7%;

[0089] Polyether modified polysiloxane 0.8-1.2%;

[0090] Propylene glycol methyl ether acetate balance.

[0091] The preparation method of the fluorosilicone modified polyurethane acrylate prepolymer comprises the following steps:

[0092] (a) Prepolymerization: 35-40 parts by weight of isophorone diisocyanate and 50-55 parts by weight of polytetramethylene ether glycol were added to a reactor under nitrogen protection. After heating to 72-76°C, 0.05-0.1 parts by weight of dibutyltin dilaurate as a catalyst was added. The reaction was kept at this temperature for 2.5-3 hours, and the NCO group content was monitored to reach 8.2-8.8 wt%.

[0093] (b) Fluorosilicon modification: adding 8-10 parts by mass of a fluorine-containing silane monomer, wherein the fluorine-containing silane monomer is tridecafluorooctylalkoxypropyltrimethoxysilane, to the product obtained in step (a), and continuing the reaction at 62-68°C for 1.5-2 hours;

[0094] (c) Acrylate end-capping: Add 0.15-0.2 parts by weight of p-hydroxyanisole as a polymerization inhibitor to the product obtained in step (b), cool to 58-62°C, and dropwise add a mixture of 7-8 parts by weight of hydroxyethyl acrylate and 4-5 parts by weight of trimethylolpropane triacrylate. Keep warm and react until the NCO group content is ≤0.1wt%;

[0095] (d) Dilution and post-treatment: adding 20-25 parts by weight of tetrahydrofuran acrylate as a reactive diluent to the product obtained in step (c), stirring and mixing, cooling to below 40° C., and discharging to obtain a fluorosilicone-modified polyurethane acrylate prepolymer.

[0096] The technical solution of the present invention is further illustrated by the following examples and comparative examples, but the protection scope of the present invention is not limited thereto.

[0097] Example 1

[0098] This embodiment provides a glasses frame with a negative ion release function, the structure of which, from the inside to the outside, is a metal base layer, a transition barrier layer, a functional release layer and a wear-resistant protective layer.

[0099] The metal base layer is made of nickel-titanium alloy material, and the specific brand is Nitinol 55.

[0100] The thickness of the transition barrier layer is set to 10 μm and the layer contains the following components:

[0101] Base resin: modified polyaryletherketone resin containing carboxyl side chains, with a carboxyl group content of 1.2 mol%;

[0102] Nano-inorganic particles: γ-alumina powder with an average particle size of 35 nanometers is selected, and the addition amount is 6.2% of the total mass of the transition barrier layer;

[0103] Metal ion chelating agent: Methylene diphosphonic acid was added as a chelating agent, accounting for 1.1% of the total mass of the layer.

[0104] The thickness of the functional release layer is set to 40 microns and contains:

[0105] Matrix resin: also uses modified polyaryletherketone resin containing carboxyl side chains;

[0106] Negative ion release filler: cerium and samarium co-doped strontium titanate-based composite mineral powder is used. The filler addition accounts for 37% of the total mass of the functional release layer, and the molar ratio of cerium to samarium is 1 to 0.95;

[0107] Silane coupling agent: add bifunctional silane containing epoxy and amino groups, with a molar ratio of epoxy to amino groups of 2.3 to 1, and the added amount is 2.1% of the total mass of the layer.

[0108] The filler pretreatment process includes: dehydration at 300 degrees Celsius for 2.5 hours under a vacuum degree of less than 0.01 Pa, followed by 500-watt radio frequency power plasma treatment for 5.5 minutes in a mixed atmosphere of nitrogen and carbon dioxide with a volume ratio of 4 to 1.

[0109] The thickness of the wear-resistant protective layer is set to 5.5 microns, and its components are calculated by mass percentage as follows:

[0110] Fluorosilicone modified polyurethane acrylate prepolymer 65%;

[0111] Dipentaerythritol hexaacrylate 12%;

[0112] 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 6%;

[0113] Polyether modified polysiloxane 1.0%;

[0114] Propylene glycol methyl ether acetate balance.

[0115] Prepolymer preparation process:

[0116] 40 parts by mass of isophorone diisocyanate and 52 parts by mass of polytetramethylene ether glycol were reacted at 75 degrees Celsius under nitrogen protection until the NCO group content reached 8.5%;

[0117] Add 10 parts by mass of tridecafluorooctylalkoxypropyltrimethoxysilane and react at 65 degrees Celsius for 1.7 hours;

[0118] Add 7.5 parts by mass of a mixture of hydroxyethyl acrylate and 4.5 parts by mass of trimethylolpropane triacrylate dropwise, and react at 60 degrees Celsius until the NCO group content is less than 0.1%;

[0119] 22 parts by mass of tetrahydrofuran acrylate was added to dilute the mixture and then cooled and discharged.

[0120] Example 2

[0121] In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows:

[0122] The metal base layer is made of 316L stainless steel.

[0123] The transition barrier layer thickness is set to 6 microns:

[0124] The base resin is polyetheretherketone;

[0125] The addition amount of nano-γ-alumina powder is 7.5%;

[0126] The metal ion chelating agent is ethylenediaminetetramethylenephosphonic acid sodium salt, and the addition amount is 0.9%.

[0127] The thickness of the functional release layer is set to 55 microns:

[0128] The amount of negative ion releasing filler added is 33%, and the molar ratio of cerium to samarium is 1 to 1.05;

[0129] The amount of silane coupling agent added was 2.2%, and the molar ratio of epoxy group to amino group was 2.2 to 1.

[0130] Filler pretreatment: dehydration at 280°C for 3 hours and plasma treatment at 600W for 5 minutes.

[0131] Wear-resistant protective layer thickness 4.5 microns:

[0132] Prepolymer 60% (preparation parameters: 35 parts of isophorone diisocyanate + 55 parts of polytetramethylene ether glycol, react until NCO = 8.2%, add 8 parts of fluorinated silane and react for 2 hours);

[0133] Dipentaerythritol hexaacrylate 15%;

[0134] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide 5%;

[0135] Polyether modified polysiloxane 0.8%.

[0136] Example 3

[0137] In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows:

[0138] The metal matrix layer is titanium alloy Ti-6Al-4V.

[0139] Transition barrier layer thickness 8 microns:

[0140] Carboxyl-modified polyaryletherketone (carboxyl content 1.4 mol %);

[0141] Nano-γ-alumina addition amount 5.0%;

[0142] The addition amount of methylene diphosphonic acid is 1.0%.

[0143] Functional release layer thickness 48 microns:

[0144] The amount of negative ion releasing filler added is 35%, and the molar ratio of cerium to samarium is 1 to 1.00;

[0145] The addition amount of silane coupling agent is 2.0%, and the epoxy / amino ratio is 2.5 to 1.

[0146] Filler pretreatment: dehydration at 320 degrees Celsius for 2 hours, plasma treatment at 400 watts for 6 minutes.

[0147] Wear-resistant protective layer thickness 5.0 microns:

[0148] Prepolymer 62% (preparation parameters: 37 parts of isophorone diisocyanate + 53 parts of polytetramethylene ether glycol reacted to NCO = 8.8%);

[0149] Dipentaerythritol hexaacrylate 13%;

[0150] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide 7%.

[0151] Comparative Example 1

[0152] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows:

[0153] No nano-γ-alumina particles are added to the transition barrier layer. Comparative Example 2

[0154] In this comparative example, the same points as Example 2 are not repeated here, and the differences are as follows:

[0155] The molar ratio of cerium to samarium in the functional release layer was changed to 1:1.5.

[0156] Comparative Example 3

[0157] In this comparative example, the same points as in Example 3 are not repeated here, and the differences are as follows:

[0158] No silane coupling agent was added to the functional release layer.

[0159] Comparative Example 4

[0160] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows:

[0161] The thickness of the transition barrier layer was reduced to 1 micron.

[0162] Comparative Example 5

[0163] In this comparative example, the same points as in Example 1 are not repeated here, and the differences are as follows:

[0164] Negative ion-releasing fillers are not plasma treated.

[0165] Performance test results and analysis

[0166] The materials of the examples and comparative examples were tested for performance according to the following test methods: nickel ion precipitation (EN 1811:2015), negative ion concentration (GB / T 30128-2013), chloride ion permeability after bending (ASTM F739), pencil hardness (GB / T 6739-2006), and cross-grid adhesion (ASTM D3359). The test results are shown in Table 1.

[0167] Table 1 Analysis and test results

[0168]

[0169] As can be seen from Table 1, in Example 1, when the transition barrier layer contains 6.2% nano-γ-alumina, its labyrinthine barrier structure extends the migration path of chloride ions. The phosphonate group in the chelating agent methylene diphosphonic acid molecules forms a five-membered chelate ring with nickel ions, fixing the free nickel ions in the area near the metal matrix. The carboxyl-modified resin binds to the oxide film on the surface of the titanium alloy through coordination bonds, improving the interfacial binding energy. The three factors work together to reduce the amount of nickel precipitation to 0.32 μg / cm² (only 15% of that in Comparative Example 1). When the thickness of the transition barrier layer in Comparative Example 4 was reduced to 1 micron, the nanoparticles were unable to form a continuous barrier, and the chloride ion permeability increased sharply.

[0170] The active carbonyl groups modified on the filler surface by plasma treatment are key sites for negative ion release. In Example 3, at a cerium-samarium molar ratio of 1:1, the lattice oxygen vacancy density reaches an optimal value, and weak mechanical stress can stimulate electron transitions, prompting the splitting of water molecules into hydroxyl anions. This process achieves a negative ion concentration of 1580 ions / cm³ and a stable sweat pH of 6.5±0.3. However, when Comparative Example 2 used a 1:1.5 ratio, lattice distortion led to energy level mismatch, resulting in a negative ion concentration of 720 ions / cm³ and a 54% decrease in release efficiency. In Comparative Example 5, which was not plasma treated, the negative ion concentration was reduced by 34% due to the lack of surface active sites.

[0171] In Example 1, when the silane coupling agent had a molar ratio of epoxy to amino groups of 2.3:1, the excess epoxy groups reacted with the resin's carboxyl groups through a ring-opening reaction to form a crosslinked network. This network absorbed energy through bond angle rotation under bending stress, resulting in an impedance attenuation rate of 12%. In Comparative Example 3, which lacked a coupling agent, the impedance attenuation rate reached 38%.

[0172] The 5H hardness of Example 3 stems from the high crosslink density of dipentaerythritol hexaacrylate. Its dense structure minimizes water vapor transmission, effectively protecting the active layer. Fluorinated segments accumulate on the coating surface, forming a barrier, while the hard microdomains in the polyurethane backbone provide a scratch-resistant framework.

[0173] Comparative Example 1 lacks both a physical barrier and chemical chelation, resulting in nickel precipitation exceeding the permitted level by 7 times. In Comparative Example 2, insufficient negative ion release causes the sweat pH to drop to 5.2, accelerating substrate corrosion. In contrast, in Example 1, the transition barrier layer reduces chloride ion permeability by >80%, the functional release layer continuously neutralizes hydrogen ions, and the wear-resistant layer blocks external abrasion and moisture penetration. This synergy ensures that the temple retains over 90% of its protective function even after 10,000 flexing cycles, surpassing the passive protection limitations of traditional technologies.

[0174] Test results show that the present invention, through the synergistic effect of three layers of functional materials, effectively blocks the penetration of corrosive ions from sweat into the metal matrix while stably releasing negative ions to neutralize acidic substances on the contact surface, significantly inhibiting the precipitation of metal ions and improving the wearing microenvironment, while ensuring the lightweight and durability of the frame structure.

[0175] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A glasses frame material with negative ion release function, characterized in that: The glasses frame material is compounded from the inside to the outside in sequence with: a metal base layer, a transition barrier layer, and a functional release layer; The transition barrier layer is in direct contact with the metal matrix layer, and the transition barrier layer is composed of a chelate-modified nanocomposite barrier material; The functional release layer covers the transition barrier layer, and the functional release layer is composed of a plasma-activated rare earth doped mineral composite material; The thickness of the transition barrier layer is 6-10 microns. The transition barrier layer comprises a transition barrier layer matrix resin, nano-inorganic particles, and a metal ion chelating agent. Based on the total mass of the transition barrier layer, the mass percentage of the nano-inorganic particles is 5.0%-7.5%, the mass percentage of the metal ion chelating agent is 0.9%-1.1%, and the balance is the transition barrier layer matrix resin. The matrix resin is polyetheretherketone or modified polyaryletherketone containing carboxyl side chains, and the content of carboxyl groups in the modified polyaryletherketone containing carboxyl side chains is 1.2-1.4 mol%; the nano inorganic particles are γ-Al2O3 powder with an average particle size D50 of 20-50 nanometers; and the metal ion chelating agent is at least one of methylenediphosphonic acid and ethylenediaminetetramethylenephosphonic acid sodium salt.

2. The eyeglass frame material with negative ion release function according to claim 1, characterized in that: The metal base layer is any one of nickel-titanium alloy, titanium alloy, and 316L stainless steel.

3. The eyeglass frame material with negative ion releasing function according to claim 1, characterized in that: The thickness of the functional release layer is 40-55 microns. The functional release layer includes a functional release layer matrix resin and a negative ion releasing filler. Based on the total mass of the functional release layer, the mass percentage of the negative ion releasing filler is 33%-37%; the matrix resin of the functional release layer is polyetheretherketone or a modified polyaryletherketone containing a carboxyl side chain, and the negative ion releasing filler is a rare earth-doped strontium titanate-based composite mineral powder, wherein the doped rare earth elements include cerium and samarium, and the molar ratio of cerium to samarium is 1:0.95-1.

05. The average particle size D50 of the negative ion releasing filler is 1.2-1.6 microns.

4. The eyeglass frame material with negative ion release function according to claim 3, characterized in that: The negative ion-releasing filler is pretreated as follows before use: the negative ion-releasing filler is dehydrated for 2-3 hours under vacuum conditions of less than 0.01 Pa and a temperature of 280-320°C; then placed in a mixed atmosphere of nitrogen and carbon dioxide with a volume ratio of 4:1, and treated in a plasma environment with a radio frequency power of 400-600 W and a frequency of 13.56 MHz for 5-6 minutes.

5. The eyeglass frame material with negative ion release function according to claim 3, characterized in that: A silane coupling agent is also added to the components of the functional release layer. The silane coupling agent contains both epoxy groups and amino groups in its molecules, wherein the molar ratio of the number of epoxy groups to the number of amino groups is 2.2-2.5:1, and the added amount of the silane coupling agent accounts for 2.0%-2.2% of the total mass of the functional release layer.

6. The eyeglass frame material with negative ion releasing function according to claim 1, characterized in that: A transparent wear-resistant protective layer is coated on the outer surface of the functional release layer. The wear-resistant protective layer is made of fluorosilicone modified polyurethane acrylate light-curing material and has a thickness of 4.5-5.5 microns.

7. The eyeglass frame material with negative ion release function according to claim 6, characterized in that: The fluorosilicone modified polyurethane acrylate light-curing material comprises the following components by mass percentage: Fluorosilicone modified polyurethane acrylate prepolymer 60-65%; Dipentaerythritol hexaacrylate 10-15%; 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide TPO 5-7%; Polyether modified polysiloxane 0.8-1.2%; Propylene glycol methyl ether acetate balance.

8. The eyeglass frame material with negative ion releasing function according to claim 7, characterized in that: The preparation method of the fluorosilicone modified polyurethane acrylate prepolymer comprises the following steps: (a) Prepolymerization: 35-40 parts by weight of isophorone diisocyanate and 50-55 parts by weight of polytetramethylene ether glycol were added to a reactor under nitrogen protection. After heating to 72-76°C, 0.05-0.1 parts by weight of dibutyltin dilaurate as a catalyst was added. The reaction was kept at this temperature for 2.5-3 hours, and the NCO group content was monitored to reach 8.2-8.8 wt%. (b) Fluorosilicon modification: adding 8-10 parts by mass of a fluorine-containing silane monomer, wherein the fluorine-containing silane monomer is tridecafluorooctylalkoxypropyltrimethoxysilane, to the product obtained in step (a), and continuing the reaction at 62-68°C for 1.5-2 hours; (c) Acrylate end-capping: Add 0.15-0.2 parts by weight of p-hydroxyanisole as a polymerization inhibitor to the product obtained in step (b), cool to 58-62°C, and dropwise add a mixture of 7-8 parts by weight of hydroxyethyl acrylate and 4-5 parts by weight of trimethylolpropane triacrylate. Keep warm and react until the NCO group content is ≤0.1wt%; (d) Dilution and post-treatment: adding 20-25 parts by weight of tetrahydrofuran acrylate as a reactive diluent to the product obtained in step (c), stirring and mixing, cooling to below 40° C., and discharging to obtain a fluorosilicone-modified polyurethane acrylate prepolymer.

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