Soft hydrophilic contact lens and material, preparation method and application thereof

Abstract

The invention discloses a soft hydrophilic contact lens as well as a material, a preparation method and application thereof, and relates to the technical field of soft hydrophilic contact lenses. Comprising the following components: hydroxyethyl methylacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N, N-dimethyl formamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2- The invention relates to an ultraviolet light absorber, which is prepared from N, N-dimethyl-[2-(2-methylpropyl-2-enoyloxy) ethyl] ammonium] propane-1-sulfonic acid inner salt, allyl-beta-cyclodextrin, 1, 4-di (methylimidazole) butane dibromo salt, a photoinitiator, a coloring agent, an ultraviolet light absorber, an auxiliary additive and an ionic cross-linking agent. The soft hydrophilic contact lens is more excellent in hydrophilicity, flexibility, optical performance and anti-pollution performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of soft hydrophilic contact lenses, in particular to a soft hydrophilic contact lens, a material thereof, a preparation method and an application. BACKGROUND

[0002] In recent years, myopia has become a global public health problem, and the incidence of myopia in adolescents is increasing year by year. With the increasing demand for vision correction, soft hydrophilic contact lenses have been widely used in the field of ophthalmology due to their comfort and good visual effect. However, soft hydrophilic contact lenses are prone to water loss during wear, and continuous water loss during wear can cause dry eye, leading to the accumulation of deposits on the lens surface, reduced vision and lens oxygen permeability, and seriously affecting the quality of wear. Therefore, it is of great significance to develop a soft hydrophilic contact lens material with good moisturizing effect to alleviate or reduce eye dryness during wear and improve the quality and comfort of wear.

[0003] The material of the traditional soft hydrophilic contact lens is usually composed of hydrophilic organic monomers, hydrophobic organic monomers and crosslinking agents, and it is difficult to simultaneously improve the mechanical properties and hydrophilic properties, and the anti-fouling performance is poor. During wear, proteins, lipids and other substances in tears are easily attached to the lens surface, forming deposits, which not only affect the clarity of the lens, but also may breed bacteria and cause eye infections, and the flexibility and adaptability are limited, and the lens is prone to discomfort during wear.

[0004] The existing soft hydrophilic contact lens also has the technical defects of complex preparation process, low production efficiency, and difficulty in ensuring the uniformity of the structure and performance of the lens. In the lens forming process, it is easy to appear defocus ring pattern blur, uneven layer thickness and other problems, which affect the optical performance and myopia prevention effect of the lens.

[0005] In order to solve the above problems, the Chinese patent with the authorization publication number CN101477214B discloses a soft hydrophilic contact lens containing polyethylene glycol and a preparation method thereof. Raw materials are mixed, then placed in a mold for thermal polymerization and post-vulcanization, and then obtained through mechanical processing, hydration, extraction, and cleaning. The contact lens is a traditional contact lens material with a first structure added with polyethylene glycol with excellent moisture retention, which forms a through copolymer with the comonomer to reduce the water evaporation of the material, improve the surface wettability, and thus improve the wearing comfort and prolong the wearing time of the wearer in a dry environment. However, although the chemical properties of polyethylene glycol are very stable under general conditions, it can react with oxygen in the air at a temperature of 120℃ or higher; and the low molecular weight polyethylene glycol has relatively large toxicity, and local application of polyethylene glycol, especially mucosal administration, can cause irritating pain; and with the increase of the molecular weight, the water solubility, vapor pressure, water absorption, and organic solvent solubility of polyethylene glycol decrease, and the freezing point, relative density, flash point, and viscosity increase, and the thermal stability is improved, but it cannot react with many chemicals. Therefore, if the reaction is not complete, the residual ingredients of polyethylene glycol used for preparing the soft hydrophilic contact lens have certain risks for the safe use of the lens. Most importantly, the hydrophilic effect of polyethylene glycol is limited, and the effect of improving the water content of the soft hydrophilic contact lens is still not ideal. SUMMARY

[0006] The present application aims to overcome the shortcomings of the prior art and provide a soft hydrophilic contact lens, a material thereof, a preparation method, and an application. The hydrophilicity, mechanical properties, wearing comfort, optical properties, and service life of the lens are improved by optimizing the lens material formula and three-layer structure design. The production efficiency and product quality uniformity are improved by improving the preparation method.

[0007] To achieve the above object, the technical scheme adopted by the present application is as follows: a soft hydrophilic contact lens material, by weight, comprising the following components: 45-55 parts of hydroxyethyl methacrylate, 2-4 parts of ethylene glycol dimethacrylate, 5-8 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 2-4 parts of 2-acrylamido-2-methylpropane sulfonic acid, 2-4 parts of N-trihydroxymethyl methacrylamide, 3-5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 0.8-1.2 parts of allyl-β-cyclodextrin, 1-3 parts of 1,4-bis(methylimidazole)butane dibromide, 0.2-0.6 parts of a photoinitiator, 0.1-0.3 parts of a colorant, 0.8-1.2 parts of an ultraviolet light absorber, 1-3 parts of an auxiliary additive, and 1-3 parts of an ionic crosslinking agent.

[0008] Preferably, the molecular weight of the polyethylene glycol dimethacrylate is 600, which is provided by Guangzhou Yuanda New Material Co., Ltd.

[0009] Preferably, the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biological Technology Co., Ltd.

[0010] Preferably, the photoinitiator is Irgacure 2959.

[0011] Preferably, the colorant is any one of phthalocyanine blue B and phthalocyanine green G.

[0012] Preferably, the ultraviolet light absorber is Ti-Pure™ R-796+.

[0013] Preferably, the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of (3-5):1.

[0014] Preferably, the ionic crosslinking agent is a mixture of carboxymethyl cellulose sodium and calcium chloride in a mass ratio of (1-3):1.

[0015] Another object of the present application is to provide a multi-ring defocus soft hydrophilic contact lens made of the soft hydrophilic contact lens material, which comprises, from inside to outside, an optical core layer, a defocus function layer, and a surface protection layer, wherein the optical core layer is made of the soft hydrophilic contact lens material; the defocus function layer has a composition formula basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 3 parts; and the surface protection layer has a composition formula basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 5 parts.

[0016] Still another object of the present application is to provide a preparation method of the multi-ring defocus soft hydrophilic contact lens, which comprises the following steps: Step S1, preparation of a prepolymer solution: adding hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, a photoinitiator, a colorant, an ultraviolet light absorber, and an auxiliary additive into a container, stirring uniformly to obtain a basic mixture; mixing an ionic crosslinking agent with deionized water uniformly, then slowly adding the basic mixture while stirring to form a prepolymer solution; Step S2, layering molding: first, the prepolymer liquid for preparing the optical core layer is injected into the mold, and preliminary curing is carried out under ultraviolet light; after the optical core layer is preliminarily cured, the out-of-focus functional layer prepolymer liquid is injected, so that it is fully attached to the optical core layer, and ultraviolet light curing is carried out again; finally, the surface protection layer prepolymer liquid is injected, the construction of the three-layer structure is completed, and the third ultraviolet light curing is carried out; Step S3, post-processing: the molded lens is taken out of the mold, soaked in a 1,4-bis(methylimidazole) butane dibromide solution at 50-60℃ for 10-20h, and after taking out, multiple cleaning is carried out with deionized water and physiological saline in sequence to remove surface residual impurities and unreacted components; then the lens is soaked in physiological saline for 18-24 hours to reach the equilibrium water content; finally, the lens is subjected to high temperature and high pressure sterilization treatment, and a multi-ring out-of-focus soft hydrophilic contact lens is obtained.

[0017] Preferably, the mass ratio of the ionic crosslinking agent to deionized water in step S1 is 1:(3-5).

[0018] Preferably, the curing time of the preliminary curing in step S2 is 10-15 minutes, and the light intensity is 50-80mW / cm 2 ; the curing time of the ultraviolet light curing again is 15-20 minutes, and the light intensity is 60-90mW / cm 2 ; the curing time of the third ultraviolet light curing is 20-25 minutes, and the light intensity is 70-100mW / cm 2 .

[0019] Preferably, the mass percentage concentration of the 1,4-bis(methylimidazole) butane dibromide solution in step S3 is 3-6%.

[0020] Preferably, the sterilization treatment condition in step S3 is 121℃, 0.1MPa, and the sterilization time is 20-30 minutes.

[0021] Still another object of the present application is to provide an application of the multi-ring out-of-focus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0022] Due to the use of the above technical solutions, the present application has the following beneficial effects: (1) The soft hydrophilic contact lens material disclosed in this invention comprises the following components by weight: 45-55 parts of hydroxyethyl methacrylate, 2-4 parts of ethylene glycol dimethacrylate, 5-8 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 2-4 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-4 parts of N-tris(hydroxymethyl)methacrylamide, 3-5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 0.8-1.2 parts of allyl-β-cyclodextrin, 1-3 parts of 1,4-di(methylimidazolium)butane dibromide, 0.2-0.6 parts of photoinitiator, 0.1-0.3 parts of colorant, 0.8-1.2 parts of ultraviolet light absorber, 1-3 parts of auxiliary additives, and 1-3 parts of ionic crosslinking agent. Through the synergistic interaction of the various components, the resulting soft hydrophilic contact lens material exhibits superior hydrophilicity, mechanical properties, wearing comfort, optical performance, and lifespan. The introduction of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt improves the compatibility between the lens and tears, enhances the lens's anti-fouling properties, and increases hydrophilicity. Allyl-β-cyclodextrin, with its unique cyclic structure, can encapsulate small molecules and, after participating in the polymerization reaction, positively impacts the lens's hydrophilicity, flexibility, and the sustained-release properties of drugs or active ingredients. Hydroxyethyl methacrylate, as the main component, provides the lens with hydrophilicity and flexibility. Ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate, as crosslinking agents, work together with methacrylic acid to form a network structure with certain strength and stability through polymerization. The addition of 2-acrylamido-2-methylpropanesulfonic acid and N-tris(hydroxymethyl)methacrylamide further modulates the material's hydrophilicity and chemical activity, enhancing its performance. Photoinitiators, colorants, UV absorbers, auxiliary additives, and ionic crosslinkers work together; photoinitiators initiate polymerization reactions, colorants impart color to the lenses, UV absorbers protect the eyes from UV damage, auxiliary additives may improve the processing performance of the material, and ionic crosslinkers enhance the degree of crosslinking and stability of the material; the synergistic effect of these components makes the contact lens material formed by this formulation superior in performance to materials with single components or simple mixtures.

[0023] (2) The soft hydrophilic contact lens material disclosed in this invention uses 1,4-di(methylimidazolium)butane dibromide, which can undergo ion exchange reactions with the carboxyl and sulfonic acid groups (introduced by methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, respectively) in the polymerized lens material to form an ionic cross-linked structure. Compared with the traditional covalent cross-linked structure, this effectively improves the flexibility of the lens, allowing it to better fit the eyeball and reduce foreign body sensation during wear. At the same time, the ionic cross-linked structure promotes the uniform distribution of ionic groups, enhances the hydrophilicity and anti-fouling ability of the lens, and significantly reduces protein deposition.

[0024] (3) The disclosed multi-ring defocus soft hydrophilic contact lens comprises, from inside to outside, an optical core layer, a defocus function layer, and a surface protection layer, wherein the optical core layer is made of the soft hydrophilic contact lens material described above; the defocus function layer has a composition formula basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 3 parts; and the surface protection layer has a composition formula basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 5 parts. The design of the three-layer structure, combined with the optimization of the characteristics of the ion cross-linked hydrogel in each layer, not only ensures stable multi-ring defocus optical performance, but also improves the overall hydrogel stability of the lens and prolongs the service life; by controlling the addition amount of methacrylic acid in each layer, the influence of ion groups on optical performance can be reduced, and the defocus effect can be optimized.

[0025] (4) The disclosed preparation method of the multi-ring defocus soft hydrophilic contact lens introduces calcium chloride and sodium carboxymethyl cellulose compound as an ion cross-linking agent, and through a special addition method during the preparation of the pre-polymer solution, the calcium ions form a dynamic ionic bond with the carboxyl groups. Unlike traditional covalent cross-linked hydrogel preparation, this method not only utilizes ionic bonds to give hydrogel good flexibility and self-adaptability when constructing a three-dimensional network, but also solves the problem of traditional lens rigidity and easy breakage through synergy with covalent cross-linking. During the layered molding process, the amount of methacrylic acid and the reaction conditions in each layer are precisely controlled to achieve a gradient distribution of the ion cross-linked structure in the three layers. This precise control process not only ensures that the performance of each layer is optimal, but also realizes the tight combination between layers, effectively solving the problem of easy delamination of traditional three-layer structure lenses. Through the reasonable selection of each step and process parameter, they can work together, so that the multi-ring defocus soft hydrophilic contact lens made has excellent flexibility, stain resistance, and optical stability, and can effectively improve the prevention and control effect of myopia in adolescents. DETAILED DESCRIPTION

[0026] The following description is used to disclose the present application so that those skilled in the art can implement the present application. The preferred embodiments in the following description are only as examples, and other obvious modifications can be thought of by those skilled in the art.

[0027] Example 1 A soft hydrophilic contact lens material comprises the following components by weight: 45 parts of hydroxyethyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 5 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 2 parts of 2-acrylamido-2-methylpropane sulfonic acid, 2 parts of N-trihydroxymethyl methacrylamide, 3 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 0.8 parts of allyl-β-cyclodextrin, 1 part of 1,4-bis(methyl imidazole)butane dibromide, 0.2 parts of a photoinitiator, 0.1 parts of a colorant, 0.8 parts of a UV light absorber, 1 part of an auxiliary additive, and 1 part of an ionic crosslinking agent.

[0028] The molecular weight of the polyethylene glycol dimethacrylate is 600, provided by Guangzhou Yuanda New Material Co., Ltd.; the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biological Technology Co., Ltd.; the photoinitiator is Irgacure 2959; the colorant is phthalocyanine blue B; the UV light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of 3:1; and the ionic crosslinking agent is a mixture of carboxymethyl cellulose sodium and calcium chloride in a mass ratio of 1:1.

[0029] A multi-ring off-focus soft hydrophilic contact lens made of the soft hydrophilic contact lens material described above, comprising, from inside to outside, an optical core layer, an off-focus functional layer, and a surface protection layer, wherein the optical core layer is made of the soft hydrophilic contact lens material described above; the off-focus functional layer has a composition formula basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 3 parts; and the surface protection layer has a composition formula basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 5 parts.

[0030] A preparation method of the multi-ring off-focus soft hydrophilic contact lens, comprising the following steps: Step S1, preparation of a prepolymer solution: hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, a photoinitiator, a colorant, a UV light absorber, and an auxiliary additive are added into a container and stirred uniformly to obtain a basic mixture; an ionic crosslinking agent is mixed uniformly with deionized water and then slowly added into the basic mixture while stirring to form a prepolymer solution; Step S2, layering molding: first, the prepolymer solution for preparing the optical core layer is injected into the mold, and preliminary curing is carried out under ultraviolet light; after the optical core layer is preliminarily cured, the out-of-focus functional layer prepolymer solution is injected to make it fully adhere to the optical core layer, and ultraviolet light curing is carried out again; finally, the surface protection layer prepolymer solution is injected to complete the construction of the three-layer structure, and ultraviolet light curing is carried out for the third time; Step S3, post-processing: the molded lens is taken out of the mold, soaked in a 1,4-bis(methylimidazole) butane dibromide solution at 50℃ for 10h, and after taking out, cleaned with deionized water and physiological saline for multiple times to remove surface residual impurities and unreacted components; then the lens is soaked in physiological saline for 18 hours to reach the equilibrium water content; finally, the lens is subjected to high temperature and high pressure sterilization treatment to obtain a multi-ring out-of-focus soft hydrophilic contact lens.

[0031] The mass ratio of the ion crosslinking agent to deionized water in step S1 is 1:3; the curing time for the preliminary curing in step S2 is 10 minutes, and the light intensity is 50mW / cm 2 ; the curing time for the ultraviolet light curing again is 15 minutes, and the light intensity is 60mW / cm 2 ; the curing time for the third ultraviolet light curing is 20 minutes, and the light intensity is 70mW / cm 2 ; the mass percentage concentration of the 1,4-bis(methylimidazole) butane dibromide solution in step S3 is 3%; the sterilization treatment conditions in step S3 are 121℃, 0.1MPa, and the sterilization time is 20 minutes.

[0032] The application of a multi-ring out-of-focus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0033] Example 2 A soft hydrophilic contact lens material, by weight, comprises the following components: 47 parts of hydroxyethyl methacrylate, 2.5 parts of ethylene glycol dimethacrylate, 6 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 2.5 parts of 2-acrylamido-2-methylpropane sulfonic acid, 2.5 parts of N-trihydroxymethyl methacrylamide, 3.5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 0.9 parts of allyl-β-cyclodextrin, 1.5 parts of 1,4-bis(methylimidazole) butane dibromide, 0.3 parts of a photoinitiator, 0.15 parts of a colorant, 0.9 parts of an ultraviolet light absorber, 1.5 parts of an auxiliary additive, and 1.5 parts of an ion crosslinking agent.

[0034] The molecular weight of the polyethylene glycol dimethacrylate is 600, which is provided by Guangzhou Yuanda New Material Co., Ltd.; the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biological Technology Co., Ltd.; the photoinitiator is Irgacure 2959; the colorant is phthalocyanine green G; the ultraviolet light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of 3.5:1; and the ionic crosslinking agent is a mixture of carboxymethyl cellulose sodium and calcium chloride in a mass ratio of 1.5:1.

[0035] A multi-ring off-focus soft hydrophilic contact lens made of the soft hydrophilic contact lens material described above, which comprises, from inside to outside, an optical core layer, an off-focus functional layer, and a surface protection layer, wherein the optical core layer is made of the soft hydrophilic contact lens material described above; the off-focus functional layer has a composition formula basically the same as that of the optical core layer, except that the amount of methyl methacrylate added is 3 parts; and the surface protection layer has a composition formula basically the same as that of the optical core layer, except that the amount of methyl methacrylate added is 5 parts.

[0036] A preparation method of the multi-ring off-focus soft hydrophilic contact lens, comprising the following steps: Step S1, preparation of a prepolymer solution: adding hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, a photoinitiator, a colorant, an ultraviolet light absorber, and an auxiliary additive into a container, stirring uniformly to obtain a basic mixed solution; mixing an ionic crosslinking agent with deionized water uniformly, then slowly adding the above basic mixed solution while stirring to form a prepolymer solution; Step S2, layered molding: first, injecting the prepolymer solution for preparing the optical core layer into a mold, and performing preliminary curing under ultraviolet light; after the optical core layer is preliminarily cured, injecting the prepolymer solution for the off-focus functional layer, so that it is fully attached to the optical core layer, and performing ultraviolet curing again; finally, injecting the prepolymer solution for the surface protection layer, completing the construction of the three-layer structure, and performing ultraviolet curing for the third time; Step S3, post-treatment: taking the molded lens out of the mold, immersing it in a 1,4-bis(methylimidazole)butane dibromide solution at 53°C for 12 hours, then cleaning it with deionized water and physiological saline multiple times to remove surface residual impurities and unreacted components; then immersing the lens in physiological saline for 20 hours to make it reach the equilibrium water content; finally, sterilizing the lens by high-temperature and high-pressure treatment to obtain a multi-ring off-focus soft hydrophilic contact lens.

[0037] The mass ratio of the ion crosslinking agent and deionized water in step S1 is 1:3.5; the curing time of the preliminary curing in step S2 is 12 minutes, and the light intensity is 60 mW / cm 2 ; the curing time of the second UV curing is 17 minutes, and the light intensity is 70 mW / cm 2 ; the curing time of the third UV curing is 22 minutes, and the light intensity is 80 mW / cm 2 ; the mass percentage concentration of the 1,4-bis(methyl imidazole) butane dibromide solution in step S3 is 4%; the sterilization condition in step S3 is 121℃, 0.1 MPa, and the sterilization time is 23 minutes.

[0038] Application of the multi-ring defocus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0039] Example 3 A soft hydrophilic contact lens material comprises the following components by weight: 50 parts of hydroxyethyl methacrylate, 3 parts of ethylene glycol dimethacrylate, 6.5 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid, 3 parts of N-trihydroxymethyl methacrylamide, 4 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 1 part of allyl-β-cyclodextrin, 2 parts of 1,4-bis(methyl imidazole) butane dibromide, 0.4 parts of a photoinitiator, 0.2 parts of a colorant, 1 part of a UV light absorber, 2 parts of an auxiliary additive, and 2 parts of an ion crosslinking agent.

[0040] The molecular weight of the polyethylene glycol dimethacrylate is 600, which is provided by Guangzhou Yuanda New Material Co., Ltd.; the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biological Technology Co., Ltd.; the photoinitiator is Irgacure 2959; the colorant is phthalocyanine blue B; the UV light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E with a mass ratio of 4:1; and the ion crosslinking agent is a mixture of carboxymethyl cellulose sodium and calcium chloride with a mass ratio of 2:1.

[0041] A multi-ring defocus soft hydrophilic contact lens made of the above-mentioned soft hydrophilic contact lens material comprises, from inside to outside, an optical core layer, a defocus functional layer, and a surface protection layer, wherein the optical core layer is made of the above-mentioned soft hydrophilic contact lens material; the composition formula of the defocus functional layer is basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 3 parts; and the composition formula of the surface protection layer is basically the same as that of the optical core layer, except that the addition amount of methacrylic acid is 5 parts.

[0042] A preparation method of the multi-ring off-focus soft hydrophilic contact lens, comprising the following steps: Step S1, preparation of prepolymer solution: add hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, photoinitiator, colorant, ultraviolet light absorber and auxiliary additive into a container, stir uniformly to obtain a basic mixed solution; mix the ionic crosslinking agent with deionized water uniformly, then slowly add the above-mentioned basic mixed solution, stirring while adding, to form a prepolymer solution; Step S2, layered molding: first inject the prepolymer solution for preparing the optical core layer into a mold, and perform preliminary curing under ultraviolet light; after the optical core layer is preliminarily cured, inject the off-focus functional layer prepolymer solution, so that it is fully attached to the optical core layer, and then perform ultraviolet curing again; finally, inject the surface protection layer prepolymer solution, complete the construction of the three-layer structure, and perform the third ultraviolet curing; Step S3, post-processing: take out the molded lens from the mold, immerse it in a 1,4-bis(methylimidazole)butane dibromide solution at 55℃ for 15h, then take it out and clean it with deionized water and physiological saline for multiple times to remove surface residual impurities and unreacted components; then immerse the lens in physiological saline for 21 hours to make it reach the equilibrium water content; finally, perform high-temperature and high-pressure sterilization treatment on the lens to obtain a multi-ring off-focus soft hydrophilic contact lens.

[0043] The mass ratio of the ionic crosslinking agent to deionized water in step S1 is 1:4; the curing time of the preliminary curing in step S2 is 13 minutes, and the light intensity is 65mW / cm 2 ; the curing time of the ultraviolet curing again is 18 minutes, and the light intensity is 75mW / cm 2 ; the curing time of the third ultraviolet curing is 23 minutes, and the light intensity is 85mW / cm 2 ; the mass percentage concentration of the 1,4-bis(methylimidazole)butane dibromide solution in step S3 is 4.5%; the sterilization treatment condition in step S3 is 121℃, 0.1MPa, and the sterilization time is 25 minutes.

[0044] The application of the multi-ring off-focus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0045] Example 4 A soft hydrophilic contact lens material comprises the following components by weight: 53 parts of hydroxyethyl methacrylate, 3.5 parts of ethylene glycol dimethacrylate, 7.5 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 3.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 3.5 parts of N-trihydroxymethyl methacrylamide, 4.5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 1.1 parts of allyl-β-cyclodextrin, 2.5 parts of 1,4-bis(methylimidazole)butane dibromide, 0.55 parts of a photoinitiator, 0.25 parts of a colorant, 1.1 parts of a UV light absorber, 2.5 parts of an auxiliary additive, and 2.5 parts of an ionic crosslinking agent.

[0046] The polyethylene glycol dimethacrylate has a molecular weight of 600 and is provided by Guangzhou Yuanda New Material Co., Ltd.; the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biological Technology Co., Ltd.; the photoinitiator is Irgacure 2959; the colorant is phthalocyanine green G; the UV light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of 4.5:1; and the ionic crosslinking agent is a mixture of carboxymethyl cellulose sodium and calcium chloride in a mass ratio of 2.5:1.

[0047] A multi-ring off-focus soft hydrophilic contact lens made of the soft hydrophilic contact lens material described above comprises, from inside to outside, an optical core layer, an off-focus functional layer, and a surface protection layer, wherein the optical core layer is made of the soft hydrophilic contact lens material described above; the off-focus functional layer has a composition formula basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 3 parts; and the surface protection layer has a composition formula basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 5 parts.

[0048] A method for preparing the multi-ring off-focus soft hydrophilic contact lens, comprising the following steps: Step S1, preparation of a prepolymer solution: hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-trihydroxymethyl methacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, a photoinitiator, a colorant, a UV light absorber, and an auxiliary additive are added into a container and stirred uniformly to obtain a basic mixture; an ionic crosslinking agent is mixed uniformly with deionized water and then slowly added into the basic mixture while stirring to form a prepolymer solution; Step S2, layering molding: first, the prepolymer solution for preparing the optical core layer is injected into the mold, and preliminary curing is carried out under ultraviolet light; after the optical core layer is preliminarily cured, the out-of-focus functional layer prepolymer solution is injected to make it fully adhere to the optical core layer, and ultraviolet light curing is carried out again; finally, the surface protection layer prepolymer solution is injected to complete the construction of the three-layer structure, and ultraviolet light curing is carried out for the third time; Step S3, post-processing: the molded lens is taken out of the mold, soaked in a 1,4-bis(methylimidazole) butane dibromide solution at 58℃ for 18h, and after taking out, multiple cleaning is carried out with deionized water and physiological saline in sequence to remove surface residual impurities and unreacted components; then the lens is soaked in physiological saline for 23 hours to make it reach the equilibrium water content; finally, the lens is subjected to high-temperature high-pressure sterilization treatment to obtain a multi-ring out-of-focus soft hydrophilic contact lens.

[0049] The mass ratio of the ion crosslinking agent to deionized water in step S1 is 1:4.5; the curing time for the preliminary curing in step S2 is 14 minutes, and the light intensity is 75mW / cm 2 ; the curing time for the ultraviolet light curing again is 19 minutes, and the light intensity is 85mW / cm 2 ; the curing time for the third ultraviolet light curing is 24 minutes, and the light intensity is 95mW / cm 2 ; the mass percentage concentration of the 1,4-bis(methylimidazole) butane dibromide solution in step S3 is 5.5%; the sterilization treatment condition in step S3 is 121℃, 0.1MPa, and the sterilization time is 28 minutes.

[0050] The application of a multi-ring out-of-focus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0051] Example 5 A soft hydrophilic contact lens material, by weight, comprises the following components: 55 parts of hydroxyethyl methacrylate, 4 parts of ethylene glycol dimethacrylate, 8 parts of polyethylene glycol dimethacrylate, 1 part of methacrylic acid, 4 parts of 2-acrylamido-2-methylpropane sulfonic acid, 4 parts of N-trihydroxymethyl methacrylamide, 5 parts of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 1.2 parts of allyl-β-cyclodextrin, 3 parts of 1,4-bis(methylimidazole) butane dibromide, 0.6 parts of a photoinitiator, 0.3 parts of a colorant, 1.2 parts of an ultraviolet light absorber, 3 parts of an auxiliary additive, and 3 parts of an ion crosslinking agent.

[0052] The polyethylene glycol dimethacrylate has a molecular weight of 600 and is provided by Guangzhou Yuanda New Materials Co., Ltd.; the allyl-β-cyclodextrin is provided by Shandong Binzhou Zhiyuan Biotechnology Co., Ltd.; the photoinitiator is Irgacure2959; the colorant is phthalocyanine blue B; the ultraviolet light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of 5:1; and the ionic crosslinking agent is a mixture of sodium carboxymethyl cellulose and calcium chloride in a mass ratio of 3:1.

[0053] A multi-ring defocusing soft hydrophilic contact lens made of the aforementioned soft hydrophilic contact lens material comprises, from the inside out, an optical core layer, a defocusing functional layer, and a surface protective layer. The optical core layer is made of the aforementioned soft hydrophilic contact lens material. The composition of the defocusing functional layer is basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 3 parts. The composition of the surface protective layer is basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 5 parts.

[0054] A method for preparing the multi-ring defocused soft hydrophilic contact lens includes the following steps: Step S1, Prepolymer Solution Preparation: Hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-trismethylolmethacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, photoinitiator, colorant, ultraviolet absorber, and auxiliary additives are added to a container and stirred until homogeneous to obtain a basic mixture. After homogeneous mixing of the ionic crosslinking agent and deionized water, the mixture is slowly added to the above basic mixture while stirring continuously to form a prepolymer solution. Step S2, Layered Molding: First, the prepolymer liquid used to prepare the optical core layer is injected into the mold and pre-cured under ultraviolet light; after the optical core layer is pre-cured, the prepolymer liquid for the defocusing functional layer is injected to make it fully adhere to the optical core layer, and then cured under ultraviolet light again; finally, the prepolymer liquid for the surface protective layer is injected to complete the construction of the three-layer structure, and then cured under ultraviolet light for the third time. Step S3, Post-processing: Remove the molded lens from the mold and soak it in a 1,4-di(methylimidazolium)butane dibromide solution at 60℃ for 20 hours. After removal, wash it several times with deionized water and physiological saline to remove residual impurities and unreacted components on the surface. Then, soak the lens in physiological saline for 24 hours to reach equilibrium water content. Finally, sterilize the lens under high temperature and high pressure to obtain a multi-ring defocus soft hydrophilic contact lens.

[0055] The mass ratio of the ionic crosslinking agent to deionized water in step S1 is 1:5; the curing time for the initial curing in step S2 is 15 minutes, and the light intensity is 80 mW / cm². 2 The second UV curing process takes 20 minutes and the light intensity is 90 mW / cm². 2 The third UV curing process took 25 minutes and the light intensity was 100 mW / cm². 2 The mass percentage concentration of the 1,4-di(methylimidazolium)butane dibromide solution in step S3 is 6%; the sterilization conditions in step S3 are 121℃, 0.1MPa, and sterilization time of 30 minutes.

[0056] Application of the aforementioned multi-ring defocus soft hydrophilic contact lens in the prevention and control of myopia in adolescents.

[0057] Comparative Example 1 This example provides a soft hydrophilic contact lens, its material, preparation method, and application, which are basically the same as those in Example 1. The difference is that 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt is not added, and an equal amount of ethylene glycol dimethacrylate is used instead of polyethylene glycol dimethacrylate.

[0058] Comparative Example 2 This example provides a soft hydrophilic contact lens, its material, preparation method, and application, which are basically the same as those in Example 1, except that allyl-β-cyclodextrin and 1,4-di(methylimidazolium)butane dibromide are not added.

[0059] To further illustrate the beneficial technical effects of the soft hydrophilic contact lenses and their materials involved in the various embodiments of the present invention, relevant performance tests were conducted on the soft hydrophilic contact lenses involved in each example. The test results are shown in Table 1. The thickness of the optical core layer of the test sample was 0.12 mm, the thickness of the defocusing functional layer was 0.1 mm, and the thickness of the surface protective layer was 0.08 mm. The test methods are as follows: Moisture content: Moisture content was tested in accordance with GB / T 11417.7-2012.

[0060] (2) Flexibility: The lens was cut into strip-shaped standard specimens with a width of 5 mm and a length of 20 mm. One end was fixed to the universal testing machine with a special clamp to ensure that the specimen was firmly fixed and free of stress concentration. The other end was subjected to a uniform bending force through the moving clamp of the testing machine, bending the specimen to 180° at a rate of 1 mm / min and holding it for 10 seconds. After the bending force was released, the time required for the specimen to return to its initial flat state was recorded using the high-precision displacement sensor and data acquisition system of the testing machine. The shorter the time, the better the flexibility. Each specimen was tested three times, and the average value was taken as the final result.

[0061] (3) Anti-fouling performance: The specific composition of the simulated tear protein solution is as follows: human serum albumin 2.0 g / L, lysozyme 0.2 g / L, lactoferrin 1.0 g / L, immunoglobulin A 0.2 g / L. The above protein components are dissolved in a buffer salt solution containing 0.9% sodium chloride, 0.02% potassium chloride, 0.02% calcium chloride, and 0.01% magnesium chloride. The pH value is adjusted to 7.4 with 1 mol / L hydrochloric acid or sodium hydroxide solution. After making up the volume, the solution is filtered through a 0.22 μm filter membrane for sterilization and stored at 4℃ for later use. The lenses are placed in the simulated tear protein solution and shaken at 37℃ for 12 hours. The remaining protein content in the solution is determined by spectrophotometry, and the protein adsorption rate is calculated.

[0062] (4) Light transmittance: The light transmittance was tested according to the method in GB / T 11417.5-2012 "Ophthalmic Contact Lenses Part 5: Test Methods for Optical Performance".

[0063] Table 1 Performance test results of soft hydrophilic contact mirrors Item Moisture content Flexibility Stain resistance Light transmittance Unit % s % % Example 1 55 2.5 15 ＞95 Example 2 57 2.1 13 ＞95 Example 3 58 1.5 10 ＞97 Example 4 60 1.3 9 ＞97 Example 5 61 1.0 7 ＞98 Comparative Example 1 49 3.8 20 ＜92 Comparative Example 2 47 4.2 23 ＜89 As can be seen from the table above, the soft hydrophilic contact mirrors and their materials involved in the embodiments of the present invention have better hydrophilicity, flexibility, and anti-fouling properties than the comparative products, and superior optical performance. The combined use of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, polyethylene glycol dimethacrylate, allyl-β-cyclodextrin, and 1,4-di(methylimidazolium)butane dibromide is beneficial to improving the above properties.

[0064] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A soft hydrophilic contact mirror material, characterized in that, By weight, it comprises the following components: 45-55 parts hydroxyethyl methacrylate, 2-4 parts ethylene glycol dimethacrylate, 5-8 parts polyethylene glycol dimethacrylate, 1 part methacrylic acid, 2-4 parts 2-acrylamido-2-methylpropanesulfonic acid, 2-4 parts N-tris(hydroxymethyl)methacrylamide, 3-5 parts 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 0.8-1.2 parts allyl-β-cyclodextrin, 1-3 parts 1,4-di(methylimidazolium)butane dibromide, 0.2-0.6 parts photoinitiator, 0.1-0.3 parts colorant, 0.8-1.2 parts ultraviolet absorber, 1-3 parts auxiliary additives, and 1-3 parts ionic crosslinking agent.

2. The soft hydrophilic contact mirror material according to claim 1, characterized in that, The molecular weight of the polyethylene glycol dimethacrylate is 600.

3. The soft hydrophilic contact mirror material according to claim 1, characterized in that, The photoinitiator is Irgacure 2959; the colorant is either phthalocyanine blue B or phthalocyanine green G.

4. The soft hydrophilic contact mirror material according to claim 1, characterized in that, The ultraviolet light absorber is Ti-Pure™ R-796+; the auxiliary additive is a mixture of glycerol and vitamin E in a mass ratio of (3-5):

1.

5. The soft hydrophilic contact mirror material according to claim 1, characterized in that, The ionic crosslinking agent is a mixture of sodium carboxymethyl cellulose and calcium chloride in a mass ratio of (1-3):

1.

6. A multi-ring defocus soft hydrophilic contact lens made of the soft hydrophilic contact lens material according to any one of claims 1-5, characterized in that, From the inside out, it includes an optical core layer, a defocusing functional layer, and a surface protective layer. The optical core layer is made of the aforementioned soft hydrophilic contact lens material. The composition of the defocusing functional layer is basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 3 parts. The composition of the surface protective layer is basically the same as that of the optical core layer, except that the amount of methacrylic acid added is 5 parts.

7. A method for preparing a multi-ring defocused soft hydrophilic contact lens according to claim 6, characterized in that, Includes the following steps: Step S1, Prepolymer Solution Preparation: Hydroxyethyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-trismethylolmethacrylamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, allyl-β-cyclodextrin, photoinitiator, colorant, ultraviolet absorber, and auxiliary additives are added to a container and stirred until homogeneous to obtain a basic mixture. After homogeneous mixing of the ionic crosslinking agent and deionized water, the mixture is slowly added to the above basic mixture while stirring continuously to form a prepolymer solution. Step S2, Layered Molding: First, the prepolymer liquid used to prepare the optical core layer is injected into the mold and pre-cured under ultraviolet light; After the optical core layer has initially cured, the defocusing functional layer prepolymer liquid is injected to ensure it fully adheres to the optical core layer, and then UV curing is performed again. Finally, the surface protective layer prepolymer liquid is injected to complete the construction of the three-layer structure, and then UV curing is performed a third time. Step S3, Post-processing: Remove the molded lens from the mold and soak it in a 1,4-di(methylimidazolium)butane dibromide solution at 50-60℃ for 10-20 hours. After removal, wash it several times with deionized water and physiological saline to remove residual impurities and unreacted components from the surface. Then, soak the lens in physiological saline for 18-24 hours to allow it to reach equilibrium water content. Finally, sterilize the lens under high temperature and high pressure to obtain a multi-ring defocused soft hydrophilic contact lens.

8. The method for preparing the multi-ring defocused soft hydrophilic contact lens according to claim 7, characterized in that, The mass ratio of the ionic crosslinking agent to deionized water in step S1 is 1:(3-5); the curing time for the initial curing in step S2 is 10-15 minutes, and the light intensity is 50-80 mW / cm². 2 The second UV curing process takes 15-20 minutes and the light intensity is 60-90 mW / cm². 2 The third UV curing step takes 20-25 minutes and the light intensity is 70-100 mW / cm². 2 .

9. The method for preparing the multi-ring defocused soft hydrophilic contact lens according to claim 7, characterized in that, The mass percentage concentration of the 1,4-di(methylimidazolium)butane dibromide solution in step S3 is 3-6%; the sterilization conditions in step S3 are 121℃, 0.1MPa, and sterilization time of 20-30 minutes.

10. The application of the multi-ring defocus soft hydrophilic contact lens according to claim 7 in the prevention and control of myopia in adolescents.