技术领域technical field
本发明涉及一种接触透镜及处理方法，具体来说，涉及一种超亲水硅水凝胶接触透镜及处理方法。The invention relates to a contact lens and a treatment method, in particular to a superhydrophilic silicon hydrogel contact lens and a treatment method.
背景技术Background technique
角膜接触透镜又称为“隐形眼镜”，是一种戴在眼球角膜上，用以矫正视力或保护眼睛的镜片。根据材料的软硬它包括硬性、半硬性、软性三种。隐形眼镜不仅从外观上和方便性方面给近视、远视、散光等屈光不正患者带来了很大的改善，而且视野宽阔、视物逼真。此外在控制青少年近视、散光发展，治疗特殊的眼病等方面也发挥了特殊的功效。Contact lenses, also known as "contact lenses", are lenses worn on the cornea of the eye to correct vision or protect the eyes. According to the softness and hardness of the material, it includes three types: rigid, semi-rigid, and soft. Contact lenses not only greatly improve patients with refractive errors such as myopia, hyperopia, and astigmatism in terms of appearance and convenience, but also have a wide field of vision and realistic vision. In addition, it has also played a special role in controlling the development of myopia and astigmatism in young people, and treating special eye diseases.
其中，软性隐形眼镜发展最为迅速，现在已经逐步成为最主要的隐形眼镜类消费产品。最初的软性接触镜以2-甲基丙烯酸羟乙酯（HEMA）作为原料制备得到的；后来逐渐发展出了以HEMA与其他亲水单体的共聚物为基材的隐形眼镜。这类隐形眼镜存在一个很大的问题就是透氧性差，不利于长时间佩戴。为了克服这一难题，科学家们突破性地向原先的原料中引入了含硅单体进行共聚，这样制备出了一种新型接触镜材料—硅水凝胶。Among them, soft contact lenses have developed the fastest and have gradually become the most important contact lens consumer products. The initial soft contact lenses were prepared from 2-hydroxyethyl methacrylate (HEMA); later, contact lenses based on copolymers of HEMA and other hydrophilic monomers were gradually developed. A big problem with this type of contact lens is that it has poor oxygen permeability, which is not conducive to long-term wearing. In order to overcome this problem, scientists made a breakthrough by introducing silicon-containing monomers into the original raw materials for copolymerization, thus preparing a new type of contact lens material - silicon hydrogel.
硅水凝胶隐形眼镜已经普及，这是与传统水凝胶隐形眼镜相比，隐形眼镜佩戴者佩戴硅水凝胶隐形眼镜可以持续更长的时间。举例来说，视特定眼镜而定，硅水凝胶隐形眼镜可经每天佩戴、每周佩戴、双周佩戴或每月佩戴而磨损或规定为每天佩戴、每周佩戴、双周佩戴或每月佩戴。硅水凝胶隐形眼镜的益处可部分归因于水凝胶中含硅部分的疏水性。Silicone hydrogel contact lenses have gained popularity, which is why contact lens wearers can wear silicone hydrogel contact lenses for a longer period of time than traditional hydrogel contact lenses. For example, depending on the particular lens, a silicone hydrogel contact lens may be worn or prescribed to be worn daily, weekly, biweekly, or monthly wear. The benefits of silicone hydrogel contact lenses can be attributed in part to the hydrophobicity of the silicon-containing moieties in the hydrogel.
但是，含硅单体的疏水性意味着由其制成的角膜接触镜难于湿润。用于生物医学装置的材料的适用性取决于该材料的可湿润性和其与如蛋白质和脂质的生物材料粘附或反应的倾向。However, the hydrophobic nature of silicon-containing monomers means that contact lenses made from them are difficult to wet. The suitability of a material for use in biomedical devices depends on the material's wettability and its propensity to adhere to or react with biological materials such as proteins and lipids.
解决硅水凝胶隐形眼镜表面疏水性的方法有很多种，可以分为物理改性和化学改性两类。There are many methods to solve the surface hydrophobicity of silicone hydrogel contact lenses, which can be divided into two categories: physical modification and chemical modification.
物理改性主要是指高能辐射改性法，其是利用等离子、α射线、γ射线、紫外射线等高能源对材料表面进行辐射改性的方法。Physical modification mainly refers to the high-energy radiation modification method, which is a method of radiation modification on the surface of materials by using high energy sources such as plasma, α-rays, γ-rays, and ultraviolet rays.
化学改性大致包括表面氧化法、接枝改性法、共聚改性法和表面活性剂改性法这几种。Chemical modification generally includes surface oxidation method, graft modification method, copolymerization modification method and surfactant modification method.
其中，解决硅水凝胶的接触镜表面的疏水性的一种常用方法是用更亲水的涂层涂覆水凝胶。这给接触镜的制造增加了额外的复杂性。而且，涂层材料的选择是困难的，确定适当的涂层厚度、涂层均一性和其他可能影响生理性能的因素也同样困难。Among them, a common approach to address the hydrophobicity of contact lens surfaces of silicone hydrogels is to coat the hydrogels with a more hydrophilic coating. This adds additional complexity to the manufacture of contact lenses. Moreover, the choice of coating material is difficult, as is determining proper coating thickness, coating uniformity, and other factors that may affect physiological performance.
之前有人尝试过将亲水高分子引入到硅水凝胶的共聚合中，这种亲水高分子通常是指聚N-乙烯基吡咯烷酮（PVP）。美国专利第6367929号公开了通过在硅氧烷水凝胶单体混合物中包括高分子量的PVP制成的表面亲水的硅氧烷水凝胶。亲水高分子圈闭于水凝胶中，其与水凝胶基质之间很少或没有共价键连接。Previous attempts have been made to introduce hydrophilic polymers, usually polyN-vinylpyrrolidone (PVP), into the copolymerization of silica hydrogels. US Patent No. 6,367,929 discloses superficially hydrophilic silicone hydrogels made by including high molecular weight PVP in the silicone hydrogel monomer mixture. Hydrophilic polymers are entrapped in the hydrogel with little or no covalent linkage to the hydrogel matrix.
发明内容Contents of the invention
技术问题：本发明所要解决的技术问题是：提供一种超亲水硅水凝胶接触透镜及处理方法，经过处理后的硅水凝胶接触透镜具有长效的超亲水性能。Technical problem: The technical problem to be solved by the present invention is: to provide a super-hydrophilic silicon hydrogel contact lens and a treatment method, and the treated silicon hydrogel contact lens has long-term super-hydrophilic performance.
技术方案：为解决上述技术问题，本发明采用如下技术方案：Technical solution: In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
一种超亲水硅水凝胶接触透镜，该接触透镜按照质量分数由以下组分组成：A superhydrophilic silicon hydrogel contact lens, the contact lens is composed of the following components according to the mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40~70%;
亲水高分子聚合物： 5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%。Cross-linking agent: 1-5%.
作为一种实施例，所述的含硅单体为甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯、甲基丙烯酸双（三甲基硅烷氧基）丙酯、甲基丙烯酸五甲基二硅氧烷基酯中的任意一种或者任意组合。As an example, the silicon-containing monomer is methyl-bis(trimethylsiloxy)-silylpropyl glyceryl methacrylate, bis(trimethylsiloxy)methacrylate ) any one or any combination of propyl ester, pentamethyldisiloxane methacrylate.
作为一种实施例，所述的亲水单体为甲基丙烯酸2-羟乙酯、N-乙烯基吡咯烷酮、N,N-二甲基丙烯酰胺、N-异丙基丙烯酰胺、甲基丙烯酰胺、乙烯基磺酸钠、苯乙烯磺酸钠、2-乙烯基吡咯、4-乙烯基吡咯中的任意一种或者任意组合。As an example, the hydrophilic monomer is 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, N,N-dimethylacrylamide, N-isopropylacrylamide, methacrylamide Any one or any combination of amide, sodium vinylsulfonate, sodium styrenesulfonate, 2-vinylpyrrole, and 4-vinylpyrrole.
作为一种实施例，所述的亲水高分子聚合物为聚N-乙烯基吡咯烷酮、聚乙二醇、或者羧丙基纤维素；所述的亲水高分子聚合物的平均分子量为1000～200000。As an example, the hydrophilic polymer is polyN-vinylpyrrolidone, polyethylene glycol, or carboxypropyl cellulose; the average molecular weight of the hydrophilic polymer is 1000- 200000.
作为一种实施例，所述的引发剂为2-羟基-2-甲基苯丙酮，或者偶氮二异丁腈；所述的交联剂为甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、1.4-己二醇二丙烯酸酯、四甘醇二丙烯酸酯或新戊二醇二丙烯酸酯中的任意一种或者任意组合。As an example, the initiator is 2-hydroxyl-2-methylpropiophenone, or azobisisobutyronitrile; the crosslinking agent is allyl methacrylate, ethylene glycol dimethyl Any one or any combination of acrylate, triethylene glycol dimethacrylate, 1.4-hexanediol diacrylate, tetraethylene glycol diacrylate or neopentyl glycol diacrylate.
一种超亲水硅水凝胶接触透镜，该接触透镜按照质量分数由以下组分组成：A superhydrophilic silicon hydrogel contact lens, the contact lens is composed of the following components according to the mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40-70%;
亲水高分子聚合物： 5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%；Cross-linking agent: 1~5%;
助剂： 0.1～0.5%；Auxiliary: 0.1～0.5%;
该助剂为着色剂、紫外光吸收剂、加工助剂中的任意一种或组合。The auxiliary agent is any one or a combination of colorants, ultraviolet absorbers, and processing aids.
一种超亲水硅水凝胶接触透镜的处理方法，其特征在于，该处理方法包括以下过程：将硅水凝胶接触透镜浸泡在质量浓度为10～20%的亲水高分子聚合物水溶液中，并在70～90℃加热8h以上，然后逐渐冷却，冷却到15～25℃，得到处理后的硅水凝胶接触透镜。A method for treating a superhydrophilic silicone hydrogel contact lens, characterized in that the treatment method comprises the following process: soaking the silicone hydrogel contact lens in an aqueous solution of a hydrophilic polymer with a mass concentration of 10-20% and heating at 70-90° C. for more than 8 hours, and then gradually cooling down to 15-25° C. to obtain a treated silicone hydrogel contact lens.
作为一种实施例，所述的硅水凝胶接触透镜按照质量分数由以下组分组成：As an example, the silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40~70%;
亲水高分子聚合物： 5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%。Cross-linking agent: 1-5%.
作为一种实施例，所述的硅水凝胶接触透镜按照质量分数由以下组分组成：As an example, the silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40-70%;
亲水高分子聚合物：5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%；Cross-linking agent: 1~5%;
助剂： 0.1～0.5%；Auxiliary: 0.1～0.5%;
该助剂为着色剂、紫外光吸收剂、加工助剂中的任意一种或组合。The auxiliary agent is any one or a combination of colorants, ultraviolet absorbers, and processing aids.
有益效果：与现有的技术相比，本发明的方法制备得到的透镜亲水性极强，持续时间长，稳定性好，并且镜片极其柔软，手感舒适。同时本发明的制备方法简单，可快速工业化生产。本发明的透镜具有的优良性能将在具体实施方式部分进行具体的验证。Beneficial effects: compared with the prior art, the lens prepared by the method of the present invention has strong hydrophilicity, long duration and good stability, and the lens is extremely soft and comfortable to the touch. Simultaneously, the preparation method of the present invention is simple and can be rapidly industrialized. The excellent performance of the lens of the present invention will be specifically verified in the specific embodiment section.
附图说明Description of drawings
图1是本发明实验中样品1的表面接触角测试状态图。Fig. 1 is the surface contact angle test state diagram of sample 1 in the experiment of the present invention.
图2是本发明实验中样品5的表面接触角测试状态图。Fig. 2 is a test state diagram of the surface contact angle of sample 5 in the experiment of the present invention.
图3是本发明实验中对比样品的表面接触角测试状态图。Fig. 3 is a test state diagram of the surface contact angle of the comparative sample in the experiment of the present invention.
图4是本发明实验中样品1浸泡纯水14天后的表面接触角测试状态图。Fig. 4 is a test state diagram of the surface contact angle of sample 1 soaked in pure water for 14 days in the experiment of the present invention.
图5是本发明实验中样品5浸泡纯水14天后的表面接触角测试状态图。Fig. 5 is a test state diagram of surface contact angle of sample 5 soaked in pure water for 14 days in the experiment of the present invention.
图6是本发明实验中对比样品浸泡纯水14天后的表面接触角测试状态图。Fig. 6 is a test state diagram of the surface contact angle of the comparative sample soaked in pure water for 14 days in the experiment of the present invention.
具体实施方式detailed description
下面结合实施例，对本发明的技术方案进行详细的说明。The technical solution of the present invention will be described in detail below in conjunction with the embodiments.
实施例1Example 1
本发明的一种超亲水硅水凝胶接触透镜，按照质量分数由以下组分组成：A kind of superhydrophilic silicone hydrogel contact lens of the present invention is made up of following components according to mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40-70%;
亲水高分子聚合物：5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%。Cross-linking agent: 1-5%.
上述物质的组合之所以会具有超亲水性是因为亲水高分子聚合物不参加反应，但由于亲水高分子聚合物是线性结构，能够在聚合形成的水凝胶网络中自由移动。这样就会有部分亲水高分子聚合物迁移到表面，从而改善硅水凝胶表面的亲水性。The reason why the combination of the above substances has superhydrophilicity is that the hydrophilic high molecular polymer does not participate in the reaction, but because the hydrophilic high molecular polymer has a linear structure, it can move freely in the hydrogel network formed by polymerization. In this way, part of the hydrophilic polymer will migrate to the surface, thereby improving the hydrophilicity of the silicone hydrogel surface.
上述制备的超亲水性镜片在使用过程中，亲水高分子由于运动，会逐渐从镜片中脱离出来，从而使镜片变得重新不亲水。而经过下面的方法后处理后，从镜片网络中运动出的高分子形成一部分在镜片内，一部分在镜片表面的情况，也有会运动脱离镜片的情况。为了保持亲水高分子量足够，就需要继续加入一定量的亲水高分子，这样可以维持住足够使镜片表面亲水的高分子的量。利用这种内部与外部同时具有亲水高分子聚合物，在进行后处理交联，可以将亲水高分子聚合物有效地固定在镜片表面，可以有效地改善表面亲水性。也就是说，由于在制备接触镜时，向其中加入的亲水高分子聚合物中含有亲水性良好的高分子，而这些高分子会在镜片聚合完成后，有部分高分子从原先形成的聚合物网络中移动到表面，从而使硅水凝胶接触镜具备了超亲水性。During the use of the super-hydrophilic lens prepared above, the hydrophilic polymer will gradually separate from the lens due to movement, so that the lens becomes non-hydrophilic again. However, after post-processing by the following methods, some of the polymers that move out of the lens network will be in the lens, and some will be on the surface of the lens, or they will move away from the lens. In order to maintain sufficient hydrophilic high molecular weight, it is necessary to continue to add a certain amount of hydrophilic high molecular weight, so that the amount of high molecular weight sufficient to make the lens surface hydrophilic can be maintained. Utilizing the internal and external hydrophilic high-molecular polymers, the hydrophilic high-molecular polymers can be effectively fixed on the surface of the lens after post-treatment cross-linking, and the hydrophilicity of the surface can be effectively improved. That is to say, when the contact lens is prepared, the hydrophilic macromolecular polymer added thereto contains polymers with good hydrophilicity, and after the lens polymerization is completed, some of the polymers will change from the original The polymer network moves to the surface, making the silicone hydrogel contact lenses superhydrophilic.
通过利用离子引发剂在水中进行引发，可以有效地将亲水高分子聚合物交联起来，这样就可以形成一个一部分在表面，一部分在内部的网络。这种方式形成的网络结构坚实，且对表面的亲水性改进明显。例如，以PVP为例，交联的机理如下所示：By initiating in water with an ionic initiator, the hydrophilic polymer can be effectively cross-linked so that a network with one part on the surface and one part on the inside can be formed. The network structure formed in this way is solid, and the hydrophilicity of the surface is significantly improved. For example, taking PVP as an example, the mechanism of crosslinking is as follows:
通过自由基聚合得到硅水凝胶接触镜。Silicone hydrogel contact lenses obtained by free radical polymerization.
作为优选，上述超亲水硅水凝胶接触透镜中，含硅单体为甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯、甲基丙烯酸双（三甲基硅烷氧基）丙酯、甲基丙烯酸五甲基二硅氧烷基酯中的任意一种或者任意组合。Preferably, in the above-mentioned superhydrophilic silicone hydrogel contact lens, the silicon-containing monomer is methyl-bis(trimethylsiloxane)-silylpropyl glyceryl methacrylate, methacrylate bis( Any one or any combination of trimethylsiloxy)propyl and pentamethyldisiloxane methacrylate.
作为优选，上述超亲水硅水凝胶接触透镜中，亲水单体为甲基丙烯酸2-羟乙酯、N-乙烯基吡咯烷酮、N,N-二甲基丙烯酰胺、N-异丙基丙烯酰胺、甲基丙烯酰胺、乙烯基磺酸钠、苯乙烯磺酸钠、2-乙烯基吡咯、4-乙烯基吡咯中的任意一种或者任意组合。Preferably, in the above-mentioned superhydrophilic silicone hydrogel contact lens, the hydrophilic monomer is 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, N,N-dimethylacrylamide, N-isopropyl Any one or any combination of acrylamide, methacrylamide, sodium vinylsulfonate, sodium styrenesulfonate, 2-vinylpyrrole, and 4-vinylpyrrole.
作为优选，上述超亲水硅水凝胶接触透镜中，亲水高分子聚合物为聚N-乙烯基吡咯烷酮、聚乙二醇、或者羧丙基纤维素。所述的亲水高分子聚合物的平均分子量为1000～200000。选择该分子量区间的高分子改善效果更好。Preferably, in the above-mentioned superhydrophilic silicone hydrogel contact lens, the hydrophilic polymer is poly-N-vinylpyrrolidone, polyethylene glycol, or carboxypropyl cellulose. The average molecular weight of the hydrophilic polymer is 1,000-200,000. The improvement effect of polymers in this molecular weight range is better.
作为优选，上述超亲水硅水凝胶接触透镜中，引发剂为2-羟基-2-甲基苯丙酮，或者偶氮二异丁腈。交联剂为甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、1.4-己二醇二丙烯酸酯、四甘醇二丙烯酸酯或新戊二醇二丙烯酸酯中的任意一种或者任意组合。Preferably, in the superhydrophilic silicone hydrogel contact lens, the initiator is 2-hydroxy-2-methylpropiophenone or azobisisobutyronitrile. The crosslinker is allyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.4-hexanediol diacrylate, tetraethylene glycol diacrylate or neopentyl glycol Any one or any combination of diacrylates.
实施例2Example 2
一种超亲水硅水凝胶接触透镜，其特征在于，该接触透镜按照质量分数由以下组分组成：A superhydrophilic silicon hydrogel contact lens is characterized in that the contact lens is composed of the following components according to mass fraction:
含硅单体： 20～50%；Silicon-containing monomer: 20-50%;
亲水单体： 40～70%；Hydrophilic monomer: 40-70%;
亲水高分子聚合物：5～20%；Hydrophilic polymer: 5-20%;
引发剂： 0.1～1%；Initiator: 0.1～1%;
交联剂： 1～5%；Cross-linking agent: 1~5%;
助剂： 0.1～0.5%；Auxiliary: 0.1～0.5%;
该助剂为着色剂、紫外光吸收剂和加工助剂中的任意一种或组合。The auxiliary agent is any one or a combination of colorants, ultraviolet absorbers and processing aids.
作为优选，上述的超亲水硅水凝胶接触透镜中，含硅单体、亲水单体、亲水高分子聚合物、引发剂和交联剂的选取与实施例1相同。例如，含硅单体为甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯、甲基丙烯酸双（三甲基硅烷氧基）丙酯、甲基丙烯酸五甲基二硅氧烷基酯中的任意一种或者任意组合。As a preference, in the above-mentioned superhydrophilic silicone hydrogel contact lens, the selection of silicon-containing monomer, hydrophilic monomer, hydrophilic high molecular polymer, initiator and crosslinking agent is the same as that in Example 1. Examples of silicon-containing monomers are methyl-bis(trimethylsiloxy)-silylpropyl glyceryl methacrylate, bis(trimethylsiloxy)propyl methacrylate, methacrylic acid Any one or any combination of pentamethyldisiloxane esters.
本实施例中增加了助剂。如本技术领域一般技术人员所了解的，除上述聚合作用引发剂外，本发明的硅水凝胶接触透镜中也可以包括其他组分，例如，着色剂、UV吸收剂和额外的加工助剂等，诸如在隐形眼镜技术中已知者。作为优选，着色剂为酞菁颜料。Auxiliaries are added in this embodiment. As will be appreciated by those of ordinary skill in the art, in addition to the polymerization initiators described above, other components may also be included in the silicone hydrogel contact lenses of the present invention, for example, colorants, UV absorbers, and additional processing aids etc., such as are known in contact lens art. Preferably, the colorant is a phthalocyanine pigment.
实施例3Example 3
一种超亲水硅水凝胶接触透镜的处理方法，包括以下过程：将硅水凝胶接触透镜浸泡在质量浓度为10～20%的亲水高分子聚合物水溶液中，并在70～90℃加热8h以上，然后逐渐冷却，冷却到15～25℃，得到处理后的硅水凝胶接触透镜。A method for treating a superhydrophilic silicone hydrogel contact lens, comprising the following process: soaking the silicone hydrogel contact lens in an aqueous solution of a hydrophilic high molecular polymer with a mass concentration of 10-20%, and heating the contact lens at 70-90 ℃ for more than 8 hours, and then gradually cooled to 15-25 ℃ to obtain the treated silicone hydrogel contact lens.
本实施例中，硅水凝胶接触透镜可以为实施例1所描述的超亲水硅水凝胶接触透镜，也可以为实施例2所描述的超亲水硅水凝胶接触透镜。In this embodiment, the silicone hydrogel contact lens can be the superhydrophilic silicone hydrogel contact lens described in Example 1, or the superhydrophilic silicone hydrogel contact lens described in Example 2.
原先制备的超亲水性镜片在使用过程中，亲水高分子由于运动，会逐渐从镜片中脱离出来，从而使镜片变得重新不亲水。经过本实施例方法处理后，从镜片网络中运动出的高分子形成一部分在镜片内，一部分在镜片表面的情况，也有会运动脱离镜片的情况。为了保持亲水高分子量足够，就需要继续加入一定量的亲水高分子。这样可以维持住足够使镜片表面亲水的高分子的量。在水溶液中加热时，会在高分子链段上产生自由基，此时，高分子之间就会相互作用而结合在一起。这样机会形成，大量的亲水高分子网络，有直接铺覆在镜片表面的，更有大量一部分在镜片内部，一部分在镜片外部的网络。这样，依靠高分子的亲水性，会使硅水凝胶接触镜具备超亲水性。During the use of the original super-hydrophilic lens, the hydrophilic polymer will gradually separate from the lens due to movement, so that the lens becomes non-hydrophilic again. After being treated by the method of this embodiment, some of the polymers that move out of the lens network are in the lens, and some are on the surface of the lens, or they may move away from the lens. In order to maintain sufficient hydrophilic high molecular weight, it is necessary to continue to add a certain amount of hydrophilic high molecular weight. This maintains a sufficient amount of polymer to render the surface of the lens hydrophilic. When heated in an aqueous solution, free radicals will be generated on the polymer chain segments, and at this time, the polymers will interact and combine together. In this way, a large number of hydrophilic polymer networks are formed, some of which are directly covered on the surface of the lens, and a large number of networks are partly inside the lens and partly outside the lens. In this way, relying on the hydrophilicity of the polymer, the silicone hydrogel contact lens will have superhydrophilicity.
本实施例中，通过将亲水高分子聚合物引入到制备硅水凝胶的反应物中进行聚合反应，再将制成的透镜放入亲水高分子聚合物水溶液中加热进行水合反应，就可以得到长效的超亲水接触镜。例如：将亲水高分子聚合物聚N-乙烯基吡咯烷酮引入到制备硅水凝胶的反应物进行聚合反应，制成的透镜，再将透镜放入聚N-乙烯基吡咯烷酮水溶液中加热，进行水合反应，得到长效的超亲水接触透镜。In this embodiment, the hydrophilic high molecular polymer is introduced into the reactant for preparing the silicon hydrogel to carry out the polymerization reaction, and then the prepared lens is put into the aqueous solution of the hydrophilic high molecular polymer and heated for hydration reaction. Long-lasting superhydrophilic contact lenses can be obtained. For example: the hydrophilic high molecular polymer polyN-vinylpyrrolidone is introduced into the reactants of the preparation of silicon hydrogel for polymerization reaction, and the lens is made, and then the lens is put into the aqueous solution of polyN-vinylpyrrolidone and heated to carry out Hydration reaction, resulting in long-lasting superhydrophilic contact lenses.
本实施例将一种超亲水高分子在反应混合物中搅拌均匀，再直接制备得到镜片；后将镜片浸泡在这种高分子的水溶液中，通过离子引发剂引发，使这种高分子交联起来，形成一个新的网络。通过这种方式，制成互穿网络（IPN）。这种方式制备得到的硅水凝胶接触镜亲水性极强，不易附着杂质，适合长时间佩戴。In this example, a superhydrophilic polymer is stirred evenly in the reaction mixture, and then the lens is directly prepared; the lens is soaked in the aqueous solution of the polymer, and the polymer is cross-linked by an ion initiator. Rise up and form a new network. In this way, an Interpenetrating Network (IPN) is made. The silicone hydrogel contact lens prepared in this way is extremely hydrophilic, not easy to attach impurities, and is suitable for long-term wearing.
本发明的硅水凝胶接触透镜，克服了硅水凝胶表面亲水性差和亲水高分子改性持续时间不够长等技术难题。The silicone hydrogel contact lens of the invention overcomes technical problems such as poor hydrophilicity of the surface of the silicone hydrogel and insufficient duration of modification of the hydrophilic polymer.
本发明的硅水凝胶接触透镜具有良好的透氧性、可见光透过率和断裂拉伸强度功效。The silicone hydrogel contact lens of the invention has good oxygen permeability, visible light transmittance and tensile strength at break.
以下试验将用于进一步说明本发明，但并非用以限制本发明的范围。任何所属领域一般技术人员都可以轻易达成的修饰和改变均包括在本案说明书揭示内容和所附权利要求书的范围内。The following experiments will be used to further illustrate the present invention, but not intended to limit the scope of the present invention. Any modifications and changes that can be easily achieved by those skilled in the art are included within the scope of the disclosure of this specification and the scope of the appended claims.
样本1：超亲水硅水凝胶接触透镜按照质量分数由以下组分组成：Sample 1: The superhydrophilic silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体：甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯3.0g；Silicon-containing monomer: methyl-bis(trimethylsiloxane)-silylpropyl glyceryl methacrylate 3.0g;
亲水单体：N,N-二甲基丙烯酰胺0.8 g、甲基丙烯酸2-羟乙酯1.12g、N-乙烯基吡咯烷酮0.48g；Hydrophilic monomers: 0.8 g of N,N-dimethylacrylamide, 1.12 g of 2-hydroxyethyl methacrylate, and 0.48 g of N-vinylpyrrolidone;
亲水高分子聚合物：聚N-乙烯基吡咯烷酮0.3g；Hydrophilic high molecular polymer: poly N-vinylpyrrolidone 0.3g;
引发剂：2-羟基-2-甲基苯丙酮0.06g；Initiator: 0.06g of 2-hydroxy-2-methylpropiophenone;
交联剂：甲基丙烯酸烯丙酯0.24g。Crosslinking agent: 0.24 g of allyl methacrylate.
样本2：超亲水硅水凝胶接触透镜按照质量分数由以下组分组成：Sample 2: The superhydrophilic silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体：甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯0.8g；Silicon-containing monomer: methyl-bis(trimethylsiloxane)-silylpropyl glyceryl methacrylate 0.8g;
亲水单体：甲基丙烯酸2-羟乙酯2.0g、N-乙烯基吡咯烷酮0.5g；Hydrophilic monomer: 2.0g of 2-hydroxyethyl methacrylate, 0.5g of N-vinylpyrrolidone;
亲水高分子聚合物：聚N-乙烯基吡咯烷酮0.496g；Hydrophilic high molecular polymer: poly N-vinylpyrrolidone 0.496g;
引发剂：2-羟基-2-甲基苯丙酮0.004g；Initiator: 0.004g of 2-hydroxy-2-methylpropiophenone;
交联剂：乙二醇二甲基丙烯酸酯0.2g。Crosslinking agent: 0.2 g of ethylene glycol dimethacrylate.
样本3：超亲水硅水凝胶接触透镜按照质量分数由以下组分组成：Sample 3: The superhydrophilic silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体：甲基-二（三甲基硅氧烷基）-甲硅烷基丙基甲基丙烯酸甘油酯0.5gSilicon-containing monomer: methyl-bis(trimethylsiloxy)-silylpropyl glyceryl methacrylate 0.5g
和甲基丙烯酸五甲基二硅氧烷基酯0.652g;And pentamethyldisiloxane methacrylate 0.652g;
亲水单体：甲基丙烯酰胺0.6g、甲基丙烯酸2-羟乙酯0.6g、N-乙烯基吡咯烷酮0.4g、乙烯基磺酸钠0.2g、4-乙烯基吡咯0.2g；Hydrophilic monomer: methacrylamide 0.6g, 2-hydroxyethyl methacrylate 0.6g, N-vinylpyrrolidone 0.4g, sodium vinylsulfonate 0.2g, 4-vinylpyrrole 0.2g;
亲水高分子聚合物：聚乙二醇0.8g；Hydrophilic high molecular polymer: polyethylene glycol 0.8g;
引发剂：偶氮二异丁腈0.008g；Initiator: azobisisobutyronitrile 0.008g;
交联剂：1.4-己二醇二丙烯酸酯0.04g。Crosslinking agent: 0.04 g of 1.4-hexanediol diacrylate.
样本4：超亲水硅水凝胶接触透镜按照质量分数由以下组分组成：Sample 4: The superhydrophilic silicone hydrogel contact lens is composed of the following components according to the mass fraction:
含硅单体：甲基丙烯酸双（三甲基硅烷氧基）丙酯0.88g；Silicon-containing monomer: 0.88g of bis(trimethylsiloxy)propyl methacrylate;
亲水单体： N-异丙基丙烯酰胺0.04g、N,N-二甲基丙烯酰胺0.36g、甲基丙烯酸2-羟乙酯1.0g、N-乙烯基吡咯烷酮0.4g、2-乙烯基吡咯 0.5g、苯乙烯磺酸钠0.5g；Hydrophilic monomers: N-isopropylacrylamide 0.04g, N,N-dimethylacrylamide 0.36g, 2-hydroxyethyl methacrylate 1.0g, N-vinylpyrrolidone 0.4g, 2-vinyl Pyrrole 0.5g, sodium styrene sulfonate 0.5g;
亲水高分子聚合物：羧丙基纤维素0.24g；Hydrophilic high molecular polymer: carboxypropyl cellulose 0.24g;
引发剂：2-羟基-2-甲基苯丙酮0.005g；Initiator: 0.005g of 2-hydroxy-2-methylpropiophenone;
交联剂：三乙二醇二甲基丙烯酸酯0.075g。Crosslinking agent: 0.075 g of triethylene glycol dimethacrylate.
样本5：将样本1制备的硅水凝胶接触透镜浸泡入PVP的水溶液中，80℃加热8h以上；后逐渐冷却，得到超亲水的硅水凝胶接触镜。Sample 5: Soak the silicone hydrogel contact lens prepared in sample 1 into an aqueous solution of PVP, heat at 80° C. for more than 8 hours, and then gradually cool to obtain a superhydrophilic silicone hydrogel contact lens.
样本6：将样本2制备的硅水凝胶接触透镜浸泡入PVP的水溶液中，80℃加热8h以上；后逐渐冷却，得到超亲水的硅水凝胶接触镜。Sample 6: Soak the silicone hydrogel contact lens prepared in sample 2 into the PVP aqueous solution, heat at 80°C for more than 8 hours, and then gradually cool to obtain a superhydrophilic silicone hydrogel contact lens.
样本7：将样本3制备的硅水凝胶接触透镜浸泡入聚乙二醇水溶液中，80℃加热8h以上；后逐渐冷却，得到超亲水的硅水凝胶接触镜。Sample 7: soak the silicone hydrogel contact lens prepared in sample 3 into polyethylene glycol aqueous solution, heat at 80° C. for more than 8 hours, and then gradually cool to obtain a super-hydrophilic silicone hydrogel contact lens.
样本8：将样本4制备的硅水凝胶接触透镜浸泡入羧丙基纤维素水溶液中，80℃加热8h以上；后逐渐冷却，得到超亲水的硅水凝胶接触镜。Sample 8: Soak the silicone hydrogel contact lens prepared in sample 4 into carboxypropyl cellulose aqueous solution, heat at 80° C. for more than 8 hours, and then gradually cool to obtain a super-hydrophilic silicone hydrogel contact lens.
对比样本：市售的普通HEMA材质的接触透镜。该透镜的透氧系数为7Barrers,断裂强度为0.2MPa,接触角约为50o,透光率大于92%。Comparative sample: a commercially available contact lens made of common HEMA material. The oxygen permeability coefficient of the lens is 7 Barrers, the breaking strength is 0.2 MPa, the contact angle is about 50o , and the light transmittance is greater than 92%.
透氧系数测试：Oxygen permeability test:
对样本1至样本8，以及对比样本，利用透氧仪器检测其透氧系数。结果如表1所示。以本发明的方法制得的接触透镜透氧性能优于市售HEMA镜片。For samples 1 to 8, as well as the comparative samples, the oxygen permeability coefficients were tested with an oxygen permeability instrument. The results are shown in Table 1. The oxygen permeability of the contact lens prepared by the method of the invention is better than that of the commercially available HEMA lens.
断裂拉伸强度测试：Tensile strength test at break:
将样本1至样本8，以及对比样本，用机械拉伸测试仪测量其断裂拉伸强度，结果如表1所示。以本发明的方法制得的接触透镜机械强度优于市售HEMA镜片。The tensile strength at break of samples 1 to 8, and the comparative sample was measured with a mechanical tensile tester, and the results are shown in Table 1. The mechanical strength of the contact lens prepared by the method of the invention is better than that of commercially available HEMA lenses.
可见光透过率测试：Visible light transmittance test:
将样本1至样本8，以及对比样本，放在磷酸缓冲液中，再将其放置在样品室中，使用721紫外分光光度计测量平均可见光透过率。测试结果如表1所示。Samples 1 to 8, and the comparative sample were placed in phosphate buffer solution, placed in the sample chamber, and the average visible light transmittance was measured using a 721 UV spectrophotometer. The test results are shown in Table 1.
表1Table 1
表面接触角测试：Surface contact angle test:
对样本1、样本5和对比样本进行表面接触角测试。接触角测试使用接触角测试系统(KSV CAM-200, KSV Ins)，用高速相机进行拍摄，将镜片铺平在载玻片上，用吸水布擦干表面，滴加2uL水，测量接触角。The surface contact angle test was carried out on sample 1, sample 5 and comparative samples. The contact angle test uses a contact angle test system (KSV CAM-200, KSV Ins) to take pictures with a high-speed camera, spread the lens on a glass slide, dry the surface with an absorbent cloth, drop 2uL of water, and measure the contact angle.
通过图1可以看出：样本1的接触角约为15o。样本1的亲水性很强。It can be seen from Figure 1 that the contact angle of sample 1 is about15o . Sample 1 is very hydrophilic.
通过图2可以看出：经过水合后处理得到的镜片，接触角约为15o。样本5的表面接触角极小，说明其表面亲水性很强；且其亲水性甚至比用亲水单体制备的镜片还要强。It can be seen from Figure 2 that the contact angle of the lens obtained after hydration treatment is about15o . The surface contact angle of sample 5 is extremely small, indicating that its surface is highly hydrophilic; and its hydrophilicity is even stronger than that of lenses prepared with hydrophilic monomers.
通过图3可以看出：对比样本的接触角约为40o，亲水效果不佳。It can be seen from Figure 3 that the contact angle of the comparative sample is about 40o , and the hydrophilic effect is not good.
再将上述样本1、样本5和对比样本分别浸泡纯水14天后，再次进行表面接触角测试。After soaking the above sample 1, sample 5 and comparative sample in pure water for 14 days, the surface contact angle test was performed again.
从图4可以看出：样本1的接触角约为 99o，亲水效果不佳。It can be seen from Figure 4 that the contact angle of sample 1 is about 99o , and the hydrophilic effect is not good.
从图5可以看出：样本5的接触角约为15o，和浸泡纯水之前的接触角差不多，样本5亲水性没有变化。这说明本方法后处理方式得到的镜片的亲水性的稳定性很好。It can be seen from Figure 5 that the contact angle of sample 5 is about 15o , which is almost the same as that before soaking in pure water, and the hydrophilicity of sample 5 has not changed. This shows that the stability of the hydrophilicity of the lens obtained by the post-treatment method of this method is very good.
从图6可以看出：对比样本的接触角约为40o，亲水效果不佳。It can be seen from Figure 6 that the contact angle of the comparative sample is about40o , and the hydrophilic effect is not good.
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| CN201510197798.8ACN104774288B (en) | 2015-04-23 | 2015-04-23 | Super-hydrophilic silicone hydrogel contact lens and treatment method thereof |
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| CN201510197798.8ACN104774288B (en) | 2015-04-23 | 2015-04-23 | Super-hydrophilic silicone hydrogel contact lens and treatment method thereof |
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| JPH08334732A (en) | Soft contact lens |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | Effective date of registration:20170717 Address after:212331 Zhenjiang city of Jiangsu province Danyang City Lu Dan Fu Lu No. 1 Patentee after:Hydron Contact Lens Co., Ltd. Address before:211189 Jiangsu Road, Jiangning District, Southeast University, No. 2, No. Patentee before:Southeast University | |
| TR01 | Transfer of patent right |