CN104945570B - A silicone hydrogel contact lens surface and the inversion processing method - Google Patents

A silicone hydrogel contact lens surface and the inversion processing method Download PDF

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CN104945570B
CN104945570B CN 201510387598 CN201510387598A CN104945570B CN 104945570 B CN104945570 B CN 104945570B CN 201510387598 CN201510387598 CN 201510387598 CN 201510387598 A CN201510387598 A CN 201510387598A CN 104945570 B CN104945570 B CN 104945570B
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contact lens
silicone hydrogel
silicon
hydrogel contact
methacrylate
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CN 201510387598
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CN104945570A (en )
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姜勇
孟帆
孟一帆
韦静
李敏
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东南大学
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Abstract

本发明公开了一种硅凝胶接触透镜,该接触透镜按照质量分数由以下组分组成:含硅单体:45~70%;含硅高分子聚合物:25~50%;引发剂:0.5~1%;交联剂:1~5%。 The present invention discloses a silicone hydrogel contact lens, the contact lens in accordance with the content of the following components: silicon-containing monomer: 45 to 70%; silicon-containing polymer: 25 to 50%; initiator: 0.5 to 1%; crosslinking agent: 1 to 5%. 该接触透镜可进行表面反转处理,从而使其具有长效的亲水性能。 The contact lens can be subjected to a surface treatment reversed, so that it has long-lasting hydrophilicity. 本发明还公开了一种硅凝胶接触透镜的表面反转处理方法,该方法可以使得硅凝胶接触透镜具有长效的亲水性能。 The present invention also discloses a method for processing a surface inversion silicone hydrogel contact lenses, so that the method may have long-lasting silicone hydrogel contact lens hydrophilic properties.

Description

一种硅凝胶接触透镜及其表面反转处理方法 A silicone hydrogel contact lens surface and the inversion processing method

技术领域 FIELD

[0001] 本发明属于接触透镜领域,具体来说,涉及一种硅凝胶接触透镜及其表面反转处理方法。 [0001] The present invention belongs to the field of contact lenses, particularly, to a silicone hydrogel contact lens surface and the inversion processing method.

背景技术 Background technique

[0002] 角膜接触透镜又称为“隐形眼镜”,是一种佩戴在眼球角膜上的镜片。 [0002] corneal contact lens also known as "contact lens" is a lens on the cornea of ​​the eye of the wearer. 角膜接触透镜在矫正视力、保护眼睛、辅助治疗以及美容等方面有着广泛的应用以及巨大的市场价值。 In corneal contact lens vision correction, eye protection, and other adjuvant therapy and beauty it has a wide range of applications and huge market value. 制造角膜接触镜的材料可以分为硬性不透气材料、硬性透气性材料、软性非亲水性材料(又称为弹性材料)和软性亲水性材料(又称为水凝胶材料)。 Contact lens materials can be divided into rigid air-impermeable material, rigid gas permeable materials, non-hydrophilic soft materials (also known as elastomeric materials) and soft hydrophilic material (also referred to as hydrogel material). 角膜接触透镜材料的良好性能对保障眼睛特别是角膜与结膜的健康非常重要,因此,生物医学材料学界非常重视角膜接触镜新材料的开发。 Corneal contact lens material of good properties, especially the cornea and conjunctiva of health is very important to protect the eyes, therefore, attach great importance to academic biomedical materials development of new contact lens materials.

[0003] 其中,水凝胶材料制造的隐形眼镜与人眼的相容性好,配戴舒适,具有一定透氧性能,是目前隐形眼镜制造材料的发展方向,也是当前最主要的隐形眼镜类消费产品。 [0003] where the compatibility of hydrogel contact lenses made of a material with a good eye, comfortable to wear, with a certain oxygen permeability, is the development direction of the contact lens manufacturing materials, and it is currently the most important class of contact lenses consumer products. 最初的软性亲水接触镜以2-甲基丙烯酸羟乙酯(HEMA)作为原料制备得到;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。 Initial hydrophilic soft contact lenses with 2-hydroxyethyl methacrylate (HEMA) as starting material to give; later evolved to a copolymer of HEMA and other hydrophilic monomers lens as a base material. 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。 There is a big problem is that this type of contact lens oxygen permeability of the poor, is not conducive to long wear.

[0004] 为了解决这个问题,许多学者进行了大量探索进而出现了具有突破性的硅氧烷水凝胶,即将含有甲基丙烯酸酯或乙烯基团的聚二甲基硅氧烷与一些亲水性单体共聚而成的水凝胶。 [0004] In order to solve this problem, many researchers to explore further appeared a lot of silicone hydrogel breakthrough, polydimethylsiloxane is about or vinyl methacrylate containing some hydrophilic groups and monomer copolymerized hydrogel. 这一设计可将硅氧烷材料的透氧性与常规无离子水凝胶材料的舒适性、润湿性与抗沉淀性能相结合。 This design can be a siloxane material comfort and oxygen permeability of conventional non-ionic hydrogel material, wettability and anti-redeposition properties in combination. 目前,硅水凝胶隐形眼镜已经得到普及,这是因为它与传统水凝胶隐形眼镜相比具有高透氧性,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。 Currently, silicon hydrogel contact lenses have gained popularity, because it has a high oxygen permeability compared with conventional hydrogel contact lenses, contact lens wearers wear silicone hydrogel contact lenses can last longer. 举例来说,视特定眼镜而定,硅水凝胶隐形眼镜可通过测定其佩戴磨损程度而规定为每天佩戴、每周佩戴、双周佩戴或每月佩戴。 For example, depending on the particular lens, silicone hydrogel contact lenses may be worn by determining which of a predetermined degree of wear and daily wear, weekly wear, biweekly wear, or monthly wear. 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。 Benefits silicone hydrogel contact lens may be partially attributed to the hydrophobic portion of the silicon-containing hydrogel.

[0005] 但是,目前广泛用于制备隐形眼镜的模具是由非极性的树脂(例如聚丙烯)制成, 其具有很强的疏水性。 [0005] However, currently widely used in the preparation of a contact lens mold is made of a non-polar resin (e.g. polypropylene), which are highly hydrophobic. 而含硅水凝胶中的含硅单体也具有极强的疏水性,这使得该水凝胶体系在模具中聚合时含硅单体自发地向镜片表面聚集,从而使制备出的含硅水凝胶具有表面疏水性。 Silicon-containing monomers and silicon-containing hydrogel also has strong hydrophobicity, which makes the polymerization system when the silicon-containing hydrogel monomer spontaneously aggregate in the mold to the lens surface, so that the prepared silicon hydrogels having a hydrophobic surface. 这种疏水的表面难于润湿,不仅会降低佩戴舒适度,还会增加对蛋白质、脂质类污染物的粘附,不利于消费者长期佩戴。 This hydrophobic surface wetting is difficult, not only will reduce the wearing comfort, but also increase the adhesion of proteins, lipids, pollutants, and the consumer is not conducive to long-term wear. 基于以上问题,含硅角膜接触镜的表面亲水改性成为各大隐形眼镜公司的研究热点。 Based on the above issue, modified silicon surface hydrophilic contact lens contact lens company become a major research focus.

[0006] 目前,解决硅水凝胶隐形眼镜表面疏水性的方法可以分为物理改性和化学改性两类。 [0006] Currently, to solve the silicone hydrogel contact lenses hydrophobic surface modification and physical methods may be divided into two types of chemical modification. 物理改性主要是指高能辐射改性法,其是利用等离子体、α射线、丫射线、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 high-energy radiation modification process, which is the use of a plasma, [alpha] rays, Ah-rays, ultraviolet rays of high energy radiation material surface modification method. 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。 Generally comprises a chemically modified surface oxidation, graft modification method, a method of copolymerization and a surfactant which several modification method.

发明内容 SUMMARY

[0007] 技术问题:本发明所要解决的技术问题是:提供一种硅凝胶接触透镜,该接触透镜可进行表面反转处理,从而使其具有长效的亲水性能;还提供一种硅凝胶接触透镜的表面反转处理方法,该方法可以使得硅凝胶接触透镜具有长效的亲水性能。 [0007] Technical Problem: The present invention solves the technical problem are: to provide a silicone hydrogel contact lens, the contact lens may be subjected to a surface treatment reversed, so that it has a long-term hydrophilic property; further provided a silicon surface inversion processing method hydrogel contact lenses, so that the method may have long-lasting silicone hydrogel contact lens hydrophilic properties.

[0008] 技术方案:为解决上述技术问题,本发明实施例采用如下技术方案: [0008] Technical Solution: To solve the above problems, embodiments of the present invention adopt the following technical solutions:

[0009] —方面,本发明实施例提供一种硅凝胶接触透镜,该接触透镜按照质量分数由以下组分组成: 含硅单体: 4 5〜7 0 °/»; 含硅高分子聚合物:2 5〜5 0 % ; [0009] - aspect, embodiments of the present invention provides a silicone hydrogel contact lens, the contact lens in accordance with the content of the following components: silicon-containing monomers: 4 5~7 0 ° / »; silicon-containing high polymer was: 0% 2 5~5;

[0010] 引发剂: 0.5〜ϊ 交联剂: 1 Ά。 [0010] initiator: 0.5~ϊ crosslinking agent: 1 Ά.

[0011] 作为一种优选方案,该接触透镜按照质量分数由以下组分组成: 含硅单体: 60%; 含硅高分子聚物:3 7.3% ; [0011] As a preferred embodiment, the mass fraction of a contact lens in accordance with the following components: silicon-containing monomer: 60%; silicon-containing polymer ionomer: 3 7.3%;

[0012] 引发剂: 0.7% ; 交联剂: 2%。 [0012] Initiator: 0.7%; crosslinking agent: 2%.

[0013] 作为一种优选方案,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐,或者由甲基丙烯酸3-[三(三甲基硅氧烷基)甲硅烷基]丙酯和甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯中的一种或者两种物质与2-(三甲基硅氧基)乙基甲基丙烯酸盐组成的混合物。 [0013] As a preferred embodiment, the silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate, or a methacrylate, 3- [tris (trimethyl siloxane yl) silyl] propyl methacrylate and methyl - bis (trimethylsiloxy) - one silylated propyl methacrylate glycerides or two substances with 2- (trimethylsiloxy the mixture yl methacrylate salts thereof).

[0014] 作为一种优选方案,所述的混合物中,2-(三甲基硅氧基)乙基甲基丙烯酸盐占接触透镜的质量分数为30〜50%。 [0014] As a preferred embodiment, the mixture of 2- (trimethylsiloxy) ethyl methacrylate mass fraction of 30 ~ 50% of the contact lens.

[0015] 作为一种优选方案,所述的含硅高分子聚合物为甲基丙烯酸酯单封端的聚二甲基硅氧烷、甲基丙烯酸酯双封端的聚二甲基硅氧烷、丙烯酸酯单封端的聚二甲基硅氧烷或者丙烯酸酯双封端的聚二甲基硅氧烷。 [0015] As a preferred embodiment, the silicon-containing polymer is a methacrylate monocapped polydimethylsiloxane, bis methacrylate terminated polydimethyl siloxane, methacrylate single ester-terminated polydimethylsiloxane or methacrylate dicapped polydimethylsiloxane.

[0016] 作为一种优选方案,所述的引发剂为2-羟基-2-甲基-1-苯基丙酮或者偶氮二异丁臆。 [0016] As a preferred embodiment, the initiator is 2-hydroxy-2-methyl azobisisobutyrate acetone or addiction.

[0017] 作为一种优选方案,所述的交联剂为甲基丙烯酸烯丙酯、二丙烯酸-1,6-己二醇酯或者三羟甲基丙烷三甲基丙烯酸酯。 [0017] As a preferred embodiment, the crosslinking agent is allyl methacrylate, diacrylates 1,6-hexanediol diacrylate or trimethylolpropane trimethacrylate.

[0018] 另一方面,本发明实施例提供一种硅凝胶接触透镜的表面反转处理方法,该处理方法包括以下过程:利用聚丙烯模具制备硅凝胶接触透镜,将制备出的硅凝胶接触透镜浸泡在氢氧化钾和甲醇的混合溶液中,并在20°C〜30°C震荡8〜12小时后,取出硅凝胶接触透镜。 [0018] On the other hand, provides a silicone hydrogel contact lens surface inversion processing method according to the present invention, the processing method comprising the following procedure: polypropylene molds prepared using silicon hydrogel contact lenses, the prepared silicon condensate plastic contact lens immersed in a mixed solution of potassium hydroxide and methanol, and, after shaking 20 ° C~30 ° C 8~12 hours, remove the silicone hydrogel contact lenses.

[0019] 作为一种优选方案,所述的方法还包括:将震荡后取出的硅凝胶接触透镜,用乙醇抽提2〜16h,再将抽提处理后的硅凝胶接触透镜浸泡于磷酸盐缓冲液中保存。 [0019] As a preferred embodiment, the method further comprising: silicone hydrogel contact lens after the shock removed, extracted with ethanol 2~16h, then extracted silicone hydrogel contact lens immersed in a phosphate treated salt buffer stored.

[0020] 作为一种优选方案,所述的混合溶液中,氢氧化钾的质量浓度为5〜10%,甲醇与水的体积比为1:7〜10。 [0020] As a preferred embodiment, the mixed solution, the concentration of potassium hydroxide of 5 to 10% by volume ratio of methanol to water is 1: 7 to 10.

[0021] 作为一种优选方案,所述的硅凝胶接触透镜按照质量分数由以下组分组成: 含硅单体: 4i〜m: 含硅高分子聚合物:2 5·〜5:0 5¾ [0021] As a preferred embodiment, the silicone hydrogel contact lenses at a mass fraction comprises the following components: silicon-containing monomers: 4i~m: silicon-containing polymer: 2 5 · ~5: 0 5¾

[0022] 引发剂: OJ〜II; 交联剂: ! [0022] initiator: OJ~II; crosslinking agent:! 〜5 %。 ~ 5%.

[0023] 作为一种优选方案,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐,或者由甲基丙烯酸3-[三(三甲基硅氧烷基)甲硅烷基]丙酯和甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯中的一种或者两种物质与2-(三甲基硅氧基)乙基甲基丙烯酸盐组成的混合物。 [0023] As a preferred embodiment, the silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate, or a methacrylate, 3- [tris (trimethyl siloxane yl) silyl] propyl methacrylate and methyl - bis (trimethylsiloxy) - one silylated propyl methacrylate glycerides or two substances with 2- (trimethylsiloxy the mixture yl methacrylate salts thereof).

[0024] 作为一种优选方案,所述的含硅高分子聚合物为甲基丙烯酸酯单封端的聚二甲基硅氧烷、甲基丙烯酸酯双封端的聚二甲基硅氧烷、丙烯酸酯单封端的聚二甲基硅氧烷或者丙烯酸酯双封端的聚二甲基硅氧烷。 [0024] As a preferred embodiment, the silicon-containing polymer is a methacrylate monocapped polydimethylsiloxane, bis methacrylate terminated polydimethyl siloxane, methacrylate single ester-terminated polydimethylsiloxane or methacrylate dicapped polydimethylsiloxane.

[0025] 有益效果:与现有的技术相比,本发明实施例的硅凝胶接触透镜经过表面反转处理方法后,硅凝胶接触透镜保留了硅凝胶的高透氧,弹性好的特性,并将疏水的镜片表面亲水化处理,使其表面亲水性持续时间长,稳定性好。 [0025] The beneficial effects: Compared with the prior art, silicone hydrogel contact lenses of the present embodiment of the invention after surface treatment inversion method, a silicone hydrogel contact lens to retain a high oxygen permeability of silicone gel, good flexibility properties, hydrophobic and hydrophilic lens surface treatment, its surface hydrophilic long duration, and good stability. 同时本发明的处理方法简单,可快速工业化生产。 While the processing method of the present invention is simple, fast industrial production. 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。 Lens of the present invention have excellent performance will be specifically verified in the Detailed Description.

具体实施方式 detailed description

[0026] 下面对本发明实施例进行详细的说明。 [0026] The following embodiments of the present invention will be described in detail.

[0027] 本发明实施例提供一种硅凝胶接触透镜,该接触透镜按照质量分数由以下组分组成: 含硅单体: 4:5〜7 0 % 含硅高分子聚合物:2 5〜m»: [0027] An embodiment provides a silicone hydrogel contact lens of the invention, the mass fraction of contact lenses in accordance with the following components: silicon-containing monomers: 4: 5 ~ 7 0% silicon-containing polymer: -5 to 2 m »:

[0028] 引发剂: 0.5〜I %; 交联剂: 1〜5%。 [0028] initiator: 0.5~I%; crosslinking agent: 1 ~ 5%.

[0029] 制备上述硅凝胶接触透镜时,将含硅单体、含硅高分子聚合物、引发剂、交联剂按照上述质量分数取量后,在烧杯中搅拌均匀后注入模具,经紫外光或热引发即可生成硅凝胶接触透镜。 [0029] the production of the silicone hydrogel contact lens, a silicon-containing monomer, a silicon-containing polymer, an initiator, a crosslinking agent according to the above-described mass fraction for quantity, stir in a beaker into the mold by UV photo or thermal initiators to generate silicone hydrogel contact lenses.

[0030] 上述实施例中,由于选用的单体相互之间的相溶性都很好,所以不需要再添加额外的溶剂来制备硅凝胶接触透镜。 [0030] In the above embodiment, since the compatibility between monomers of choice are each well, then it is not necessary to prepare silicone hydrogel contact lenses add additional solvent.

[0031] 上述实施例中,作为优选,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称:TMSEMA);或者,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称:TMSEMA)和甲基丙烯酸3-[三(三甲基硅氧烷基)甲硅烷基]丙酯(文中简称:TRIS)组成的混合物;或者,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称: TMSEMA)和甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯(文中简称:SiMA) 组成的混合物;或者,所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称: TMSEMA)、甲基丙烯酸3-[三(三甲基硅氧烷基)甲硅烷基]丙酯(文中简称:TRIS)和甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯(文中简称:SiM)组成的混合物。 [0031] In the above embodiment, preferably, the silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA); or, a silicon-containing single body is 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA) and methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (hereinafter abbreviated : mixture TRIS) thereof; or said silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA) and methyl - bis (trimethylsiloxy alkyl) - silylpropyl glycerol methacrylate (hereinafter abbreviated: SiMA) consisting of a mixture; or a silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA), methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (hereinafter abbreviated: TRIS) and methyl - bis (trimethylsiloxy) - silylpropyl glycerol methacrylate (hereinafter abbreviated: SiM) mixtures thereof. 作为优选,所述的混合物中,2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称:TMSEMA)占接触透镜的质量分数为30〜50%。 Advantageously, said mixture, 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA) mass fraction of 30 ~ 50% of the contact lens. 混合物中有充足的TMSEMA,即带有三甲基硅活性基团的单体,才可以使硅凝胶镜片在后续反转处理中发生较为明显的表面反转效果,进而得到亲水的表面。 Mixture sufficient TMSEMA, i.e. trimethylsilyl monomer having a reactive group, it may be obvious that the silicone hydrogel lens surface inversion effects in a subsequent reversal process, and further to obtain a hydrophilic surface.

[0032] 上述实施例中,作为优选,所述的含硅高分子聚合物为甲基丙烯酸酯单封端的聚二甲基硅氧烷(文中简称:PDMS-MA)、甲基丙烯酸酯双封端的聚二甲基硅氧烷(文中简称: MA-PDMS-MA)、丙烯酸酯单封端的聚二甲基硅氧烷(文中简称:PDMS-DA)或者丙烯酸酯双封端的聚二甲基硅氧烷(文中简称:DA-PDMS-DA)。 [0032] In the above embodiment, preferably, the silicon-containing polymer is a methacrylate monocapped polydimethylsiloxane (hereinafter abbreviated: PDMS-MA), blocked bis methacrylate terminated polydimethylsiloxane (hereinafter abbreviated: MA-PDMS-MA), mono acrylate-terminated polydimethylsiloxane (hereinafter abbreviated: PDMS-DA) or acrylic acid esters of bis-terminated polydimethylsiloxane siloxane (hereinafter abbreviated: DA-PDMS-DA). 优选的,含硅高分子聚合物在接触透镜中的质量含量至少为40%。 Preferably, the mass content of the silicon-containing polymer in a contact lens is at least 40%. 更优选的,含娃高分子聚合物在接触透镜中的质量含量为50%。 More preferably, the mass content of the polymer containing the baby in the contact lens is 50%. 因为组合物中具有充足的含硅氧烷高分子,才能使制备的接触透镜具有较高的透氧性。 Because the composition has sufficient siloxane containing polymer prepared in order to make a contact lens having high oxygen permeability. 所述的含硅高分子聚合物的平均分子量为1000〜3000。 The average molecular weight of the silicon-containing polymer of 1000~3000. 选择该分子量区间的高分子硅凝胶镜片的聚合效果更好。 The molecular weight of the polymeric effect selection section more polymeric silicon hydrogel lenses.

[0033] 所述的引发剂为2-羟基-2-甲基-1-苯基丙酮(文中简称:D-1173)或者偶氮二异丁腈(文中简称:AIBN)。 [0033] The initiator is 2-hydroxy-2-methyl-1-phenyl-propanone (hereinafter abbreviated: D-1173) or azobisisobutyronitrile (hereinafter abbreviated: AIBN). 所述的交联剂为甲基丙烯酸烯丙酯(文中简称:EGDMA)、二丙烯酸-1, 6-己二醇酯(文中简称:HDDA)或者三羟甲基丙烷三甲基丙烯酸酯(文中简称:TMPTMA)。 The crosslinking agent is allyl methacrylate (hereinafter abbreviated: EGDMA), -1 diacrylate, 1,6-hexanediol acrylate (hereinafter abbreviated: HDDA) or trimethylolpropane trimethacrylate (hereinafter abbreviation: TMPTMA).

[0034] 为提高上述实施例的硅凝胶接触透镜的亲水性能,对硅凝胶接触透镜表面进行反转处理。 [0034] In order to improve the hydrophilic properties of the silicone hydrogel contact lenses of the above-described embodiments, the silicone hydrogel contact lens to the surface inversion processing. 该反转处理方法包括以下过程:利用聚丙烯模具制备硅凝胶接触透镜,将制备出的硅凝胶接触透镜浸泡在氢氧化钾和甲醇的混合溶液中,并在20 °C〜30 °C震荡8〜12小时后, 取出硅凝胶接触透镜。 The inversion processing method comprising the following procedures: preparing a polypropylene mold silicone hydrogel contact lenses, the silicone hydrogel contact lens immersed in the prepared mixed solution of methanol and potassium hydroxide, and 20 ° C~30 ° C 8~12 hours after the shock, silicone hydrogel contact lenses removed.

[0035] 经过上述表面反转处理后,为了除去硅凝胶接触透镜中未反应的单体和残留的甲醇,将硅凝胶接触透镜用无水乙醇抽提2〜16h,最后将硅凝胶接触透镜保存在磷酸盐缓冲液中。 [0035] After the surface of the above-described inversion process, silicone hydrogel contact lenses to remove unreacted monomer and residual methanol, the silicone hydrogel contact lenses with absolute ethanol extract 2~16h, finally silicone gel the contact lens is stored in phosphate buffer. 作为优选,磷酸盐缓冲液的pH值为6〜8。 Advantageously, pH of phosphate buffer is 6 ~ 8.

[0036] 在上述实施例的反转处理方法中,所述的混合溶液中,氢氧化钾的质量浓度为5〜 10%,甲醇与水的体积比为1:7〜10。 [0036] In the processing method of reversing the above embodiment, the mixed solution, the concentration of potassium hydroxide of -5 to 10% by volume ratio of methanol to water is 1: 7 to 10.

[0037] 在上述反转处理方法中,硅凝胶接触透镜按照质量分数由以下组分组成: 含娃单体: 45〜7.0%. 含娃高分子聚合物:2:5:〜5:0 %;. [0037] In the inversion processing method, a silicon hydrogel contact lens in accordance with the content of the following components: monomer containing baby: baby 45~7.0% polymer containing: 2: 5: ~ 5: 0 % ;.

[0038] 引发剂: (U〜1%; 交联剂: 1〜5 %。 [0038] initiator: (U~1%; crosslinking agent: 1 ~ 5%.

[0039] 在上述硅凝胶接触透镜中,含硅单体中含有2-(三甲基硅氧基)乙基甲基丙烯酸盐(文中简称:TMSEMA) JMSEMA的前体是甲基丙烯酸羟乙酯(文中简称:HEMA) AEMA是一种亲水单体,其分子中的羟基具有很大极性以及高表面自由能的特性。 [0039] In the silicone hydrogel contact lens, a silicon-containing monomer containing 2- (trimethylsiloxy) ethyl methacrylate (hereinafter abbreviated: TMSEMA) JMSEMA precursor B are hydroxyethyl methacrylate ester (hereinafter abbreviated: HEMA) AEMA is a hydrophilic monomer having a hydroxyl group in its molecule polar characteristics and large high surface free energy. HEMA可赋予隐形眼镜良好的表面亲水性。 HEMA contact lenses can impart excellent surface hydrophilicity. 含硅单体或含硅高分子聚合物因硅原子的作用而具有疏水,极性小,表面自由能低的特点。 Silicon-containing monomer or the silicon-containing polymer by the action of the silicon atoms and having a hydrophobic, polar small, low surface free energy characteristics. 将含硅单体与含硅高分子聚合物引入接触透镜材料中,可以极大提高接触透镜的透氧性和弹性。 The silicon-containing monomers and silicon-containing polymer incorporated in the contact lens material, can greatly improve the oxygen permeability and elastic contact lenses. 由于以上特性差异,一方面,HEMA与含硅单体及含硅高分子聚合物的竞聚率相差大,共聚时会出现明显相分离而无法用于接触透镜的制作;另一方面,使用聚丙烯模具制备接触透镜时,模具表面自由能较低,当含硅化合物与HEMA等其他亲水单体共聚时,含硅化合物凭借自身较低的表面自由能优先在镜片表面富集,造成镜片表面亲水性差。 Due to the above differences in characteristic, on the one hand, HEMA silicon-containing monomer reactivity ratios with the silicon-containing polymer and a large difference, there will be significant phase separation of the copolymerization can not be used to make contact lenses; on the other hand, poly preparing propylene contact lens molds, the mold surface free energy is low, when the silicon-containing compound and HEMA and other hydrophilic monomers, silicon-containing compound can be preferentially enriched in the free surface of the lens by virtue of its lower surface, resulting in the lens surface hydrophilic poor.

[0040] 如下面的式⑴所示,将HEMA与三甲基氯硅烷反应可得到TMSEMA JMSEMA是含硅封端羟基的甲基丙烯酸酯类单体。 [0040] As shown in the following formula ⑴, the HEMA the reaction with trimethylchlorosilane is obtained TMSEMA JMSEMA silicon-containing methacrylate monomer capped terminal hydroxy group.

[0041] [0041]

Figure CN104945570BD00071

[0042] 由于羟基被极性很低的硅氧基封闭,极性降低,表面自由能降低可以与含硅高分子良好地发生共聚反应得到透光率好,透氧性高,弹性好的硅凝胶镜片。 [0042] Since the low polar hydroxyl groups are blocked siloxy, decreased polarity, the surface free energy can be reduced with the silicon-containing polymer obtained good copolymerization good light transmittance, high oxygen permeability, good elasticity silicon hydrogel lenses. 另一方面,使用TMSEM代替HEMA后,HEM的羟基被硅氧基封闭,表面自由能大大降低,在使用聚丙烯模具制作接触透镜的过程中,TMSEMA可以占据表面位置。 On the other hand, instead of after use TMSEM HEMA, HEM siloxy hydroxyl groups are blocked, the surface free energy greatly reduced during the use of the polypropylene contact lens mold made of, TMSEMA surface may occupy positions. 经后续表面反转处理后,接触透镜表面的TMSEMA转化为HEMA,从而使亲水单体HEMA出现在硅凝胶表面,进而增加了接触透镜表面亲水性。 After subsequent inversion processing surface, the contact lens surface TMSEMA into HEMA, HEMA such that the hydrophilic monomer present in the surface of the silicone gel, thereby increasing the surface hydrophilicity of contact lenses. 表面反转的原理如式⑵所示。 The principle of surface inversion formula ⑵. TMSEMA的结构中具有三甲基硅酯结构。 TMSEMA structure having the trimethylsilyl ester structures. 三甲基硅酯很敏感,极易在质子性溶剂及碱的作用下温和地水解生成HEMA,从而使表面上疏水的三甲基硅基团脱去,露出亲水的羟基。 Trimethylsilyl ester is very sensitive, easily hydrolyzed HEMA gently under the action of a protic solvent and a base, so that trimethylsilyl groups on the hydrophobic surface removed, exposing the hydrophilic hydroxyl group. 在这一过程中,疏水基团转化为亲水基团,镜片的表面性质发生了反转。 In this process, the hydrophobic group into a hydrophilic group, the surface properties of a lens inversion occurs. 该反转处理方法所需的条件十分简单、温和,易于实现工业化生产与批量操作。 Conditions required for the inversion processing method is very simple, gentle, and easy to implement industrial production and batch operations.

[0043] [0043]

Figure CN104945570BD00072

[0044] 本实施例的硅凝胶接触透镜具有高透氧性。 [0044] The silicone hydrogel contact lenses of the present embodiment has a high oxygen permeability. 这是因为硅凝胶接触透镜中的含硅高分子聚合物、TRIS、SiMA均属于硅氧烷,硅氧烷具有卓越的透氧性能。 This is because the silicon-containing polymer silicone hydrogel contact lenses, TRIS, SiMA belong, silicone has excellent oxygen permeability. 同时该接触透镜有一定弹性,经过表面反转处理后,该镜片具有长效良好的表面亲水性。 Meanwhile, the contact lens has a certain elasticity, the surface after inversion process, the lens having a good long-term surface hydrophilicity.

[0045] 下面例举具体实施例,通过实验来验证本发明实施例的硅凝胶接触透镜所具有的良好性能。 [0045] In particular embodiments exemplified below, to verify the silicone hydrogel contact lens of Example of the present invention has excellent properties by experiment.

[0046] 按照表1所示,将各种单体按照相应的质量进行混合,制成硅凝胶接触透镜。 [0046] as shown in Table 1, the various monomers are mixed in appropriate quality, made of silicone hydrogel contact lenses. 然后按照表3所示,对各实施例进行表面反转处理。 Then as shown in Table 3, each example of the surface inversion processing. 具体过程如下: Specific process is as follows:

[0047] 按表1所示,将各种单体按照相应的质量进行混合,其中,实施例1、2在避光条件下搅拌22小时,实施例3、4可以不避光搅拌24小时,实施例5、6、7在避光条件下搅拌25小时。 [0047] as shown in Table 1, the various monomers are mixed in appropriate quality, in which Examples 1 and 2 stirred for 22 hours in the dark, Examples 3 and 4 may not be stirred in the dark for 24 hours, Example 5,6,7 stirred in the dark for 25 hours. 将搅拌好的混合物注入到接触透镜制作模具中,模具选用聚丙烯模具。 The stirred mixture was poured into a contact lens forming mold, which selection polypropylene molds. 其中,实施例1、2放在紫外光灯下引发2小时,实施例3、4在120 °C的烘箱中固化24小时,实施例5、6、7放在紫外光灯下引发2小时。 Wherein, in Examples 1 and 2 under ultraviolet light initiator 2 hours, Examples 3 and 4 was cured for 24 hours in an oven to 120 ° C in Example placed under ultraviolet light initiator 5,6,7 2 h. 将制作好的硅凝胶接触透镜脱模,将硅凝胶接触透镜浸泡在包含氢氧化钾和甲醇的混合溶液中,在一定温度下震荡一定时间,将硅凝胶接触透镜取出后用乙醇提纯, 最后浸泡在磷酸盐缓冲液中保存。 The silicone hydrogel contact lens made a good release, the silicone hydrogel contact lens immersed in a mixed solution containing potassium hydroxide and methanol and shaken for a certain time at a certain temperature, the silicone hydrogel contact lens is removed after purification by ethanol , the last saved soaked in phosphate buffer. 反转处理中的具体工艺参数见表3。 Specific process parameters inversion process is shown in Table 3.

[0048] 对比例:采用与实施例1组合物相同的比例制备出硅凝胶镜片,不进行后续的表面反转处理,直接用乙醇抽提,磷酸盐缓冲液冲洗后进行静态接触角测试。 [0048] Comparative Example: The static contact angle after the test was prepared in the same composition of Comparative Example 1 embodiment the silicone hydrogel lenses, without subsequent surface inversion process, the direct extraction with ethanol, phosphate buffer flushing.

[0049] 表1 [0049] TABLE 1

[0050] [0050]

Figure CN104945570BD00081

[0051] 表1中各物质在娃凝胶接触透镜中的质量占比如表2所示: [0051] The mass of each substance in Table 1 baby hydrogel contact lenses, such as shown in Table 2 account for:

[0052] 表2 [0052] TABLE 2

Figure CN104945570BD00082

Figure CN104945570BD00091

[0056] 将实施例I -7与对比例的样品透镜进行表面接触角测试。 [0056] Example I -7 contact angle with the surface of the sample lens ratio. 接触透镜表面接触角测试方法为本领域常规方法。 The contact angle of the contact lens surface test methods conventional in the art. 依照国标GB/T11417.7滴液法进行接触角测试,测试结果如表4 所示。 Contact angle tested according to the national standard GB / T11417.7 dropping method, test results are shown in Table 4.

[0057] 表4 [0057] TABLE 4

[0058] [0058]

Figure CN104945570BD00092

[0059] 表4中,利用实施例和对比例制备的镜片进行接触角测量。 [0059] Table 4, using the examples and the lens ratio for the preparation of contact angle measurements. 每个实施例和对比例重复做了4组镜片用于测量接触角,分别对应平行组1、平行组2、平行组3和平行组4。 And each Comparative Example 4 repeated the set of lenses used for measuring the contact angle, a corresponding parallel-group, parallel-group 2, parallel group, and group 34 in parallel. 平均值是指每个实施例中平行组1、平行组2、平行组3和平行组4测得的接触角的算术平均值。 Refers to an average value parallel group, two parallel-group, parallel-group, parallel-group arithmetic mean Examples 3 and 4, the contact angle measured for each embodiment. 从表4 可以看出,通过表面反转处理,实施例1-7制备的硅凝胶接触透镜的表面接触角明显小于对比例的接触角。 As seen from Table 4, by reversing the surface treatment, prepared in Example 1-7 embodiment of surface contact angle silicone hydrogel contact lenses is significantly smaller than the contact angle scale. 因此,实施例1 -7经过本申请中的表面反转处理后,镜片具有良好的亲水性。 Thus, embodiments 1-7 of the present application, after inversion processing surface, a lens having good hydrophilicity. 同时,该表面反转处理方法对于热固和光固的方法都适用。 Meanwhile, the surface treatment method for inversion and thermosetting curing are suitable methods.

[0060] 将实施例1-7与对比例的样品透镜在磷酸盐缓冲液中保存一定天数后,再进行表面接触角测试,所得接触角的平均值如表5所示。 [0060] 1-7 and the average of the ratio of the sample after stored for a certain number of days a lens in a phosphate buffer, and then subjected to a surface contact angle, the contact angle obtained as shown in Table 5 of EXAMPLE.

[0061] 表5 [0061] TABLE 5

[0062] [0062]

Figure CN104945570BD00093

[0063] 从表5可以看出,使用本申请的表面反转处理的透镜的亲水性具有长效性和稳定性。 [0063] As can be seen from Table 5, the hydrophilic lens used in this application have a surface inversion processing and long-term stability. 例如,实施例1的接触透镜表面接触角平均值为49,而由相同材料制成,没有进行反转处理的对比例为137.4,并且维持15天后实施例1和对比例的接触透镜表面接触角没有明显改变。 For example, an embodiment of a contact lens surface in Example 49 is the average value of the contact angle, and made of the same material, no comparative 137.4 inversion processing, and maintained for 15 days in Example 1 and Comparative contact lens surface contact angle It did not change significantly. 因此,经过本申请的表面反转处理的透镜的亲水性具有长效性和稳定性。 Thus, the hydrophilic surface of the lens after inversion processing of the present application and having long-term stability.

Claims (2)

  1. 1. 一种硅凝胶接触透镜的表面反转处理方法,其特征在于,该处理方法包括以下过程: 利用聚丙烯模具制备硅凝胶接触透镜,将制备出的硅凝胶接触透镜浸泡在氢氧化钾和甲醇的混合溶液中,并在20°C〜30°C震荡8〜12小时后,取出硅凝胶接触透镜; 该接触透镜按照质量分数由以下组分组成: 含硅单体: 45〜70%; 含硅高分子聚合物:25〜50%; 引发剂: 0.5〜1%; 交联剂: 卜5%; 所述的含硅单体为2-(三甲基硅氧基)乙基甲基丙烯酸酯,或者由甲基丙烯酸3-[三(三甲基硅氧烷基)甲硅烷基]丙酯和甲基-二(三甲基硅氧烷基)-甲硅烷基丙基甲基丙烯酸甘油酯中的一种或者两种物质与2-(三甲基硅氧基)乙基甲基丙烯酸酯组成的混合物;所述的含硅高分子聚合物为甲基丙烯酸酯单封端的聚二甲基硅氧烷、甲基丙烯酸酯双封端的聚二甲基硅氧烷、丙烯酸酯单封端的聚二甲基硅 1. A method of processing a surface inversion silicone hydrogel contact lens, wherein the processing method comprises the following procedures: preparing a mold of polypropylene silicone hydrogel contact lenses, the silicone hydrogel contact lens immersed in the prepared hydrogen a mixed solution of methanol and potassium hydroxide, and, after shaking 20 ° C~30 ° C 8~12 hours, a silicone hydrogel contact lens; contact lens according to the mass fraction consists of the following components: silicon-containing monomer: 45 ~ 70%; silicon-containing polymer: 25~50%; initiator: 0.5~1%; crosslinking agent: Bu 5%; said silicon-containing monomer is 2- (trimethylsiloxy) ethyl methacrylate, or a methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate and methyl - bis (trimethylsiloxy) - silyl propyl a substrate methacrylic acid glycerides or a mixture of two substances with 2 consisting of ethyl methacrylate (trimethylsiloxy); said silicon-containing polymer of methacrylate monomers terminated polydimethylsiloxane, bis methacrylate-terminated polydimethylsiloxanes, acrylate monomer terminated polydimethylsiloxane 氧烷或者丙烯酸酯双封端的聚二甲基硅氧烷; 所述2-(三甲基硅氧基)乙基甲基丙烯酸酯占接触透镜的质量分数为30〜50%。 Oxyalkyl acrylate or bis-terminated polydimethylsiloxane; the 2- (trimethylsiloxy) ethyl methacrylate mass fraction of 30 ~ 50% of the contact lens.
  2. 2. 按照权利要求1所述的硅凝胶接触透镜的表面反转处理方法,其特征在于,所述的混合溶液中,氢氧化钾的质量浓度为5〜10%,甲醇与水的体积比为1:7〜10。 2. The surface treatment method of reversing silicone hydrogel contact lens according to claim, wherein said mixed solution, the concentration of potassium hydroxide of 5 to 10%, the volume ratio of methanol and water 1: 7 to 10.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074450A (en) * 1991-11-05 1993-07-21 博士伦有限公司 Wettable silicone hydrogel compositions and methods for their manufacture
CN1180416A (en) * 1995-04-04 1998-04-29 诺瓦提斯公司 Extended wear ophthalmic lens
CN1218816A (en) * 1997-10-09 1999-06-09 庄臣及庄臣视力产品有限公司 Siloxanes hydrogel polymers
CN1441814A (en) * 2000-03-22 2003-09-10 庄臣及庄臣视力保护公司 Hydrogel with internal wetting agent
CN1842559A (en) * 2003-06-30 2006-10-04 庄臣及庄臣视力保护公司 Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes
CN1989426A (en) * 2004-02-11 2007-06-27 庄臣及庄臣视力保护公司 (Meth)acrylamide monomers containing hydroxy and silicone functionalities and polymers made therefrom
CN101088029A (en) * 2004-12-22 2007-12-12 博士伦公司 Polymerizable surfactants and their use as device forming comonomers
WO2009032266A2 (en) * 2007-09-04 2009-03-12 University Of Florida Dispersions of microparticles and microgels in hydrogels for drug delivery
CN101641206A (en) * 2007-03-22 2010-02-03 诺瓦提斯公司 Prepolymers with dangling polysiloxane-containing polymer chains
CN102027391A (en) * 2008-06-12 2011-04-20 赢创罗姆有限公司 Hydrogel based on copolymers containing silicone
CN102257408A (en) * 2008-12-18 2011-11-23 诺瓦提斯公司 Method for making silicone hydrogel contact lenses
CN102675658A (en) * 2011-03-07 2012-09-19 远东新世纪股份有限公司 Method for preparing polysiloxane hydrogel with high moisture content
CN103435746A (en) * 2013-09-03 2013-12-11 东南大学 Amino acid zwitter ion hydrogel material and preparation method thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074450A (en) * 1991-11-05 1993-07-21 博士伦有限公司 Wettable silicone hydrogel compositions and methods for their manufacture
CN1180416A (en) * 1995-04-04 1998-04-29 诺瓦提斯公司 Extended wear ophthalmic lens
CN1218816A (en) * 1997-10-09 1999-06-09 庄臣及庄臣视力产品有限公司 Siloxanes hydrogel polymers
CN1441814A (en) * 2000-03-22 2003-09-10 庄臣及庄臣视力保护公司 Hydrogel with internal wetting agent
CN1842559A (en) * 2003-06-30 2006-10-04 庄臣及庄臣视力保护公司 Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes
CN1989426A (en) * 2004-02-11 2007-06-27 庄臣及庄臣视力保护公司 (Meth)acrylamide monomers containing hydroxy and silicone functionalities and polymers made therefrom
CN101088029A (en) * 2004-12-22 2007-12-12 博士伦公司 Polymerizable surfactants and their use as device forming comonomers
CN101641206A (en) * 2007-03-22 2010-02-03 诺瓦提斯公司 Prepolymers with dangling polysiloxane-containing polymer chains
WO2009032266A2 (en) * 2007-09-04 2009-03-12 University Of Florida Dispersions of microparticles and microgels in hydrogels for drug delivery
CN102027391A (en) * 2008-06-12 2011-04-20 赢创罗姆有限公司 Hydrogel based on copolymers containing silicone
CN102257408A (en) * 2008-12-18 2011-11-23 诺瓦提斯公司 Method for making silicone hydrogel contact lenses
CN102675658A (en) * 2011-03-07 2012-09-19 远东新世纪股份有限公司 Method for preparing polysiloxane hydrogel with high moisture content
CN103435746A (en) * 2013-09-03 2013-12-11 东南大学 Amino acid zwitter ion hydrogel material and preparation method thereof

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