CN1371263A - 用于外科植入物的疏水结合的亲水性涂层组合物 - Google Patents

用于外科植入物的疏水结合的亲水性涂层组合物 Download PDF

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CN1371263A
CN1371263A CN00812277A CN00812277A CN1371263A CN 1371263 A CN1371263 A CN 1371263A CN 00812277 A CN00812277 A CN 00812277A CN 00812277 A CN00812277 A CN 00812277A CN 1371263 A CN1371263 A CN 1371263A
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A·R·莱波尤弗
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Abstract

本发明公开了用于植入物的亲水涂层。涂层疏水结合在植入物上,但与植入物的表面不发生共价交联或共价粘附。

Description

用于外科植入物的疏水结合的亲水性涂层组合物
技术领域
本发明涉及用于外科植入物的涂层材料。具体讲，本发明涉及疏水结合在外科植入物表面的亲水性共聚物。
背景技术
既有刚性又可折叠的可植入眼镜材料是已知的。眼科植入物中最常用的刚性材料是聚甲基丙烯酸甲酯(“PMMA”)。可折叠的眼内透镜(“IOL”)材料通常可分成三类：聚硅氧烷材料、水凝胶材料和非水凝胶(“疏水的”)丙烯酸材料。例如可参考“可折叠的眼内透镜”(Ed.Martin etal.，SlackIncorporated，Thorofare，New Jersey(1993))。对于本申请来说，疏水丙烯酸材料是室温下吸水小于约5％的丙烯酸材料。
眼科植入物中所使用的聚硅氧烷和非水凝胶丙烯酸材料在植入物插入眼内期间或之后可损坏内皮细胞，也可能损坏其它细胞或组织。这些材料通常是疏水和/或发粘的并可将细胞拖离与植入物接触的眼组织。尤其在晶状IOL｀s植入囊袋(capsular bag)和虹膜之间的情况下，甚至在植入物到达其目标位置之后植入物与周围的细胞或组织存在显著物理接触。
发明概述
本发明涉及用作外科植入物，尤其是含聚硅氧烷或非水凝胶丙烯酸材料的眼科植入物的亲水涂层组合物。更具体地说，本发明涉及用作植入物的涂层材料，其中所述涂层材料含(甲基)丙烯酸2-苯乙酯和N-乙烯基吡咯烷酮(“NVP”)的共聚物。该涂层材料可吸收约40-90％的水。尽管本发明的涂层材料的含水量相对高，但它的韧性足以经受使用镊子进行折叠或操作，而不断裂。
本发明还涉及在植入物的表面上涂覆涂层的方法，其中所述涂层含(甲基)丙烯酸2-苯乙酯和NVP的共聚物，该共聚物没有交联单体。该方法包括将共聚物溶于溶剂中以形成涂层溶液，使所述涂层溶液与植入物的表面接触，和干燥该涂覆的植入物。
发明详述
除非另有说明，所有的量均以重量％表示。
本发明的涂层材料是(甲基)丙烯酸2-苯乙酯和NVP的共聚物。通过疏水或“物理”(即非共价)交联方式，涂层材料附着于基质上。涂层材料还通过非共价交联方式进行内部交联。该涂层材料可吸收约40-90％的水，优选约65-75％的水。共聚物单体的比例取决于所需的含水量，各自的浓度范围通常是，(甲基)丙烯酸2-苯乙酯为约25-60％和NVP为约40-75％。优选甲基丙烯酸2-苯乙酯(“2-PEMA”)和NVP的共聚物。在优选的方案中所需的含水量为约65-75％，共聚的涂层材料含约35-45％2-PEMA和约40-50％NVP。
使(甲基)丙烯酸2-苯乙酯和NVP组分与聚合引发剂(通常约2％或更低)结合以形成涂层组合物并固化该涂层组合物，从而制备共聚的涂层材料。可使用任何类型的聚合引发剂，包括热引发剂和光引发剂。优选的引发剂是苯甲酰氧化膦引发剂，用蓝光活化的2，4，6-三甲基苯甲酰二苯基氧化膦(“TPO”)。合适的热引发剂包括常规的过氧化物过辛酸叔丁酯和双偶氮异丁腈(bisazoisobutronitrile)。合适的UV引发剂包括苯偶姻甲醚和Darocur1173。
除了(甲基)丙烯酸2-苯乙酯、NVP和聚合引发剂外，涂层共聚物任选地包括一种或多种选自下列的组分：可与(甲基)丙烯酸2-苯乙酯和NVP组分共聚的UV吸收剂、可与(甲基)丙烯酸2-苯乙酯和NVP组分共聚的阻挡蓝光的色料、降低混浊或开裂的反应性增塑剂和在涂层共聚物内部减少交联的链转移剂。
紫外吸收发色团可以是任何吸收波长短于约400nm光的化合物，但不吸收任何实质性量的可见光。合适的可共聚的紫外吸收化合物是美国专利No.4304895中公开的取代2-羟基二苯甲酮和美国专利No.4528311中公开的2-羟基-5-丙烯酰苯基-2H-苯并三唑。最优选的紫外吸收化合物是2-(3｀-甲代烯丙基-2｀-羟基-5｀-甲基苯基)苯并三唑。合适的可共聚的阻挡蓝光的发色团包括美国专利No.5470932中公开的那些。若选择蓝光活化的聚合引发剂和加入阻挡蓝光的色料，则必须调整聚合引发剂的种类或浓度以使任何干扰最小化。
合适的反应性增塑剂或软化剂包括聚乙二醇(200-2000)单(甲基)丙烯酸酯和聚乙二醇(200-2000)单甲基醚单(甲基)丙烯酸酯，其中优选甲基丙烯酸酯类，且最优选聚乙二醇(400)单甲基醚单甲基丙烯酸酯。视需要或所需，反应性增塑剂的量在约5-25％范围内。取决于植入物的功能和涂层的厚度，可容许一定程度的混浊或开裂，从而可不要求反应性增塑剂。
链转移剂，若存在的话，典型地加入量为0.01-0.4％。许多链转移剂是本领域已知的。合适的链转移剂的实例包括1-十二烷硫醇和2-巯基乙醇。
固化涂层共聚物后，通过提取以除去水溶性组分和低分子量疏水组分来纯化该涂层共聚物。这可通过两步提取来完成，其中第一步是含水提取和第二步是非含水的提取。所得的涂层共聚物典型地在水中提取12-20小时以除去含水的可提取组分，如N-乙烯基吡咯烷酮或低分子量聚乙烯吡咯烷酮。涂层共聚物在水中被提取之后，将其溶解在有机溶剂如二氯甲烷中。将所得的含溶解聚合物的溶液加入到挥发性脂族溶剂(如庚烷或己烷)浴中，以沉淀该涂层聚合物。通过例如使用烧结玻璃滤器过滤和接着干燥，优选室温下真空干燥以收集沉淀的涂层聚合物。
纯化涂层聚合物之后，通过将涂层聚合物溶于溶剂或溶剂的混合物，如50∶50(重量份)乙醇和2-戊酮的混合物以制备涂层溶液。溶剂或溶剂的混合物的选择应使得能获得透明、均匀的涂层溶液，同时溶剂或溶剂混合物不会蒸发得太快以至于留下混浊的涂层。
涂层溶液中的涂层共聚物浓度取决于所需的涂层厚度。其它影响涂层厚度的因素包括涂层溶液的粘度、涂层溶液和植入物的温度和所选择溶剂的蒸发速率。通常，本发明的涂层厚度不多于1微米，优选约0.5微米厚。最小约0.01微米的涂层厚度可能是必须的，这使得涂层能经受植入物的任何操作(如IOL的折叠)和在植入或在患者的目标位置长期放置期间所引起的任何磨损。在浸渍涂层法中，涂层溶液中约4-5％的涂层共聚物浓度将典型地制备出约0.5微米厚的涂层。
利用常规的技术，如纺丝或浸渍涂层法，将涂层溶液涂覆到植入物上，其中优选浸渍涂层。优选快速浸渍植入物，使涂层溶液中溶剂对植入物引起的任何溶胀最小。
在植入物上涂覆涂层之后，干燥该涂层，其中优选两步干燥法。首先使涂覆的植入物在空气中干燥到大部分或所有溶剂已挥发(通常15分钟)，第二，在高温，约40-100℃下烘烤涂覆的植入物以尽可能除去残留的溶剂。优选的干燥方法包括室温空气干燥15分钟，接着70℃下烘烤约30分钟。
利用多种溶剂或溶剂混合物，包括制备涂层溶液中用作基础溶剂的相同溶剂在内，可容易地除去涂层，但涂层不能用水除去。
在操作涂覆的植入物之前，优选水化涂层数小时，以使涂层避免开裂或其它损坏。
适于用本发明亲水性涂层涂覆的植入物优选由疏水丙烯酸材料制备，但也可以是聚硅氧烷或硅氧烷-丙烯酸共聚物。优选的疏水丙烯酸材料是美国专利Nos.5,290,892和5,693,095(此处将其全部内容引入参考)中所公开的那些聚合材料。若植入物是IOL，则本发明的涂层可与用作“硬质”IOL(即以展开的状态插入)或“可折叠”或“软质”IOL(即以可折叠或压缩状态插入)的基质材料结合使用。合适的待涂覆的IOL材料包括美国专利Nos.5,693,095或5,331,073中所公开的那些。可在整个IOL或仅在部分IOL上涂覆该涂层。此处所使用的“植入物”包括隐形眼镜。
为了制备待涂覆的植入材料，使其能接受涂层，在涂覆本发明的涂层组合物之前，将待涂覆的表面暴露于反应性等离子体气体是必须或所需的。合适的反应性等离子体气体包括氧化气体如氧气。合适的等离子体室是Advanced Plasma Systems，Inc制造的P2CIM B-系列等离子体室。使用这样一种等离子体室，其中合适的等离子体参数包括：功率＝400W，等离子体气体＝氧气；等离子体气体的压力＝225mTorr；暴露时间＝4-6分钟。
下述实施例用于阐述但不是限制本发明：
实施例1-4
制备下表1所示的配料并在聚丙烯夹板模具(10mm×20mm×0.9mm)中固化。使用Kulzer Palatray CU蓝光仪(12-14mW/cm2)，将实施例1-3的配料在蓝光下暴露1小时进行固化。实施例4的配料在75℃下加热1小时，接着在100℃下加热1小时以固化。
共聚物的纯化
接着，提取固化的共聚物以除去任何含水和不含水的可浸出物。固化实施例1-4的配料后，将其在去离子水中提取过夜，接着用烘箱在110-120℃下烘干。若共聚物没有充分干燥，在疏水溶剂中会形成凝胶。然后将干燥的配料溶于二氯甲烷，从而制备约10％(重量份)的溶液，并向100cc的甲苯中加入该溶液。接着将所得的溶液转移到500-cc烧瓶中，并在60℃下使用旋转蒸发仪除去二氯甲烷。之后，向溶液中加入足量甲苯，使每一份的总重量为约100g。然后冷却溶液到室温。在达到室温之后，在搅拌下向400-cc己烷中快速加入每一种溶液，沉淀所需的共聚物，溶液中残留低分子量、非亲水性可浸出物。弃去溶剂和在300cc新鲜己烷(纯度99+％)中浸渍共聚物沉淀(粉末)数小时。再次弃去己烷和室温下将共聚物在高真空(＜0.2mm Hg)下放置2小时，得到所需的纯化的共聚物。
涂层溶液的制备
将纯化的共聚物各自溶解在50∶50(重量份)乙醇∶2-戊酮溶剂中，得到所需的浓度(典型地4-5％)。制备4.2％的实施例#1的共聚物溶液，分别制备4.6％，4.0％和4.0％的实施例2-4的共聚物溶液。通过Gelman玻璃纤维高级分离片(Acrodisc)(1微米)过滤所得的溶液，得到无颗粒的涂层溶液。
涂层的涂覆
使用1.8％Perkadox-16作为热引发剂，制备含65％丙烯酸2-苯乙酯，30％甲基丙烯酸2-苯乙酯，1.8％邻甲代烯丙基Tinuvin P和3.2％二丙烯酸1，4-丁二酯的共聚物。在如上所述的夹板模具中固化该共聚物，用丙酮提取约2小时，室温下在空气中干燥约1小时，然后在烘箱中在100℃下干燥约1小时。以确定的板片形式存在的该材料用作所有实施例的植入物/基质材料(“植入板片”)。
将植入板片浸渍在涂层溶液中。应注意由于溶剂会溶胀样品，应使样品在涂层溶液中的浸渍时间最短。使涂覆的植入物室温下在空气中干燥约15分钟，接着在70℃下烘烤30分钟。涂层共聚物没有渗吸入植入板片的表面，且不与基质反应(即通过共价键)。可使用多种有机溶剂或溶剂混合物，包括制备涂层溶液所使用的相同的溶剂原料在内，容易地除去该涂层。
为了证明涂层不溶于水，将实施例2-4中的涂覆样品在去离子水中放置3月，然后暴露于0.05％刚果红染料(可与乙烯基吡咯烷酮络合)的含水溶液中。所有样品均变红。轻轻擦拭或用湿的手指摩擦，不会除去涂层。
                          表1
             (所有量均是重量份，除非特别说明)
    组分     1     2     3     4
    2-PEMA     29.32     39.69     39.99     -
    2-PEA*     -     -     -     29.80
    NVP     54.64     44.54     44.15     69.16
 PEG(400)单甲基醚单甲基丙烯酸酯     14.84     14.72     14.84     -
    1-十二烷硫醇     -     -     0.06     0.07
    Lucurin TPO**     1.18     1.05     0.96     -
    过辛酸叔丁酯     -     -     -     0.96
    ％水     88.7     65.9     72.2     73.5
    折射率     1.360     1.398     1.386     1.38
*2-苯基乙氧基丙烯酸酯
**2，4，6-三甲基-苯甲酰二苯基氧化膦
实施例5-7
除了涂层共聚物含有下表2所示的组分外，根据实施例1-4的上述步骤制备涂覆的植入板片。使用Kulzer Palatray CU仪固化实施例5和6的配料1小时。使用相同的仪器固化实施例7的配料0.75小时。在所有的三个实施方案中，制备溶于50∶50(重量份)乙醇∶2-戊酮溶剂的4-5％共聚物溶液作为涂层溶液，通过Gelman玻璃纤维高级分离片过滤并通过浸渍涂层法将其涂覆到植入板片上。室温下在空气中干燥涂覆的植入板片15分钟，然后在70℃下烘烤30分钟。
这些实施例表明NVP与甲基丙烯酸甲酯或甲基丙烯酸4-苯丁酯的共聚物水解时，与NVP与2-PEMA的共聚物相比，产生严重的混浊。实施例6中仅有9.1％含水可提取物且水解时仅轻微混浊。相比之下，实施例5和7水解时是不透明的。实施例5开裂严重并在去离子水中在55℃下加热时开始崩解。实施例7得到20.6％的含水可提取物。
                   表2
             (所有量均是重量份)
    组分     5     6     7
甲基丙烯酸4-苯丁酯  1.5038   -     -
    2-PEMA  -   1.2519     -
    甲基丙烯酸甲酯  -   -     1.2688
    NVP  3.4992   3.5067     3.4979
    Lucirin TPO  0.0537   0.0553     0.0484
    ％水  N/A   73.5     92.3
实施例8
除了涂层共聚物含有下表3所示的组分外，根据实施例1-4的上述步骤制备涂覆的植入板片。如以上实施例1-4的实施方案，使用KulzerPalatray CU仪固化涂层1小时。制备溶于50∶50(重量份)乙醇∶2-戊酮溶剂的5.7％涂层共聚物溶液作为涂层溶液。将植入板片浸入涂层料中之后，使涂覆的植入板片室温下空气干燥，接着在80℃下烘烤20分钟。接着将涂覆的板片室温下置于去离子水中过夜，然后轻轻擦拭或用湿的手指摩擦涂层并进行生雾(即呼吸)试验。呼气时将板片靠近嘴。若存在涂层，在板片上几乎没有任何冷凝。然而若涂层不再存在，则表面会生雾。在该实施方案中，试验板片生雾，表明在轻轻擦拭或用湿的手指摩擦涂层时涂层已被除去。
                   表3
            (所有量均是重量份)
    组分     8
    2-PEMA     39.57
    GMMA     29.52
 PEG(400)单甲基醚单甲基丙烯酸酯     29.66
    1-十二烷硫醇     0.40
    Lucirin TPO     0.84
    ％水     71.5
    折射率(水解)     1.388
通过一些优选的实施方案已描述了本发明，然而，应当理解的是其它具体的形式或变化也可包括在本发明范围内，而没有脱离其精神或主要特征。因此，上述的实施方案被认为各方面均是示例性而不是限制性的，本发明的范围通过所附的权利要求而不是前述的说明书来表示。

Claims (12)

1.一种用于外科植入物的共聚物涂层组合物，其中该涂层组合物含非共价交联的(甲基)丙烯酸2-苯乙酯和N-乙烯基吡咯烷酮(“NVP”)的共聚物，和该涂层组合物可吸收约40-90％的水。
2.权利要求1的涂层组合物，其中(甲基)丙烯酸2-苯乙酯是甲基丙烯酸2-苯乙酯。
3.权利要求1的涂层组合物，其中涂层组合物可吸收约65-75％的水。
4.权利要求1的涂层组合物，其中共聚物含约25-60％(甲基)丙烯酸2-苯乙酯和约40-75％N-乙烯基吡咯烷酮。
5.权利要求4的涂层组合物，其中共聚物含约35-45％(甲基)丙烯酸2-苯乙酯和约40-50％N-乙烯基吡咯烷酮。
6.权利要求1的涂层组合物，其中涂层组合物进一步含一种或多种选自下列的组分：可与(甲基)丙烯酸2-苯乙酯和NVP组分共聚的UV吸收剂、可与(甲基)丙烯酸2-苯乙酯和NVP组分共聚的阻挡蓝光的色料、反应性增塑剂和链转移剂。
7.权利要求6的涂层组合物，其中涂层组合物含选自聚乙二醇(200-2000)单(甲基)丙烯酸酯和聚乙二醇(200-2000)单甲基醚单(甲基)丙烯酸酯的反应性增塑剂。
8.权利要求7的涂层组合物，其中反应性增塑剂是聚乙二醇(400)单甲基醚单甲基丙烯酸酯。
9.权利要求6的涂层组合物，其中涂层组合物含选自1-十二烷硫醇和2-巯基乙醇的链转移剂。
10.一种含涂层和基质的涂覆的外科植入物，其中通过疏水的相互作用将涂层附着在基质上，该涂层的厚度为约0.01-1微米，和该涂层含非共价交联的(甲基)丙烯酸2-苯乙酯和N-乙烯基吡咯烷酮(“NVP”)的共聚物，使得涂层可吸收约40-90％的水。
11.权利要求10的涂覆的外科植入物，其中基质含疏水丙烯酸材料。
12.一种向外科植入物上涂覆涂层的方法，包括下述步骤：
a)制备未交联的含(甲基)丙烯酸2-苯乙酯和N-乙烯基吡咯烷酮的共聚物，使得共聚物可吸收约40-90％的水，
b)使用由含水步骤和有机溶剂步骤组成的两步提取法纯化步骤a)中形成的共聚物，
c)通过将步骤b)中纯化的共聚物溶于有机溶剂以形成涂层溶液，
d)向植入物上涂覆涂层溶液，
e)干燥植入物上的涂层溶液，使得步骤b)中纯化的共聚物疏水附着在植入物上。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101945675A (zh) * 2007-12-21 2011-01-12 伊西康公司 带涂层的组织工程支架
US9119710B2 (en) 2005-09-08 2015-09-01 Calhoun Vision, Inc. Adjustable optical elements with enhanced ultraviolet protection

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE386075T1 (de) * 1999-04-12 2008-03-15 Cornell Res Foundation Inc Hydrogel-formendes system mit hydrophoben und hydrophilen komponenten
US6723815B2 (en) 1999-09-02 2004-04-20 Alcon, Inc. Covalently-bound, hydrophilic coating compositions for surgical implants
US6632905B2 (en) * 1999-09-02 2003-10-14 Alcon Universal Ltd. Covalently-bound, hydrophilic coating compositions for surgical implants
US7157538B2 (en) * 2004-08-13 2007-01-02 Alcon, Inc. Covalently-bound, hydrophilic coating compositions for surgical implants
PT1864181T (pt) * 2005-03-01 2016-10-06 Carl Zeiss Vision Australia Holdings Ltd Revestimentos para elementos de lentes oftálmicas
WO2009015256A2 (en) * 2007-07-25 2009-01-29 Alcon, Inc. High refractive index ophthalmic device materials
US8293858B1 (en) 2009-01-14 2012-10-23 Novartis Ag Ophthalmic and otorhinolaryngological device materials containing a reactive NVP macromer
TWI528608B (zh) 2011-11-21 2016-04-01 財團法人工業技術研究院 環境敏感電子元件之封裝體

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR207867A1 (es) * 1974-07-04 1976-11-08 Smith & Nephew Res Un copolimero hidrogel ligeramente entrelazado
US4638040A (en) 1983-06-03 1987-01-20 Minnesota Mining And Manufacturing Company Acrylate and methacrylate monomers and polymers
US4578504A (en) 1983-06-03 1986-03-25 Minnesota Mining And Manufacturing Company Acrylate and methacrylate monomers and polymers
US4673539A (en) 1983-06-03 1987-06-16 Minnesota Mining And Manufacturing Company Process for thermoformed articles
US4786446A (en) 1985-05-17 1988-11-22 Minnesota Mining And Manufacturing Company Process of forming a hydroxy-substitute polymeric shaped article
US4921884A (en) 1987-02-26 1990-05-01 Minnesota Mining And Manufacturing Company Hydroxy-substituted polymeric shaped hydrogel article
US5130160A (en) 1987-04-10 1992-07-14 University Of Florida Ocular implants and methods for their manufacture
US5108776A (en) 1987-04-10 1992-04-28 University Of Florida Ocular implants and methods for their manufacture
US5290548A (en) 1987-04-10 1994-03-01 University Of Florida Surface modified ocular implants, surgical instruments, devices, prostheses, contact lenses and the like
US5094876A (en) 1987-04-10 1992-03-10 University Of Florida Surface modified surgical instruments, devices, implants, contact lenses and the like
US4931519A (en) 1987-06-02 1990-06-05 Warner-Lambert Company Copolymers from n-alkyl-3-alkenylene-2-pyrrolidone
US5002792A (en) 1988-08-11 1991-03-26 Medtronic, Inc. Process for making biomedical devices utilizing thermoplastic hydrophilic gels
US5326584A (en) * 1989-04-24 1994-07-05 Drexel University Biocompatible, surface modified materials and method of making the same
JPH06502782A (ja) * 1990-10-05 1994-03-31 ユニヴァーシティ　オブ　フロリダ 改良された眼科用インプラントとその製造方法
US5290892A (en) 1990-11-07 1994-03-01 Nestle S.A. Flexible intraocular lenses made from high refractive index polymers
US5135297A (en) 1990-11-27 1992-08-04 Bausch & Lomb Incorporated Surface coating of polymer objects
US5152787A (en) 1990-12-19 1992-10-06 Eastman Kodak Company Intraocular gradient-index lenses used in eye implantation
WO1994003129A1 (en) 1992-08-07 1994-02-17 Keravision Inc. Hybrid intrastromal corneal ring
US5603774A (en) 1993-09-27 1997-02-18 Alcon Laboratories, Inc. Method for reducing tackiness of soft acrylic polymers
US5470932A (en) 1993-10-18 1995-11-28 Alcon Laboratories, Inc. Polymerizable yellow dyes and their use in opthalmic lenses
EP0774983B1 (en) 1995-06-07 2002-12-04 Alcon Laboratories, Inc. Improved high refractive index ophthalmic lens materials
US5554187A (en) 1995-08-18 1996-09-10 Rizzo, Iii; Joseph Medication dispensing intra-ocular lens system
ATE225147T1 (de) * 1997-08-07 2002-10-15 Alcon Lab Inc Intrakorneale diffraktive linse
US5891931A (en) 1997-08-07 1999-04-06 Alcon Laboratories, Inc. Method of preparing foldable high refractive index acrylic ophthalmic device materials
JP4144920B2 (ja) 1997-08-20 2008-09-03 興和株式会社 軟質眼内レンズ材料
DE19738345C1 (de) 1997-09-02 1999-05-06 Mdp Medical Device Polymers Gm Intraokularlinse
US6310116B1 (en) 1997-10-09 2001-10-30 Kuraray Co., Ltd. Molded polymer article having a hydrophilic surface and process for producing the same
ATE206314T1 (de) 1998-04-15 2001-10-15 Alcon Lab Inc Beschichtungszusammensetzung für intraocularen linsen
US6329485B1 (en) 1998-12-11 2001-12-11 Bausch & Lomb Incorporated High refractive index hydrogel compositions for ophthalmic implants

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9119710B2 (en) 2005-09-08 2015-09-01 Calhoun Vision, Inc. Adjustable optical elements with enhanced ultraviolet protection
US10470874B2 (en) 2005-09-08 2019-11-12 Rxsight, Inc. Adjustable optical elements with enhanced ultraviolet protection
CN101945675A (zh) * 2007-12-21 2011-01-12 伊西康公司 带涂层的组织工程支架

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