CN1441814A - 具有内润湿剂的水凝胶 - Google Patents

具有内润湿剂的水凝胶 Download PDF

Info

Publication number
CN1441814A
CN1441814A CN01809889A CN01809889A CN1441814A CN 1441814 A CN1441814 A CN 1441814A CN 01809889 A CN01809889 A CN 01809889A CN 01809889 A CN01809889 A CN 01809889A CN 1441814 A CN1441814 A CN 1441814A
Authority
CN
China
Prior art keywords
hydrogel
hydrophilic polymer
pvp
polyvinylpyrolidone
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN01809889A
Other languages
English (en)
Other versions
CN1217969C (zh
Inventor
D·C·图尔纳
A·C·麦登
D·G·范德拉安
R·B·斯蒂芬
R·N·罗维
J·D·福德
F·F·莫洛克
G·A·希尔
A·阿利
K·P·麦克卡贝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson and Johnson Vision Care Inc
Original Assignee
Johnson and Johnson Vision Care Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson and Johnson Vision Care Inc filed Critical Johnson and Johnson Vision Care Inc
Publication of CN1441814A publication Critical patent/CN1441814A/zh
Application granted granted Critical
Publication of CN1217969C publication Critical patent/CN1217969C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

本发明提供了通过将高分子量亲水性聚合物引入到硅氧烷水凝胶单体混合物中制备的可湿性硅氧烷水凝胶。亲水性聚合物被包埋在水凝胶中，其中在它与水凝胶基体之间存在很少或没有共价键键合。

Description

具有内润湿剂的水凝胶
发明领域
本发明涉及疏水性聚合物。更具体地，本发明涉及当用内润湿剂制备时，适合用于生物医学设备如眼科透镜的疏水性聚合物。
材料用于生物医学设备的适应性取决于许多因素，通常包括材料的润湿性能和它与生物材料如蛋白和脂肪粘附或反应的倾向性。在眼科应用如接触透镜(隐形眼镜)和眼内植入物中，氧渗透性也是重要的考虑因素。高氧渗透性一般是所希望的，良好的可湿性和抗与生物材料粘附或反应的性能也是所希望的。
硅氧烷水凝胶对于制备生物医学设备如接触透镜能够是特别理想的材料，因为它们一般具有高氧渗透性。然而，它们的疏水本性使得由它们制备的设备难以润湿。解决该问题的一种方法是用更亲水的涂料涂布水凝胶。这样额外增加了生产它们的复杂性。另外，涂料选择是困难的，影响生理学性能的适当涂层厚度、涂层均匀性和其它因素的确定也是困难的。
US专利5,219,965和它的后继专利提出了通过在用于制备聚合物体如接触透镜的单体混合物中引入具有疏水部分、亲水部分、链转移剂和不饱和端基的大分子单体来改性该物体的表面性能的方法。大分子单体能够包括分子量为500-10,000的聚-N-乙烯基吡咯烷酮，其中1,000-5,000的分子量是最优选的。大分子单体被聚合成水凝胶并且改进了聚合物的可湿性。然而这种改进一般没有达到能够由水凝胶制备透镜而不需使用亲水涂料的这种程度。无论如何，在不需要透镜涂料的情况下增强生物医学设备如接触透镜的可湿性将被认为是本领域中的重大进步。
US专利4,045,547和4,042,552提出了将大量(14.25-35wt％)的聚乙烯基吡咯烷酮(PVP)聚合到聚(甲基丙烯酸羟乙酯)(HEMA)型接触透镜配方上的方法。聚合在不考虑水的存在的情况下进行。PVP的分子量没有提及。
US专利4,833,196；4,791,175和4,678,838涉及将聚-N-乙烯基内酰胺引入到用于制备接触透镜的聚合物中的方法。聚乙烯基吡咯烷酮(PVP)是优选的聚内酰胺。低分子量(～40,000道尔顿)PVP通过首先与臭氧反应使PVP氢过氧化和然后让PVP与其它单体聚合来以共价键键合于用于形成透镜的单体上。
US专利5,198,477在主要由含乙烯基的单体制备的大环形成的互穿聚合物网络内使用低分子量(～25,000道尔顿)PVP。该PVP似乎被交联成互穿网络。
发明概述
本发明是通过将高分子量亲水聚合物引入到硅氧烷水凝胶单体混合物中制备的可湿性硅氧烷水凝胶。亲水性聚合物被包埋在水凝胶中，在它和水凝胶基体之间很少或没有共价键连接。
在本发明的一个方面中，高分子量亲水性聚合物被包埋在硅氧烷水凝胶基体中。
在本发明的另一个方面中，高分子量亲水性聚合物是聚乙烯基吡咯烷酮。
在本发明的再一个方面中，高分子量亲水性聚合物具有100,000-500,000道尔顿的分子量(Mw)；优选分子量是至少约300,000道尔顿。
在本发明的还一个方面中，从本发明的硅氧烷水凝胶制备眼科透镜。发明详述
这里使用的术语“单体”是指能够被聚合的低分子量化合物(即，一般具有低于700的数均分子量)，以及含有能够进一步聚合的官能团的中到高分子量化合物或聚合物，有时称之为大分子单体(即，一般具有高于700的数均分子量)。因此，应当理解术语“含硅氧烷的单体”和“亲水性单体”包括单体，大分子单体和预聚物。预聚物是部分聚合的单体或能够进一步聚合的单体。
“含硅氧烷的单体”是指在单体、大分子单体或预聚物中含有至少两个[-Si-O-]重复单元的单体。优选，全部Si和所连接的O以含硅氧烷的单体的总分子量的20wt％以上，和更优选30wt％以上的量存在于含硅氧烷的单体中。优选的本发明的含硅氧烷的单体具有以下结构式：
Figure A0180988900061
结构式I其中R51是H或CH3，q是1或2并且对于每个q、R52、R53和R54独立是乙基、甲基、苄基、苯基或包括1-100重复Si-O单元的单价硅氧烷链，p是1-10，r＝(3-q)，X是O或NR55，其中R55是H或具有1-4个碳原子的单价烷基，a是0或1，L是优选包括2-5个碳原子的二价连接基团，它还可以任选包括醚或羟基，例如聚乙二醇链。
能够用于形成本发明的硅氧烷水凝胶的结构式I的含硅氧烷的单体的实例是甲基丙烯酰氧基丙基双(三甲基甲硅烷氧基)甲基硅烷，甲基丙烯酰氧基丙基五甲基二硅氧烷，(3-甲基丙烯酰氧基-2-羟基丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷。优选的含硅氧烷的单体是单甲基丙烯酰氧基烷基终端的聚二甲基硅氧烷(“mPDMS”)，如在结构式II中表示的那些：
                       结构式II其中b＝0-100，R57是任何可以包括杂原子的C1-10脂族或芳族基团；前提是R57在它键接于Si的部位没有被官能化。C3-8烷基是优选的，丁基，尤其仲丁基是最优选的。R56是烯属不饱和部分；优选是单个可聚合的乙烯基。更优选它是甲基丙烯酰基部分，但它还能够是丙烯酰基或苯乙烯部分或其它类似部分。
优选其它含硅氧烷的单体与结构式I的含硅氧烷的单体结合以形成本发明的软接触透镜。在这一方面，甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷(TRIS)，在US4,711,943中描述的TRIS的酰胺类似物，和在US5,070,215中描述的乙烯基氨基甲酸酯或碳酸酯类似物也适合使用。事实上，任何已知用于制备硅氧烷水凝胶的含硅氧烷的单体都能够与结构式I的含硅氧烷的单体结合使用以形成本发明的软接触透镜。在1997年10月9日提出的US专利申请序列号08/948,128(这里引用供参考)公开了可用于该目的的许多含硅氧烷的单体。能够与结构式I的含硅氧烷的单体结合使用以形成本发明的硅氧烷水凝胶的其它单体的一些实例是在1998年3月2日提出、在这里引用作参考的标题为硅氧烷水凝胶聚合物的U.S.序列号09/033,348(Vanderlaan等人)中公开的含羟烷基胺官能化硅氧烷的单体。能够使用包括以下结构式的嵌段或无规单体的线性或支化羟烷基胺官能化单体：
Figure A0180988900071
结构式III其中：n是0-500，m是0-500，(n+m)＝10-500，更优选20-250；R2、R4、R5、R6和R7独立地是一价烷基，或芳基，它可以进一步被醇、酯、胺、酮、羧酸或醚基取代，优选是未取代的单价烷基或芳基；R1、R3和R8独立地是一价烷基或芳基，它可以进一步被醇、酯、胺、酮、羧酸或醚基取代，优选是未取代的一价烷基或芳基，或是以下含氮结构：
Figure A0180988900072
结构式IV前提是R1、R3和R8中的至少一个符合结构式IV，其中R9是二价烷基如-(CH2)s-，其中s是1-10，优选3-6，最优选3；R10和R11独立地是H，可以进一步被醇、酯、胺、酮、羧酸或醚基取代的单价烷基或芳基，或具有以下结构式：结构式V其中R14是H，或一价可聚合的基团，包括丙烯酰基，甲基丙烯酰基，苯乙烯基，乙烯基，烯丙基或N-乙烯基内酰胺，优选H或甲基丙烯酰基；R16是H，能够进一步被醇、酯、胺、酮、羧酸或醚基取代的一价烷基或芳基，或包括丙烯酸根、甲基丙烯酸根、苯乙烯基、乙烯基、烯丙基或N-乙烯基内酰胺的可聚合的基团，优选被醇或甲基丙烯酸根取代的烷基；R12、R13和R15独立地是H，一价烷基或芳基，它们能够进一步被醇、酯、胺、酮、羧酸或醚基取代，或R12与R13，或R15与R13能够键接在一起形成环结构，前提是至少一些在单体上的结构式IV基团包括可聚合的基团。R12、R13和R15优选是H。
在供选择实施方案中，本发明的硅氧烷水凝胶还可以包括亲水性单体。任选用于制备本发明的水凝胶聚合物的亲水性单体可以是在现有技术中公开用于制备水凝胶的任何亲水性单体。在这些实施方案中使用的优选亲水性单体要么含丙烯酸，要么含乙烯基。这些亲水性单体本身可以用作交联剂。术语“乙烯基型”或“含乙烯基的”单体是指含有乙烯基(-CH＝CH2)的单体并且一般是高反应性的。这些亲水性含乙烯基的单体已知可相对容易地聚合。“丙烯酸型”或“含丙烯酸的”单体是含有丙烯酸基(CH2＝CRCOX)的那些单体，其中R是H或CH3，X是O或N，它们也已知可容易地聚合，如N，N-二甲基丙烯酰胺(DMA)，甲基丙烯酸2-羟乙酯(HEMA)，甲基丙烯酸甘油酯，2-羟乙基甲基丙烯酰胺，聚单甲基丙烯酸乙二醇酯，甲基丙烯酸和丙烯酸。
可以引入到本发明的硅氧烷水凝胶的亲水性含乙烯基的单体包括如N-乙烯基内酰胺(例如N-乙烯基吡咯烷酮(NVP)，N-乙烯基-N-甲基乙酰胺，N-乙烯基-N-乙基乙酰胺，N-乙烯基-N-乙基甲酰胺，N-乙烯基甲酰胺)，其中NVP是优选的。
能够在本发明中使用的其它亲水性单体包括一个或多个端部羟基被含有可聚合的双键的官能团置换的聚氧化乙烯多元醇。实例包括聚乙二醇，乙氧基化烷基葡糖苷，乙氧基化双酚A，它们与一摩尔或多摩尔当量的封端基团如甲基丙烯酸异氰酸基乙酯(“IEM”)，甲基丙烯酸酐，甲基丙烯酰氯，乙烯基苯甲酰氯等反应，以产生具有通过连接结构部分如氨基甲酸酯或酯基键接于聚亚乙基多元醇的一个或多个端部可聚合的烯属基团的聚亚乙基多元醇。
还有其它的实例是在U.S.专利No.5,070,215中公开的亲水性碳酸乙烯酯或氨基甲酸乙烯酯单体，在U.S.专利No.4,910,277中公开的亲水性噁唑酮单体，和聚右旋糖酐。其它适合的亲水性单体对本领域的熟练技术人员来说是显而易见的。
可以引入到本发明的聚合物中的更优选的亲水性单体包括亲水性单体如N，N-二甲基丙烯酰胺(DMA)，甲基丙烯酸2-羟乙酯(HEMA)，甲基丙烯酸甘油酯，2-羟乙基甲基丙烯酰胺，N-乙烯基吡咯烷酮(NVP)，聚单甲基丙烯酸乙二醇酯，甲基丙烯酸和丙烯酸，其中DMA是最优选的。
能够存在于用于形成本发明的硅氧烷水凝胶的反应混合物中的其它单体包括紫外线吸收单体，反应性色辉物(tint)等。其它加工助剂如脱模剂或润湿剂也能够加入到反应混合物中。
除了以上确定的亲水性单体以外，用于形成本发明的透镜的聚合物混合物还包括一种或多种高分子量亲水性聚合物。亲水性聚合物可用作内润湿剂。即，它们浸透到引入它们的水凝胶中，从而大大改进了可湿性。优选地，这种作用达到使通常需要疏水涂料以便具有良好的生理相容性的疏水水凝胶能够不用涂料来制成而且还具有例如与眼表面具有良好的生理相容性的这样一种程度。然而，如果需要，还可以将亲水性涂料如聚丙烯酸施涂于水凝胶的表面。当这样做时，其中引入润湿剂的水凝胶通过减少组织和水凝胶内疏水区域的接触而改进了水凝胶的生理相容性(相对于没有该润湿剂的涂层透镜)。
用作内润湿剂的亲水性聚合物是聚酰胺，聚内酰胺，聚酰亚胺和聚内酯。优选，它们是氢键接受物，在水环境中由于与水形成的氢键因此有效地变得更亲水。无论如何，在不存在水的疏水水凝胶基体中引入亲水性聚合物有利于与疏水性聚合物如硅氧烷的相容性。在随后与水接触时(即水合)，它们使硅氧烷变得可润湿。
优选，这些亲水性聚合润湿剂是在聚合物骨架中引入环状部分的线性聚合物。该环状部分甚至更优选是环状酰胺或酰亚胺环状结构部分。这类聚合物优选包括例如聚乙烯基吡咯烷酮和聚乙烯基咪唑，但如聚二甲基丙烯酰胺之类的聚合物也有这种功能，可以使用。聚乙烯基吡咯烷酮是最优选的亲水性聚合润湿剂。
在本发明中用作润湿剂的亲水性聚合物具有高平均分子量(Mw不低于50,000道尔顿，优选100,000-500,000道尔顿)。更优选的分子量范围是300,000-400,000，其中320,000-370,000的范围是最优选的。亲水性聚合物的分子量还能够用以动态粘度测量为基础的所谓K值来表示，如在Encyclopedia of Polymer Science andEngineering的N-Vinyl Amide Polymers(E.S.Barabas)，第二版，17卷，198-257页，John Wiley & Sons，Inc.中所述。以这种方式表示，具有46-100的K值的亲水性聚合物是优选的。亲水性聚合物以使得大约1-15wt％的润湿剂(例如PVP)存在于最终水凝胶配方中的量使用。优选3-8％存在于最终水凝胶配方中。当以这里所述的方式作为水凝胶基体的一部分制备时，这些聚合物被引入到本发明的水凝胶配方中，没有形成连接水凝胶的大量共价键。缺乏大量的共价键合意味着在可以存在少量共价键合的同时，附随的是润湿剂保留在水凝胶基体中。无论存在什么附带共价键合，其本身不足以保持润湿剂在水凝胶基体中。事实上，保持润湿剂与水凝胶相关的最主要的作用是包埋。根据本说明书，当聚合物以物理方式保持在水凝胶基体内时，聚合物被“包埋”。这通过润湿剂的聚合物链在水凝胶聚合物基体内的缠结来进行。然而，范德华力、偶极-偶极相互作用、静电吸引和氢键键合也能够以次要程度有助于该包埋。
本发明的水凝胶通过制备大分子单体和该大分子单体与单体混合物的其它组分的聚合来以最佳方式制备。在本说明书中使用的术语“大分子单体”是指通过一种或多种硅氧烷与一种或多种丙烯酸或甲基丙烯酸材料的基团转移聚合(GTP)形成的预聚物。以这种身份使用的甲基丙烯酸酯或丙烯酸酯能够将羟基结构部分贡献给整个大分子单体配方。因此，甲基丙烯酸甲酯虽然有益于整个大分子单体配方，但作为单独的(甲基)丙烯酸酯组分，本身还不足以形成本发明的大分子单体。然而，它与羟基甲基丙烯酸酯一起作为(甲基)丙烯酸酯组分是足够的。本发明的优选的大分子单体是羟基甲基丙烯酸酯或丙烯酸酯、三甲基硅氧烷和聚二甲基硅氧烷的GTP反应产物。更优选，大分子单体是甲基丙烯酸2-羟乙酯(HEMA)，甲基丙烯酸甲酯(MMA)，甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷(TRIS)和单甲基丙烯酰氧基丙基终端的单丁基终端的聚二甲基硅氧烷(mPDMS)的GTP反应产物。最优选的是，18-21(甚至更优选大约19.1)摩尔HEMA与大约2-3(甚至更优选大约2.8)摩尔MMA，大约7-9(甚至更优选大约7.9)摩尔TRIS，和2.5-4.5(甚至更优选大约3.3)摩尔mPDMS结合。大分子单体的GTP形成通过使用二月桂酸二丁基锡作为催化剂让上述物料结合物与2.0mol/mol的异氰酸3-异丙烯基-α，α-二甲基苄基酯反应来完成。该反应一般在大约60-120℃下进行大约2-10小时。
水凝胶通过使以下反应混合物(有时称之为“单体混合物”)反应来制备：大分子单体；含硅氧烷的单体，任选的亲水性聚合物(非润湿剂)，交联剂，和高分子量亲水性聚合物(润湿剂)。单体混合物在没有水和任选有有机稀释剂的情况下反应。水凝胶通过该反应混合物的反应产物的水合来完成。优选，硅氧烷包括Si7-9单甲基丙烯酰氧基终端的聚二甲基硅氧烷和三甲基甲硅烷氧基硅烷。更优选的是，单体混合物包括大分子单体，Si7-9单甲基丙烯酰氧基终端的聚二甲基硅氧烷；甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷，“TRIS”；二甲基丙烯酰胺，“DMA”；甲基丙烯酸羟乙酯，“HEMA”；三甘醇二甲基丙烯酸酯，“TEGDMA”；聚乙烯基吡咯烷酮，“PVP”；添加剂和光引发剂。
总含硅氧烷的单体的优选范围是反应混合物(单体混合物+大分子单体)中反应性组分的大约5-100wt％，更优选大约10-90wt％，和最优选大约15-80wt％。在以上本发明中倘若存在的任选的亲水性单体的优选范围是反应混合物中反应性组分的大约5-80wt％，更优选大约10-60wt％，和最优选大约20-50wt％。高分子量亲水性聚合物(润湿剂)的优选范围是1-15wt％，更优选3-10wt％，和最优选5-8wt％。稀释剂的优选范围是总反应混合物的大约0-70wt％，更优选大约0-50wt％，和最优选大约0-20wt％。稀释剂的需要量根据反应性组分的性质和相对量来变化。
最优选，反应混合物包括最优选的大分子单体(如上所述)；Si7-9单甲基丙烯酰氧基终端的聚二甲基硅氧烷(～28wt％)；甲基丙烯酰氧基三(三甲基甲硅烷氧基)硅烷，“TRIS”(～14wt％)；二甲基丙烯酰胺，“DMA”(～26wt％)；甲基丙烯酸羟乙酯，“HEMA”(～5％)；三甘醇二甲基丙烯酸酯，“TEGDMA”(～1％)；聚乙烯基吡咯烷酮，“PVP”(～5％)；剩余部分包括少量的添加剂和光引发剂。聚合最优选在20％(全部单体和稀释剂共混物的wt％)二甲基-3-辛醇稀释剂的存在下进行。
在反应混合物中优选包括聚合催化剂。聚合催化剂可以是在中度升温下产生自由基的化合物如过氧化月桂酰，过氧化苯甲酰，过碳酸异丙酯，偶氮双异丁腈等，或者聚合催化剂是光引发剂体系如芳族α-羟基酮或叔胺+二酮。光引发剂体系的示例是1-羟基环己基苯基酮，2-羟基-2-甲基-1-苯基-丙-1-酮，双(2，6-二甲氧基苯甲酰基)-2，4，4-三甲基戊基氧化膦(DMBAPO)，和樟脑醌和4-(N，N-二甲氨基)苯甲酸乙酯的混合物。催化剂以催化有效量，例如大约0.1到大约2重量份/100重量份的反应性单体在反应混合物中使用。反应混合物的聚合能够根据所使用的聚合引发剂适当选择的热或可见光或紫外线或其它方式来引发。另外，引发能够不用光引发剂，例如低电压电子束来进行。然而，当使用光引发剂时，优选的引发剂是1-羟基环己基苯基酮和双(2，6-二甲氧基苯甲酰基)-2，4，4-三甲基苯基氧化膦(DMBAPO)的混合物，优选的聚合引发方法是可见光。
通常，在固化反应混合物之后，所得聚合物用溶剂处理以除去稀释剂(如果使用)或任何痕量的未反应组分，将聚合物水化以形成水凝胶。所使用的溶剂可以是水(或水溶液如生理盐水)，或根据用于制备本发明的水凝胶的稀释剂(如果使用)的溶解度特性和任何残留的未聚合的单体的溶解度特性，最初使用的溶剂可以是有机液体如乙醇，甲醇，异丙醇，它们的混合物，或类似物，或一种或多种这些有机液体与水的混合物，随后用纯水(或生理盐水)萃取，以生产出包括用水溶胀的所述单体的聚合物的硅氧烷水凝胶。在聚合物水化后的硅氧烷水凝胶优选包括硅氧烷水凝胶总重量的10-55wt％水，更优选20-50wt％水，和最优选25-45wt％水。这些硅氧烷水凝胶特别适合于制备接触透镜或眼内透镜，优选软接触透镜。
在接触透镜的生产中已知有多种方法用于模塑反应混合物，包括旋转浇铸和静态浇铸。旋转浇铸方法公开在U.S.专利No.3,408,429和3,660,545中，静态浇铸方法公开在U.S.专利No.4,113,224和4,197,266中。生产包括本发明聚合物的接触透镜的优选方法是硅氧烷水凝胶的直接模塑，该方法是经济的，并且能够精确控制水化透镜的最终形状。对于该方法，将反应混合物置于具有最终所需硅氧烷水凝胶的形状的模具中，从而产生最终所需产物的近似形状的聚合物。然后，该聚合物混合物任选先后用溶剂和水处理，产生具有十分类似于初始模塑聚合物制品的尺寸和形状的最终尺寸和形状的硅氧烷水凝胶。该方法能够用于形成接触透镜，并另外描述在U.S.专利4,495,313；4,680,336；4,889,664和5,039,459(这里引用供参考)中。在生产硅氧烷水凝胶之后，如果需要，透镜可以用亲水性涂料涂布。在现有技术中已经公开了将亲水性涂料加入到透镜的一些方法，包括U.S.专利3,854,982，3,916,033，4,920,184和5,002,794；WO91/04283和EPO93810399。
本发明的反应混合物能够通过本领域中那些熟练人员已知的任何方法来形成，如振动或搅拌，以及通常通过早先描述的方法来形成聚合物制品或设备。对于一些单体反应混合物，优选在稍高于室温的温度，如30-40℃，或甚至高达80℃，或在室温以下，如0-10℃下使反应混合物聚合，以便防止各组分的相分离。
本发明的硅氧烷水凝胶具有高氧渗透性。它们具有通过极谱法测定的在40barrer和300barrer之间的O2Dk值。氧渗透性的极谱法测量如下进行。将透镜放置在传感器上，然后用网架覆盖在上边。使用由4mm直径金阴极和银环阳极组成的极谱氧传感器测定通过透镜扩散的氧。参考值是使用该方法对商购接触透镜测定的那些值。购自Bausch& Lomb的Balafilcon A透镜获得了大约79barrer的测量结果。Etafilcon透镜获得了20-25barrer的测量结果。
在实施例中，使用以下缩写：
TRIS    3-甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷
DMA     N，N-二甲基丙烯酰胺
THF         氢呋喃
TMI         间-异丙烯基苄基异氰酸二甲基酯
HEMA        甲基丙烯酸2-羟乙酯
MMA         甲基丙烯酸甲酯
TBACB       间氯苯甲酸四丁基铵
mPDMS       800-1000MW单甲基丙烯酰氧基丙基终端的聚二甲基
            硅氧烷
3M3P        3-甲基-3-丙醇
Norbloc     2-(2’-羟基-5-甲基丙烯酰氧基乙基苯基)-2H-苯并三
            唑
CGI 1850    1-羟基环己基苯基酮和双(2，6-二甲氧基苯甲酰基)-
            2，4，4-三甲基戊基氧化膦的1∶1(wgt)共混物
PVP         聚(N-乙烯基吡咯烷酮)
IPA         异丙醇
实施例1大分子单体形成
在14℃，在N2氛围下，向13.75ml的TBACB在THF中的1M溶液，30.0g的双(二甲基氨基)甲基硅烷，61.39g对二甲苯，154.28g甲基丙烯酸甲酯和1892.3g甲基丙烯酸2-(三甲基甲硅烷氧基)乙酯在4399.78g THF中的溶液中添加191.75g的1-三甲基甲硅烷氧基-1-甲氧基-2-甲基丙烯。在260分钟过程内添加另外30ml的TBACB的THF溶液(0.40M)，在这期间，使反应混合物放热，然后冷却到30℃。在添加甲基丙烯酸2-(三甲基甲硅烷氧基)乙酯之后60分钟，加入467.56g甲基丙烯酸2-(三甲基甲硅烷氧基)乙酯，3636.6g mPDMS和3673.84g TRIS和20.0g双(二甲氨基)甲基硅烷的溶液，让混合物放热；然后冷却到30℃，并保持2小时。然后添加10.0g的双(二甲氨基)甲基硅烷，154.26g的甲基丙烯酸甲酯和1892.13g甲基丙烯酸2-(三甲基甲硅烷氧基)乙酯的溶液，再次让混合物放热。在2小时后，添加2加仑的无水THF，随后在使溶液冷却到34℃之后添439.69g水，740.6g甲醇和8.8g二氯乙酸的溶液。通过用油浴在110℃下加热将混合物回流4.5小时，然后在135℃下蒸馏掉挥发物，添加甲苯以便除去水，直到达到110℃的蒸汽温度为止。
将反应烧瓶冷却到110℃，再添加443g TMI和5.7g二月桂酸二丁基锡的溶液。使混合物反应3.5小时，然后冷却到30℃。在减压下蒸发甲苯，获得了灰白色无水蜡状反应性大分子单体。大分子单体的理论OH含量是1.69mmol/g。
实施例2-14
从来自实施例1的大分子单体和在表1中所述的其它组分的共混物制备接触透镜，在75℃下在可见光下固化。(所有组分量按反应性组分的wt％给出，只有稀释剂以最终单体-稀释剂共混物的wt％给出)。所使用的PVP作为“POLYVINYLPYRROLIDONE(PVP K90)”由ICNBiomedicals，Inc.销售。在固化后，打开模具，将透镜释放到水和乙醇的1∶1共混物中，然后在乙醇中沥滤以除去任何残留的单体和稀释剂。最后，透镜在生理硼酸盐缓冲盐水中平衡。
表1
 实施例2  实施例3  实施例4  实施例5  实施例6  实施例7  实施例8  实施例9  实施例10  实施例11  实施例12  实施例13  实施例14
 大分子单体TRISDMAmPDMSNorblocCGI1850PVP  24203320210  25173217216  25173017218  25182818218  21202820218  25183218214  25193219212  2519.53219.5211  2519.753219.75210.5  19203720211  25173017218  25173017218  25173017218
 ％稀释剂(3M3P)  20  20  20  20  20  20  20  20  20  20  20  25  30
 ％EWC1标准偏差  34.50.3  50.20.3  48.60.2  48.50.2  46.80.3  44.10.1  41.30.3  38.30.2  36.00.2  42.70.1  48.60.2  53.00.2  51.10.3
 模量标准偏差  764  593  597  5911  4911  603  664  772  764  633  597  565  534
 断裂伸长率％标准偏差  33238  24448  22071  26148  28950  28369  29535  28052  30939  32522  22071  25346  26441
  Dk ec2Dk3   112.3139.8   76.098.2   75.999.1   97.9133.3   107.8138.8   95.8123.5   99.8126.0   92.3114.9   94.1114.9   81.298.3   75.999.1   80.5102.6   89.0113.0
  DCA4前标准偏差 12514 7118 588 5315 598 557 10019 12717 1176 13915 588 6113 6912
  后标准偏差脂类摄入Conc.标准偏差   4077.930.46   4053.550.42   4072.850.41   3653.3450.11   3834.1650.85   4533.260.54   4364.2450.355   3396.4850.63   4637.0150.335   3775.810.2   4072.850.41   383.7850.365   3952.830.24
1、平衡水含量。2、氧渗透性，边缘校正，按Barrer计。3、氧渗透性，非边缘校正，按Barrer计。4、动态接触角，使用Wilhelmy天平用生理硼酸盐缓冲盐水测量。
实施例15可湿性
按照实施例2的工序，从8％(wt)PVP(K90，购自ICN Biomedica1s，Inc.)，20％来自实施例1的大分子单体，28.5％mPDMS，8.0％TRIS，5.0％HEMA，26％DMA，1.5％TEGDMA，2.0％Norbloc和1.0％CGI 1850的共混物制备透镜，其中在共混物中具有作为稀释剂的37.5％(基于总单体/稀释剂共混物)3M3P。这些透镜在临床研究中戴用，发现具有可湿性和舒适感。以上透镜(n＝10只眼)与ACUVUE(n＝12只眼)历史对照物比较，发现100％可润湿(在戴用时没有看到非润湿点)；就镜前泪膜无损伤性眼泪消散时间(PLTF-NIBUT)而论是相似的(7.1±2.7对ACUVUE12.7±4.7)；以及根据50-点标准是舒适的(44.3±4.5对ACUVUE46.8±2.8)。
实施例16(对比)K-值29-32 PVP的萃取
按照实施例2的工序从20％(wt)40,000Mw PVP(购自SigmaChemicals，平均分子量10,000，K值(特性粘度)29-32)，12％来自实施例1的大分子单体，20％TRIS，39％HEMA，5％DMA，3％TEGDMA和1％DAROCUR 1173的共混物制备接触透镜，在共混物中具有作为稀释剂的50％(基于总单体/稀释剂共混物)己醇，只是从模具中取出透镜，不进行初始萃取。称重各透镜，在5.0m1水或甲醇中萃取，分析萃取物与时间的关系。表2中的结果说明，相对低分子量的PVP从甲醇中的聚合物基质中扩散出来。在2小时之后几乎所有PVP跑出。然而，在水中，PVP没有从透镜基体中完全失去。在24小时之后扩散达到稳定水平，其中没有发现进一步的PVP释出。
将在甲醇中沥滤的透镜放入硼酸盐缓冲盐水中。这些透镜与硼酸盐缓冲盐水的动态接触角是104°(前)和41°(后)，还说明该相对低分子量PVP没有充分保留在聚合物基体中，以在醇萃取中存留下来。表2-K-值29-32 PVP的萃取
     用超声波破碎的PVP的萃取(总％)
   时间(hr)   甲醇中     水中
    0.25     71      14
    0.50     78      16
    1.00     87      29
    1.50     95      35
    2.00     93      41
    3.00     108      51
   18.00     114      72
   24.00     114      82
   27.50     106      80
   43.00     114      79
   48.00     107      80
*数值由于该试验的正常实验变异性而能够超过100％。
实施例17-K-值80-100PVP的萃取
按照实施例2的工序从8％(wt)360,000Mw PVP(购自SigmaChemicals，平均分子量360,000，K值(特性粘度)80-100)，20％来自实施例1的大分子单体，35％mPDMS，5％HEMA，26％DMA，2％TEGDMA，2％Norbloc和2％CGI 1850的共混物制备接触透镜，在共混物中具有作为稀释剂的50％(基于总单体/稀释剂共混物)3M3P，只是从模具中取出透镜，不进行初始萃取。称重各透镜，在10.0ml水或IPA中萃取，分析萃取物与时间的关系。表3中的结果说明，该高分子量PVP大多数保留在透镜中，即使在用侵蚀性有机溶剂萃取之后。表3-K-值80-100PVP的萃取
    用超声波破碎的PVP的萃取(总％)*
  时间(hr)     IPA中     水中
    0.17      14      17
    0.33      20      21
    0.58      13      21
    0.92      20      21
    1.08      23      21
     1.5      21      22
    2.00      22      23
    2.50      21      23
    3.00      20      23
实施例18-灰尘附着试验，易加工性
按照实施例2的工序从5％(wt)PVP(购自Sigma Chemicals，平均分子量360,000，K值(特性粘度)80-100)，18％来自实施例1的大分子单体，28％mPDMS，14％TRIS，5％HEMA，26％DMA，1％TEGDMA，2％Norbloc和1％CGI 1850的共混物制备透镜，在共混物中具有作为稀释剂的20％(基于总单体/稀释剂共混物)3，7-二甲基-3-辛醇。这些透镜之一在家庭灰尘在硼酸盐缓冲盐水中的分散体中振荡，用10秒数字擦具清洗，用比较器检验。粘附于该表面的灰尘量是粘附于不用PVP制备的类似处理的透镜的灰尘量的大约25％或25％以下。另外，发现用PVP制备的透镜更不粘着于其它透镜及玻璃和塑料表面，因此使得它们在加工过程中更容易处理。

Claims (29)

1、可湿性硅氧烷水凝胶，包括以下组分的反应产物：
a)含硅氧烷的大分子单体，
b)含硅氧烷的反应混合物，和
c)比硅氧烷反应混合物包含的硅氧烷更亲水的高分子量聚合物，
其中所述亲水性聚合物包埋在所述硅氧烷水凝胶中。
2、权利要求1的水凝胶，其中所述亲水性聚合物是均聚物。
3、权利要求1的水凝胶，其中所述亲水性聚合物是从至少两种不同单体的组合制备的共聚物。
4、权利要求1的水凝胶，其中所述亲水性聚合物选自聚酰胺，聚内酰胺，聚酰亚胺，聚内酯和聚右旋糖酐。
5、权利要求1的水凝胶，其中所述亲水性聚合物在其整个骨架中引入环状部分。
6、权利要求4的水凝胶，其中所述聚乙烯基聚合物是聚乙烯基吡咯烷酮。
7、权利要求6的水凝胶，其中所述聚乙烯基吡咯烷酮具有高于大约50,000的数均分子量。
8、权利要求6的水凝胶，其中所述聚乙烯基吡咯烷酮具有高于大约80,000的数均分子量。
9、权利要求4的水凝胶，其中所述聚乙烯基吡咯烷酮具有高于100,000的数均分子量。
10、眼科透镜，其通过将高分子量亲水性聚合物加入到硅氧烷水凝胶单体混合物中并将所述亲水性聚合物包埋在由所述硅氧烷水凝胶单体混合物形成的水凝胶中来制备。
11、权利要求10的眼科透镜，其中含大量羟基的大分子单体构成单体混合物的一部分。
12、权利要求10的水凝胶，其中所述亲水性聚合物是均聚物。
13、权利要求10的水凝胶，其中所述亲水性聚合物是由至少两种不同单体的混合物制备的共聚物。
14、权利要求10的眼科透镜，其中所述亲水性聚合物选自聚酰胺、聚内酰胺、聚酰亚胺、聚内酯和聚右旋糖酐。
15、权利要求14的眼科透镜，其中所述亲水性聚合物是聚乙烯基吡咯烷酮。
16、权利要求15的眼科透镜，其中所述聚乙烯基吡咯烷酮具有至少50,000的重均分子量。
17、权利要求15的眼科透镜，其中所述聚乙烯基吡咯烷酮具有至少80,000的重均分子量。
18、权利要求15的眼科透镜，其中所述聚乙烯基吡咯烷酮具有至少100,000的重均分子量。
19、制备硅氧烷水凝胶的方法，包括：
a)将硅氧烷水凝胶单体混合物与高分子量亲水性聚合物在聚合条件下结合，和
b)回收其中包埋有所述亲水性聚合物的硅氧烷水凝胶。
20、权利要求19的水凝胶，其中所述单体混合物包括具有大羟基含量的大分子单体。
21、权利要求19的水凝胶，其中所述亲水性聚合物是均聚物。
22、权利要求19的水凝胶，其中所述亲水性聚合物是从至少两种不同单体的组合制备的共聚物。
23、权利要求19的水凝胶，其中所述亲水性聚合物选自聚酰胺、聚内酰胺、聚酰亚胺、聚内酯和聚右旋糖酐。
24、权利要求23的水凝胶，其中所述亲水性聚合物是聚乙烯基吡咯烷酮。
25、权利要求23的水凝胶，其中所述聚乙烯基吡咯烷酮具有至少大约50,000的重均分子量。
26、权利要求23的水凝胶，其中所述聚乙烯基吡咯烷酮具有至少大约80,000的重均分子量。
27、权利要求23的水凝胶，其中所述聚乙烯基吡咯烷酮具有至少大约100,000的重均分子量。
28、由权利要求19的方法制备的制品。
29、由权利要求19的方法制备的眼科透镜。
CN018098894A 2000-03-22 2001-03-22 具有内润湿剂的水凝胶 Expired - Lifetime CN1217969C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/533,062 2000-03-22
US09/533,062 US6367929B1 (en) 1998-03-02 2000-03-22 Hydrogel with internal wetting agent

Publications (2)

Publication Number Publication Date
CN1441814A true CN1441814A (zh) 2003-09-10
CN1217969C CN1217969C (zh) 2005-09-07

Family

ID=24124308

Family Applications (1)

Application Number Title Priority Date Filing Date
CN018098894A Expired - Lifetime CN1217969C (zh) 2000-03-22 2001-03-22 具有内润湿剂的水凝胶

Country Status (11)

Country Link
US (1) US6367929B1 (zh)
EP (2) EP2258736B1 (zh)
JP (1) JP2003528183A (zh)
KR (1) KR100748379B1 (zh)
CN (1) CN1217969C (zh)
AR (1) AR030691A1 (zh)
AU (2) AU2001247656B2 (zh)
BR (1) BRPI0109443B8 (zh)
CA (1) CA2404133C (zh)
TW (1) TWI229683B (zh)
WO (1) WO2001070837A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101695874B (zh) * 2005-02-22 2013-10-30 庄臣及庄臣视力保护公司 水凝胶加工
CN102115515B (zh) * 2010-01-05 2014-06-18 远东新世纪股份有限公司 增进硅酮水胶润湿性的共聚物、包含其的硅酮水胶组合物及由此制得的眼用物品
CN104945570A (zh) * 2015-07-03 2015-09-30 东南大学 一种硅凝胶接触透镜及其表面反转处理方法
CN109790243A (zh) * 2016-10-06 2019-05-21 庄臣及庄臣视力保护公司 三嵌段预聚物及其在有机硅水凝胶中的用途

Families Citing this family (298)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7468398B2 (en) 1994-09-06 2008-12-23 Ciba Vision Corporation Extended wear ophthalmic lens
US5760100B1 (en) 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US7052131B2 (en) 2001-09-10 2006-05-30 J&J Vision Care, Inc. Biomedical devices containing internal wetting agents
US6822016B2 (en) 2001-09-10 2004-11-23 Johnson & Johnson Vision Care, Inc. Biomedical devices containing internal wetting agents
US7461937B2 (en) * 2001-09-10 2008-12-09 Johnson & Johnson Vision Care, Inc. Soft contact lenses displaying superior on-eye comfort
US20070043140A1 (en) * 1998-03-02 2007-02-22 Lorenz Kathrine O Method for the mitigation of symptoms of contact lens related dry eye
AU4980199A (en) * 1998-07-08 2000-02-01 Sunsoft Corporation Interpenetrating polymer network hydrophilic hydrogels for contact lens
SE9900935D0 (sv) * 1999-03-16 1999-03-16 Pharmacia & Upjohn Bv Macromolecular compounds
US6414049B1 (en) * 2000-03-22 2002-07-02 Johnson & Johnson Vision Care, Inc. Stable initiator system
US6372815B1 (en) * 2000-04-18 2002-04-16 Ocular Sciences Inc Ophthalmic lenses and compositions, and methods for producing same
US6861123B2 (en) * 2000-12-01 2005-03-01 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lens
US20040151755A1 (en) * 2000-12-21 2004-08-05 Osman Rathore Antimicrobial lenses displaying extended efficacy, processes to prepare them and methods of their use
US6858164B2 (en) * 2001-01-26 2005-02-22 Ricoh Company Limited Silicone-oil soluble polymer, image display medium using the silicone-oil soluble polymer and image display device using the image display medium
WO2003015704A2 (en) 2001-08-17 2003-02-27 University Of Pittsburgh Administration of estradiol metabolites for the treatment or prevention of obesity, metabolic syndrome, diabetes, and vascular and renal disorders
US6943267B1 (en) 2001-08-24 2005-09-13 Utah State University Thiophosphonate inhibitors of phosphatase enzymes and metallophosphatases
US20120245248A1 (en) * 2001-09-10 2012-09-27 Azaam Alli Silicone hydrogels formed from reaction mixtures free of hydrophilic monomers
AU2008200230B2 (en) * 2001-09-10 2011-12-22 Johnson & Johnson Vision Care, Inc. Biomedical devices containing internal wetting agents
US20080279936A1 (en) * 2001-10-10 2008-11-13 The University Of Pittsburgh Estradiol metabolites for reduction of endothelin production
US6891010B2 (en) 2001-10-29 2005-05-10 Bausch & Lomb Incorporated Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes
AR038269A1 (es) * 2002-01-09 2005-01-12 Novartis Ag Articulos polimericos que tienen un recubrimiento lubrico, y metodo para fabricarlos
US6765713B2 (en) * 2002-04-10 2004-07-20 Ricoh Company, Ltd. Electrophoretic composition, image display medium using same and image display device
US6936641B2 (en) * 2002-06-25 2005-08-30 Johnson & Johnson Vision Care, Inc. Macromer forming catalysts
US20070138692A1 (en) * 2002-09-06 2007-06-21 Ford James D Process for forming clear, wettable silicone hydrogel articles
US20080299179A1 (en) * 2002-09-06 2008-12-04 Osman Rathore Solutions for ophthalmic lenses containing at least one silicone containing component
US20040150788A1 (en) * 2002-11-22 2004-08-05 Ann-Margret Andersson Antimicrobial lenses, processes to prepare them and methods of their use
US8158695B2 (en) * 2002-09-06 2012-04-17 Johnson & Johnson Vision Care, Inc. Forming clear, wettable silicone hydrogel articles without surface treatments
US20040120982A1 (en) * 2002-12-19 2004-06-24 Zanini Diana Biomedical devices with coatings attached via latent reactive components
US7368127B2 (en) * 2002-12-19 2008-05-06 Johnson & Johnson Vision Care, Inc. Biomedical devices with peptide containing coatings
US20060194775A1 (en) * 2003-02-20 2006-08-31 University Of Pittsburgh Estradiol metabolites for the treatment of pulmonary hypertension
CN100406015C (zh) * 2003-02-20 2008-07-30 匹兹堡大学 用于治疗肺动脉高血压的雌二醇代谢物
JP5138218B2 (ja) * 2003-03-07 2013-02-06 ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド 透明で湿潤性のシリコーン・ヒドロゲル物品を形成するための希釈剤
ES2634840T5 (es) 2003-04-24 2022-12-22 Coopervision Int Ltd Lentes de contacto de hidrogel y sistemas de envase y procedimientos de producción de los mismos
US7368589B2 (en) * 2003-10-31 2008-05-06 Johnson & Johnson Vision Care, Inc. Purification of silicone containing compounds by supercritical fluid extraction
US7416737B2 (en) * 2003-11-18 2008-08-26 Johnson & Johnson Vision Care, Inc. Antimicrobial lenses, processes to prepare them and methods of their use
US7786185B2 (en) 2004-03-05 2010-08-31 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising acyclic polyamides
US9322958B2 (en) 2004-08-27 2016-04-26 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
CN102323629B (zh) 2004-08-27 2015-08-19 库柏维景国际控股公司 硅水凝胶隐形眼镜
US7473738B2 (en) * 2004-09-30 2009-01-06 Johnson & Johnson Vision Care, Inc. Lactam polymer derivatives
US7249848B2 (en) * 2004-09-30 2007-07-31 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising reactive, hydrophilic, polymeric internal wetting agents
DE102004053314A1 (de) * 2004-11-04 2006-05-11 Wacker Chemie Ag Verfahren zur Herstellung von mit Silikon modifizierten Polymerisaten
KR20070103481A (ko) * 2005-02-07 2007-10-23 존슨 앤드 존슨 비젼 케어, 인코포레이티드 콘택트 렌즈 관련 안구 건조증의 완화방법
CN103933614B (zh) 2005-02-14 2016-03-02 庄臣及庄臣视力保护公司 舒适的眼用器件及其制造方法
US8158037B2 (en) 2005-04-08 2012-04-17 Johnson & Johnson Vision Care, Inc. Photochromic materials having extended pi-conjugated systems and compositions and articles including the same
US20060226402A1 (en) * 2005-04-08 2006-10-12 Beon-Kyu Kim Ophthalmic devices comprising photochromic materials having extended PI-conjugated systems
US9052438B2 (en) 2005-04-08 2015-06-09 Johnson & Johnson Vision Care, Inc. Ophthalmic devices comprising photochromic materials with reactive substituents
US20060227287A1 (en) * 2005-04-08 2006-10-12 Frank Molock Photochromic ophthalmic devices made with dual initiator system
US9804295B2 (en) * 2005-05-05 2017-10-31 Novartis Ag Ophthalmic devices for sustained delivery of active compounds
MY146558A (en) * 2005-08-09 2012-08-30 Coopervision Int Holding Co Lp Compositions and methods for producing silicone hydrogel contact lenses
US20070037897A1 (en) * 2005-08-12 2007-02-15 Guigui Wang Method for making contact lenses
US20070185014A1 (en) * 2006-02-09 2007-08-09 The Schepens Eye Research Institute, Inc. Methods and compositions for modulating conjunctival goblet cells
US9052529B2 (en) 2006-02-10 2015-06-09 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
US8414804B2 (en) 2006-03-23 2013-04-09 Johnson & Johnson Vision Care, Inc. Process for making ophthalmic lenses
US20070222095A1 (en) * 2006-03-23 2007-09-27 Diana Zanini Process for making ophthalmic lenses
US7858000B2 (en) * 2006-06-08 2010-12-28 Novartis Ag Method of making silicone hydrogel contact lenses
US8231218B2 (en) 2006-06-15 2012-07-31 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US7540609B2 (en) * 2006-06-15 2009-06-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
JP2008020918A (ja) * 2006-06-15 2008-01-31 Coopervision Internatl Holding Co Lp 湿潤性シリコーンヒドロゲルコンタクトレンズ及び関連組成物及び方法
US7572841B2 (en) * 2006-06-15 2009-08-11 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US9474645B2 (en) * 2006-06-21 2016-10-25 Johnson & Johnson Vision Care, Inc. Punctal plugs for the delivery of active agents
US9173773B2 (en) * 2006-06-21 2015-11-03 Johnson & Johnson Vision Care, Inc. Punctal plugs for the delivery of active agents
AU2007272558B2 (en) * 2006-07-12 2010-12-09 Novartis Ag Actinically crosslinkable copolymers for manufacturing contact lenses
WO2008055085A1 (en) 2006-10-30 2008-05-08 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
US8507577B2 (en) * 2006-10-31 2013-08-13 Johnson & Johnson Vision Care, Inc. Process for forming clear, wettable silicone hydrogel articles
GB0623299D0 (en) * 2006-11-22 2007-01-03 Sauflon Cl Ltd Contact lens
AR064286A1 (es) 2006-12-13 2009-03-25 Quiceno Gomez Alexandra Lorena Produccion de dispositivos oftalmicos basados en la polimerizacion por crecimiento escalonado fotoinducida
CN101641615B (zh) 2007-03-22 2012-06-06 诺瓦提斯公司 具有悬挂的亲水性聚合物链的含硅酮预聚物
EP2129513B1 (en) 2007-03-22 2016-08-03 Novartis AG Prepolymers with dangling polysiloxane-containing polymer chains
US7828432B2 (en) * 2007-05-25 2010-11-09 Synergeyes, Inc. Hybrid contact lenses prepared with expansion controlled polymeric materials
JP5508261B2 (ja) * 2007-07-10 2014-05-28 ボーシュ アンド ローム インコーポレイティド 架橋剤及び二重ラジカル硬化ポリマー
TWI551305B (zh) * 2007-08-31 2016-10-01 諾華公司 相對黏稠封裝溶液之用途
EP2188655B1 (en) 2007-08-31 2012-01-04 Novartis AG Contact lens packaging solutions
WO2009070443A1 (en) * 2007-11-29 2009-06-04 Bausch & Lomb Incorporated Process for making biomedical devices
US8044111B2 (en) 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
US7802883B2 (en) 2007-12-20 2010-09-28 Johnson & Johnson Vision Care, Inc. Cosmetic contact lenses having a sparkle effect
JP5355588B2 (ja) 2007-12-20 2013-11-27 ノバルティス アーゲー コンタクトレンズを製造する方法
CN101918865B (zh) * 2008-01-14 2012-12-26 库柏维景国际控股公司 可聚合隐形眼镜调配物及自调配物所得的隐形眼镜
CA2712094C (en) 2008-02-08 2013-05-28 Asahi Kasei Aime Co., Ltd. Hydrophilic polysiloxane macromonomer, and production and use of the same
US20090244479A1 (en) * 2008-03-31 2009-10-01 Diana Zanini Tinted silicone ophthalmic devices, processes and polymers used in the preparation of same
TWI542338B (zh) * 2008-05-07 2016-07-21 壯生和壯生視覺關懷公司 用於活性劑之控制釋放的眼用裝置
US20090295004A1 (en) * 2008-06-02 2009-12-03 Pinsly Jeremy B Silicone hydrogel contact lenses displaying reduced protein uptake
US8894602B2 (en) 2010-09-17 2014-11-25 Johnson & Johnson Vision Care, Inc. Punctal plugs with directional release
JP5721267B2 (ja) 2008-07-21 2015-05-20 ノバルティス アーゲー シリコーンハイドロゲルコンタクトレンズを製造する方法
US8079703B2 (en) 2008-07-21 2011-12-20 Novartis Ag Silicone-containing polymeric materials with hydrolyzable groups
US8470906B2 (en) * 2008-09-30 2013-06-25 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels having improved hydrolytic stability
US20100081772A1 (en) * 2008-09-30 2010-04-01 Diana Zanini Process for forming silicone hydrogel articles having improved optical properties
US20130203812A1 (en) 2008-09-30 2013-08-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels comprising pharmaceutical and/or nutriceutical components and having improved hydrolytic stability
US20100109176A1 (en) 2008-11-03 2010-05-06 Chris Davison Machined lens molds and methods for making and using same
WO2010056687A2 (en) 2008-11-13 2010-05-20 Novartis Ag Silicone hydrogel materials with chemically bound wetting agents
CN102209745B (zh) * 2008-11-13 2013-11-27 诺华股份有限公司 含末端亲水聚合物链的聚硅氧烷共聚物
TWI506333B (zh) 2008-12-05 2015-11-01 Novartis Ag 用以傳遞疏水性舒適劑之眼用裝置及其製造方法
US9421127B2 (en) 2009-03-31 2016-08-23 Johnson & Johnson Vision Care, Inc. Punctal plugs
TWI495459B (zh) * 2009-03-31 2015-08-11 Johnson & Johnson Vision Care 淚管塞（二）
TW201043211A (en) * 2009-03-31 2010-12-16 Johnson & Johnson Vision Care Inc Punctal plugs
US8642712B2 (en) * 2009-05-22 2014-02-04 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
WO2010133680A1 (en) 2009-05-22 2010-11-25 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8827447B2 (en) 2009-07-09 2014-09-09 Bausch & Lomb Incorporated Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers
KR101738186B1 (ko) * 2009-07-09 2017-05-19 보오슈 앤드 롬 인코포레이팃드 모노 에틸렌계 불포화 중합성 기를 함유하는 폴리카르보실록산 단량체
US9039174B2 (en) 2009-07-09 2015-05-26 Bausch & Lomb Incorporated Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers
US7994356B2 (en) * 2009-07-09 2011-08-09 Bausch & Lomb Incorporated Mono ethylenically unsaturated polycarbosiloxane monomers
US7915323B2 (en) * 2009-07-09 2011-03-29 Bausch & Lamb Incorporated Mono ethylenically unsaturated polycarbosiloxane monomers
JP6023589B2 (ja) * 2009-10-01 2016-11-09 クーパーヴィジョン インターナショナル ホウルディング カンパニー リミテッド パートナーシップ シリコーンヒドロゲルコンタクトレンズおよびシリコーンヒドロゲルコンタクトレンズの製造方法
EP2510051A1 (en) * 2009-12-07 2012-10-17 Novartis AG Methods for increasing the ion permeability of contact lenses
TWI483996B (zh) * 2009-12-08 2015-05-11 Novartis Ag 具有共價貼合塗層之聚矽氧水凝膠鏡片
EP2513711B1 (en) * 2009-12-14 2017-07-12 Novartis AG Methods for making silicone hydrogel lenses from water-based lens formulations
WO2011116206A1 (en) 2010-03-18 2011-09-22 Johnson & Johnson Vision Care, Inc. Silicone (meth)acrylamide monomer, polymer, ophthalmic lens, and contact lens
JP5720103B2 (ja) * 2010-03-18 2015-05-20 東レ株式会社 シリコーンハイドロゲル、眼用レンズおよびコンタクトレンズ
US9259352B2 (en) 2010-03-29 2016-02-16 Johnson & Johnson Vision Care, Inc. Punctal plugs
US9259351B2 (en) 2010-03-29 2016-02-16 Johnson & Johnson Vision Care, Inc. Punctal plugs
JP5604154B2 (ja) 2010-04-02 2014-10-08 株式会社メニコン ポリマー材料、眼用レンズ及びコンタクトレンズ
US8877103B2 (en) 2010-04-13 2014-11-04 Johnson & Johnson Vision Care, Inc. Process for manufacture of a thermochromic contact lens material
US8697770B2 (en) 2010-04-13 2014-04-15 Johnson & Johnson Vision Care, Inc. Pupil-only photochromic contact lenses displaying desirable optics and comfort
US9522980B2 (en) 2010-05-06 2016-12-20 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
US8480227B2 (en) 2010-07-30 2013-07-09 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
CN103052496A (zh) 2010-07-30 2013-04-17 库柏维景国际控股公司 由水溶性乙烯醇共聚物形成的眼科装置模具、其中模制的眼科装置和相关方法
WO2012016097A2 (en) 2010-07-30 2012-02-02 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8821457B2 (en) 2010-09-08 2014-09-02 Johnson & Johnson Vision Care, Inc. Punctal plug containing drug formulation
WO2012047961A1 (en) 2010-10-06 2012-04-12 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
CA2811013C (en) 2010-10-06 2016-01-19 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US9187601B2 (en) 2010-10-06 2015-11-17 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof
US9612363B2 (en) 2010-11-04 2017-04-04 Johnson & Johnson Vision Care, Inc. Silicone hydrogel reactive mixtures comprising borates
EP2637847B1 (en) 2010-11-10 2014-07-23 Novartis AG Method for making contact lenses
US20120157938A1 (en) 2010-12-16 2012-06-21 Tokarski Jason M Punctal plug with drug core retention features
WO2012118672A2 (en) 2011-02-28 2012-09-07 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
MX2013009217A (es) 2011-02-28 2014-09-08 Coopervision Int Holding Co Lp Lentes de contacto de hidrogel de silicona que tienen niveles aceptables de perdida de energia.
AU2012223584B8 (en) 2011-02-28 2014-08-14 Coopervision International Limited Dimensionally stable silicone hydrogel contact lenses
WO2012118674A2 (en) 2011-02-28 2012-09-07 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
ES2529351T3 (es) 2011-02-28 2015-02-19 Coopervision International Holding Company, Lp Lentes de contacto de hidrogel de silicona dimensionalmente estables
US9296159B2 (en) 2011-02-28 2016-03-29 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
EP2681614B1 (en) 2011-02-28 2021-05-05 CooperVision International Limited Wettable silicone hydrogel contact lenses
BR112013021486B1 (pt) 2011-02-28 2021-06-22 Coopervision International Holding Company, Lp Método para fabricação de uma lente de contato de hidrogel, lente de contato de hidrogel e lote e embalagem da dita lente
CN103764724B (zh) 2011-02-28 2016-04-06 库柏维景国际控股公司 硅酮水凝胶隐形眼镜以及相关组合物和方法
WO2012118675A2 (en) 2011-02-28 2012-09-07 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses
AU2012256403B2 (en) 2011-03-17 2016-10-20 Corning Incorporated Synthetic coating for cell culture
US20130203813A1 (en) 2011-05-04 2013-08-08 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US9170349B2 (en) 2011-05-04 2015-10-27 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US9301874B2 (en) 2011-05-06 2016-04-05 Johnson & Johnson Vision Care, Inc. Punctal plugs for controlled release of therapeutic agents
HUE027812T2 (en) 2011-06-09 2016-11-28 Novartis Ag Nano-textured silicone hydrogel lenses
US20130083287A1 (en) 2011-09-30 2013-04-04 Johnson & Johnson Vision Care, Inc. Method of creating a visible mark on lens using a leuco dye
US20130083286A1 (en) 2011-09-30 2013-04-04 Johnson & Johnson Vision Care, Inc. Method of creating a visible mark on lens using a leuco dye
US9188702B2 (en) 2011-09-30 2015-11-17 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having improved curing speed and other properties
WO2013055746A1 (en) 2011-10-12 2013-04-18 Novartis Ag Method for making uv-absorbing ophthalmic lenses by coating
US9505184B2 (en) 2011-11-15 2016-11-29 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US8721322B2 (en) 2011-11-30 2014-05-13 Johnson & Johnson Vision Care, Inc. Injection molding device and method
US8784867B2 (en) 2011-12-21 2014-07-22 Novartis Ag Contact lenses containing carotenoid and method for making same
US9125808B2 (en) 2011-12-23 2015-09-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
US9156934B2 (en) 2011-12-23 2015-10-13 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising n-vinyl amides and hydroxyalkyl (meth)acrylates or (meth)acrylamides
US9588258B2 (en) 2011-12-23 2017-03-07 Johnson & Johnson Vision Care, Inc. Silicone hydrogels formed from zero diluent reactive mixtures
US8937110B2 (en) 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having a structure formed via controlled reaction kinetics
US9140825B2 (en) 2011-12-23 2015-09-22 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
US8937111B2 (en) 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising desirable water content and oxygen permeability
US8911227B2 (en) 2012-01-11 2014-12-16 Johnson & Johnson Vision Care, Inc. Device for injection molding silicone rubber
US8808256B2 (en) 2012-01-16 2014-08-19 Johnson & Johnson Vision Care, Inc. Eye drug delivery system
US8940812B2 (en) 2012-01-17 2015-01-27 Johnson & Johnson Vision Care, Inc. Silicone polymers comprising sulfonic acid groups
US20130220346A1 (en) 2012-02-28 2013-08-29 Victor Lust Balloon punctal plug
US10209534B2 (en) 2012-03-27 2019-02-19 Johnson & Johnson Vision Care, Inc. Increased stiffness center optic in soft contact lenses for astigmatism correction
US9297929B2 (en) * 2012-05-25 2016-03-29 Johnson & Johnson Vision Care, Inc. Contact lenses comprising water soluble N-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
US10073192B2 (en) 2012-05-25 2018-09-11 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
IN2014DN09503A (zh) 2012-05-25 2015-07-17 Johnson & Johnson Vision Care
US9244196B2 (en) 2012-05-25 2016-01-26 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
NZ700848A (en) * 2012-06-14 2016-08-26 Novartis Ag Azetidinium-containing copolymers and uses thereof
US9423528B2 (en) 2012-06-25 2016-08-23 Johnson & Johnson Vision Care, Inc. Method of making silicone containing contact lens with reduced amount of diluents
US20130341811A1 (en) 2012-06-25 2013-12-26 Johnson & Johnson Vision Care, Inc. Lens comprising low and high molecular weight polyamides
TWI496838B (zh) * 2012-11-30 2015-08-21 Pegavision Corp 矽水膠組成物及以該組成物製備之矽水膠鏡片
EP2932314B1 (en) 2012-12-17 2017-02-01 Novartis AG Method for making improved uv-absorbing ophthalmic lenses
US20140268028A1 (en) 2013-03-15 2014-09-18 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having clay treatment applied thereto
US9250357B2 (en) 2013-03-15 2016-02-02 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having reduced amount of silicon on the surface
US9568645B2 (en) 2013-09-30 2017-02-14 Novartis Ag Silicone hydrogel lenses with relatively-long thermal stability
MY179469A (en) 2013-09-30 2020-11-06 Alcon Inc Method for making uv-absorbing ophthalmic lenses
SG11201602210WA (en) 2013-10-31 2016-05-30 Novartis Ag Method for producing ophthalmic lenses
CN105793022B (zh) 2013-12-13 2017-09-19 诺华股份有限公司 用于制备接触镜片的方法
SG11201603699SA (en) 2013-12-17 2016-07-28 Novartis Ag A silicone hydrogel lens with a crosslinked hydrophilic coating
US9459377B2 (en) 2014-01-15 2016-10-04 Johnson & Johnson Vision Care, Inc. Polymers comprising sulfonic acid groups
AU2015201321A1 (en) 2014-03-31 2015-10-15 Johnson & Johnson Vision Care, Inc. Silicone acrylamide copolymer
AU2015201371A1 (en) 2014-03-31 2015-10-15 Johnson & Johnson Vision Care, Inc. Silicone acrylamide copolymer
CA2940207C (en) 2014-04-25 2019-09-10 Novartis Ag Hydrophilized carbosiloxane vinylic monomers
US9720138B2 (en) 2014-08-26 2017-08-01 Novartis Ag Poly(oxazoline-co-ethyleneimine)-epichlorohydrin copolymers and uses thereof
HUE046948T2 (hu) 2014-08-26 2020-03-30 Novartis Ag Eljárás stabil bevonat felvitelére szilikon hidrogél kontaktlencsékre
AU2015321646B2 (en) 2014-09-26 2017-11-30 Alcon Inc. Polymerizable polysiloxanes with hydrophilic substituents
GB2536410A (en) * 2015-03-06 2016-09-21 The Queen's Univ Of Belfast Coating composition and uses thereof
JP2018511823A (ja) 2015-03-11 2018-04-26 フロリダ大学 リサーチファウンデーション インコーポレイティッド ジェミニハイドロゲルにおける潤滑のメッシュサイズ制御
WO2017083774A1 (en) 2015-11-11 2017-05-18 Onefocus Vision, Inc. Accommodating lens with cavity
WO2017093834A1 (en) 2015-12-03 2017-06-08 Novartis Ag Contact lens packaging solutions
CN108367517A (zh) 2015-12-15 2018-08-03 诺华股份有限公司 用于生产具有润滑表面的接触镜片的方法
MX2018007420A (es) 2015-12-15 2018-08-15 Novartis Ag Reticuladores vinilicos de polidiorganosiloxano hidrofilizados y sus usos.
MY184638A (en) 2015-12-15 2021-04-13 Alcon Inc Method for applying stable coating on silicone hydrogel contact lenses
CA3003986C (en) 2015-12-15 2020-07-21 Novartis Ag Polymerizable polysiloxanes with hydrophilic substituents
US10138316B2 (en) 2015-12-15 2018-11-27 Novartis Ag Amphiphilic branched polydiorganosiloxane macromers
US11125916B2 (en) 2016-07-06 2021-09-21 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising N-alkyl methacrylamides and contact lenses made thereof
US10371865B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising polyamides
US10370476B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising high levels of polyamides
BR112019000204A2 (pt) 2016-07-06 2019-04-16 Johnson & Johnson Vision Care, Inc. óptica central de dureza aumentada em lentes de contato macias para correção de astigmatismo
US11021558B2 (en) 2016-08-05 2021-06-01 Johnson & Johnson Vision Care, Inc. Polymer compositions containing grafted polymeric networks and processes for their preparation and use
US10301451B2 (en) 2016-10-11 2019-05-28 Novartis Ag Chain-extended polydimethylsiloxane vinylic crosslinkers and uses thereof
JP6839295B2 (ja) 2016-10-11 2021-03-03 アルコン インク． 重合性ポリジメチルシロキサン−ポリオキシアルキレンブロックコポリマー
CA3035490C (en) 2016-10-26 2021-09-14 Novartis Ag Amphiphilic branched polydiorganosiloxane macromers
WO2018089699A1 (en) 2016-11-11 2018-05-17 Onefocus Vision, Inc. Accommodating cavity lens shaped with photocleavable insert
MY197057A (en) 2017-06-07 2023-05-23 Alcon Inc Method for producing silicone hydrogel contact lenses
RU2766412C2 (ru) 2017-06-07 2022-03-15 Алькон Инк. Силикон-гидрогелевые контактные линзы
ES2889123T3 (es) 2017-06-07 2022-01-11 Alcon Inc Lentes de contacto de hidrogel de silicona
US10752720B2 (en) 2017-06-26 2020-08-25 Johnson & Johnson Vision Care, Inc. Polymerizable blockers of high energy light
US10723732B2 (en) 2017-06-30 2020-07-28 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl phenanthrolines as polymerizable blockers of high energy light
US10526296B2 (en) 2017-06-30 2020-01-07 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl naphthotriazoles as polymerizable blockers of high energy light
US10809181B2 (en) 2017-08-24 2020-10-20 Alcon Inc. Method and apparatus for determining a coefficient of friction at a test site on a surface of a contact lens
KR101994668B1 (ko) 2017-10-18 2019-07-02 한국화학연구원 습윤성 하이드로겔 콘택트렌즈
KR101963234B1 (ko) 2017-11-01 2019-03-29 (주)지오메디칼 하이드록시에틸메타크릴레이트 및 솔비톨 용액중합체가 코팅된 콘택트렌즈 및 그 제조방법
CN117492231A (zh) 2017-12-13 2024-02-02 爱尔康公司 周抛和月抛水梯度接触镜片
US11034789B2 (en) 2018-01-30 2021-06-15 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing localized grafted networks and processes for their preparation and use
US10961341B2 (en) 2018-01-30 2021-03-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use
US11993037B1 (en) 2018-03-02 2024-05-28 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US11543683B2 (en) 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US20210061934A1 (en) 2019-08-30 2021-03-04 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US10996491B2 (en) 2018-03-23 2021-05-04 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
KR20190131953A (ko) 2018-05-18 2019-11-27 주식회사 인터로조 콘택트렌즈용 코팅액 조성물, 그 제조방법 및 이를 이용한 코팅방법
KR102326436B1 (ko) 2018-05-18 2021-11-15 주식회사 인터로조 콘택트렌즈용 코팅액 조성물, 그 제조방법 및 이를 이용한 코팅방법
US11046636B2 (en) 2018-06-29 2021-06-29 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US10932902B2 (en) 2018-08-03 2021-03-02 Johnson & Johnson Vision Care, Inc. Dynamically tunable apodized multiple-focus opthalmic devices and methods
US20200073145A1 (en) 2018-09-05 2020-03-05 Johnson & Johnson Vision Care, Inc. Vision care kit
US11493668B2 (en) 2018-09-26 2022-11-08 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US11099300B2 (en) 2018-12-03 2021-08-24 Alcon Inc. Method for producing coated silicone hydrogel contact lenses
US11459479B2 (en) 2018-12-03 2022-10-04 Alcon Inc. Method for making coated silicone hydrogel contact lenses
WO2020175382A1 (ja) * 2019-02-26 2020-09-03 株式会社メニコン ポリマー材料
US11724471B2 (en) 2019-03-28 2023-08-15 Johnson & Johnson Vision Care, Inc. Methods for the manufacture of photoabsorbing contact lenses and photoabsorbing contact lenses produced thereby
SG11202108875UA (en) 2019-04-10 2021-10-28 Alcon Inc Method for producing coated contact lenses
US11667742B2 (en) 2019-05-03 2023-06-06 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
US11708440B2 (en) 2019-05-03 2023-07-25 Johnson & Johnson Surgical Vision, Inc. High refractive index, high Abbe compositions
US11578176B2 (en) 2019-06-24 2023-02-14 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lenses having non-uniform morphology
US11958824B2 (en) 2019-06-28 2024-04-16 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US20200407324A1 (en) 2019-06-28 2020-12-31 Johnson & Johnson Vision Care, Inc. Polymerizable fused tricyclic compounds as absorbers of uv and visible light
US20210003754A1 (en) 2019-07-02 2021-01-07 Johnson & Johnson Vision Care, Inc. Core-shell particles and methods of making and using thereof
US11891526B2 (en) 2019-09-12 2024-02-06 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
WO2021090169A1 (en) 2019-11-04 2021-05-14 Alcon Inc. Contact lenses with surfaces having different softness
JP2023504385A (ja) 2019-12-16 2023-02-03 アルコン インク． 湿潤性シリコーンヒドロゲルコンタクトレンズ
US11360240B2 (en) 2019-12-19 2022-06-14 Johnson & Johnson Vision Care, Inc. Contact lens containing photosensitive chromophore and package therefor
EP4097155A4 (en) 2020-01-27 2024-01-24 Clearlab SG Pte Ltd ACTINICALLY CROSS-LINKABLE POLYSILOXANE-POLYGLYCERIN BLOCK COPOLYMERS, METHOD FOR THEIR PRODUCTION AND USE THEREOF
US20210301088A1 (en) 2020-03-18 2021-09-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing transition metal complexes as high energy visible light filters
WO2021224855A1 (en) 2020-05-07 2021-11-11 Alcon Inc. Method for producing silicone hydrogel contact lenses
KR102330855B1 (ko) 2020-05-29 2021-11-24 (주)메디오스 실리콘 하이드로겔 콘택트 렌즈 및 이의 제조방법
WO2021245551A1 (en) 2020-06-02 2021-12-09 Alcon Inc. Method for making photochromic contact lenses
US11853013B2 (en) 2020-06-15 2023-12-26 Johnson & Johnson Vision Care, Inc. Systems and methods for indicating the time elapsed since the occurrence of a triggering event
US20210388141A1 (en) 2020-06-16 2021-12-16 Johnson & Johnson Vision Care, Inc. Imidazolium zwitterion polymerizable compounds and ophthalmic devices incorporating them
US12116443B2 (en) 2020-06-16 2024-10-15 Johnson & Johnson Vision Care, Inc. Amino acid-based polymerizable compounds and ophthalmic devices prepared therefrom
EP4189469B1 (en) 2020-07-28 2024-09-25 Alcon Inc. Contact lenses with softer lens surfaces
TW202225787A (zh) 2020-09-14 2022-07-01 美商壯生和壯生視覺關懷公司 單指觸動隱形眼鏡包裝
TW202231215A (zh) 2020-09-14 2022-08-16 美商壯生和壯生視覺關懷公司 單一觸碰式隱形眼鏡盒
US20220113558A1 (en) 2020-10-13 2022-04-14 Johnson & Johnson Vision Care, Inc. Contact lens position and rotation control using the pressure of the eyelid margin
WO2022090967A1 (en) 2020-10-28 2022-05-05 Alcon Inc. Method for making photochromic contact lenses
JP2023547481A (ja) 2020-10-29 2023-11-10 ジョンソン・アンド・ジョンソン・サージカル・ビジョン・インコーポレイテッド 高い屈折率及びアッベ数を有する組成物
EP4240578A1 (en) 2020-11-04 2023-09-13 Alcon Inc. Method for making photochromic contact lenses
EP4240579A1 (en) 2020-11-04 2023-09-13 Alcon Inc. Method for making photochromic contact lenses
AU2021396636A1 (en) 2020-12-13 2023-01-19 Johnson & Johnson Vision Care, Inc. Contact lens packages and methods of opening
WO2022130089A1 (en) 2020-12-18 2022-06-23 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US12049606B2 (en) 2021-01-12 2024-07-30 Johnson & Johnson Vision Care, Inc. Compositions for ophthalmologic devices
US20220281193A1 (en) 2021-03-08 2022-09-08 Alcon Inc. Method for making photofunctional contact lenses
WO2022208450A1 (en) 2021-04-01 2022-10-06 Alcon Inc. Method for making photochromic contact lenses
US12054499B2 (en) 2021-06-30 2024-08-06 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
US20230023885A1 (en) 2021-06-30 2023-01-26 Johnson & Johnson Vision Care, Inc. Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use
CA3173598A1 (en) 2021-09-13 2023-03-13 Johnson & Johnson Vision Care, Inc. Contact lens packages and methods of handling and manufacture
WO2023052890A1 (en) 2021-09-29 2023-04-06 Johnson & Johnson Vision Care, Inc. Anthraquinone-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
WO2023052889A1 (en) 2021-09-29 2023-04-06 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
US20230176251A1 (en) 2021-09-29 2023-06-08 Johnson & Johnson Vision Care, Inc. Ophthalmic lenses and their manufacture by in-mold modification
US11912800B2 (en) 2021-09-29 2024-02-27 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
US11708209B2 (en) 2021-11-05 2023-07-25 Johnson & Johnson Vision Care, Inc. Touchless contact lens packages and methods of handling
TW202335928A (zh) 2021-12-08 2023-09-16 美商壯生和壯生視覺關懷公司 具鏡片升高臂的隱形眼鏡包裝及拿取方法
TW202415312A (zh) 2021-12-08 2024-04-16 美商壯生和壯生視覺關懷公司 開槽式隱形眼鏡包裝盒及處理方法
WO2023111838A1 (en) 2021-12-13 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens packages with sliding or tilting lens transfer and methods of handling
EP4448405A1 (en) 2021-12-14 2024-10-23 Johnson & Johnson Vision Care, Inc. Contact lens packages having twisting or thimble levers and methods of handling
WO2023111852A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. No-touch contact lens packages and methods of handling
WO2023111851A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. Solutionless contact lens packages and methods of manufacture
WO2023111941A1 (en) 2021-12-16 2023-06-22 Johnson & Johnson Vision Care, Inc. No-touch contact lens packages and methods of handling
TW202337346A (zh) 2021-12-16 2023-10-01 美商壯生和壯生視覺關懷公司 增壓或真空密封的隱形眼鏡包裝
EP4448410A1 (en) 2021-12-17 2024-10-23 Johnson & Johnson Vision Care, Inc. Contact lens packages having a pivot mechanism and methods of handling
CN118742238A (zh) 2021-12-17 2024-10-01 强生视力健公司 接触镜片分配器
US20230296807A1 (en) 2021-12-20 2023-09-21 Johnson & Johnson Vision Care, Inc. Contact lenses containing light absorbing regions and methods for their preparation
US20230348718A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Light-filtering materials for biomaterial integration and methods thereof
US20230350230A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Using particles for light filtering
US11733440B1 (en) 2022-04-28 2023-08-22 Johnson & Johnson Vision Care, Inc. Thermally stable nanoparticles and methods thereof
US11971518B2 (en) 2022-04-28 2024-04-30 Johnson & Johnson Vision Care, Inc. Shape engineering of particles to create a narrow spectral filter against a specific portion of the light spectrum
US20230348717A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Particle surface modification to increase compatibility and stability in hydrogels
US20230364832A1 (en) 2022-04-28 2023-11-16 Alcon Inc. Method for making uv and hevl-absorbing ophthalmic lenses
US20230350100A1 (en) 2022-04-29 2023-11-02 Alcon Inc. Method for making silicone hydrogel contact lenses
WO2023228054A1 (en) 2022-05-23 2023-11-30 Alcon Inc. Method for making hevl-filtering contact lenses
WO2023228055A1 (en) 2022-05-23 2023-11-30 Alcon Inc. Uv/hevl-filtering contact lenses
WO2023242688A1 (en) 2022-06-16 2023-12-21 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing photostable mimics of macular pigment and other visible light filters
WO2024038390A1 (en) 2022-08-17 2024-02-22 Alcon Inc. A contact lens with a hydrogel coating thereon
US12064018B2 (en) 2022-09-27 2024-08-20 Johnson & Johnson Vision Care, Inc. Contact lens package with draining port
US20240099435A1 (en) 2022-09-27 2024-03-28 Johnson & Johnson Vision Care, Inc. Flat contact lens packages and methods of handling
US20240122321A1 (en) 2022-10-18 2024-04-18 Johnson & Johnson Vision Care, Inc. Contact lens packages having an absorbent member
US20240165019A1 (en) 2022-11-21 2024-05-23 Bausch + Lomb Ireland Limited Methods for Treating Eyetear Film Deficiency
US20240228466A1 (en) 2022-12-15 2024-07-11 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
WO2024134384A1 (en) 2022-12-21 2024-06-27 Johnson & Johnson Vision Care, Inc. Compositions for ophthalmologic devices
WO2024134383A1 (en) 2022-12-21 2024-06-27 Johnson & Johnson Vision Care, Inc. Compositions for ophthalmologic devices
WO2024134382A1 (en) 2022-12-21 2024-06-27 Johnson & Johnson Vision Care, Inc. Compositions for ophthalmologic devices
WO2024134380A1 (en) 2022-12-21 2024-06-27 Johnson & Johnson Vision Care, Inc. Compositions for ophthalmologic devices
US20240239586A1 (en) 2023-01-13 2024-07-18 Johnson & Johnson Vision Care, Inc. Contact lens packages having an absorbent member
WO2024161344A1 (en) 2023-02-02 2024-08-08 Alcon Inc. Water gradient silicone hydrogel contact lenses
WO2024194792A1 (en) 2023-03-20 2024-09-26 Johnson & Johnson Vision Care, Inc. Ophthalmic lenses and their manufacture by in-mold modification
WO2024201156A1 (en) 2023-03-28 2024-10-03 Johnson & Johnson Vision Care, Inc. Grafted opthalmic devices containing deactivated regions and processes for their preparation and use

Family Cites Families (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CS108895A (zh) 1961-12-27
NL128305C (zh) 1963-09-11
US3334898A (en) 1965-08-05 1967-08-08 Doris M Mccrory Weighted foot-attached training device
US3916033A (en) 1971-06-09 1975-10-28 High Voltage Engineering Corp Contact lens
US3854982A (en) 1972-05-12 1974-12-17 Hydroplastics Inc Method for preparing hydrophilic polymer grafts including irradiation
US3808178A (en) 1972-06-16 1974-04-30 Polycon Laboratories Oxygen-permeable contact lens composition,methods and article of manufacture
US4042552A (en) 1972-09-19 1977-08-16 Warner-Lambert Company Composition for hydrophilic lens blank and method of casting
US4113224A (en) 1975-04-08 1978-09-12 Bausch & Lomb Incorporated Apparatus for forming optical lenses
US4197266A (en) 1974-05-06 1980-04-08 Bausch & Lomb Incorporated Method for forming optical lenses
US4045547A (en) 1974-11-21 1977-08-30 Warner-Lambert Company Fabrication of soft contact lens and composition therefor
US4123408A (en) * 1976-11-26 1978-10-31 American Optical Corporation Hydrogel contact lens
US4495313A (en) 1981-04-30 1985-01-22 Mia Lens Production A/S Preparation of hydrogel for soft contact lens with water displaceable boric acid ester
ATE19639T1 (de) 1981-11-27 1986-05-15 Tsuetaki George F Polymere fuer kontaktlinsen und kontaktlinsen auf basis dieser polymere.
JPS61123609A (ja) 1984-11-20 1986-06-11 Green Cross Corp:The フツ素含有ポリマ−および医用酸素透過体
US4680336A (en) 1984-11-21 1987-07-14 Vistakon, Inc. Method of forming shaped hydrogel articles
US4711943A (en) 1985-04-26 1987-12-08 Sola U.S.A. Inc. Hydrophilic siloxane monomers and dimers for contact lens materials, and contact lenses fabricated therefrom
DE3517615C2 (de) 1985-05-15 1987-04-09 Titmus Eurocon Kontaktlinsen GmbH, 8750 Aschaffenburg Verfahren zur Hydrophilierung eines Siliconkautschukformkörpers an seiner Oberfläche
DE3708308A1 (de) 1986-04-10 1987-10-22 Bayer Ag Kontaktoptische gegenstaende
US4678838A (en) 1986-08-04 1987-07-07 Ciba-Geigy Corporation Particulate hydroperoxidized poly-N-vinyl lactam, its preparation and use thereof
US4791175A (en) 1986-08-04 1988-12-13 Ciba-Geigy Corporation Particulate hydroperoxidized poly-n-vinyl lactam, its preparation and use thereof
US4833196A (en) 1986-08-04 1989-05-23 Ciba-Geigy Corporation Particulate hydroperoxidized poly-N-vinyl lactam, its preparation and use thereof
US4786657A (en) 1987-07-02 1988-11-22 Minnesota Mining And Manufacturing Company Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate
US4810764A (en) 1988-02-09 1989-03-07 Bausch & Lomb Incorporated Polymeric materials with high oxygen permeability and low protein substantivity
US4910277A (en) 1988-02-09 1990-03-20 Bambury Ronald E Hydrophilic oxygen permeable polymers
US4954587A (en) 1988-07-05 1990-09-04 Ciba-Geigy Corporation Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
DE3838710A1 (de) * 1988-11-15 1990-05-17 Sued Chemie Ag Katalysator auf der basis von kristallinen alumosilikaten
US5039459A (en) 1988-11-25 1991-08-13 Johnson & Johnson Vision Products, Inc. Method of forming shaped hydrogel articles including contact lenses
US4889664A (en) 1988-11-25 1989-12-26 Vistakon, Inc. Method of forming shaped hydrogel articles including contact lenses
US4954586A (en) 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5070215A (en) 1989-05-02 1991-12-03 Bausch & Lomb Incorporated Novel vinyl carbonate and vinyl carbamate contact lens material monomers
US5034461A (en) 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5115056A (en) 1989-06-20 1992-05-19 Ciba-Geigy Corporation Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof
US5002794A (en) 1989-08-31 1991-03-26 The Board Of Regents Of The University Of Washington Method of controlling the chemical structure of polymeric films by plasma
KR920701271A (ko) 1989-09-14 1992-08-11 메이-자이 창 개선된 임상성능을 갖는 기체 투과성 소프트 콘택트렌즈
US5079319A (en) 1989-10-25 1992-01-07 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5010141A (en) 1989-10-25 1991-04-23 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5314960A (en) 1990-04-10 1994-05-24 Permeable Technologies, Inc. Silicone-containing polymers, oxygen permeable hydrophilic contact lenses and methods for making these lenses and treating patients with visual impairment
US5057578A (en) 1990-04-10 1991-10-15 E. I. Du Pont De Nemours And Company Silicone-containing block copolymers and macromonomers
US5371147A (en) 1990-10-11 1994-12-06 Permeable Technologies, Inc. Silicone-containing acrylic star polymers, block copolymers and macromonomers
WO1992007013A1 (en) 1990-10-11 1992-04-30 Permeable Technologies, Inc. Novel silicone-containing polymers and oxygen permeable hydrophilic contact lenses therefrom
US5135297A (en) 1990-11-27 1992-08-04 Bausch & Lomb Incorporated Surface coating of polymer objects
US5219965A (en) 1990-11-27 1993-06-15 Bausch & Lomb Incorporated Surface modification of polymer objects
DE69121581T2 (de) 1990-11-27 1997-03-20 Bausch & Lomb Inc., Rochester, N.Y. Oberflächenaktive makromonomere
AU647880B2 (en) 1991-02-28 1994-03-31 Ciba-Geigy Ag Contact lenses made from thermoformable material
JPH06510811A (ja) 1991-09-12 1994-12-01 ボシュ　アンド　ロム　インコーポレイテッド ぬれ性のシリコーンヒドロゲル組成物および方法
CA2116849C (en) 1991-09-12 2001-06-12 Yu-Chin Lai Wettable silicone hydrogel compositions and methods
US5352714A (en) 1991-11-05 1994-10-04 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
BR9206889A (pt) 1991-11-05 1995-05-02 Bausch & Lomb Método para melhorar a molhabilidade de hidrogéis, composição de hidrogel, dispositivo biomédico e lente de contato
AU3469893A (en) 1992-01-15 1993-08-03 Allergan, Inc. Hydrogel compositions and structures made from same
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5260000A (en) 1992-08-03 1993-11-09 Bausch & Lomb Incorporated Process for making silicone containing hydrogel lenses
US5336797A (en) 1992-12-30 1994-08-09 Bausch & Lomb Incorporated Siloxane macromonomers
US5321108A (en) 1993-02-12 1994-06-14 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5760100B1 (en) 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
JP3441024B2 (ja) * 1995-03-10 2003-08-25 旭化成アイミー株式会社 親水性含フッ素シロキサンモノマー及びその樹脂からなる眼科用レンズ材料
JPH08334732A (ja) * 1995-06-05 1996-12-17 Seiko Epson Corp ソフトコンタクトレンズ
US6201065B1 (en) 1995-07-28 2001-03-13 Focal, Inc. Multiblock biodegradable hydrogels for drug delivery and tissue treatment
JP2762251B2 (ja) 1995-10-13 1998-06-04 正司 下町 昇降機用搬出入装置及びパレット
DE69625941T2 (de) 1995-12-07 2003-06-18 Bausch & Lomb Inc., Rochester Polysiloxanzusammensetzungen mit niedrigem wassergehalt und reduziertem modul
US5710302A (en) 1995-12-07 1998-01-20 Bausch & Lomb Incorporated Monomeric units useful for reducing the modules of silicone hydrogels
DE69705057T2 (de) * 1996-09-20 2001-09-20 Bausch & Lomb Inc., Rochester Verfahren und zusammensetzung zur wiederbenetzung von kontaktlinsen und linderung der augentrockenheit
US6020445A (en) 1997-10-09 2000-02-01 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US5998498A (en) 1998-03-02 1999-12-07 Johnson & Johnson Vision Products, Inc. Soft contact lenses
US5959117A (en) 1998-08-10 1999-09-28 Bausch & Lomb Monomers useful for contact lens materials
US6099852A (en) * 1998-09-23 2000-08-08 Johnson & Johnson Vision Products, Inc. Wettable silicone-based lenses

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101695874B (zh) * 2005-02-22 2013-10-30 庄臣及庄臣视力保护公司 水凝胶加工
CN102115515B (zh) * 2010-01-05 2014-06-18 远东新世纪股份有限公司 增进硅酮水胶润湿性的共聚物、包含其的硅酮水胶组合物及由此制得的眼用物品
CN104945570A (zh) * 2015-07-03 2015-09-30 东南大学 一种硅凝胶接触透镜及其表面反转处理方法
CN104945570B (zh) * 2015-07-03 2017-06-09 东南大学 一种硅凝胶接触透镜及其表面反转处理方法
CN109790243A (zh) * 2016-10-06 2019-05-21 庄臣及庄臣视力保护公司 三嵌段预聚物及其在有机硅水凝胶中的用途
CN109790243B (zh) * 2016-10-06 2022-01-18 庄臣及庄臣视力保护公司 三嵌段预聚物及其在有机硅水凝胶中的用途

Also Published As

Publication number Publication date
KR20030065306A (ko) 2003-08-06
CN1217969C (zh) 2005-09-07
WO2001070837A1 (en) 2001-09-27
CA2404133A1 (en) 2001-09-27
AR030691A1 (es) 2003-09-03
EP2258736A1 (en) 2010-12-08
AU4765601A (en) 2001-10-03
BRPI0109443A (pt) 2004-01-13
BRPI0109443B8 (pt) 2021-07-06
EP2258736B1 (en) 2019-07-31
CA2404133C (en) 2011-07-05
AU2001247656B2 (en) 2005-05-26
EP1268590A1 (en) 2003-01-02
EP1268590B1 (en) 2019-08-28
BRPI0109443B1 (pt) 2013-01-22
JP2003528183A (ja) 2003-09-24
KR100748379B1 (ko) 2007-08-10
TWI229683B (en) 2005-03-21
US6367929B1 (en) 2002-04-09

Similar Documents

Publication Publication Date Title
CN1217969C (zh) 具有内润湿剂的水凝胶
JP4781587B2 (ja) ソフト・コンタクト・レンズ
EP2014724B9 (en) Wettable hydrogels comprising acyclic polyamides
JP4493745B2 (ja) ソフトコンタクトレンズ
EP1425052B1 (en) Biomedical devices containing internal wetting agents
EP1800150B1 (en) Wettable hydrogels comprising reactive, hydrophilic, polymeric internal wetting agents
CN1231303A (zh) 硅氧烷水凝胶聚合物
EP1809344B1 (en) Biomedical devices containing amphiphilic block copolymers
EP1601723B1 (en) Diluents for forming clear, wettable silicone hydrogel articles
AU2001247656A1 (en) Hydrogel with internal wetting agent
KR20080102365A (ko) 비반응성 실리콘 함유 예비중합체로부터 형성된 실리콘함유 중합체
CN1218816A (zh) 硅氧烷水凝胶聚合物
CN115735141A (zh) 衍生自接枝聚合物网络的眼科装置及其制备和使用方法
AU2008200230A1 (en) Biomedical devices containing internal wetting agents

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20050907

CX01 Expiry of patent term