CN1249443A - 以硅氧烷为基础的可润湿透镜 - Google Patents

以硅氧烷为基础的可润湿透镜 Download PDF

Info

Publication number
CN1249443A
CN1249443A CN99120233A CN99120233A CN1249443A CN 1249443 A CN1249443 A CN 1249443A CN 99120233 A CN99120233 A CN 99120233A CN 99120233 A CN99120233 A CN 99120233A CN 1249443 A CN1249443 A CN 1249443A
Authority
CN
China
Prior art keywords
silane
coupling agent
vinyl
hydrophilic polymer
aminopropyl
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
CN99120233A
Other languages
English (en)
Other versions
CN1196010C (zh
Inventor
J·S·詹
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 Products 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 Products Inc filed Critical Johnson and Johnson Vision Products Inc
Publication of CN1249443A publication Critical patent/CN1249443A/zh
Application granted granted Critical
Publication of CN1196010C publication Critical patent/CN1196010C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
    • A61F2/16—Intraocular lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

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)
  • Ophthalmology & Optometry (AREA)
  • Biomedical Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Transplantation (AREA)
  • Engineering & Computer Science (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Eyeglasses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明提供一种以硅氧烷为基础的生物医学器件,通过官能硅烷化学剂的使用,它表现出改善的润湿性及生物相容性。更具体地说,本发明提供一种器件,其至少1面具有官能硅烷偶合剂及亲水聚合物。

Description

以硅氧烷为基础的可润湿透镜
本发明涉及以硅氧烷为基础的生物医学器件。具体地说，本发明提供以硅氧烷为基础的诸如润湿性及生物相容性改善的接触透镜之类生物医学器件。
用于人体内或体表的器件是熟知的。此种器件的表面化学组成在决定器件的综合功效上起着关键作用。例如，包括导管、移植片固定模及植入物在内的许多器件，要求具有不生物沾污的表面，就是说，蛋白质、脂质及细胞不粘附在该表面上。某些情况下，为此种器件开发出的材料，在强度、透光率、柔软等方面虽然理想，然而，在使用中容易沾脏。在这种情况下，就必须或者研制新材料，或者设法改变材料的表面特性。
在眼镜片，特别是隐形镜片的情况下，许多材料具备要求的透氧性、机械及光学性能，然而会很快变脏。另外，材料的表面能可能低到令镜片的亲水性不足的程度，就是说它们无法被泪水润湿。用这种材料制作的隐形镜片可能会带着不舒服，且会紧紧地贴在角膜上，造成角膜上皮严重受损的危险。
已采用多种方法对器件进行改性以改善其表面性能。例如，一类对硅橡胶聚合物制作的接触透镜改性的已知方法采用在接触透镜表面接枝上亲水性聚合物。然而，用这类方法的缺点在于，它们生产出的透镜表面粗糙不平或者带有针孔。
美国专利4,332,922公开一种方法，将硅橡胶透镜表面转变为含SiH基团的低聚硅氧烷，然后将该SiH基团转变为SiOH基团，或者令该基团与含烯键化合物进行反应以使表面成为亲水的。然而，这种解决方案在化学上受到限制。
采用等离子体技术涂布疏水底层的各种方法是已知的。然而，所有这类等离子体方法都要求让底层暴露于真空中，这既麻烦，又常常行不通。因此，目前需要一种能克服已知方法的某些缺点的表面改性方法。
发明详述及优选实施方案
本发明提供以硅氧烷聚合物为基础的可润湿生物医学器件。在一种实施方案中，本发明提供一种制造生物医学器件的方法，包括、主要由并由下列步骤组成：让以硅氧烷聚合物为基础的生物医学器件至少1面与反应有效数量1种或多种官能硅烷偶合剂进行接触，以及涂布上有效涂布量1种或多种亲水聚合物。在另一种实施方案中，本发明提供一种生物医学器件，包括、主要由并由生物医学器件组成，该器件至少1面上带有反应有效数量1种或多种官能硅烷偶合剂以及有效涂布量1种或多种亲水聚合物。
所谓“生物医学器件”是指旨在用于人体组织或体液之内、其(表面)上，或二者情况下的任何器件。此种器件的例子包括但不限于，移植片固定模、植入物、导管及眼镜片。在优选的实施方案中，该生物医学器件是眼镜片，包括但不限于，隐形镜片或眼内镜片。更优选的是，该器件是隐形镜片。在优选的实施方案中，本发明包括、主要由并由以硅氧烷聚合物为基础的接触透镜及其制法组成，其中该透镜的至少1面带有反应有效数量1种或多种官能硅烷偶合剂以及有效涂布量1种或多种亲水聚合物。
所谓“以硅氧烷聚合物为基础的”是指一种部分地或全部由硅氧烷组成的或含硅氧烷的聚合物制成的器件。此种聚合物的例子包括但不限于，硅氧烷、硅氧烷共混物、硅氧烷水凝胶、聚氨酯-硅氧烷水凝胶等。硅氧烷的说明例子包括但不限于：如美国专利3,228,741中所描述的聚二甲基硅氧烷、聚二甲基-共乙烯基甲基硅氧烷(polydimethyl-covinylmethylsiloxane)以及硅橡胶；如美国专利3,341,490中所描述的硅氧烷共混物；以及如美国专利3,518,324中所描述的硅氧烷组合物，这些专利均全文并入本文作为参考。
有用的硅氧烷材料包括但不限于，通过对硅氧烷预聚物实施交联获得的交联聚硅氧烷。尤其合适的材料包括但不限于，容易发生氢化硅烷化的有机聚硅氧烷聚合物混合物，其预聚物将包含乙烯基基团及氢化物基团，并且具有通式聚二烃基-共乙烯基烃基硅氧烷及聚二烃基-共烃基氢硅氧烷，其中烃基基团是单价烃基基团，包括但不限于，C1～C7基团；芳基基团，包括但不限于，苯基、甲苯基、二甲苯基及联苯基；卤代芳基，包括但不限于氯苯基；以及环烷基等等。更为优选的材料是硅氧烷水凝胶，尤其是由包含--丙烯酸封端的聚硅氧烷预聚物、庞大聚硅氧烷基烷基的(甲基)丙烯酸酯单体以及如美国专利5,387,632、5,358,995、5,023,305、5,034,461、4,954,586、4,780,515及4,343,927(这些均全文并入本文作为参考)所描述的亲水性单体--的单体混合物制备的硅氧烷水凝胶。具体的例子包括但不限于，三甲基甲硅烷基甲基的(甲基)丙烯酸酯，五甲基二甲硅烷氧基乙基的(甲基)丙烯酸酯、三(三甲基甲硅烷氧基)甲硅烷基丙基的(甲基)丙烯酸酯、甲基二(三甲基甲硅烷氧基)甲基甲硅醚基丙基的(甲基)丙烯酸酯、叔丁基四甲基甲硅醚基乙基的(甲基)丙烯酸酯等。
本领域技术人员将会懂得，产生待涂布表面的配方可包含其他单体及添加剂。例如，可使用紫外吸收性单体、活性染料、加工助剂等等。
所谓“官能硅烷偶合剂”是指任何已知的硅烷偶合剂。优选的硅烷偶合剂具有通式X3Si(CH2)nY，其中n是0～3，优选n＝3，X是可水解基团，优选Cl、CH3O-或C2H5O-，Y是有机官能团。具体的Y基团可由本领域技术人员根据准备施涂到所述表面上去的亲水聚合物涂层的类型便当地确定。例如，要求的涂层是乙烯基聚合物时，则可使用乙烯基Y基团。有机官能团的例子包括但不限于，丙烯酸、氨基、氯、环氧基、缩水甘油氧基(glycidoxy)、巯基、甲基丙烯酸基、乙烯基等等。
官能硅烷偶合剂的例子包括但不限于，乙烯基苄基阳离子硅烷、乙烯基-三(β-甲氧基乙氧基)硅烷、乙烯基三乙酸基硅烷、γ-甲基丙烯酸基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-(β-氨乙基)氨丙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷、β-(3，4-环氧环己基)-乙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷及其混合物。典型的硅烷偶合剂均有市售供应。
虽不拟囿于下面的理论，但本发明相信，偶合剂在与以硅氧烷聚合物为基础的表面相接触时，将与该表面起反应，形成硅氧烷键。因此，偶合剂的活性端基就被化学地锚固在该表面上，并从而可用来与需要的亲水聚合物涂层相键合。
在本发明的器件中，至少1面包含反应有效数量1种或多种官能硅烷偶合剂。“反应有效数量”是足以将化学惰性表面转变为能够涂布上所欲亲水聚合物涂层的活性表面的偶合剂数量。
为了制作本发明器件，让偶合剂与器件表面相接触。对于实施该接触的温度和压力并无严格要求。偶合剂可以以偶合剂的水溶液形式与该表面接触。替代地，也可使用偶合剂与醇，如甲醇、乙醇或丙醇，或者与有机溶剂，如苯、甲苯、己烷等的溶液。一般地，所用溶液的浓度，以溶液总重量为基准，为约1～约15wt％，优选约2～约5wt％。视所选偶合剂而定，可能需要使用酸或碱催化剂。
优选的是，在偶合剂与该表面接触之前，以任意方便的手段对表面进行处理，以便暴露出与偶合剂硅氧烷端基产生键合的部位。例如，可采用酸或碱腐蚀或等离子体来处理该表面。
该表面与偶合剂进行接触的方法有多种多样，可选用其中任何一种。例如，可将表面浸泡在偶合剂溶液中，或者将溶液滴到该表面上。作为另一种替代方案，可这样来实现接触：将偶合剂涂布到模具表面上。然后，用已知方法，如注塑，将硅氧烷预聚物加入到模具中，并进行聚合。
又一种实施接触的替代方案是将偶合剂与要成形为器件的硅氧烷预聚物进行共混。固化后，部分偶合剂有机官能团将会处于器件表面上，并从而可供与聚合物涂层起反应之用。
作为进一步的接触替代方案，偶合剂可与聚合物涂料预先掺混。然后，将聚合物涂料涂布到器件表面上，并进行聚合。
要知道，在不同的器件表面上可使用不同的偶合剂，因此可以用各种各样聚合物来涂布表面。例如，乙烯基硅烷偶合剂可随同甲基丙烯酸羟乙基酯涂料一起涂布到正面，而氨基硅烷偶合剂可随同聚乙二醇涂料一起涂布到背面。
还应当指出的是，除了官能硅烷偶合剂之外，还可使用其他偶合剂。合适的偶合剂包括但不限于钛酸酯偶合剂。
涂布器件表面所需要的亲水聚合物可由适当的单体生成。例如，可用来生成亲水聚合物涂层的单体包括但不限于，丙烯酸、甲基丙烯酸、丙烯酸羟乙基酯、甲基丙烯酸羟乙基酯、丙烯酰胺、甲基丙烯酰胺、N，N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮、二甲基氨基甲基-及二甲基氨基乙基的丙烯酸酯及甲基丙烯酸酯、丙烯酸羟丙基酯及甲基丙烯酸羟丙基酯、甘油的丙烯酸酯及甲基丙烯酸酯、二乙二醇的单丙烯酸酯及单甲基丙烯酸酯、三乙二醇的丙烯酸酯及甲基丙烯酸酯、乙烯醇、环氧乙烷、环氧丙烷以及上述的混合物等。优选的是，亲水聚合物涂层由下列成分构成：羟乙基的(甲基)丙烯酸酯、(甲基)丙烯酰胺、N，N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮、乙二醇、环氧乙烷、乙烯醇、丙烯酸、环氧乙烷二醋酸(ethyleneoxide bisacetic acid)或者上述的混合物。
该聚合物和/或单体可采用任何方便的方法涂布到器件表面。例如，可将单体的水溶液或在有机溶剂中的溶液涂布到透镜上，然后，采用任何已知的方法使单体聚合。采用有效涂布量，也就是足以赋予涂布表面以要求水平亲水性的数量。就典型而言，所使用的单体和/或聚合物浓度，以溶液总重量为基准，为约0.1～约15wt％，优选约1～约10wt％。替代地，也可使用不带水或有机溶剂的单体和/或聚合物。
虽然本发明的最重要用途是提供可润湿表面，然而，本领域技术人员懂得，本发明也可用于在器件表面涂布任意层数的涂层。
本发明通过下面的非限定性例子将得到进一步的阐明。
实施例
实例1～5
由聚二甲基硅氧烷(“PDMS”)制成的硅氧烷透镜，以5体积％γ-氨丙基三乙氧基硅烷水溶液进行表面处理，然后以ETAFILCONTM A单体混合物对其进行涂布。10min紫外线固化之后，获得聚甲基丙烯酸羟乙基酯涂层。测定了有涂层及无涂层透镜及薄膜的动态接触角，结果示于表1中。
表1
前进角(Advancing Angle)(°)   标准偏差
PDMS透镜(透镜底层)     118     9
Etafilcon A涂布的PDMS透镜     72     21
PDMS薄膜(薄膜底层)     115     4
Etafilcon A涂布的PDMS薄膜     89     5
ACUVUETM透镜     81     10
该结果显示，官能硅烷偶合剂-处理的透镜及薄膜表现出良好的润湿性。
实例6～7
由硅氧烷与氟聚合物组合制成的接触透镜，以5体积％γ-氨丙基三乙氧基硅烷的甲醇溶液进行表面处理，然后，涂布0.1wt％聚环氧乙烷双(醋酸)水溶液。测定了有涂层及无涂层透镜的动态接触角，结果示于表2中。该结果显示，涂层表面表现出良好的润温性。
表2
    前进角(°)     标准偏差
  未涂布底层     111     10
  涂层透镜     80     16

Claims (10)

1.一种包括生物医学器件的器件，该器件的至少1面具有反应有效数量1种或多种官能硅烷偶合剂以及有效涂布量1种或多种亲水聚合物。
2.权利要求1的器件，其中官能硅烷偶合剂具有通式X3Si(CH2)nY，其中n是0～3，X是Cl、CH3O-或C2H5O-，Y是有机官能团。
3.权利要求1的器件，其中偶合剂的有机官能团是丙烯酸、氨基、氯、环氧基、缩水甘油氧基、巯基、甲基丙烯酸基或乙烯基。
4.权利要求1的器件，其中偶合剂是乙烯基苄基阳离子硅烷、乙烯基-三(β-甲氧基乙氧基)硅烷、乙烯基三乙酸基硅烷、γ-甲基丙烯酸基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-(β-氨乙基)氨丙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷、β-(3，4-环氧环己基)-乙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷及其混合物。
5.权利要求1的器件，其中偶合剂是γ-氨丙基三乙氧基硅烷。
6.权利要求1的器件，其中1种或多种亲水聚合物是(甲基)丙烯酸羟乙基酯聚合物、(甲基)丙烯酰胺聚合物、N，N-二甲基丙烯酰胺聚合物、N-乙烯基吡咯烷酮聚合物、聚乙二醇、聚环氧乙烷、聚乙烯醇、聚丙烯酸、聚环氧乙烷二醋酸或者上述的混合物。
7.一种包括接触透镜的器件，透镜的至少1面具有反应有效数量1种或多种官能硅烷偶合剂以及有效涂布量1种或多种亲水聚合物，其中硅烷偶合剂选自乙烯基苄基阳离子硅烷、乙烯基-三(β-甲氧基乙氧基)硅烷、乙烯基三乙酸基硅烷、γ-甲基丙烯酸基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-(β-氨乙基)氨丙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷、β-(3，4-环氧环己基)-乙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷及其混合物，而亲水聚合物则选自聚(甲基)丙烯酸羟乙基酯、聚(甲基)丙烯酰胺、聚N，N-二甲基丙烯酰胺、聚N-乙烯基吡咯烷酮、聚乙二醇、聚环氧乙烷、聚乙烯醇、聚丙烯酸、聚环氧乙烷二醋酸或者上述的混合物。
8.权利要求7的器件，其中偶合剂是γ-氨丙基三乙氧基硅烷。
9.权利要求7的器件，其中亲水聚合物是聚甲基丙烯酸羟乙基酯。
10.权利要求7的器件，其中亲水聚合物是聚环氧乙烷。
CNB991202333A 1998-09-23 1999-09-23 以硅氧烷为基础的可润湿透镜 Expired - Fee Related CN1196010C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/159034 1998-09-23
US09/159,034 US6099852A (en) 1998-09-23 1998-09-23 Wettable silicone-based lenses

Publications (2)

Publication Number Publication Date
CN1249443A true CN1249443A (zh) 2000-04-05
CN1196010C CN1196010C (zh) 2005-04-06

Family

ID=22570803

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB991202333A Expired - Fee Related CN1196010C (zh) 1998-09-23 1999-09-23 以硅氧烷为基础的可润湿透镜

Country Status (11)

Country Link
US (1) US6099852A (zh)
EP (1) EP0989418A3 (zh)
JP (1) JP2000137195A (zh)
KR (1) KR20000034933A (zh)
CN (1) CN1196010C (zh)
AR (1) AR025805A1 (zh)
AU (1) AU757262B2 (zh)
BR (1) BR9904255B1 (zh)
CA (1) CA2283041A1 (zh)
SG (1) SG85676A1 (zh)
TW (1) TWI229759B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265329B (zh) * 2007-03-16 2011-06-22 马雄明 一种表面带引发剂的聚二甲基硅氧烷及其制法和用途
CN112789065A (zh) * 2018-10-01 2021-05-11 微仙美国有限公司 医疗设备

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6367929B1 (en) * 1998-03-02 2002-04-09 Johnson & Johnson Vision Care, Inc. Hydrogel with internal wetting agent
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
US6440571B1 (en) * 1999-05-20 2002-08-27 Bausch & Lomb Incorporated Surface treatment of silicone medical devices with reactive hydrophilic polymers
WO2001034312A1 (en) * 1999-11-05 2001-05-17 Bausch & Lomb Incorporated Surface treatment of non-plasma treated silicone hydrogel contact lenses
WO2001034311A1 (en) * 1999-11-05 2001-05-17 Bausch & Lomb Incorporated Surface treatment of rigid gas permeable contact lenses
US6599559B1 (en) * 2000-04-03 2003-07-29 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
US6689480B2 (en) * 2000-05-10 2004-02-10 Toray Industries, Inc. Surface-treated plastic article and method of surface treatment
US6773107B2 (en) * 2000-08-17 2004-08-10 Novartis Ag Soft translating contact lens for presbyopia
EP1315985B1 (en) * 2000-08-24 2017-07-26 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6852353B2 (en) 2000-08-24 2005-02-08 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
MXPA03002322A (es) * 2000-09-19 2003-06-24 Bausch & Lomb Metodo para aplicar un recubrimiento a lentes polimericas.
US6861123B2 (en) * 2000-12-01 2005-03-01 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lens
US7060288B2 (en) * 2001-02-28 2006-06-13 Timothy Charles Hughes Biomedical devices
US20050064012A1 (en) * 2001-07-17 2005-03-24 Baylor College Of Medicine Process for causing myopic shift in vision
US7879267B2 (en) * 2001-08-02 2011-02-01 J&J Vision Care, Inc. Method for coating articles by mold transfer
GB0122393D0 (en) * 2001-09-17 2001-11-07 Polybiomed Ltd Treating metal surfaces to enhance bio-compatibility
US7270678B2 (en) * 2002-06-28 2007-09-18 Bausch & Lomb Incorporated Surface modification of functional group-containing medical devices with catalyst-containing reactive polymer system
US7083646B2 (en) * 2002-06-28 2006-08-01 Bausch & Lomb Incorporated Surface modification of functional group-containing intraocular lenses
US20070138692A1 (en) * 2002-09-06 2007-06-21 Ford James D Process for forming clear, wettable silicone hydrogel articles
US20040120982A1 (en) * 2002-12-19 2004-06-24 Zanini Diana Biomedical devices with coatings attached via latent reactive components
US20060193894A1 (en) * 2005-02-28 2006-08-31 Jen James S Methods for providing biomedical devices with hydrophilic antimicrobial coatings
US20070048349A1 (en) * 2005-08-29 2007-03-01 Bausch & Lomb Incorporated Surface-modified medical devices and methods of making
WO2007058373A1 (en) * 2005-11-16 2007-05-24 Fujifilm Corporation Surface-hydrophilic structure
JP5094081B2 (ja) * 2005-11-17 2012-12-12 富士フイルム株式会社 親水性部材及びその製造方法
US7572841B2 (en) 2006-06-15 2009-08-11 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US7540609B2 (en) 2006-06-15 2009-06-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US8231218B2 (en) 2006-06-15 2012-07-31 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US9173773B2 (en) * 2006-06-21 2015-11-03 Johnson & Johnson Vision Care, Inc. Punctal plugs for the delivery of active agents
US9474645B2 (en) * 2006-06-21 2016-10-25 Johnson & Johnson Vision Care, Inc. Punctal plugs for the delivery of active agents
US8012591B2 (en) * 2006-09-21 2011-09-06 Fujifilm Corporation Hydrophilic composition and hydrophilic member
JP2008086855A (ja) * 2006-09-29 2008-04-17 Fujifilm Corp 生化学用器具
JP2008238711A (ja) * 2007-03-28 2008-10-09 Fujifilm Corp 親水性部材及び下塗り組成物
US20090029179A1 (en) * 2007-05-14 2009-01-29 Fujifilm Corporation Two-liquid composition, hydrophilic composition and hydrophilic member
JP2009227809A (ja) * 2008-03-21 2009-10-08 Fujifilm Corp 親水性組成物及び親水性処理部材
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
US8894602B2 (en) 2010-09-17 2014-11-25 Johnson & Johnson Vision Care, Inc. Punctal plugs with directional release
US20100109176A1 (en) 2008-11-03 2010-05-06 Chris Davison Machined lens molds and methods for making and using same
US8163358B2 (en) * 2009-02-18 2012-04-24 Synergeyes, Inc. Surface modification of contact lenses
TWI495459B (zh) * 2009-03-31 2015-08-11 Johnson & Johnson Vision Care 淚管塞（二）
US9421127B2 (en) 2009-03-31 2016-08-23 Johnson & Johnson Vision Care, Inc. Punctal plugs
TW201043211A (en) * 2009-03-31 2010-12-16 Johnson & Johnson Vision Care Inc Punctal plugs
US9259351B2 (en) 2010-03-29 2016-02-16 Johnson & Johnson Vision Care, Inc. Punctal plugs
US9259352B2 (en) 2010-03-29 2016-02-16 Johnson & Johnson Vision Care, Inc. Punctal plugs
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
KR101889246B1 (ko) 2010-07-30 2018-08-16 노파르티스 아게 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
US8821457B2 (en) 2010-09-08 2014-09-02 Johnson & Johnson Vision Care, Inc. Punctal plug containing drug formulation
US20120157938A1 (en) 2010-12-16 2012-06-21 Tokarski Jason M Punctal plug with drug core retention features
US8672476B2 (en) 2011-03-24 2014-03-18 Johnson & Johnson Vision Care, Inc. Contact lenses with improved movement
US8801176B2 (en) 2011-03-24 2014-08-12 Johnson & Johnson Vision Care, Inc. Contact lenses with improved movement
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
US9005700B2 (en) 2011-10-12 2015-04-14 Novartis Ag Method for making UV-absorbing ophthalmic lenses
US8721322B2 (en) 2011-11-30 2014-05-13 Johnson & Johnson Vision Care, Inc. Injection molding device and method
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
US20130220346A1 (en) 2012-02-28 2013-08-29 Victor Lust Balloon punctal plug
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
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
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
US10338408B2 (en) 2012-12-17 2019-07-02 Novartis Ag Method for making improved UV-absorbing ophthalmic lenses
SG11201603699SA (en) 2013-12-17 2016-07-28 Novartis Ag A silicone hydrogel lens with a crosslinked hydrophilic coating
WO2016032926A1 (en) 2014-08-26 2016-03-03 Novartis Ag Method for applying stable coating on silicone hydrogel contact lenses
CN108369291B (zh) 2015-12-15 2021-07-20 爱尔康公司 用于将稳定的涂层施加在硅酮水凝胶接触镜片上的方法
HUE057348T2 (hu) 2017-12-13 2022-05-28 Alcon Inc Eljárás MPS-kompatibilis hidrogradiens kontaktlencsék elõállítására
WO2019202651A1 (ja) 2018-04-17 2019-10-24 三菱電機株式会社 電動機の診断装置
WO2020000934A1 (zh) * 2018-06-28 2020-01-02 浙江清华柔性电子技术研究院 硅橡胶的表面处理方法
US11578176B2 (en) 2019-06-24 2023-02-14 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lenses having non-uniform morphology

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3070573A (en) * 1958-08-18 1962-12-25 Dow Corning Method of grafting olefins onto organosilicon compounds by the use of ozone
US3008920A (en) * 1959-04-27 1961-11-14 Dow Chemical Co Method of inhibiting homopolymerization in graft copolymers with copper salts
US3925178A (en) * 1970-04-17 1975-12-09 Hymie D Gesser Contact lenses
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
US4332922A (en) * 1980-07-18 1982-06-01 Titmus Eurocon Process for rendering silicone rubber contact lenses hydrophilic
US4311573A (en) * 1980-10-08 1982-01-19 American Hospital Supply Corporation Process for graft copolymerization of a pre-formed substrate
US4589964A (en) * 1980-10-08 1986-05-20 American Hospital Supply Corporation Process for graft copolymerization of a pre-formed substrate
FR2565699A1 (fr) * 1984-06-11 1985-12-13 Suwa Seikosha Kk Procede de modification de la surface d'une matiere de base comprenant des motifs carbonate et ester d'allyle, pour former ensuite un revetement superficiel dur, dans le cas de lentilles pour verres ophtalmiques
US4731080A (en) * 1985-01-18 1988-03-15 Galin Miles A Coated intraocular lens
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
US5263992A (en) * 1986-10-17 1993-11-23 Bio-Metric Systems, Inc. Biocompatible device with covalently bonded biocompatible agent
JP2551580B2 (ja) * 1987-04-30 1996-11-06 ホ−ヤ株式会社 コンタクトレンズの親水化方法
CA2021933A1 (en) * 1989-07-27 1991-01-28 Hiroshi Hosono Process for preparation of anti-fogging coating
GB9118597D0 (en) * 1991-08-30 1991-10-16 Biocompatibles Ltd Polymer treatments
EP0561507A1 (en) * 1992-03-16 1993-09-22 Mizu Systems, Inc. Method for grafting preformed hydrophilic polymers onto hydrophobic polymer substrates
JPH06218038A (ja) * 1993-01-27 1994-08-09 Kuraray Co Ltd 医療用具
US5936703A (en) * 1993-10-13 1999-08-10 Nof Corporation Alkoxysilane compound, surface processing solution and contact lens
ATE219381T1 (de) * 1995-02-07 2002-07-15 Fidia Advanced Biopolymers Srl Verfahren zur beschichtung von gegenständen mit hyaluronsäure, dessen derivaten und halbsynthetischen polymeren
CA2224780A1 (en) * 1995-06-30 1997-01-23 Wojciech Stanislaw Gutowski Improved surface treatment of polymers
US5804318A (en) * 1995-10-26 1998-09-08 Corvita Corporation Lubricious hydrogel surface modification
US6013855A (en) * 1996-08-06 2000-01-11 United States Surgical Grafting of biocompatible hydrophilic polymers onto inorganic and metal surfaces
WO1998022541A2 (en) * 1996-11-08 1998-05-28 Ikonos Corporation Method for coating substrates
US5792331A (en) * 1996-12-19 1998-08-11 Dionex Corporation Preformed polymer coating process and product
JPH11255926A (ja) * 1998-03-13 1999-09-21 Toray Ind Inc シリコーン成型品およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265329B (zh) * 2007-03-16 2011-06-22 马雄明 一种表面带引发剂的聚二甲基硅氧烷及其制法和用途
CN112789065A (zh) * 2018-10-01 2021-05-11 微仙美国有限公司 医疗设备

Also Published As

Publication number Publication date
BR9904255B1 (pt) 2011-05-31
AU757262B2 (en) 2003-02-13
TWI229759B (en) 2005-03-21
US6099852A (en) 2000-08-08
KR20000034933A (ko) 2000-06-26
AR025805A1 (es) 2002-12-18
BR9904255A (pt) 2001-04-17
CN1196010C (zh) 2005-04-06
JP2000137195A (ja) 2000-05-16
SG85676A1 (en) 2002-01-15
EP0989418A2 (en) 2000-03-29
CA2283041A1 (en) 2000-03-23
EP0989418A3 (en) 2001-04-04
AU4876799A (en) 2000-03-30

Similar Documents

Publication Publication Date Title
CN1196010C (zh) 以硅氧烷为基础的可润湿透镜
KR100886580B1 (ko) 하이드로겔 제품의 금형내 피복방법
CA2767171C (en) Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers
EP2483737B1 (en) Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses
TWI229683B (en) Hydrogel with internal wetting agent
US7825170B2 (en) Contact lenses
CN101977972B (zh) 包含反应性嵌段共聚物的涂覆溶液
EP1971376B1 (en) Silicone containing polymers formed from non-reactive silicone containing prepolymers
US9039174B2 (en) Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers
US20070161810A1 (en) Process for making cationic hydrophilic siloxanyl monomers
JP2005507963A (ja) ビニルカーボネート末端封鎖フッ素化側鎖ポリシロキサンをベースにしたシリコーンヒドロゲル
CN101484194A (zh) 通过迈克尔加成反应对聚合物制品表面的改性
WO2014143926A1 (en) Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers
US20040258727A1 (en) Ophthalmic biomaterials and preparation thereof
CN1313842C (zh) 接触透镜涂层选择及其制造工艺
JP2015515514A (ja) 親水性マクロマーおよびそれを含むヒドロゲル
WO2007064565A1 (en) Method for coating lens material
JP2008504395A (ja) コンタクトレンズの表面改質の改良用新規プレポリマー
US7247387B1 (en) Material and process for controlled thin polymeric coatings on plastic surface
JPH10221651A (ja) コンタクトレンズ

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20050406

Termination date: 20130923