CN1196010C - 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 PDFInfo
- Publication number
- CN1196010C CN1196010C CNB991202333A CN99120233A CN1196010C CN 1196010 C CN1196010 C CN 1196010C CN B991202333 A CNB991202333 A CN B991202333A CN 99120233 A CN99120233 A CN 99120233A CN 1196010 C CN1196010 C CN 1196010C
- Authority
- CN
- China
- Prior art keywords
- silane
- vinyl
- coupling agent
- aminopropyl
- functional
- 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.)
- Expired - Fee Related
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)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Materials For Medical Uses (AREA)
- Eyeglasses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (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
技术领域
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。
背景技术
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。
发明内容
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,该器件的至少一面具有反应有效量的一种或多种官能硅烷偶合剂以及涂布有效量的一种或多种亲水聚合物,所述聚合物由至少一种选自下列的单体形成: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、乙二醇、环氧乙烷、乙烯基醇、丙烯酸、环氧乙烷二醋酸以及上述的混合物。
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,其中该透镜的至少一面具有反应有效量的一种或多种官能硅烷偶合剂以及涂布有效量的一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湿性。
表2
前进角(°) | 标准偏差 | |
未涂布底层 | 111 | 10 |
涂层透镜 | 80 | 16 |
Claims (9)
1.一种生物医学器件,该器件的至少一面具有反应有效量的一种或多种官能硅烷偶合剂以及涂布有效量的一种或多种亲水聚合物,所述聚合物由至少一种选自下列的单体形成: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、乙二醇、环氧乙烷、乙烯基醇、丙烯酸、环氧乙烷二醋酸以及上述的混合物。
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、CH30-或C2H50-,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。
6.一种接触透镜,透镜的至少一面具有反应有效量的一种或多种官能硅烷偶合剂以及涂布有效量的一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丙烯酸羟乙基酯、聚甲基丙烯酸羟乙基酯、聚丙烯酰胺、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。
7.权利要求6的接触透镜,其中偶合剂是γ-氨丙基三乙氧基硅烷。
8.权利要求6的接触透镜,其中亲水聚合物是聚甲基丙烯酸羟乙基酯。
9.权利要求6的接触透镜,其中亲水聚合物是聚环氧乙烷。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/159,034 US6099852A (en) | 1998-09-23 | 1998-09-23 | Wettable silicone-based lenses |
US09/159034 | 1998-09-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1249443A CN1249443A (zh) | 2000-04-05 |
CN1196010C true 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) |
Families Citing this family (72)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7052131B2 (en) | 2001-09-10 | 2006-05-30 | J&J Vision Care, Inc. | Biomedical devices containing internal wetting agents |
US6367929B1 (en) * | 1998-03-02 | 2002-04-09 | Johnson & Johnson Vision Care, Inc. | Hydrogel with internal wetting agent |
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 |
AU1448901A (en) * | 1999-11-05 | 2001-06-06 | Bausch & Lomb Incorporated | Surface treatment of rigid gas permeable contact lenses |
AU1583601A (en) * | 1999-11-05 | 2001-06-06 | Bausch & Lomb Incorporated | Surface treatment of non-plasma treated silicone hydrogel 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 |
EP1319037A1 (en) | 2000-09-19 | 2003-06-18 | Bausch & Lomb Incorporated | Method for applying polymeric lens coating |
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 |
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 |
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 |
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 |
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 |
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 |
TWI599813B (zh) | 2010-07-30 | 2017-09-21 | 諾華公司 | 水合隱形鏡片 |
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 |
US9170349B2 (en) | 2011-05-04 | 2015-10-27 | Johnson & Johnson Vision Care, Inc. | Medical devices having homogeneous charge density and methods for making same |
US20130203813A1 (en) | 2011-05-04 | 2013-08-08 | 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 |
WO2013055746A1 (en) | 2011-10-12 | 2013-04-18 | Novartis Ag | Method for making uv-absorbing ophthalmic lenses by coating |
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 |
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 |
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 |
WO2014095690A1 (en) | 2012-12-17 | 2014-06-26 | 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 |
SG11201700232SA (en) | 2014-08-26 | 2017-03-30 | Novartis Ag | Method for applying stable coating on silicone hydrogel contact lenses |
SG11201803726VA (en) | 2015-12-15 | 2018-06-28 | Novartis Ag | Method for applying stable coating on silicone hydrogel contact lenses |
WO2019116141A1 (en) | 2017-12-13 | 2019-06-20 | Novartis Ag | Method for producing mps-compatible water gradient contact lenses |
EP3783376B1 (en) | 2018-04-17 | 2022-04-27 | Mitsubishi Electric Corporation | Electric motor diagnosing device |
EP3816215A4 (en) * | 2018-06-28 | 2022-03-30 | Institute of Flexible Electronics Technology of Thu, Zhejiang | PROCESS FOR SURFACE TREATMENT OF SILICONE RUBBER |
WO2020072481A1 (en) * | 2018-10-01 | 2020-04-09 | Microvention, Inc. | Medical devices |
US11578176B2 (en) | 2019-06-24 | 2023-02-14 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogel contact lenses having non-uniform morphology |
CN116948351B (zh) * | 2023-06-08 | 2024-08-20 | 江苏视科新材料股份有限公司 | 一种硅水凝胶材料的制备方法 |
Family Cites Families (25)
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 |
US4589964A (en) * | 1980-10-08 | 1986-05-20 | American Hospital Supply Corporation | Process for graft copolymerization of a pre-formed substrate |
US4311573A (en) * | 1980-10-08 | 1982-01-19 | 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 |
TR199700760T1 (xx) * | 1995-02-07 | 1998-02-21 | Fidia Advanced Biopolymers, Srl | Nesnelerin hiyaluronik asit ile kaplanmas�. |
EP0835279B1 (en) * | 1995-06-30 | 2003-12-17 | Commonwealth Scientific And Industrial Research Organisation | 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 |
-
1998
- 1998-09-23 US US09/159,034 patent/US6099852A/en not_active Expired - Lifetime
-
1999
- 1999-09-08 SG SG9904398A patent/SG85676A1/en unknown
- 1999-09-16 AU AU48767/99A patent/AU757262B2/en not_active Ceased
- 1999-09-20 BR BRPI9904255-0A patent/BR9904255B1/pt not_active IP Right Cessation
- 1999-09-21 KR KR1019990040604A patent/KR20000034933A/ko not_active Application Discontinuation
- 1999-09-22 AR ARP990104768A patent/AR025805A1/es active IP Right Grant
- 1999-09-22 JP JP11269140A patent/JP2000137195A/ja active Pending
- 1999-09-22 EP EP99307497A patent/EP0989418A3/en not_active Withdrawn
- 1999-09-23 CN CNB991202333A patent/CN1196010C/zh not_active Expired - Fee Related
- 1999-09-23 CA CA002283041A patent/CA2283041A1/en not_active Abandoned
- 1999-10-21 TW TW088116336A patent/TWI229759B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
AU4876799A (en) | 2000-03-30 |
EP0989418A3 (en) | 2001-04-04 |
SG85676A1 (en) | 2002-01-15 |
CA2283041A1 (en) | 2000-03-23 |
US6099852A (en) | 2000-08-08 |
TWI229759B (en) | 2005-03-21 |
CN1249443A (zh) | 2000-04-05 |
AU757262B2 (en) | 2003-02-13 |
JP2000137195A (ja) | 2000-05-16 |
KR20000034933A (ko) | 2000-06-26 |
BR9904255A (pt) | 2001-04-17 |
EP0989418A2 (en) | 2000-03-29 |
AR025805A1 (es) | 2002-12-18 |
BR9904255B1 (pt) | 2011-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1196010C (zh) | 以硅氧烷为基础的可润湿透镜 | |
CA2767171C (en) | Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers | |
KR100886580B1 (ko) | 하이드로겔 제품의 금형내 피복방법 | |
CN101341191B (zh) | 用可聚合的阳离子亲水性基团封端的含硅单体 | |
TWI229683B (en) | Hydrogel with internal wetting agent | |
CN101977972B (zh) | 包含反应性嵌段共聚物的涂覆溶液 | |
EP2483737B1 (en) | Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses | |
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 | |
JP2009215533A (ja) | ポリシロキサンベースのプレポリマーおよびヒドロゲル | |
WO2007027500A2 (en) | Surface-modified medical devices and methods of making | |
WO2014143926A1 (en) | Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers | |
US20040258727A1 (en) | Ophthalmic biomaterials and preparation thereof | |
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 | |
US20080004410A1 (en) | Hydrophilic macromonomers having alpha,beta-conjugated carboxylic terminal group and medical devices incorporating same | |
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 |