CN1171642C - 改进的高折光指数眼科透镜材料 - Google Patents

改进的高折光指数眼科透镜材料 Download PDF

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CN1171642C
CN1171642C CNB961906022A CN96190602A CN1171642C CN 1171642 C CN1171642 C CN 1171642C CN B961906022 A CNB961906022 A CN B961906022A CN 96190602 A CN96190602 A CN 96190602A CN 1171642 C CN1171642 C CN 1171642C
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C·弗里曼
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D·L·吉克森
M·卡拉克里
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A·R·里伯奥夫
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Abstract

公开了改进的、高折射指数的、伸长率为至少150%的丙烯酸类材料。这些特别适用作眼内透镜材料的材料含有两种主要单体：芳基丙烯酸类疏水单体和亲水单体。

Description

改进的高折光指数眼科透镜材料
发明领域
本发明涉及改进的眼科透镜材料。尤其是涉及特别适合用作眼内透镜(IOL)材料的柔软、高折光指数的眼科透镜材料。
发明背景
随着近来小切口白内障手术的发展，人们越来越多地强调发展适用于人工透镜的柔软、可折叠的材料。一般，这些材料分成三类：水凝胶、硅氧烷和丙烯酸类。
一般，水凝胶材料具有较低的折光指数，要达到给定的折光能力，光学透镜必须较厚，这使得水凝胶和其它材料相比，不能满足需要。硅氧烷材料通常比水凝胶具有较高的折光指数，但在以折叠状态被置于眼中以后，会倾向于迅速展开。迅速的展开有可能破坏角膜内皮和/或使人眼的透镜囊破裂。丙烯酸类材料是所需的，因为它们总是有较高的折光指数，并且与硅氧烷材料相比可以较慢地或可控制地展开。
美国专利No.5,290,892公开了一种适于用作眼内透镜的丙烯酸类材料。这些丙烯酸类材料含有两种芳基丙烯酸类单体作为主要组分。由这些丙烯酸类材料制成的眼内透镜，在通过小切口插入时可以被卷曲或折叠。
美国专利No.5,331,073也公开了一种柔软的丙烯酸类眼内透镜材料。这些材料包含两种由它们各自均聚物的性质定义的丙烯酸单体作为主要组分。第一种单体是其均聚物的折光指数值至少为约1.50的单体。第二种单体是其均聚物的玻璃化转变温度小于约22℃的单体。这些眼内透镜材料还包含一种交联组分。此外，这种材料可以非必要地含有区别于前三个组分的第四组分，它衍生自亲水单体。这种材料优选具有总共低于约15％(重量)的亲水组分。
发明概要
现已发现不仅可用作眼内透镜，而且可用作其它眼科设备如接触透镜、角膜修复(kervatoprosthes)以及角膜环或内镶物的改进的柔软、可折叠丙烯酸类透镜材料。这些材料仅含有两种主要组分：一种芳基丙烯酸类疏水单体和一种亲水单体。本发明的材料为包含至少90％(重量)的这两种主要单体组分的共聚物，条件是亲水组分的量不大于芳基丙烯酸类疏水组分的量。材料剩余部分包括至多10％(重量)的一种或多种添加组分，例如交联剂、紫外光吸收剂和蓝色光吸收剂组分。
在其它方面，本发明基于如下发现，适用于可折叠眼内透镜材料的丙烯酸类共聚物可仅用一种主要丙烯酸类疏水单体和一种主要亲水单体共聚合成。
在其它方面，本发明还基于如下发现，不同于其它适用于眼内透镜材料的丙稀酸类共聚物，本发明的共聚物在生理环境中基本上是不闪光的。
发明的具体描述：
本发明的改进丙烯酸类材料是包括仅两种主要单体组分的共聚物：一种芳基丙稀酸类疏水组分和一种亲水组分。
适用于本发明材料中的芳基丙烯酸类疏水单体如下式所示
Figure C9619060200071
式中，X为H或CH3；m为0-6；Y可以没有，可以是O、S或NR，其中R是H、CH3、CnH2n+1(n＝1-10)、异-OC3H7、C6H5或CH2C6H5；和Ar是非取代的芳香环或被基团H、CH3、C2H5、正-C3H7、异-C3H7、OCH3、C6H11、Cl、Br、C6H5或CH2C6H5取代的芳香环。
上述结构式的单体描述于美国专利No.5,290,892中，其全部内容在这里被引作参考。适用于本发明材料的芳基丙烯酸类疏水单体优选为其中m为2-4、Y没有或是O、Ar是苯基的那些疏水单体。最优选的是丙烯酸2-苯基乙酯和甲基丙烯酸4-苯基丁酯。
适用于本发明的芳基丙烯酸类疏水单体的均聚物具有小于3％(重量)、优选小于2％(重量)的平衡水含量，其量由环境条件下在去离于水中重量分析确定。
适用于本发明的亲水单体含有至少一个不饱和反应性官能基团。不饱和反应性官能基团优选为乙烯基、丙烯酸酯或甲基丙烯酸酯基团。
适用于本发明材料中的亲水单体的均聚物具有至少10％(重量)、优选至少25％(重量)的平衡水含量，其量由环境条件下在去离子水中重量分析确定。
适用于本发明中的亲水单体包括：丙烯酸2-羟乙酯；甲基丙烯酸2-羟乙酯；2-N-丙烯酸乙酯吡咯烷酮；丙烯酸2-羟基-3-苯氧基丙酯；丙烯酸2，3-二羟基丙酯；甲基丙烯酸2，3-二羟基丙酯；2-N-乙烯基吡咯烷酮；聚氧化乙烯：200单甲醚的单甲基丙烯酸酯；聚氧化乙烯：200的单甲基丙烯酸酯；聚氧化乙烯：1000的二甲基丙烯酸酯。
优选的适用于本发明的亲水单体包括丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯以及聚氧化乙烯：1000的二甲基丙烯酸酯。
本发明的材料为含有总计约90％(重量)的上述两种主要组分的共聚物，条件是亲水组分的量不大于芳基丙烯酸类疏水组分的量。
本发明的共聚物材料是交联的。适用于本发明共聚物中的可共聚的交联剂可以是任何具有一个以上不饱和基团的终端烯属不饱和化合物。也可以使用多种交联单体的混合物。适宜的交联剂例如包括：二甲基丙烯酸乙二醇酯，二甲基丙稀酸二甘醇酯，甲基丙烯酸烯丙酯，二甲基丙烯酸1，3-丙二醇酯，甲基丙稀酸烯丙酯，二甲基丙烯酸1，6-己二醇酯，二甲基丙烯酸1，4-丁二醇酯等。优选的交联剂为二丙烯酸1，4-丁二醇酯(BDDA)。通常，交联组分的量为至少0.1％(重量)。
除芳基丙烯酸类疏水单体、亲水单体以及一种或多种交联组分外，本发明的透镜材料也可以包含总计至多10％(重量)的、有其它作用的添加组分，例如聚合引发剂以及反应性的紫外线和/或蓝色光吸收剂。
优选的聚合引发剂为过氧化物自由基引发剂，例如叔丁基(过氧化-2-乙基)己酸酯和过氧化二碳酸二(叔丁基环己基)酯(Perka-dox16，购自Akzo chemical Inc.Chicago.Illnois)。引发剂用量为约5％(重量)或更少。
优选的反应性紫外线吸收剂为2-(2′-羟基-3′-甲代烯丙基-5′-甲基苯基)苯并三唑(O-甲代烯丙基Tinuvin P(“oMTP”)，购自Polysciences，Inc.，Warrington，Pennsylvania)。紫外线吸收剂的存在量为约0.1-5％(重量)。
适宜的反应性蓝色光吸收剂化合物为描述于普通受让的、共同待批的美国专利申请流水号08/138,663中的那些引发剂，其全部内容在这里被引为参考。蓝色光吸收剂存在量为约0.01-0.5％(重量)。
上述两种主要单体的特定组合以及任一添加组分的确定和其用量由最终完成的眼科透镜的所需性能决定。所选的组分和其比例优选应使本发明改进的丙烯酸类透镜材料具有如下性质，以使本发明材料特别适用于将通过5mm或更小的切口而被插入的眼内透镜。
更具体地，本发明提供一种眼内透镜，其光学元件部分含有约80％(重量)的丙烯酸2-苯基乙酯、约15％(重量)的甲基丙烯酸2-羟乙酯、交联单体、紫外线吸收剂和聚合引发剂。
透镜材料的折光指数优选为至少约1.50，其值由阿贝折光仪于589nm处测定(钠光源)。由折光指数小于1.50的材料制成的镜片必定比由折光指数较高材料制成的、具有相同折光能力的镜片要厚。由此，由折光指数小于1.50的材料制成的眼内透镜镜片在其植入时通常需要较大的切口。
透镜材料的玻璃化转变温度(“Tg”)(它影响材料的折叠和展开特性)优选为约-20～+25℃，更优选约-5～+16℃。Tg由差示扫描量热仪在10℃/min下测定，其值由热熔曲线转变的中点值决定。
透镜材料应具有至少150％、优选至少200％、更优选300-600％的伸长率。这一性质表明透镜在折叠时通常不会断裂、撕裂或裂开。聚合物样品的伸长率由哑铃形拉伸试样测定，试样总长20mm，夹紧区长4.88mm，试样总宽2.49mm，窄部宽0.833mm，圆角半径8.83mm，厚0.9mm。试样测试在23±2℃及50±5％相对湿度的标准实验室条件下，使用带有2000g荷载的Instron 1122型材料试验机进行。夹持距离设置为14mm，十字头速度设置为20mm/min，试样被拉伸至700％伸长或直至被破坏。伸长(应变)值就是试样被破坏时的位移与最初夹持距离之比。在应力—应变曲线上，100％应变处的斜率值即是模量。应力值取试样的最大承受载荷，通常是试样断裂时的载荷。
本发明的透镜材料在生理环境中基本上是不闪光(glistenings)的。闪光是透镜内水蒸汽凝结的结果。虽然闪光对由丙烯酸类材料制成的眼内透镜的功能没有什么不利的影响，但出于美观人们还是希望最大限度地减小或消除它。一般生理温度为约37℃。该温度下在潮湿或液态环境中，本发明材料基本上不闪光。很难量化什么是“基本上不闪光”。然而为提供一些参考框架，这里所用的“基本上不闪光”通常意味着，以下述测试方法计算，材料平均不超过约1-2个闪光点/mm2。一般，这一平均值将远小于1。
存在闪光点的测定是将透镜试样放置在一个充满去离子水的测试室当中，为目测将玻璃在该室的底部和顶部滑动。为目测将该测试室放置于37±1℃的水浴中7±1和14±2天。然后将该室放置在加热的显微镜平台上，温度为37±1℃，在40～200放大倍数下观察透射光。
由本发明材料制做的眼内透镜可任意设计，它们可以被卷曲或折叠成很小的截面以能够通过较小的切口。例如，眼内透镜可以是众所周知的单片或多片设计，并且包含光学和接触元件。光学元件是起透镜作用，而接触元件象胳膊一样附在光学元件上保证其在眼中处于合适的位置。光学和接触元件可由相同或不同材料制成。之所以被称作“多片透镜”，是因为光学元件和接触元件是分别制成的，然后将接触元件附在光学元件上。在单片透镜中，光学元件和接触元件是由一片材料形成的。基于材料，从材料中切出或车出接触元件形成眼内透镜。
除眼内透镜外，本发明材料也可适用于其它眼科设备，如接触透镜、角膜修复以及角膜环或角膜内镶物。
本发明将通过下面的实施例进一步说明，但这些实施例是说明性的而非限制性的。
下面表1所示的实施例1-8说明本发明的材料。实施例1-8中的每一配方均按如下方式制备，所用的所有反应性单体基本上无阻聚剂。将表1所列的配方组分混合后，每一配方均通过搅拌混合，经0.2μm聚四氟乙烯过滤器纯化，然后按下述注入到一个聚丙烯眼内透镜模或一个25×12×1mm的片模中。将眼内透镜模具的底部的腔充满，然后将眼内透镜模具的上部置于底部之上，并且通过配对的、机制成的阴阳槽锁定。为制成片，片模底部的腔先被充满配料，然后上部严格密封置于其上。模具可以在惰性氮气下、或可在标准实验室气氛下被充满。在固化过程中为保持模的几何形状，在模上使用一种弹簧夹紧装置。将被夹紧的模放入对流空气炉内，并用表1所列的固化条件固化。在聚合过程结束时，将模具打并将固化的眼内透镜或聚合物片取出，用丙酮萃取出任何未反应完的原料。
按测试规程，用透镜或片材作为合适的试样，评价表1所示的固化材料的物理性能(按照上述的操作规程)。列出的所有配方制得的样品基本上均不含气泡。
                                                                   表1
                                                                     实施例
组分 1 2 3 4 5 6 7 8
HEA 30 35
  HEMA   9.8  11.8   14.7
  PEA 63.5 58.5   83.5  81.5   78.6
  PEMA 63.1
  4-PBMA   84   87.6
  PEO   9.6
  PEGMEMA 29.1
  BDDA 3.1 5 5   3.1  3.1   3.1
  OMTP   0.6   1 1.7 0.5 0.5   1.8  1.8   1.8
  AMA   29
  TEGDA   1.5
  DDDA
  GMMA   7.2
  P16   1.8  1.8   1.8
  tBPO 1 1
  BP   2.9   2.7 2.9
  固化   2小时/80℃+3小时/100℃   2小时/80℃+3小时/100℃ 2小时/80℃+3小时/100℃ 1小时/35℃-1小时/50℃-2小时/100℃ 1小时/35℃-1小时/50℃-2小时/100℃   10分钟内由25℃升至70℃，保持7小时，在30分钟内升至100℃，保持7小时  10分钟内由25℃升至70℃，保持7小时，在30分钟内升至100℃，保持7小时   10分钟内由25℃升至70℃，保持7小时，在30分钟内升至100℃，保持7小时
  玻璃化温度   8.5   15.1 10.7 0 0   10  10   11
  应力   1276   1439 1320 724 681   982  1000   1230
  应变％   461   246 343 392 392   640  610   610
  模量   362   1250 623 91 89   97  141   212
  折光指数(干)折光指数(湿)   1.53781.5295   1.5409 1.5337 1529 1.526   1.5441.544  1.5441.543   1.5431.540
HEA：丙烯酸2-羟乙酯
HEMA：甲基丙烯酸2-羟乙酯
PEA：丙烯酸2-苯基乙酯
PEMA：甲基丙烯酸2-苯基乙酯
4-PBMA：甲基丙烯酸4-苯基丁酯
AMA：甲基丙烯酸丙酯
PEO：聚氧化乙烯：1000的二甲基丙烯酸酯
oMTP：o-甲代烯丙基Tinuvin P
BP：过氧化苯甲酰
DDDA：二丙烯酸1，12-十二烷二醇酯
GMMA：甲基丙烯酸2，3-二羟丙酯
TEGDA：二丙烯酸三甘醇酯
BDDA：二丙烯酸1，4-丁二醇酯
PEGMEMA：聚氧化乙烯：200单甲醚的单甲基丙烯酸酯
tBPO：叔丁基(过氧化-2-乙基)己酸酯
P16：过氧化二碳酸二-(4-叔丁基环己基)酯
实施例9：亲水单体丙烯酸2-羟基-3-苯氧基丙酯的合成
将1，2环氧基-3-苯氧基丙烷(50g)、丙烯酸(48g，100％过量)、1，4-苯醌(0.082g)和四甲基溴化铵(1.8g)置于烧瓶中，于110-120℃搅拌条件下加热两小时。反应完后，将挥发性物质在100℃、0.1-0.2mmHg的条件下真空蒸馏掉。然后将粗产物在釜温170-175℃下蒸馏。将单体溶解在Mecl中，用1％NaOH碱洗涤后接着用水洗。然后将此溶液用无水硫酸镁干燥。通过#4滤纸过滤，将溶剂在50℃下在rot-o-vap上汽提。
实施例10：亲水单体丙烯酸2-吡咯烷酮-N-2-乙酯的合成
第1步：N-(2-羟乙基)-2-吡咯烷酮(NHEP)的合成
在配有斜冷凝器和冷凝物接收器的250ml烧瓶中，加入107.7g2-氨基乙醇和126.6g丁内酯。室温下几分钟后发生剧烈的放热反应，温度最高达115℃。放热结束后，将烧瓶置于195-200℃的硅油浴中22.5小时，收集馏出物(主要是水)。然后将产物于115-150℃、在高真空(0.1-0.15mmHg)下去除挥发性物质。然后升温至170-190℃，将产物(NHEP)蒸馏出。
第2步：丙烯酸2-吡咯烷酮-N-2-乙酯(NEAP)的合成
在配有斜冷凝器和冷凝物接收器的颈口63的500ml烧瓶中加入71g NHEP、125g丙烯酸甲酯、4.1g吩噻嗪和2.4g钛酸四丁酯。将装有物料的烧瓶置于105-108℃的硅油浴中并收集丙烯酸甲酯和甲醇的共沸物。反应釜持续搅拌，反应21小时后，在65℃和rot-o-vap下丙烯酸甲酯和甲醇共沸物被汽提出，向烧瓶中再加入120g新丙烯酸甲酯并将反应持续至总反应时间48小时。(如上述)rot-o-vap下再次将丙稀酸甲酯和甲醇共沸物汽提出。然后将粗产物NEAP置于65℃和高真空下汽提出剩余丙烯酸甲酯和甲醇共沸物。将产物在140-150℃、0.1mmHg下蒸馏(直接接收)。
第3步：最后纯化
将50g A941-500活性-I碱式氧化铝(60-325目)加入到分离柱中并用苯淋洗。将NEAP馏出物用苯稀释50％(重量)并置于分离柱中，随之再加入苯。共收集412g洗脱液并于60℃将苯在ro-tovap汽提，然后于22℃保持高真空30分钟。加入足量去离子水于NEAP中制得30％的单体溶液；接着大部分吩噻嗪沉淀出来。溶液过滤后每次用100ml醚萃取，共三次，以去除微量的吩噻嗪。然后在室温和高空气流速中、接着在室温和高真空下保持2小时蒸去水分。

Claims (29)

1.一种伸长率至少150％的共聚物，包含总计至少90％(重量)的两种主要单体，其中一种主要单体为芳基丙烯酸类疏水单体，其结构式为：
Figure C961906020002C1
其中，X是H或CH3；
m为0-6；
Y可以不存在，可以是O、S或NR，其中R是H、CH3、CnH2n+1(n＝1-10)、异-OC3H7、C6H5或CH2C6H5；和
Ar是任何取代或非取代的芳香环，取代基H、CH3、C2H5、正-C3H7、异-C3H7、OCH3、C6H11、Cl、Br、C6H5或CH2C6H5；其均聚物具有3％或更少的平衡水含量；
另一主要单体是含有至少一个反应性不饱和官能基的亲水单体，其存在量不超过芳基丙烯酸类疏水单体的量，其均聚物具有至少10％的平衡水含量；并且
其中该共聚物还含有具有多个可聚合烯属不饱和基团的交联单体。
2.权利要求1的共聚物，其中，m为2-4，Y不存在或为O，Ar为苯基。
3.权利要求2的共聚物，其中，芳基丙烯酸类疏水单体选自丙烯酸2-苯基乙酯和甲基丙烯酸4-苯基丁酯。
4.权利要求1的共聚物，其中，亲水单体的不饱和官能基选自乙烯基、丙烯酸酯基和甲基丙烯酸酯基。
5.权利要求4的共聚物，其中，亲水单体选自丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、2-N-丙烯酸乙酯基吡咯烷酮、丙烯酸2-羟基-3-苯氧基丙酯、甲基丙烯酸2，3-二羟基丙酯、2-N-乙烯基吡咯烷酮、聚氧化乙烯：200单甲醚的单甲基丙烯酸酯；聚氧化乙烯：200的单甲基丙烯酸酯和聚氧化乙烯：1000的二甲基丙烯酸酯。
6.权利要求5的共聚物，其中，亲水单体选自丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯和聚氧化乙烯：1000的二甲基丙烯酸酯。
7.权利要求1的共聚物，它还含有一种或多种选自聚合引发剂、反应性紫外线吸收剂和反应性兰色光吸收剂的组分。
8.权利要求1的共聚物，其中，共聚物的折光指数为至少1.50。
9.权利要求1的共聚物，其中，共聚物的Tg为约-20℃至+25℃。
10.权利要求9的共聚物，其中，共聚物的Tg为约-5℃至+16℃。
11.权利要求1的共聚物，其中，共聚物的伸长率为至少200％。
12.权利要求11的共聚物，其中，共聚物的伸长率为300％-600％。
13.权利要求8的共聚物，其中，共聚物的Tg为-5℃至+16℃，伸长率为300％-600％。
14.一种眼科透镜，它含有一种伸长率至少为150％的共聚物，该共聚物含有总计至少90％(重量)的两种主要单体，其中一种主要单体为芳基丙烯酸类疏水单体，其结构式为：
Figure C961906020003C1
其中，X是H或CH3；
m为0-6；
Y可以不存在，可以是O、S或NR，其中R是H、CH3、CnH2n+1(n＝1-10)、异-OC3H7、C6H5或CH2C6H5；
Ar是任何取代或非取代的芳香环，取代基是H、CH3、C2H5、正-C3H7、异-C3H7、OCH3、C6H11、Cl、Br、C6H5或CH2C6H5；其均聚物具有3％或更少的平衡水含量；
另一主要单体是含有至少一个反应性不饱和官能基的亲水单体，其存在量不超过芳基丙烯酸类疏水单体的量，其均聚物具有至少10％的平衡水含量；并且
其中该共聚物还含有具有多个可聚合烯属不饱和基团的交联单体；
而所述透镜的闪光特性为平均不超过约1-2个闪光点/mm2。
15.权利要求14的眼科透镜，其中，该透镜是一种眼内透镜。
16.权利要求15的眼内透镜，其中，m为2-4，Y不存在或为O，Ar为苯基。
17.权利要求16的眼内透镜，其中，芳基丙烯酸类疏水单体选自丙烯酸2-苯基乙酯和甲基丙烯酸4-苯基丁酯。
18.权利要求16的眼内透镜，其中，亲水单体的不饱和官能基选自乙烯基、丙烯酸酯基和甲基丙烯酸酯基。
19.权利要求18的眼内透镜，其中，亲水单体选自丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、2-N-丙烯酸乙酯基吡咯烷酮、丙烯酸2-羟基-3-苯氧基丙酯、甲基丙烯酸2，3-二羟基丙酯、2-N-乙烯基吡咯烷酮、聚氧化乙烯：200单甲醚的单甲基丙烯酸酯、聚氧化乙烯：200的单甲基丙烯酸酯和聚氧化乙烯：1000的二甲基丙烯酸酯。
20.权利要求19的眼内透镜，其中，亲水单体选自丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯和聚氧化乙烯：1000的二甲基丙烯酸酯。
21.权利要求15的眼内透镜，它还含有一种或多种选自聚合引发剂、反应性紫外线吸收剂和反应性兰色光吸收剂的组分。
22.权利要求21眼内透镜，其中，聚合引发剂是过氧化物自由基引发剂。
23.权利要求22的眼内透镜，其中，反应性紫外线吸收剂是2-(2′-羟基-3′-甲代烯丙基-5′-甲基苯基)苯并三唑。
24.权利要求15的眼内透镜，其中该眼内透镜的折光指数为至少1.50。
25.权利要求15的眼内透镜，其中，该眼内透镜的Tg为约-20℃至+25℃。
26.权利要求25的眼内透镜，其中，该眼内透镜的Tg为约-5℃至+16℃。
27.权利要求15的眼内透镜，其中，该眼内透镜的伸长率为至少200％。
28.权利要求27的眼内透镜，其中，该眼内透镜的伸长率为300％-600％。
29.一种眼内透镜，其光学元件部分含有约80％(重量)的丙烯酸2-苯基乙酯、约15％(重量)的甲基丙烯酸2-羟乙酯、交联单体、紫外线吸收剂和聚合引发剂。
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SE9403392D0 (sv) * 1994-10-06 1994-10-06 Pharmacia Ab Intraocular lens materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI513768B (zh) * 2011-06-01 2015-12-21 Novartis Ag 疏水性丙烯酸系眼內水晶體材料

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CA2195092C (en) 2002-07-09
JP2001316426A (ja) 2001-11-13
WO1996040303A1 (en) 1996-12-19
HK1012586A1 (en) 1999-08-06
EP0774983B1 (en) 2002-12-04
KR100331456B1 (ko) 2002-10-25
DE69625161D1 (de) 2003-01-16
JPH10504059A (ja) 1998-04-14
EP0774983A1 (en) 1997-05-28
DE69625161T2 (de) 2003-04-17
AU5742896A (en) 1996-12-30
ES2183953T3 (es) 2003-04-01
ATE228862T1 (de) 2002-12-15
US5693095A (en) 1997-12-02
KR970704482A (ko) 1997-09-06
MX9701015A (es) 1997-05-31
CN1155845A (zh) 1997-07-30
JP3206004B2 (ja) 2001-09-04
TW374771B (en) 1999-11-21
PT774983E (pt) 2003-03-31
DK0774983T3 (da) 2003-03-03
CA2195092A1 (en) 1996-12-19
AU696001B2 (en) 1998-08-27

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