CN1329638A - 由聚烯烃掺混物制备的二次电池隔板和微孔膜及其制备方法 - Google Patents

由聚烯烃掺混物制备的二次电池隔板和微孔膜及其制备方法 Download PDF

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CN1329638A
CN1329638A CN99814232A CN99814232A CN1329638A CN 1329638 A CN1329638 A CN 1329638A CN 99814232 A CN99814232 A CN 99814232A CN 99814232 A CN99814232 A CN 99814232A CN 1329638 A CN1329638 A CN 1329638A
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microporous membrane
film
membrane according
ionizing radiation
ion
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CN1170877C (zh
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李相英
安秉寅
宋宪植
金明万
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LG Corp
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LG Chemical Co Ltd
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Abstract

本发明的目的是提供一种由聚烯烃掺混物制得的微孔膜、其制备方法和一种二次电池隔板,其中聚烯烃掺混物具有优异的电解质润湿性、刺穿强度和关闭性能。本发明提供一种微孔膜和制备这种微孔膜的方法,其特征在于,所述微孔膜通过流延或吹塑方法对含有两种或多种聚烯烃的掺混物模塑成膜,从而制备微孔膜;和所述微孔膜是通过退火或拉伸所得的模塑膜而制得的;为了达到以上目的在形成孔之前或之后用离子辐射照射微孔膜对其表面进行处理。而且,由于它们优异的刺穿强度、关闭特性和在强大外部电流作用下的隔板耐熔性,由这种微孔膜作为隔板的二次电池,特别是锂离子二次电池或碱性电池是更安全的;在电池组装中由于隔板的优异电解质润湿性,生产率能大大增加;而且由于薄的隔板和高的机械强度,二次电池可获得高的电荷密度。

Description

由聚烯烃掺混物制备的二次电池隔板和微孔膜及其制备方法
               相关申请的交叉参考
本申请基于1998年12月8日递交韩国工业产权局的98—53667号申请，这里引入它的内容作参考。
                     发明背景
(a)发明领域
本发明涉及到由聚烯烃掺混物制备的多孔膜、其制备方法和用于二次电池的隔板。
(b)相关技术的描述
电池隔板基本将阴极和阳极隔离开，阻止了两电极的熔融连接短路，同时允许电解质或离子通过。
虽然电池隔板自身的材料是惰性的，不影响电能的存储和输出，但是它的物理性能对电池的功能和安全性有很大的影响。此外，即使根据本领域中电池的各种化学体系和类型，当前使用了多种隔板，但因为特殊的锂二次电池要求使用与各种的传统电池所用的隔板性质不同的隔板，研究仍然在进行当中。
电池隔板所需的基本性能包括提供阴极和阳极间的物理隔离、便于电解质或离子通过的低电阻、优异的电解质润湿性、电池组装和使用所需的机械强度，提供高电荷密度所需的最小的隔板厚度等。
特别地，在电池组装过程中隔板对电解质的润湿性直接并极大地影响生产率。也就是说，将阴极、阳极和隔板缠绕起来，然后放入装有电解质的罐中组装糊状筒时，隔板润湿性应该是好的，以致于使电解质能渗透入紧紧缠绕的糊状筒中，这一点是很重要的。因此，在电池领域，通过给疏水的隔板提供亲水性能从而增加电解质的渗透率是一个重要的问题。
除了以上基本性能外，在电池组装过程中隔板直接接触有坚硬表面的阴极或阳极，或在实际应用过程中当电池经受重复的放电和充电，在电池内部形成树枝状晶体时，在隔板上能形成引起短路的瑕疵。为了阻止这种情况发生，隔板的刺穿强度应该是足够高的。
作为不同于电池隔板以上基本性能的特定性能、隔板的安全性是相当必要的，因为正如在外部短路中，当大量的电流流过时，这个特征通过隔板的微孔闭合，使电池通路断开。
由隔板微孔的闭合引起的电池断路现象称作“隔板关闭”。而且在微孔闭合后温度上升的过程中防止隔板的熔化也是非常重要的。
隔板完全关闭之后电流应该为零。然而这种情况极少发生，因为即使在隔板关闭开始后温度仍会稳定地升高到一定程度，所以实施关闭并同时控制温度增加是困难的。当隔板太早变形，电极会直接熔融，这是非常危险的。因此，在熔融温度以上总是使隔板维持其形状是相当重要的。
隔板材料是影响隔板安全特征如关闭性能和抗熔融性的一个因素。虽然聚乙烯熔点低，其早期关闭特点使得其易于抑制与微孔关闭相关的温度增加，所以它主要用在当前的锂离子电池中，但是它有机械性能差的缺点。
然而，根据所需的隔板关闭性能、抗熔融性和机械性能，有时聚乙烯同聚丙烯一起使用。
欧洲专利715,364、718,901、723,304和美国专利5,240,655、5,342,695和5,472,792及日本待审的公开专利4-181651等中公开了通过层压聚乙烯和聚丙烯制备锂离子电池隔板的方法。
然而，这种方法有缺点，因为难于制备薄的隔板，处理工艺是精密的，且由于层间的粘合力弱，聚乙烯层容易与聚丙烯层脱层。
另外，美国专利5.385,777和5,480.745介绍了使用聚乙烯和聚丙烯掺和底物制备微孔膜的方法。然而，很明显这种方法的实用性是不够的，因为这种方法没有商业化，其相关的润湿性也是相对较差的。
利用聚烯烃制备多孔膜的方法主要分为干法和湿法，其中对与形成大量微孔有关的拉伸过程来说，单轴和双轴方法是已知的。
虽然理论上或在实验室中可使用许多方法，但市场上得到的用于隔板的微孔膜是通过湿法利用填料或蜡和溶剂生产的和通过干法不使用溶剂生产的。湿法相对来说是熟知的，其使电池隔板具有优异的刺穿强度。
实际上，当使用各种类型的聚烯烃制备微孔膜时，在130℃产生的聚乙烯的关闭初始温度是很好的，然而机械强度不好。另一方面，聚丙烯有优异的机械强度，然而因为其关闭初始温度高于160℃，所以它存在安全问题。
本发明的综述
因此，本发明提供一种利用掺混的聚烯烃制备具有优异关闭和机械性能的微孔膜，并将其应用于二次电池隔板中以改善以上问题的方法。
而且，虽然掺和这些聚烯烃制备成微孔膜，但是它们在电池电解质中的润湿性是低的，因为它们是疏水的。因此，本发明中对微孔膜的表面进行处理以改善润湿性。
另外，在制备多孔膜的方法中，干法是不使用溶剂的简单的方法。然而，干法使电池隔板具有相对差的刺穿强度。而本发明利用干法制备了具有优异刺穿强度的微孔膜。
本发明的一个目的是提供由聚烯烃掺混物制备的具有优异电解质润湿性、刺穿强度和关闭性能的微孔膜，及其制备方法和将微孔膜应用到二次电池隔板的方法。
本发明的另一目的是用聚乙烯和聚丙烯的掺混物制备电池隔板以改善关闭性能，通过用离子辐射照射其表面改善疏水材料膜的润湿性，并且改善用干法制备的微孔膜的刺穿强度。
优选实施方案的详细描述
在如下的详细描述中，简单地通过对实施本发明的发明者所认为的最好模式的说明，只显示和描述了本发明的优选实施方案。应意识到的是，在不偏离本发明的情况下，可在各个明显的方面修改本发明。因此，本质上来说可将描述认为是说明性的，而不是限制性的。
本发明提供一种微孔膜，其特征在于，它的制备方法包括如下步骤：通过流延或吹塑用含有两种或多种聚烯烃的掺混物模塑成膜，通过退火或拉伸所述模塑膜而制成微孔膜，并进行表面处理，即在微孔形成之前或之后用离子辐射照射膜。
而且，在本发明中将由如上制备方法制备的微孔膜用作隔离锂离子二次电池或碱性二次电池的阴极和阳极的隔板。
本发明中聚乙烯包括低密聚乙烯(LDPE)，线型低密聚乙烯(LLDPE)，高密聚乙烯(HDPE)等，其中树脂有0.05-60g/(10min)的熔体指数，聚丙烯有0.5-20g/(10min)的熔体指数。
本发明的掺混物包括重量比为1∶9至9∶1的高熔点聚丙烯和低熔点聚乙烯的混合物。而且，为了改善隔板的功能，可将适当数量的添加剂加入掺混物中。这些添加剂包括抗氧剂、增塑剂、阻燃剂、颜料、相容剂等。
用适当的混合机器如密炼机或双螺杆挤出机等将聚丙烯、聚乙烯和必要的添加剂掺和在一起。
利用热塑性树脂的一般的模塑膜方法如流延或吹塑将所得的掺混物模塑成膜。
虽然对于模塑膜没有任何特殊的限制，但优选较低的处理温度，牵伸比通常大于20，牵伸速度优选10至100米/分，其中牵伸比是卷绕速度除以口模中树脂的线速度的值。
为了将结晶度和弹性恢复比增加到50％以上，进行退火。退火可利用如下方法：将膜粘附到受热的金属盘上的方法，膜在烘箱中加热的，在烘箱内部或外部通过在辊上缠绕或不缠绕膜用远红外线辐射加热膜的方法，或用如聚对苯二甲酸乙二醇酯膜双层缠绕辊，并在烘箱中加热辊的方法等。退火温度设定在低于膜熔点约50℃的温度和熔点之间，或通过分阶段改变温度而调节。多于30秒的退火时间是有益的。当退火时间少于10秒时，因为膜退火不够的，弹性恢复比率的增加是不明显的。
利用如下两种方法通过拉伸工艺可将由如上退火方法得到的膜制备成有微孔的微孔膜。
首先，在膜的玻璃化转变温度到比具有最低熔点的聚乙烯的熔点低45℃的温度范围内将膜单轴或双轴拉伸至前体膜的10至120％，然后，一边在低于聚乙烯熔点45℃的温度至聚丙烯的熔点温度范围内升高温度，一边拉伸至前体膜的50至170％。
拉伸完成后，将温度固定在5℃或比聚丙烯膜的熔点更低，而将膜维持在一种施加张力的状态，也可以收缩至前体膜的5至100％。
在如上退火过程的之前或之后和拉伸过程的中间或之后通过离子辐射照射进行膜表面处理。
本发明使用离子束，其中一种或多种含能离子颗粒选自于电子、氢、氧、氦、氟、氖、氩、氪、空气和N2O。
而且，当发射离子辐射时同时引入反应气体，一种或多种反应气体是选自于氢气、氧气、氮气、氨气、一氧化碳、二氧化碳、四氟化碳、甲烷和N2O。
不仅离子束，而且咖吗(γ)射线、等离子体、电子束等都能用于离子辐射的发射。
如上所提及的方法描述了制备具有最佳物理性能的隔板的总过程，其中根据所需的最终物理性能可以忽略部分步骤或增添额外的步骤。已测定了使用如上方法制备的微孔膜的如下物理性能：1〕厚度2〕空气渗透性：JIS P 81173〕孔隙率：美国材料试验协会(ASTM)D28734〕孔径：汞孔度计5〕拉伸强度和拉伸模量：ASTM D8826〕刺穿强度7〕关闭温度8〕熔融温度9〕润湿性：基于含有1摩尔LiPF6和碳酸二甲酯的碳酸亚乙酯混合物的相对渗透率。
实施例
实施例1
在双螺杆挤出机中混合后，得到70wt％的熔体指数为2.0g/(10min)、熔点为164℃的聚丙烯和30wt％的熔体指数为3.0g/(10min)、熔点为128℃的聚乙烯的掺混物，利用带T-口模的单螺杆挤出机和卷绕设备制备前体膜。所用的挤出温度是200℃，牵伸比是132。
在干燥炉中于110℃的温度下将制得的前体膜退火10分钟。
用辊拉伸的方法，在室温下将上述膜单轴拉伸至伸长率为前体膜长度的60％。
在完成室温拉伸后，在80℃下用退火辊将膜再拉伸到前体膜长的180％。
完成拉伸后，在利用100℃下的退火辊装置提供的拉伸状态下，加热膜两分钟，然后冷却形成微孔膜。
将所得的微孔膜置于10-5至10-6乇的真空室中，用离子枪在膜的两边发射氩离子颗。离子束能量和离子发射量分别为是2keV和1018个离子/平方厘米。
制得的微孔膜的物理性能如表1所示。
实施例2
用与实施例1相同的方法制备前体膜，在干燥炉中于75℃的温度下将前体膜退火15分钟。
在与实施例1相同的条件下通过离子照射的方法表面处理这种膜，通过与实施例1相同条件下的拉伸方法在室温和高温下拉伸膜以获得微孔膜。
制得的微孔膜的物理性能如表1所示。
实施例3
用与实施例1相同的方法制备前体膜，将所得的前体膜置于10-5至10-6乇的真空室中，用离子枪在膜的两边发射氩离子(Ar+)颗粒。离子束能量和离子照射量各为2keV和1012个离子/平方厘米。
如实施例2所述，将所得的膜在干燥炉中于75℃的温度下退火15分钟。通过与实施例1相同条件下的拉伸方法在室温和高温下拉伸膜以获得微孔膜。
制得的微孔膜的物理性能如表1所示。
实施例4
在双螺杆挤出机中混合45wt％的熔体指数为2.0g/(10min)，熔点为164℃的聚丙烯和55wt％的熔体指数为1.0g/(10min)，熔点为134℃的聚丙烯后，用带T-口模的单螺杆挤出机和卷绕设备制备前体膜。使用的挤出温度是210℃，牵伸比为170。
制得的前体膜在干燥炉中90℃下退火1分钟。
用辊拉伸的方法，在室温下将上述膜单轴拉伸到伸长率为前体膜长度的30％。
在完成室温拉伸后，在100℃下用退火辊将膜再拉伸到前体膜的180％。
完成这一拉伸后，在用退火辊(固定温度在100℃)使膜处于应力状态下，加热膜1分钟，膜再次收缩为前体膜长的60％，冷却可得到微孔膜。
将得到的微孔膜放入真空度为10-5到10-6乇的真空室中，以4ml/min的速率通入反应性氧气，使其分布于膜的周围，并用离子枪发射氢离子颗粒(H2 +)到膜的两面对膜进行表面处理。离子束能量和离子发射量分别为0.3keV和1018个离子/平方厘米。
制得的微孔膜的物理性能如表1所示。
实施例5
通过与实施例4相同的方法制得前体膜后，在80℃下于干燥炉中对这个前体膜退火15分钟。
除了使用反应性的CO2气体与实施例4不同，使用与实施例4相同条件的离子发射方法进行表面处理后，使用与实施例4具有相同条件的拉伸方法在室温和高温下对膜进行拉伸，从而得到微孔膜。
制得的微孔膜的物理性能如表1所示。
实施例6
通过与实施例4相同的方法制得前体膜后，将这一前体膜放入真空度为10-5到10-6乇的真空室中，以4ml/min的速率通入反应性氧气，使其分布于膜的周围，并用离子枪发射氢离子颗粒(H2 +)到膜的两面对膜进行表面处理。离子束能量和离子发射量分别是0.3keV和1015个离子/cm2。
按照实施例4的条件，在90℃下，在干燥炉中对制得的膜退火1分钟。使用与实施例1具有相同条件的拉伸方法在室温和高温下对膜进行拉伸，从而得到微孔膜。
制得的微孔膜的物理性能如表1所示。
实施例7
在双螺杆挤出机中混合60wt％的熔体指数为1.0g/(10min)，熔点为161℃的聚丙烯和40wt％的熔体指数为0.5g/(10min)，熔点为125℃的聚乙烯后，用带T-口模的单螺杆挤出机和卷绕设备制备前体膜。所用挤出温度为237℃，牵伸比为85。
制得的前体膜于120℃下在干燥炉中退火1分钟。
用辊拉伸的方法，在60℃下，将上述膜单轴拉伸到伸长率为前体膜长度的55％。
在完成室温拉伸后，在110℃下用退火辊将膜再次拉伸到前体膜的145％。
完成这一拉伸后，使用退火辊(固定温度在150℃)使膜处于应力状态下，加热5分钟，前体膜收缩50％，冷却可得到微孔膜。
在空气中，将咖吗(γ)射线发射到制得的微孔膜上。发射量为1.5Mrad.
制得的微孔膜的物理性能如表1所示。对比例1
通过与实施例1相同的方法制得前体膜后，在65℃下于干燥炉中对这个前体膜退火10分钟。使用与实施例1具有相同条件的拉伸方法在室温和高温下对膜进行拉伸，从而得到微孔膜。
制得的微孔膜的物理性能如表1所示。对比例2
通过与实施例4相同的方法制得前体膜后，在105℃下于干燥炉中对这个前体膜退火1分钟。使用与实施例4具有相同条件的拉伸方法在室温和高温下对膜进行拉伸，从而得到微孔膜。
制得的微孔膜的物理性能如表1所示。对比例3
使用带T-口模的单螺杆挤出机和卷绕设备，用熔体指数为2.0g/(10min)，熔点为164℃的聚丙烯制备前体膜。使用挤出温度是230℃，牵伸比为120。
制得的前体膜在140℃下在干燥炉中下退火3分钟。
用辊拉伸的方法，在50℃下，将上述膜单轴拉伸到伸长率为前体膜长度的70％。
在完成室温拉伸后，在130℃下用退火辊将膜再拉伸到前体膜的140％。
完成这一拉伸后，使用退火辊(固定温度在150℃)使膜处于应力状态，加热膜5分钟，冷却可得到微孔膜。
将得到的微孔膜放入真空度为10-5到10-6乇的真空室中，用离子枪发射氩离子颗粒(Ar+)到膜的两面对膜进行表面处理。离子束能量和离子发射数量分别是0.6keV和1017个离子/平方厘米。
制得的微孔膜的物理性能如表1所示。对比例4
使用带T-口模的单螺杆挤出机和卷绕设备，用熔体指数为3.0g/(10min)，熔点为128℃的聚乙烯制备前体膜。所用挤出温度为200℃，牵伸比为155。
制得的前体膜100℃下在干燥炉中下退火15分钟。
用辊拉伸的方法，在0℃下，将上述膜单轴拉伸到伸长率为前体膜长度的30％。
在完成上述拉伸后，在100℃下用退火辊将膜再拉伸到前体膜长度的170％。
完成这一拉伸后，使用退火辊(固定温度在110℃)使膜处于应力状态，加热膜5分钟，冷却可得到微孔膜。
将得到的微孔膜放入真空度为10-5到10-6乇的真空室中，以8ml/min的速率通入反应性氮气，使其分布于膜的周围，并用离子枪发射氩离子颗粒(Ar+)到膜的两面对膜进行表面处理。离子束能量和离子发射量分别是1.0keV和1015个离子/平方厘米。
制得的微孔膜的物理性能如表1所示。
表1
    分类  实施例1   实施例2   实施例3  实施例4  实施例5  实施例6 实施例  对比例1  对比例2  对比例3  对比例4
   膜厚(μm)  25   25   25  25  25  25  27  25  25  27  25
   孔径(μm)  0.05   0.04   0.04  0.06  0.05  0.05  0.04  0.04  0.05  0.03  0.07
   孔隙率(％)  39   36   36  41  37  36  38  36  35  40  44
   透气率(sec/100cm3)  580   670   650  600  750  740  840  660  735  630  490
   刺穿强度(g)  460   455   470  430  410  460  510  410  375  480  310
   拉伸强度(kgf/cm2) 1650 1480 1610 1520 1390 1490 1710 1300 1150 1800 1160
   拉伸模量(kgf/cm2)  9800   9300   9500  8600  8100  8400  11200  8100  6400  10800  8400
   关闭温度(℃)  142   141   142  134  133  135  136  141  134  165  130
   熔融温度(℃)  176   170   169  164  164  164  172  169  161  168  134
   润湿性EC/DMC＝4/6                  △  ○  △  ○
   润湿性EC/DMC＝5/5     ○   ○    ○  ○  ○  ×  △  ×  △
   润湿性EC/DMC＝6/4  ○   △   △    △  △  △  ×  ×  ×  ×
   润湿性EC/DMC＝7/3  △   ×   ×  ○  ×  ×  ×  ×  ×  ×  ×
：润湿性非常好；
○：润湿性好；
△：润湿性一般；
×：润湿性差。
根据本发明制得的聚烯烃掺混物制得的微孔膜有非常好的电解质润湿性，刺穿强度，及关闭性能，且由于这种膜可以由掺混物浇铸成单层，所以隔板的厚度可以进一步降低。
进一步地说，用这种微孔膜作为隔板的二次电池具有卓越的刺穿强度，关闭性能，且在通入大的电流时隔板具有抗熔融性，因而是安全的。进一步地，由于隔离电解质极好的润湿性，这种电池在制作过程中容易达到高的生产率。此外，用作隔板的这种微孔膜厚度薄，且隔板机械强度高，因而可能达到高的电荷密度。
尽管已参照优选实施方案对本发明进行了详细描述，但本领域的熟练人员仍可以在不背离所附根据权利要求的宗旨和范围的情况下，对本发明作各种修改和取代。

Claims (19)

1.一种通过下列步骤制备的微孔膜：
a)通过流延或吹塑将含有两种或多种聚烯烃的掺混物模塑成膜；
b)通过退火或拉伸模塑膜制成微孔膜；
c)在形成孔之前或之后用离子辐射照射对微孔膜表面进行处理。
2.根据权利要求1所述的微孔膜，其中所述掺混物包含熔点相差10℃以上的两种或多种聚烯烃混合物。
3.根据权利要求1所述的微孔膜，其中所述掺混物包含由高熔点的聚丙烯和低熔点的聚乙烯以1∶9到9∶1的重量比混合而成的混合物。
4.根据权利要求1所述的微孔膜，其中在所述膜的一面或两面用离子辐射进行表面处理。
5.根据权利要求1所述的微孔膜，其中离子辐射的表面处理辐照方法通过将含能离子颗粒在真空条件下辐照到膜上而提高了膜的亲水性和/或机械性能。
6.根据权利要求1所述的微孔膜，其中离子辐射的表面处理辐照方法在真空条件下通入反应性气体，通过将含能离子颗粒发射到膜上改善了膜的亲水性和/或机械性能。
7.根据权利要求5或6所述的微孔膜，其中一种或多种含能离子颗粒选自于电子、氢、氧、氦、氟、氖、氩、氪、空气和N2O。
8.根据权利要求6所述的微孔膜，其中一种或多种反应气体选自于氢气、氧气、氮气、氨气、一氧化碳、二氧化碳、四氟化碳、甲烷和N2O。
9.根据权利要求1所述的微孔膜，其中离子辐射选自离子、咖吗(γ)射线、等离子体、电子束。
10.一种包括下列步骤的制备微孔膜的方法：
a)通过使用T-模挤出机或吹塑将含有两种或多种聚烯烃的掺混物模塑成膜；
b)通过退火或拉伸模塑膜制备微孔膜；
d)在形成孔之前或之后用离子辐射照射对微孔膜表面进行处理。
11.根据权利要求10所述的制备微孔膜的方法，其中所述掺混物包含熔点相差10℃以上的两种或多种聚烯烃混合物。
12.根据权利要求10所述的制备微孔膜的方法，其中所述掺混物包含由高熔点的聚丙烯和低熔点的聚乙烯以1∶9到9∶1的重量比混合而成的混合物。
13.根据权利要求10所述的制备微孔膜的方法，其中在所述膜的一面或两面用离子辐射进行表面处理。
14.根据权利要求10所述的制备微孔膜的方法，其中离子辐射的表面处理辐照方法通过将含能离子颗粒在真空条件下辐照到膜上而提高了膜的亲水性和/或机械性能。
15.根据权利要求10所述的制备微孔膜的方法，其中离子辐射的表面处理辐照方法在真空条件下通入反应性气体，通过将含能离子颗粒发射到膜上改善了膜的亲水性和/或机械性能。
16.根据权利要求14或15所述的制备微孔膜的方法，其中一种或多种含能离子颗粒选自于电子、氢、氧、氦、氟、氖、氩、氪、空气和N2O。
17.根据权利要求15所述的制备微孔膜的方法，其中一种或多种反应气体选自于氢气、氧气、氮气、氨气、一氧化碳、二氧化碳、四氟化碳、甲烷和N2O。
18.根据权利要求10所述的制备微孔膜的方法，其中离子辐射选自离子、咖吗(γ)射线、等离子体、电子束。
19.含有如权利要求10制备的微孔膜的锂离子二次电池隔板或碱性二次电池隔板。
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CN105355812A (zh) * 2015-12-14 2016-02-24 苏州锂盾储能材料技术有限公司 一种锂电隔膜的制备方法
CN105355812B (zh) * 2015-12-14 2018-06-19 苏州锂盾储能材料技术有限公司 一种锂电隔膜的制备方法
CN115483499A (zh) * 2021-12-30 2022-12-16 青岛蓝科途膜材料有限公司 一种湿法多层复合锂离子电池隔膜及其制备方法和应用

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KR100371398B1 (ko) 2003-05-12
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JP2002531669A (ja) 2002-09-24
DE69915380D1 (de) 2004-04-08
US20060188786A1 (en) 2006-08-24
EP1157067B1 (en) 2004-03-03
EP1157067A4 (en) 2002-11-04
EP1157067A1 (en) 2001-11-28
DE69915380T2 (de) 2005-02-24
CN1170877C (zh) 2004-10-13
WO2000034384A1 (en) 2000-06-15

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