CN1351621A - 通过从聚氨酯分散液中电沉积制备的聚氨酯薄膜 - Google Patents
通过从聚氨酯分散液中电沉积制备的聚氨酯薄膜 Download PDFInfo
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Abstract
一种聚氨酯薄膜的制备方法,包括从聚氨酯分散液中将膜电沉积到底物上。本发明电沉积方法的一个优点是无需常规凝固方法中的从膜中去除凝结剂的附加步骤。另一优点是通过使用电沉积,最大程度地减少了脱水过程中必须除去的水的量。第三个优点是所得的膜比通过常规凝固技术制备的膜在厚度方面更具均匀性。本发明可应用于,例如,医药用途。
Description
本发明涉及聚氨酯薄膜,并且更具体说本发明涉及由水分散液制备的聚氨酯薄膜。
尽管表面上可与水反应,但人们早就知道多异氰酸酯聚合物可以用于制备聚氨酯含水分散液。聚氨酯分散液通常是通过链增长有机二异氰酸酯或多异氰酸酯与具有两个或多个活性氢原子的有机化合物如聚亚烷基醚二醇、聚(亚烷基醚-亚烷基硫醚)二醇、醇酸树脂、聚酯和聚酯酰胺的反应产物来制备的,经常使用有机溶剂。二异氰酸酯以化学计量过量使用,以便反应产物(也称作聚氨酯/脲/硫脲预聚物)是异氰酸酯封端的。聚氨酯预聚物制备的实例描述于US专利3,178,310、3,919,173、4,442,259、4,444,976和4,742,095。
据报导,聚氨酯分散液可用于制备如下不同物料:涂料和胶粘料(US专利4,292,226);挠性溶剂阻挡层(US专利4,431,763);粘合剂(US 4,433,095)和薄膜(US 4,501,852)。薄膜,更确切说浸渍制作薄膜的方法,可以是很多制品制作工艺的一部分。薄膜用途的实例包括手套,器官袋,避孕套,渗透袋等。尽管已知这些用途可以用聚氨酯分散液来制作,但发现常规的聚氨酯分散液有时具有不足的物理或加工性能,从而使它们不能成为这些用途的优选原料。而且,使用溶剂对某些用途具有不利影响。
聚氨酯是多元醇与多异氰酸酯的反应产物。一般来说,用于制备聚氨酯分散液的多异氰酸酯是脂族异氰酸酯,如US 5,494,960中公开的脂族异氰酸酯。也已知可以使用芳族多异氰酸酯如甲苯二异氰酸酯(TDI)和亚甲基二苯基二异氰酸酯(MDI)以及多异氰酸亚甲基多苯基酯。
已知聚氨酯薄膜通过诸如凝固和铸塑的方法来制备。尽管这些方法是经常使用的,但它们不是没有问题的。例如,在凝固方法中,经常需要通过洗涤或浸沥去除形成的膜中凝结剂的步骤。这些步骤往往导致不期望的附加脱水步骤、不期望的废物料流和增加了附加操作所带来的成本。
因此,在由水分散液制备聚氨酯薄膜的领域中,人们期望所制备的薄膜具有足以使它们在常规薄膜用途中使用的物理和加工性能。如果这种薄膜可以由分散液制备,而分散液是在不存在有机溶剂的情况下制备的,则将是更合意的。如果这种薄膜的制备中不包括不期望的额外步骤制备,则将是更加合意的。
一方面,本发明是一种聚氨酯薄膜的制备方法,包括从聚氨酯分散液中将膜电沉积到底物上。
另一方面,本发明是通过包括从聚氨酯分散液中将膜电沉积到底物上的方法制备的聚氨酯薄膜。
本发明电沉积方法的一个优点是无需常规凝固方法中的从膜中去除凝结剂的附加步骤。另一优点是通过使用电沉积,最大程度地减少了脱水过程中必须除去的水的量。第三个优点是所得的膜比通过常规凝固技术制备的膜在厚度方面更具均匀性。
本发明可应用于,例如,手套、避孕套、医药用袋、血管成形术囊、药箱、面罩、血压胶管管头。本发明还可以部分应用于与药物给药机械有关的用途中,包括导管、药管、垫圈和o-环。此外,本发明可应用于很多非医药项目,例如,非药用手套,泳帽,工具把柄,工厂用帽和塞子,挡风玻璃刮水器套,玩具气球,玩具,电器部件,覆盖膜和垫圈。
本发明的薄膜可以由足以稳定储藏但不是稳定到不能被电沉积的任何聚氨酯预聚物分散液来制备。分散液可以按任何方式来制备,以便得到的分散液可以用来制备对薄膜的预期用途来说具有可接受物理性质的薄膜。分散可以通过间歇式方法或通过连续式方法来进行。如果通过间歇式方法来进行,优选,通过反相工艺来进行分散,其中首先将少量水,包括少量阴离子表面活性剂,添加到连续预聚物相中并且混合,然后加入更多的水,同时混合,直至相反转。
当通过连续式方法制备本发明的分散液时,优选通过高内相比(HIPR)工艺来制备。这种工艺是已知的并且公开于例如US专利5,539,021(Pate等)和WO98/41552 A1(Jakubowski等)。当通过任一种方法制备时,所得的分散液应当具有足够使分散液稳定的颗粒尺寸。本发明分散液的颗粒尺寸为0.9-0.05,优选0.5-0.07并且更优选0.4-0.10微米。首选,本发明分散液的颗粒尺寸为0.15微米。
本发明的聚氨酯分散液由非离子聚氨酯预聚物制备。本发明的非离子预聚物用脂族或芳族二异氰酸酯来制备。优选,二异氰酸酯是选自MDI、TDI及其混合物的芳族二异氰酸酯。通常使用的TDI具有任何可普通获得的异构体分布。最常可获得的TDI具有80% 2,4-异构体和20% 2,6-异构体的异构体分布。本发明中,也可以使用具有其它异构体分布的TDI,但经常是在明显较高的成本下。
当本发明的配方中使用MDI时,它优选具有99%-90%的P,P’异构体含量。更优选,当本发明的配方中使用MDI时,它优选具有98-92%的P,P’异构体含量。首选,当本发明的配方中使用MDI时,它优选具有94%的P,P’异构体含量。具有这种异构体分布的MDI可以在MDI加工过程中通过蒸馏来制备,它还可以通过掺混可普通获得的产物如ISONATE 125M*和ISONATE 500P*来制备。(*ISONATE 125M和ISONATE500P是Dow化学公司的商业名称)。
当使用TDI和MDI的混合物来制备本发明的预聚物时,将它们按99%MDI-80%MDI的MDI/TDI之比掺混。更优选,当使用TDI和MDI的混合物来制备本发明的预聚物时,将它们按98%MDI比90%MDI的MDI/TDI之比掺混。首选,当使用TDI和MDI的混合物来制备本发明的预聚物时,将它们按96%MDI的MDI/TDI之比掺混。优选,本发明的预聚物用MDI或用MDI和TDL的混合物来制备。更优选,本发明的预聚物用MDI作为唯一的芳族二异氰酸酯来制备。
在本发明的一个实施方案中,本发明的预聚物由包括含活性氢的物质的配方来制备。在本发明的优选的实施方案中,含活性氢的物质是二醇的混合物。二醇混合物的一个组分是具有0-25wt%环氧乙烷端基封闭的高分子量聚氧丙烯二醇。二醇混合物的另一组分是低分子量二醇。
本发明配方中的聚醚二醇可以通过制备聚醚多元醇领域的普通技术人员已知的可用于制备这种二醇的任何方法来制备。优选,聚醚二醇通过在碱性催化剂的存在下烷氧基化双官能引发剂来制备。例如,可用于本发明的聚醚是由乙二醇的两步烷氧基化获得的产物(首先是环氧丙烷,然后是环氧乙烷,在KOH作为催化剂的存在下)。
本发明预聚物配方中二醇混合物的高分子量聚醚二醇组分优选是具有0-25wt%环氧乙烷端基封闭的聚氧丙烯二醇。优选,该组分的分子量为1,000-4,000,更优选1,200-2,500,首选1,800-2,200。正如规定的,聚醚二醇被0-25%的环氧乙烷封端。优选,高分子量二醇被5-25%环氧乙烷封端,更优选,10-15%的环氧乙烷。
本发明一些预聚物配方中的低分子量二醇组分也可以是烷氧基化双官能引发剂的产物。优选,该组分也是聚氧丙烯二醇,但它还可以是混合的环氧乙烷环氧丙烷多元醇,只要所用的烷氧基化物的至少75wt%(如果存在的话)是环氧丙烷。诸如丙二醇,二甘醇,双丙甘醇等二醇也可以用于本发明的配方。预聚物配方中的低分子量二醇组分(如果存在的话)的分子量为60-750,优选62-600,首选125-500。
本发明的预聚物可以按制备聚氨酯预聚物领域的普通技术人员已知的可用于制备所说预聚物的任何方式来制备。优选,将芳族二异氰酸酯和聚醚二醇混合物放一起并且在足以制备聚氨酯预聚物的反应条件下加热。本发明预聚物配方的化学计量是使二异氰酸酯过量存在。优选,本发明预聚物的异氰酸酯含量(也已知为%NCO)为1-9wt%,更优选2-8wt%,首选3-7wt%。
当预聚物配方中的含活性氢的物质是低分子量二醇和高分子量聚醚二醇的混合物时,可选择地用双官能胺扩链剂将本发明的预聚物扩链。当预聚物配方中的含活性氢的物质是高分子量聚醚二醇并且不包括低分子量二醇时,双官能胺扩链剂不是可选择的而是必需的。优选,在制作分散液用的水中存在双官能胺扩链剂。当使用时,胺扩链剂可以是任何异氰酸酯反应性二胺或具有另外异氰酸酯反应性基团并且分子量为60-450的胺,但优选选自:胺化聚醚二醇,哌嗪,氨基乙基乙醇胺,乙醇胺,乙二胺及其混合物。优选,将胺扩链剂溶解于制作分散液用的水中。
本发明的预聚物是非离子型的。在制备本发明薄膜用的预聚物的主链中没有掺入离子型基团或没有离子型基团连接在主链上。用于制备本发明分散液的阴离子表面活性剂是外稳定剂并且不掺入到本发明薄膜的聚合物主链中。
将本发明的预聚物分散在含有表面活性剂的水中。优选,表面活性剂是阴离子表面活性剂。在制备本发明分散液的实践中,优选在将预聚物分散在水中之前先将表面活性剂引入水中,但将表面活性剂和预聚物同时引入水中也不超出本发明的范围。本发明中可以使用任何阴离子表面活性剂,但优选的阴离子表面活性剂是十二烷基苯磺酸钠。
本发明分散液的固形物含量可以为30wt%-60wt%。不是必须要用具有这种固形物含量的分散液来制备薄膜。尽管分散液本身是在尽可能高的固形物含量下储藏和运送以便减少储藏体积和运送成本至最低,但可按需要在最终使用之前将分散液稀释。薄膜制备的厚度通常决定着分散液中所必需的固形物含量。当制备薄膜时,本发明分散液的wt%固形物含量可以是5-60%,优选10-40%,并且制备检验手套时首选为15-25wt%。较高的固形物百分含量导致电沉积的较快沉积速度。对于其它用途,可以改变薄膜厚度和所用分散液的相应固形物含量。
对很多薄膜用途而言,所用的聚合物必须具有类似于用于那些用途中多数常规材料的物理性能。例如,对检验手套用途来说,本发明的薄膜可以具有小于5%的拉伸残余形变。本发明薄膜在诸如检验手套的用途中超过天然胶乳的一个显著优点在于本发明的薄膜具有明显较低的引起穿用手套的人们产生过敏性反应的危险。
本发明薄膜的另一个益处在于它们可以被自剥离式地制备。在制备检验手套的领域中,这种能力也已知为″不含粉末″,根据手套偶尔用一层滑石粉、玉米淀粉等制备和出售,以防止聚合物自身粘连,由此使其更容易戴上手套。本发明的薄膜可以通过在预聚物配方中包含蜡来自剥离(self-releasing)制作。优选,蜡是巴西棕榈蜡。优选,从可能不会引起与之接触的皮肤过敏性反应的蜡中选择所用的蜡。因此,本申请特别优选食用级蜡。当使用时,优选将蜡以0.1-2wt%的浓度含在用于分散预聚物配方所用的水中。
除上面提及的蜡外,本发明的薄膜中还可以包含其它添加剂。本发明的薄膜中可以使用由分散液制备薄膜领域中普通技术人员已知的任何可用的添加剂,只要它们的存在不使薄膜的性能退化到薄膜不再适合其所期待的用途便可。可以将添加剂按任何已知的可用方式掺入到薄膜中,包括(但不限于此)包含在预聚物配方中并且包含在制作分散液所用的水中。例如,可用二氧化钛来给本发明的薄膜着色。其它可用的添加剂包括碳酸钙、氧化硅、消泡剂、杀虫剂、碳颗粒等。
在使用电沉积形成本发明的聚氨酯薄膜中,通过给分散液施加电场迫使分散液颗粒向电极方向移动。颗粒在电极处聚集并且在电极上形成沉积层。如果需要,可以在电沉积之后进行可选择的致密化步骤。本发明中,通过给底物连接上电源来制作底物使它具有电荷。优选,制作具有正电荷的底物,也就是说,将其制成阳极。底物可以用任何稳定的阳极材料来制作,例如,不产生金属离子的阳极材料。稳定的阳极材料包括,例如,玻璃,陶瓷材料,石墨,各种不锈钢,掺杂锑的氧化锡以及塑料,所说的塑料是未改性的或通过添加剂制作得足够传导。
通过改变参数诸如分散液中的百分固形物、所施加的电压和处理持续期间可以控制膜厚度。
电沉积所用的电压应当选择为致使所得的膜具有特定用途所需的厚度和品质。总的来说,较高的电压导致沉积较快,并由此得到较厚的膜。优选,施加的电压对照Ag/AgCl参比电极为至少0.5V,更优选至少2.0V,并且首选至少4.0V。
作为沉积的方式,可以使用″无电压进料″、″加电压进料″或″升电压″。″无电压进料″是首先将底物放入含聚氨酯分散液的浴中,接着施加电压。″加电压进料″是将底物放下到预先施加电压的分散液浴中。″升电压″是将底物放下到低电压或没有电压的浴中,然后以设定的速率增加所施加的电压,直至达到所需的设定点。
施加的时间取决于所需的厚度、分散液浓度和施加的电压。总的来说,施加的电压越长,所得的膜越厚。所需的厚度取决于最终的用途。
可以测定膜沉积在底物上时的电流。电流降低说明膜确实正在形成,由此产生电阻并降低电流。如果需要,可以在电沉积步骤之后进行多种常规的涂布技术,如浸涂等。
以下的实施例仅出于举例说明的目的并且没有限制本发明范围的意图。除非另外说明,所有百分数以重量百分数计。
实施例
以下物料在下面的实施例中使用:·聚醚多元醇是具有12.5%环氧乙烷端基封闭的2000分子量的聚氧丙烯二醇。·低分子量二醇是425分子量的所有聚氧丙烯二醇。·多异氰酸酯A是具有98% 4,4’异构体含量和125异氰酸酯当量的MDI。·多异氰酸酯B是具有50% 4,4’异构体含量和125异氰酸酯当量的MDI。·表面活性剂是十二烷基苯磺酸钠的22%水溶液。·二胺是230分子量的聚氧丙烯二胺。
实施例1
制备聚氨酯预聚物,通过将52.0份聚醚多元醇和14.7份低分子量二醇掺混,然后将掺混物加热至50℃。然后,将该物料与29.1份多异氰酸酯A和4.2份多异氰酸酯B掺混,所说的多异氰酸酯B也加温至50℃。加入少量苯甲酰氯,以中和多元醇中残留的碱。然后,将掺混物在70℃下加热4小时,然后试验测定NCO含量。NCO含量为5.84%。
制备聚氨酯分散液,通过使用高剪切混合器在2500rpm下运转,将200g预聚物与13g水和28.5g表面活性剂掺混。缓慢加入附加的水,直至观察到相反转。加入附加的水,包括以0.15NCO化学计量浓度的二胺,直至达到固形物含量为46.6%。
聚氨酯薄膜的制备是通过将与12伏电池正端连接的镍棒浸泡到分散液中,然后电池负端的电线浸泡在分散液中。5分钟后,取出镍棒并且在环境条件下放置5分钟。然后,将镍棒在常温的蒸馏水浴中浸沥5分钟。然后将镍棒在80℃下加热90分钟。然后,从棒上剥落下膜并且在80℃下加热另外30分钟。制备测试样,并且根据使用ASTM D 412-92进行测试。试验结果显示膜的拉伸强度为1782psi;100%伸长时应力为313psi;并且断裂伸长率为540%。
实施例2-7
制备聚氨酯预聚物,通过将52.0份聚醚多元醇和14.7份低分子量二醇掺混,并且将掺混物加热至50℃。然后将该物料与已加热至50℃的29.1份多异氰酸酯A和4.2份多异氰酸酯B掺混。加入少量苯甲酰氯以中和多元醇中残留的碱。然后将掺混物在70℃下加热4小时,然后试验测定NCO含量。NCO含量为5.84%。
制备聚氨酯分散液,通过使用高剪切混合器在2500rpm下运转,将200g预聚物与13g水和28.5g表面活性剂掺混。缓慢加入附加的水,直至观察到相反转。加入附加的水,直至达到下表所示的所需固形物含量。
用涂布有Sb-掺杂氧化锡的玻璃制造透明电极。施加下表中所示的电压并且对照Ag/AgCl参比电极进行测定。反电极是1-英寸x1-英寸Pt箔。电压持续表中所示的时间,期间让聚氨酯分散液沉积在电极上。沉积之后,将电极排水2分钟,然后在70℃下干燥。所得的膜是均匀透明膜。表
实施例8
实施例 | 分散液中的%固形物 | 电压(对照Ag/AgCl) | 处理期限(分钟) | 净增重量(mg) |
2 | 5 | +2.0 | 2 | 2.3 |
3 | 46 | +2.0 | 2 | 70 |
4 | 46 | +2.0 | 2 | 70 |
5 | 46 | +2.0 | 5 | 100 |
6 | 46 | +2.0 | 2 | 57 |
7 | 46 | +4.0 | 2 | 74 |
用不锈钢制造一1英寸x1英寸的电极。前面用玻璃珠喷击清理,以产生均匀粗糙度的表面。将电极放入5%固形物含量的分散液中。将电极的电势保持在+2.0V(对照Ag/AgCl参比电极)。反电极是1英寸x1英寸Pt箔。起始电流为2.7mA。经60分钟运行后,电流缓慢降至1.2mA。将膜在70℃下干燥。
Claims (10)
1.一种聚氨酯薄膜的制备方法,包括从聚氨酯分散液中将膜电沉积在底物上。
2.权利要求1的方法,其中电沉积还包括给底物施加相对于Ag/AgCl参比电极为至少0.5V的电压;并且让聚氨酯分散液沉积在底物上。
3.权利要求1的方法,其中分散液分两步或更多步过程形成,其中
(1)第一步形成非离子型预聚物,并且在随后的步骤中,
(2)在阴离子型表面活性剂的存在下形成预聚物的水分散液,这两个步骤在基本上不存在有机溶剂的情况下进行。
4.权利要求3的方法,其中预聚物由包括二异氰酸酯和含活性氢的物质的聚氨酯预聚物配方制备。
5.权利要求4的方法,其中二异氰酸酯是其中之一:
(a)脂族二异氰酸酯;或
(b)选自MDI、TDI及其混合物的芳族二异氰酸酯;并且含活性氢的物质是其中之一:
(a)高分子量二醇和低分子量二醇的混合物;或
(b)高分子量二醇,其中当含活性氢的物质不含低分子量二醇时,将预聚物分散在含有双官能胺扩链剂的水中。
6.权利要求5的聚氨酯薄膜,其中高分子量二醇是具有0-25%环氧乙烷端基封闭的高分子量聚氧丙烯二醇。
7.权利要求1的方法,其中分散液具有颗粒尺寸为0.9微米-0.05微米。
8.权利要求1的方法,其中分散液的固形物含量为5-60wt%。
9.一种聚氨酯薄膜,含有:
通过包括从聚氨酯分散液中将膜电沉积到底物上的方法制备的膜。
10.权利要求9的聚氨酯薄膜,其中膜的形状为手套、避孕套、医药用袋、血管成形术囊或导管。
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CN00807921.8A Pending CN1351621A (zh) | 1999-04-14 | 2000-04-13 | 通过从聚氨酯分散液中电沉积制备的聚氨酯薄膜 |
Country Status (12)
Country | Link |
---|---|
US (1) | US6514572B1 (zh) |
EP (1) | EP1173494A1 (zh) |
JP (1) | JP2002542064A (zh) |
CN (1) | CN1351621A (zh) |
AR (1) | AR024253A1 (zh) |
AU (1) | AU4347700A (zh) |
CA (1) | CA2369994A1 (zh) |
CO (1) | CO5160370A1 (zh) |
MX (1) | MXPA01010349A (zh) |
NO (2) | NO20001904L (zh) |
PL (1) | PL351073A1 (zh) |
WO (1) | WO2000061652A1 (zh) |
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KR101137663B1 (ko) * | 2003-02-20 | 2012-04-20 | 인비스타 테크놀러지스 에스.에이.알.엘 | 폴리(우레아/우레탄)의 수성 분산액을 포함하는 물품 |
US20060149020A1 (en) * | 2003-04-21 | 2006-07-06 | Eduard Mayer | Polyurethane dispersion (PUD) with improved isopropanol resistance, flexibility and softness |
US7045573B2 (en) * | 2003-04-21 | 2006-05-16 | Bayer Materialscience Llc | Polyurethane dispersion (PUD) with improved isopropanol resistance, flexibility and softness |
US20040249106A1 (en) | 2003-06-03 | 2004-12-09 | Gindin Lyubov K. | Modified polyurethanes |
US8566965B2 (en) | 2011-10-31 | 2013-10-29 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles having a welded seam that possess strength and elasticity |
US9707715B2 (en) | 2011-10-31 | 2017-07-18 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles having a welded seam made from a multi-layer film |
CN103976508B (zh) * | 2014-05-24 | 2015-10-07 | 浙江奥康鞋业股份有限公司 | 耐磨耐水解的鞋垫 |
US12083387B1 (en) * | 2022-02-24 | 2024-09-10 | Topgolf Callaway Brands Corp. | High elongation golf ball coating |
WO2024047166A1 (en) * | 2022-09-01 | 2024-03-07 | Polyu Gmbh | Aqueous polyurethane dispersion, and its manufacturing method and use |
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-
2000
- 2000-04-12 NO NO20001904A patent/NO20001904L/no not_active Application Discontinuation
- 2000-04-13 CN CN00807921.8A patent/CN1351621A/zh active Pending
- 2000-04-13 JP JP2000611589A patent/JP2002542064A/ja active Pending
- 2000-04-13 CA CA002369994A patent/CA2369994A1/en not_active Abandoned
- 2000-04-13 MX MXPA01010349A patent/MXPA01010349A/es unknown
- 2000-04-13 CO CO00027497A patent/CO5160370A1/es unknown
- 2000-04-13 AR ARP000101722A patent/AR024253A1/es not_active Application Discontinuation
- 2000-04-13 EP EP00923331A patent/EP1173494A1/en not_active Withdrawn
- 2000-04-13 AU AU43477/00A patent/AU4347700A/en not_active Abandoned
- 2000-04-13 US US09/548,915 patent/US6514572B1/en not_active Expired - Fee Related
- 2000-04-13 PL PL00351073A patent/PL351073A1/xx unknown
- 2000-04-13 WO PCT/US2000/009967 patent/WO2000061652A1/en not_active Application Discontinuation
-
2001
- 2001-10-12 NO NO20014967A patent/NO20014967L/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
NO20001904L (no) | 2000-10-16 |
WO2000061652A1 (en) | 2000-10-19 |
JP2002542064A (ja) | 2002-12-10 |
PL351073A1 (en) | 2003-03-10 |
NO20014967D0 (no) | 2001-10-12 |
MXPA01010349A (es) | 2002-03-27 |
AR024253A1 (es) | 2002-09-25 |
NO20014967L (no) | 2001-11-26 |
US6514572B1 (en) | 2003-02-04 |
CA2369994A1 (en) | 2000-10-19 |
CO5160370A1 (es) | 2002-05-30 |
AU4347700A (en) | 2000-11-14 |
EP1173494A1 (en) | 2002-01-23 |
NO20001904D0 (no) | 2000-04-12 |
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