CN1283209A - 脂族、低逸出、可烧结的热塑性聚氨酯模塑组合物 - Google Patents
脂族、低逸出、可烧结的热塑性聚氨酯模塑组合物 Download PDFInfo
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Abstract
本发明涉及能以适用于制备粒面烧结膜的烧结粉料形式进行熔体加工而且仅由线型脂族组分制备的聚氨酯模塑组合物。其多元醇组分由30～80重量份平均分子量Mn为1000～2200的脂族聚碳酸酯二醇和70～20重量份平均分子量Mn为1000～2400的聚己二酸丁二醇酯和/或聚己内酯二醇构成。此外,该混合物含有以该多元醇混合物为基准计的当量比为2.3∶1.0～6.2∶1.0的1,6－六亚甲基二异氰酸酯和作为增链剂的1,4－丁二醇,以该多元醇混合物为基准计的1,4－丁二醇的当量比为1.3∶1.0～5.2∶1.0。
Description
本发明涉及能以适用于制备粒面烧结膜的烧结粉料形式进行熔体加工而且仅由线型脂族组分制备的聚氨酯模塑组合物。其多元醇组分由30～80重量份平均分子量为1000～2200的脂族聚碳酸酯二醇和70～20重量份平均分子量为1000～2400的聚己二酸丁二醇酯和／或聚己内酯二醇构成。此外，该混合物含有以该多元醇混合物为基准计的当量比为2．3∶1．0～6．2∶1．0的1，6-六亚甲基二异氰酸酯和作为增链剂的1，4-丁二醇，以该多元醇混合物为基准计的1，4-丁二醇的当量比为1．3∶1．0～5．2∶1．0。
由异氰酸酯基团与多元醇中和增链剂中的羟基总数的当量比乘以100所得到的NCO特征指数是96～99。
粒面烧结膜用于汽车仪表板的表面装饰，至今一直用聚氯乙烯生产，其氯含量和重金属比例以及增塑剂含量在汽车回收和使用过程中都会产生问题。例如，已经知道，在太阳光下增塑剂会释放出各种气体，这在挡风板内侧上的有问题的膜中是一个越来越明显的事实。
用于生产合成革，同时也可用于挤塑和注塑工艺的商业上可得到的热塑性聚氨酯虽然适合于采用烧结粉料工艺进行熔体加工，但是，尤其所制得的膜的光稳定性和热稳定性不能符合汽车工业对仪表板用膜所期望的要求。
芳族热塑性聚氨酯由于含有芳族二异氰酸酯成分，因而光稳定性差。在色彩明亮的情况下，由于光的作用会产生相当明显的泛黄现象，而且甚至黑色的膜也会改变其颜色和光泽。
DE-AS 1694135叙述了一种由较高分子量的线型多羟基化合物和含有至少2个能与异氰酸酯基团反应的低分子量增链剂，例如1，4-丁二醇制备交联聚氨酯的方法，其中所述多羟基化合物由含有70～90％(重量)由1，6-己二醇与碳酸二芳基酯反应制备的己二醇聚碳酸酯和10～30％(重量)由其它的己二酸、1，6-己二醇和2，2′-二甲基丙烷-1，3-二醇二异氰酸酯形成的混合聚酯的混合物组成。只使用芳族二异氰酸酯。聚氨酯的交联是通过使过量的二异氰酸酯而达到的。由这些原料制得的聚氨酯弹性体保留了原有的由聚碳酸酯赋予的高度耐水解性。此外，这种弹性体与只用纯粹的1，6-己二醇聚碳酸酯作为多元醇组分制备的弹性体相比还具有改善的耐低温性能和加工性能。这种改善的加工性能在液相中，例如，在浇铸工艺过程中具有特殊的意义，因为在加工温度下所用的聚酯-聚碳酸酯混合物的粘度比纯粹的己二醇聚碳酸酯的粘度低，这就是所形成的膜能以无泡方式更容易地进行浇铸的原因。用这种工艺制造的产品可用在机械工程和汽车制造中，而有关这类材料任选的成型表面的软化范围和耐热性则未作任何说明。
基于H12-MDI的脂族热塑性聚氨酯虽然耐光性好，但其耐热性对于用在汽车仪表板上而言是不够的。由于强烈的阳光照射，在玻璃挡风板后面汽车内的仪表板上温度会升至100℃以上，此温度已落在这类聚氨酯材料的软化范围内。用这种材料不能达到高达130℃的粒面稳定性和高达120℃的热光稳定性。
DE-C4203307公开了一种聚氨酯模塑组合物，这种组合物能以烧结粉料的形式进行熔体加工用于制造粒面烧结膜，所述粉料只由线型脂族组分构成。其多元醇组分由60～80重量份平均分子量为2000的脂族聚碳酸酯二醇和40～20重量份基于己二酸、己二醇和新戊二醇的、平均分子量为2000的多聚二醇构成。此外，该混合物含有以该多元醇混合物为基准计的当量比为2．8∶1．0～4．2∶1．0的1，6-六亚甲基二异氰酸酯和作为增链剂的1，4-丁二醇，以该多元醇混合物为基准计的1，4-丁二醇的当量比为1．3∶1．0～3．3∶1．0。该模塑组合物的缺点是其结雾性能不符某些汽车制造厂商的指标要求。
因此，本发明的目的是寻找一种能以烧结粉料形式进行熔体加工的聚氨酯模塑组合物，该组合物能满足汽车制造厂商对仪表板领域中塑料的要求，因此具有下列性能：
-柔软和类似革的手感；
-耐光性，即在光的作用下不泛黄，也不改变光泽；
-高达130℃的粒面稳定性和高达120℃的热光稳定性；
-柔软范围高于140℃；
-具有明确的熔点；
-从熔点开始起就是低粘度熔体；
-拉伸强度高；
-抗撕裂和抗撕裂扩展；
-与现有技术的聚氨酯模塑组合物相比，低分子量和可缩合的化
合物的释放量较少；
-与仪表盘板体的聚氨酯背衬泡沫的粘着力良好。
本发明的目的是通过提供—种能以烧结粉料形式进行加工的热塑性聚氨酯模塑组合物而达到的，该模塑组合物是由下列组分进行反应而制得的：
100重量份的多元醇混合物，其中包含：
30～80重量份的脂族聚碳酸酯二醇，其平均分子量为1000～
2200，优选1000～2200，和
70～20重量份的聚已二酸丁二醇酯或聚己内酯二醇，其平均
分子量为1000～2400，优选1800～2400，与
1，6-六亚甲基二异氰酸酯，其以上述多元醇混合物为基准计的当量比为2．3∶1．0～6．2∶1．0，和
作为增链剂的1，4-丁二醇，其以上述多元醇混合物为基准计的当量比为1．3∶1．0～5．2∶1．0，
其中由异氰酸酯基团与多元醇混合物和增链剂中的羟基总数的当量比乘以100而得到的NCO特征指数是96～99。
该聚氨酯模塑组合物只从脂族组分制备，即仅仅由下列组分制备：
100重量份的多元醇混合物，其中包含：30～80重量份的脂族聚碳酸酯二醇，其OH值为112．2～51，相当于平均分子量为1000～2200，优选的OH值为62．3～51，相当于平均分子量为1800～2200，和70～20重量份的聚己二酸丁二醇酯或聚己内酯二醇，各自的OH值为112．2～46．7，相当于平均分子量Mn为1000～2400，优选的OH值为62．3～46．7，相当于平均分子量为1800～2400；
1，6-六亚甲基二异氰酸酯，其以上述多元醇为基准计的当量比为2．3∶1．0～6．2∶1．0；和
作为增链剂的1，4-丁二醇，其以上述多元醇混合物为基准计的当量比为1．3∶1．0～5．2∶1．0。
由异氰酸酯基团与多元醇混合物和增链剂中的羟基总数的当量比乘以100而得到的NCO特征指数是96～99，这意味着二异氰酸酯的量不足。
聚己二酸丁二醇酯是丁二醇与己二酸的含羟基聚合产物，而聚己内酯二醇是己内酯的含羟基聚合产物。
在按照挤出机工艺或注带工艺连续制备本发明的聚氨酯模塑组合物过程中最好是使用催化剂。适用的催化剂是现有技术中已知的常用的叔胺，例如三乙胺、二甲基环己基胺、N-甲基吗啉、N，N′-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂双环[2．2．2]辛烷等，以及特别是有机金属化合物，例如钛酸酯、铁化合物、锡化合物如二乙酸锡、二辛酸锡、二月桂酸锡或脂族羧酸的二烷基锡盐如二乙酸二丁基锡、二月桂酸二丁基锡等。优选的催化剂是有机金属化合物，特别是钛酸酯、铁或锡化合物。二辛酸锡和二月桂酸二丁基锡是更特别优选的。
按照本发明的聚氨酯模塑组合物完全不含任何增塑剂。除了TPU组分和任选的催化剂外还可加入其它辅助材料和添加剂。其例子包括润滑剂如脂肪酸酯、其金属皂、脂肪酸酰胺和聚硅氧烷化合物、防粘剂、抑制剂、对水解、光、热和褪色的稳定剂、阻火剂、染料、颜料、无机和有机填料以及增强剂，它们可以按照现有技术的方法制备，并且也可以分类。有关所提到的辅助材料和添加剂的进一步详情可从专门的文献获得，例如，J．H．Saunders，K．C．Frisch：“高聚物”，卷XVI，聚氨酯，第1和2部分，Interscience出版社，1962和1964，R．
H．Müller(编)：Taschenbuch der Kunststoff-Additive，第3版，Hanser Verlag，慕尼黑1989或DE-A-2901774。
使热气体(如空气或氮气)通过模塑组合物粒料可以明显克服热塑性聚氨酯模塑组合物的结雾行为和缩合物形成的缺点。通常将该粒料在80～110℃处理5-20小时，按照DIN 75201标准(120℃16小时)测得的缩合物量小于1．5mg／10g。
按照本发明的模塑组合物适用于制备各种模制品，例如膜，尤其粒面烧结膜。按照本发明的聚氨酯模塑组合物可按照众所周知的“粉料搪塑工艺”以粉料形式在加热的模具中进行烧结，形成皮膜。为此所需的粉料可从按照本发明的聚氨酯模塑组合物的粒料经过冷碾磨而制得。将碾磨后的物料引入到一例敞开的加热的模具中，然后在短时间内烧结在该加热表面的内壁上。待模具冷却后，就可以将该搪塑的皮膜揭下。因此该工艺类似于制造由PVC皮膜制造的仪表板覆盖物所用的工艺。这种工艺可参见特别是，例如，DE-A-3932923，作为“粉料搪塑工艺”。
由于具有180℃的明确熔点和从熔点一开始起就存在低粘度熔体，所以该粉料仅在短时间内就能烧结在加热的模具的内壁上，形成没有小孔没有气泡的均匀的膜，而且由于按照本发明的模塑组合物具有高度的结晶倾向，因此仅在冷却到100℃之后就能形成膜，而不受损坏。所有这些因素都使得用本发明的模塑组合物进行的烧结工艺特别经济。
由这种聚氨酯模塑组合物制备的烧结膜具有高的拉伸强度和优异的抗撕裂性及抗撕裂扩展性。这种膜具有柔软的类似革的手感，在光的作用下不易泛黄或改变光泽，甚至在淡色的情况下也是如此。
在热光老化(110～120℃)期间粒面不会发生变化，类似地，在130℃的炉栅上贮存时进行的热老化期间也不会发生任何变化。
由按照本发明的聚氨酯模塑组合物制备的烧结膜是稳定的，例如用于交通运输工具如飞机、船舶、火车或汽车的表面装璜，尤其用作仅表板的装饰，都是稳定的，因为这类膜是以独特的方式粘贴到仪表板的聚氨酯背衬泡沫上去的。因此，本发明还涉及按照本发明的膜在交通运输工具中，特别在汽车中用作仪表板的表面装璜的用途。
实施例
实施例1
混合物的组成：
70．00重量份聚碳酸酯二醇，其=2000
30．00重量份聚己内酯二醇，其=2000
30．10重量份六亚甲基二异氰酸酯，
11．70重量份1，4-丁二醇。
制备方法
采用一步法进行制备。将聚碳酸酯二醇、聚己内酯二醇、六亚甲基二异氰酸酯和1，4-丁二醇预热到90℃、使其在挤出机中聚合，然后造粒。在配混阶段中将传统的添加剂加入到粒料中，然后在液氮冷却下碾磨成具有50～400μm粒度分布的微细粉料。
实施例2
混合物的组成：
70．00重量份聚碳酸酯二醇，其=2000
34．00重量份聚己二酸丁二醇酯，其=2250
30．20重量份六亚甲基二异氰酸酯，
11．70重量份1，4-丁二醇。
制备方法
采用一步法进行制备。将聚碳酸酯二醇、聚己二酸丁二醇酯、六亚甲基二异氰酸酯和1，4-丁二醇预热到90℃。使其在挤出机中聚合，然后造粒。在配混阶段中将添加剂(UV稳定剂、抗氧化剂、脱膜剂)加入到粒料中，然后在液氮冷却下碾磨成具有50～500μm粒度分布的微细粉料。
按照DIN 75201标准(“汽车内部配件材料结雾性能的测定”)将实施例1和2制得的材料和按照DE-C4203307的实施例1制得的对比材料进行结雾试验。另外，在100℃平衡3小时后测定剩余光泽度。结果总结于表1。表1
| 剩余光泽度(％) | 缩合物(mg)* | |
| 对比例1(按照DE-C4203307) | 88 | 4．4 |
| 实施例1 | 93 | 3．0 |
| 实施例2 | 92 | 2．9 |
| 实施例3a | 1．4 | |
| 实施例3b | 1．0 |
*可缩合部分在120℃16小时内测定。
实施例3
将实施例2制得的TPU粒料暴露于90℃的空气流中(汽提)。
a)8小时
b)16小时
然后按照DIN 75201标准将物料进行结雾试验。结果重显于表1中。
这些结果清楚地表明按照本发明的材料具有汽车工业所要求的＞90％的剩余光泽度，而且释放出的缩合物比按照对比例1的材料少。
Claims (6)
1．一种能以烧结粉料形式进行加工的热塑性聚氨酯模塑组合物，该组合物是由下列组分进行反应而制得的：
100重量份的多元醇混合物，其中包含：
30～80重量份的脂族聚碳酸酯二醇，其平均分子量为1000～
2200，和
70～20重量份的聚己二酸丁二醇酯或聚己内酯二醇，其平均
分子量为1000～2400，与
1，6-六亚甲基二异氰酸酯，其以上述多元醇混合物为基准计的当量比为2．3∶1．0～6．2∶1．0，和
作为增链剂的1，4-丁二醇，其以上述多元醇混合物为基准计的当量比为1．3∶1．0～5．2∶1．0，
其中由异氰酸酯基团与多元醇混合物和增链剂中的羟基总数的当量比乘以100而得到的NCO特征指数是96～99。
2．一种连续制备按照权利要求1的模塑组合物的方法，其中聚氨酯各组分的反应是在催化剂存在下进行的。
3．由按照权利要求1的聚氨酯模塑组合物制得的模制品。
4．由按照权利要求1的聚氨酯模塑组合物制得的膜。
5．按照权利要求3的模制品作为运输工具中表面装饰的用途。
6．一种改善热塑性聚氨酯的结雾性能并减少其缩合物量(按DIN75201测定)的方法，其特征在于将造粒后的热塑性聚氨酯进行热气流处理。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19757569A DE19757569A1 (de) | 1997-12-23 | 1997-12-23 | Aliphatische, emissionsarme, sinterfähige thermoplastische Polyurethanformmassen |
| DE19757569.2 | 1997-12-23 |
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| CN1283209A true CN1283209A (zh) | 2001-02-07 |
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| CN98812550A Pending CN1283209A (zh) | 1997-12-23 | 1998-12-10 | 脂族、低逸出、可烧结的热塑性聚氨酯模塑组合物 |
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| US (1) | US6420510B1 (zh) |
| EP (1) | EP1042386B1 (zh) |
| JP (1) | JP2001527142A (zh) |
| KR (1) | KR20010024803A (zh) |
| CN (1) | CN1283209A (zh) |
| AU (1) | AU2269899A (zh) |
| BR (1) | BR9814398A (zh) |
| CA (1) | CA2315765A1 (zh) |
| DE (2) | DE19757569A1 (zh) |
| ES (1) | ES2181323T3 (zh) |
| PT (1) | PT1042386E (zh) |
| TW (1) | TW568936B (zh) |
| WO (1) | WO1999033895A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101120034B (zh) * | 2005-02-18 | 2011-02-16 | 旭化成化学株式会社 | 聚碳酸酯二醇 |
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| DE19942393C2 (de) * | 1999-07-15 | 2002-07-18 | Bayer Ag | Weiche, elastische Polyurethanfolien, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US6559266B2 (en) | 1999-11-22 | 2003-05-06 | Bayer Corporation | Aliphatic thermoplastic polyurethanes, a process for producing them and the use thereof |
| GB0222522D0 (en) | 2002-09-27 | 2002-11-06 | Controlled Therapeutics Sct | Water-swellable polymers |
| AU2003268720A1 (en) * | 2002-10-01 | 2004-04-23 | Sanyo Electric Co., Ltd. | Polyol mixture, reactive hot-melt composition obtained from the mixture, and molded article obtained with the composition |
| GB0417401D0 (en) | 2004-08-05 | 2004-09-08 | Controlled Therapeutics Sct | Stabilised prostaglandin composition |
| DE102006021734A1 (de) * | 2006-05-09 | 2007-11-15 | Bayer Materialscience Ag | Aliphatische, sinterfähige, thermoplastische Polyurethanformmassen mit verbessertem Ausblühverhalten |
| GB0613333D0 (en) | 2006-07-05 | 2006-08-16 | Controlled Therapeutics Sct | Hydrophilic polyurethane compositions |
| GB0613638D0 (en) | 2006-07-08 | 2006-08-16 | Controlled Therapeutics Sct | Polyurethane elastomers |
| GB0620685D0 (en) | 2006-10-18 | 2006-11-29 | Controlled Therapeutics Sct | Bioresorbable polymers |
| KR100985513B1 (ko) * | 2010-03-26 | 2010-10-05 | 한국신발피혁연구소 | 엠보성형이 우수한 용액형 폴리우레탄 수지 조성물 및 그 제조방법 |
| EP2918618A1 (de) | 2014-03-10 | 2015-09-16 | Bayer MaterialScience AG | Aliphatische thermoplastische Polyurethane, ihre Herstellung und Verwendung |
| KR20200093670A (ko) * | 2017-12-14 | 2020-08-05 | 바스프 에스이 | 낮은 유리 전이 온도를 갖는 열가소성 폴리우레탄의 제조 방법 |
| JP7188685B2 (ja) * | 2018-05-11 | 2022-12-13 | サンユレック株式会社 | ポリウレタン樹脂組成物 |
| JP7527924B2 (ja) | 2020-10-05 | 2024-08-05 | 株式会社フコク | ポリウレタン化合物 |
| CN112322027B (zh) * | 2020-11-17 | 2022-02-18 | 美瑞新材料股份有限公司 | 高强度哑光热塑性聚氨酯弹性体组合物及其制备和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1694135B2 (de) | 1967-02-28 | 1975-08-28 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von vernetzten Polyurethanen |
| US3509233A (en) * | 1968-04-02 | 1970-04-28 | Bayer Ag | Hydrolysis resistant elastomeric poly (carbonate urethanes) |
| US4174436A (en) * | 1975-12-31 | 1979-11-13 | Naturin-Werk Becker & Co. | Polyurethanes and food casings made therefrom |
| DE2658138A1 (de) | 1976-12-22 | 1978-07-06 | Bayer Ag | Substituierte 2-phenylimino-thiazolidine, verfahren zu ihrer herstellung sowie ihre verwendung als ektoparasitizide |
| DE2658136C2 (de) * | 1976-12-22 | 1982-09-23 | Fa. Carl Freudenberg, 6940 Weinheim | Thermoplastisch verarbeitbare Polyurethanformmasse |
| DE2901774A1 (de) | 1979-01-18 | 1980-07-24 | Elastogran Gmbh | Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung |
| JPS60157856A (ja) * | 1984-01-27 | 1985-08-19 | 旭硝子株式会社 | 積層安全ガラス |
| US4931486A (en) * | 1988-12-02 | 1990-06-05 | The Dow Chemical Company | Poly(alkylene carbonate) polyols as antistatic additives for polyurethanes |
| DE3916874A1 (de) * | 1989-05-24 | 1990-11-29 | Basf Ag | Weiche, elastische polyurethan-folien, verfahren zu ihrer herstellung und ihre verwendung |
| DE3932923A1 (de) | 1989-10-03 | 1991-04-18 | Benoac Fertigteile Gmbh | Verfahren zur herstellung on slush-haeuten nach dem powder-slush-verfahren sowie vorrichtung zur herstellung von slush-haeuten |
| JPH03292376A (ja) * | 1990-04-10 | 1991-12-24 | Toyobo Co Ltd | ガラス飛散防止用コーティング剤 |
| EP0539802A1 (de) * | 1991-10-28 | 1993-05-05 | Bayer Ag | Freifliessende, thermoplastisch verarbeitbare und dabei nachvernetzende, gegebenenfalls expandierbare Polyurethan-Pulver (-Zubereitungen) |
| DE4209709A1 (de) * | 1992-03-25 | 1993-09-30 | Bayer Ag | Freifließende, thermoplastisch verarbeitbare und dabei nachvernetzende, gegebenenfalls expandierbare Polyurethan-Pulver (-Zubereitungen) |
| DE4203307C1 (zh) * | 1992-02-06 | 1992-12-03 | Fa. Carl Freudenberg, 6940 Weinheim, De | |
| KR100200003B1 (ko) * | 1993-03-01 | 1999-06-15 | 시바타 미노루 | 열가소성 폴리우레탄 |
| DE19800287A1 (de) * | 1998-01-07 | 1999-07-08 | Bayer Ag | Aliphatische sinterfähige thermoplastische Polyurethanformmassen mit reduzierter mechanischer Festigkeit |
-
1997
- 1997-12-23 DE DE19757569A patent/DE19757569A1/de not_active Withdrawn
-
1998
- 1998-12-10 CA CA002315765A patent/CA2315765A1/en not_active Abandoned
- 1998-12-10 DE DE59804842T patent/DE59804842D1/de not_active Expired - Fee Related
- 1998-12-10 EP EP98966284A patent/EP1042386B1/de not_active Expired - Lifetime
- 1998-12-10 BR BR9814398-0A patent/BR9814398A/pt not_active IP Right Cessation
- 1998-12-10 PT PT98966284T patent/PT1042386E/pt unknown
- 1998-12-10 ES ES98966284T patent/ES2181323T3/es not_active Expired - Lifetime
- 1998-12-10 CN CN98812550A patent/CN1283209A/zh active Pending
- 1998-12-10 WO PCT/EP1998/008043 patent/WO1999033895A1/de not_active Application Discontinuation
- 1998-12-10 JP JP2000526565A patent/JP2001527142A/ja active Pending
- 1998-12-10 US US09/581,771 patent/US6420510B1/en not_active Expired - Fee Related
- 1998-12-10 AU AU22698/99A patent/AU2269899A/en not_active Abandoned
- 1998-12-10 KR KR1020007006950A patent/KR20010024803A/ko not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101120034B (zh) * | 2005-02-18 | 2011-02-16 | 旭化成化学株式会社 | 聚碳酸酯二醇 |
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| Publication number | Publication date |
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| CA2315765A1 (en) | 1999-07-08 |
| AU2269899A (en) | 1999-07-19 |
| BR9814398A (pt) | 2000-10-10 |
| DE19757569A1 (de) | 1999-06-24 |
| TW568936B (en) | 2004-01-01 |
| WO1999033895A1 (de) | 1999-07-08 |
| JP2001527142A (ja) | 2001-12-25 |
| DE59804842D1 (en) | 2002-08-22 |
| US6420510B1 (en) | 2002-07-16 |
| EP1042386A1 (de) | 2000-10-11 |
| ES2181323T3 (es) | 2003-02-16 |
| EP1042386B1 (de) | 2002-07-17 |
| PT1042386E (pt) | 2002-11-29 |
| KR20010024803A (ko) | 2001-03-26 |
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