CN1345394A - 真空绝缘板 - Google Patents
真空绝缘板 Download PDFInfo
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Abstract
具有作为芯层的微孔片材和塑料薄膜覆盖层的真空绝缘板,其中该塑料薄膜包括至少具有下面层顺序的7层,(1)聚烯烃热封层(I);(2)粘结或粘合层(II);(3)阻气层(III);(4)粘结或粘合层(II);(5)聚烯烃层(IV);(6)粘结或粘合层(II);(7)基本上包括用铝或SiOx或第2或第3主族金属氧化物蒸镀的聚酯和/或聚酰胺和/或聚丙烯的层(V)。
Description
本发明涉及具有改进的绝缘效果的真空绝缘板,适于制备这种真空绝缘板的不透气塑料薄膜和这种真空绝缘板在致冷设备中的应用。
作为优异的绝缘材料,真空绝缘板(“VIP”)在热绝缘的所有领域中引起了普遍的关注,但是尤其表现在家用致冷设备中。通常在它们绝缘效果方面它们优于硬质聚氨酯泡沫材料超过二倍,其中该泡沫材料通常用于家用致冷设备中。常见的真空板是通过用薄膜覆盖微孔支撑材料并在真空中将它们熔接的方法来制备的。真空绝缘板中的压力通常小于1mbar,因为仅仅在如此低的压力下才能达到所需的绝缘效果。在现有的通常真空绝缘板中,原则上应该区分开两种类型的真空绝缘板:
与EP0463311或DE4019870A1、EP0396961B1和EP0446486A2或DE4008480中相一致的用塑料薄膜覆盖的微孔沉淀硅酸(Kieselsure),和如美国专利4669632中举例说明的用铝复合薄膜覆盖的微孔塑料泡沫材料。
基于微孔沉淀硅酸(Kieselsure)芯层的真空绝缘板的缺点在于它是将粉状材料用作原料,于是该真空绝缘板具有在平面上明显的厚度公差和偏差,从而使在将其装入致冷设备中时情况变得复杂。
基于塑料泡沫材料芯层的真空绝缘板的缺点在于塑料泡沫材料仅具有非常小的对气体特别是对水蒸气的吸收本领,结果是对于使用这些其他情况特别适用的真空绝缘板芯层材料的所用薄膜的气密性是极为重要的。常见的塑料材料阻气薄膜不会获得所需的阻气效果,如EP0517026A1中举例描述的那样。虽然气体吸收物质或者与气体反应的物质(“吸气剂”)能够加入到芯层中来俘获分散其中的气体并由此保持真空绝缘板中的低压,但是这种措施并不总是达到所需要求。由于这种原因,优选应用铝复合薄膜来作为整个阻气层以保持真空绝缘板中的真空。然而这种铝复合薄膜在其边缘上分散了太多的热量,使得真空绝缘板的大部分绝缘效果损失。当然,这种效果仅当在全部致冷设备中测量热传递时才能够被检测到。当根据DIN 18164Teil 1和2来测量导热性系数时是不能检测到这种边缘效应的影响的。
尽管如此,由于它们的尺寸能够精确地与要求相符合,并且能够简单且便宜的生产成非常平坦(平面)的片材,所以基于塑料泡沫材料芯层的真空绝缘板已经获得了显著的市场位置。然而,前述由双面铝箔边缘产生的热传递的缺点限制了它们的进一步广泛应用。
因此,本发明的目的在于提供能够具有基于塑料泡沫材料芯层的真空绝缘板的优点,也就是平坦(平面)表面和尺寸的精确可加工性能,但避免了或者基本减少了由边缘效应产生的绝缘性能的损耗的真空绝缘板。
通过具有作为芯层的微孔片材和高度不透气层塑料薄膜的覆盖层的真空绝缘板(VIP)来实现本发明目的,其中该塑料薄膜包括至少具有下面层顺序的7层
(1)聚烯烃热封层(I)
(2)粘结或粘合层(II)
(3)阻气层(III)
(4)粘结或粘合层(II)
(5)聚烯烃层(IV)
(6)粘结或粘合层(II)
(7)基本上包括用铝或SiOx或第2或第3主族金属氧化物蒸镀的聚酯和/或聚酰胺和/或聚丙烯的层(V)。
通过应用本发明的真空绝缘板能够获得明显小于0.01cm3/m2dbar的氧气扩散和明显小于0.02g/m2d的水蒸气扩散,结果是由此制备的真空绝缘板的绝缘效果的持久性符合实际要求。当根据现有技术应用铝复合薄膜时,没有发现由边缘效应导致的绝缘性能的损耗。
可将聚烯烃均聚物或聚烯烃共聚物用作聚烯烃热封层(I)。优选为线性低密度聚乙烯(“LLDPE”),聚丁烯(“PB”),乙酸乙基乙烯酯(“EVA”),高密度聚乙烯(“HDPE”),离子交联聚合物(“I”)和这些物质的混合物。根据本发明由前述材料通过多层共挤来制备聚烯烃热封层(I)的多层实施例也是可能的。聚烯烃热封层(I)的厚度优选为20-200μm,特别优选为50-100μm。
作为粘结或粘合层,优选应用市场上提供的粘合剂例如特别是双组份聚氨酯粘合剂。然而也可以应用聚烯烃粘合剂,优选聚乙烯均聚物、乙烯/丙烯酸乙酯(“EAA”)或乙烯/甲基丙烯酸(“EMMA”)。粘合剂层或粘合层(II)的厚度优选至多为6μm,特别优选2-6μm。
阻气层(III)优选基本上由聚乙烯醇(“PVOH”),乙烯/乙烯醇共聚物(“EVOH”)和/或由聚酰胺或由PA和EVOH的混合物组成,或者在多层的实施例中,由PA和EVOH层型组合物或PA和EVOH的混合物的层型组合物组成,并且优选至少单轴拉伸。必要时,其可具有阻气漆涂层,优选丙烯酸清漆。阻气层(III)的厚度优选为10-120μm,在单层的实施例中特别优选为10-20μm。
聚烯烃层(IV)优选基本上由聚乙烯,聚丙烯或者聚乙烯共聚物组成。根据本发明该层厚度优选为5-500μm,特别优选为50-200μm。这里已经发现相对厚的聚烯烃层(IV)赋予了真空绝缘板特别更光滑和更均匀的表面。在安装致冷设备时,这对与真空绝缘板的粘合是特别有利的。在折叠的VIP情况下,用粘合剂润湿的表面通常对真空绝缘板的粘合是不充分的。
在保留层的对面一侧上,优选通过常见的方法用铝、SiOx或第2或第3主族金属氧化物蒸镀聚酯和/或聚酰胺和/或聚丙烯的层(V),并且可以任选地在未蒸镀一侧上提供有阻气层清漆,优选用丙烯酸清漆。层(V)优选为用铝蒸镀过的基本上由聚酯或者聚丙烯组成的层,优选其厚度为30-80nm。层(V)的厚度优选为10-40μm,特别优选为10-20μm。
也作为本发明主题的该至少7层的塑料薄膜可以在一个或多个层中,含有通常量的常见添加剂和辅助剂例如润滑剂、防结块剂和抗静电剂。
已经发现的是特别通过相对厚的聚烯烃层(IV)与优选为聚乙烯醇的阻气层(III)和被蒸镀层(V)的组合获得了意想不到的高不渗透性。这里,将在整个结构中的阻气层(III)直接安排到热封层的下面并且由此阻止潮气也是重要的。
根据本发明优选的是使用塑料泡沫材料作为芯层的真空绝缘板。塑料泡沫材料可以为聚氨酯或者聚苯乙烯泡沫材料。通过研磨并压制的塑料泡沫来制备的片材也是适用于此的,如EP0791155B1中所描述的那样。
作为芯层优选应用的是本发明的微孔、开孔发泡片材,特别是得自聚氨酯或聚苯乙烯的片材。在进一步优选的实施例中,任选通过添加合适的粘接剂来压制形成片材的研磨、闭孔发泡材料来作为本发明真空绝缘板的芯层。由此本发明的真空绝缘板的生产能够并入废旧泡沫的回收过程中。
真空绝缘板的制备通常通过将作为芯层的微孔片材放入用本发明薄膜预先制成的袋(内侧为聚烯烃/热封层(I))中,然后在10-3-1torr的真空中封住仍然开口的边缘。在真空室充气之后就获得了本发明的真空绝缘板。
虽然芯层的吸收能力低,但是本发明薄膜的高不透气性赋予了真空绝缘层足够的耐用性。尽管如此,如果要应用吸气剂来确保真空绝缘板的耐用性,则所用的量可以相应地小一些。如果合适应用少量的结合水蒸气的物质也是足够的。吸气剂优选的实例为:
为了结合大气中的组分氧气和氮气,可应用碱和碱土金属;为了结合湿气和二氧化碳,可应用碱土金属氧化物;仅为了结合湿气,可用市场上提供的硅胶和分子筛。由这些材料合适配制的吸气剂为市场上所提供的。
本发明薄膜在特定的实施方案中也可以被仅仅用作制备薄膜袋的一面,其中,相对面上用铝阻气层形成常见的多层薄膜,其中该铝层优选包括厚度为6-20μm和PE层厚度为50-200μm。在这个实施方案中热绝缘性基本没有因边缘效应受影响。
本发明的真空绝缘板可以广泛用作在建筑中绝缘、工业绝缘和特别是在致冷设备中绝缘的高性能绝缘材料。
当应用在致冷设备中时,该真空绝缘板通常占用了部分的绝缘体积-致冷设备通常使用硬质聚氨酯泡沫材料绝缘。由此能够在不增加壁厚的情况下使能量节约达30%。
实施例:
测量方法:
根据下面方法测定本发明多层薄膜的性能:
根据DIN53380测定薄膜的氧气、氮气和二氧化碳的渗透性。
根据DIN53122测定薄膜的水蒸气渗透性。
根据DIN18164 Teil1和Teil2来测定导热系数λ。
在实施例7中详细描述了外壳指数(透过致冷设备外壳的热传递)的测定。
下面借助于如下实施例来更加详细的对本发明的主题进行描述:
1.薄膜:
应用下面实施例中的薄膜来说明本发明薄膜的高阻气效果:
实施例a:
层I:乙烯/醋酸乙烯酯共聚物的聚烯烃封层,3.5%醋酸乙烯酯,50μm
层II:双组份的聚氨酯粘合剂,2μm
层III:聚乙烯醇阻气层,双轴拉伸,12μm
层II:双组份的聚氨酯粘合剂,2μm
层IV:聚乙烯层,120μm
层II:双组份的聚氨酯粘合剂,2μm
层V:喷涂金属的双轴拉伸聚对苯二甲酸乙二酯薄膜,12μm
实施例b:
层I:乙烯/醋酸乙烯酯共聚物的聚烯烃封层,3.5%醋酸乙烯酯,50μm
层II:双组份的聚氨酯粘合剂,2μm
层III:聚乙烯醇阻气层,双轴拉伸,12μm
层II:双组份的聚氨酯粘合剂,2μm
层IV:聚乙烯层,120μm
层II:双组份的聚氨酯粘合剂,2μm
层V:喷涂金属的双轴拉伸聚丙烯薄膜,20μm
实施例c:
层I:乙烯/醋酸乙烯酯共聚物的聚烯烃封层,3.5%醋酸乙烯酯,50μm
层II:双组份的聚氨酯粘合剂,2μm
层III:在两面上均用PVDC涂漆的PVOH层的阻气层
层II:双组份的聚氨酯粘合剂,2μm
层IV:聚乙烯层,120μm
层II:双组份的聚氨酯粘合剂,2μm
层V:喷涂金属的双轴拉伸聚对苯二甲酸乙二酯薄膜,12μm
实施例d:
层I:乙烯/醋酸乙烯酯共聚物的聚烯烃封层,3.5%醋酸乙烯酯,50μm
层II:双组份的聚氨酯粘合剂,2μm
层III:共挤的PA/EVOH/PA层的阻气层
层II:双组份的聚氨酯粘合剂,2μm
层IV:聚乙烯层,120μm
层II:双组份的聚氨酯粘合剂,2μm
层V:喷涂金属的双轴拉伸聚对苯二甲酸乙二酯薄膜,12μm
比较例e:(根据EP0517026A1,Combithen PXX):
第一层:聚烯烃层,50μm
第二层:双组份的聚氨酯粘合剂,2μm
第三层:聚乙烯醇层,12μm
第四层:双组份的聚氨酯粘合剂,2μm
第五层:聚烯烃层,120μm
第六层:双组份的聚氨酯粘合剂,2μm
第七层:聚乙烯醇层,12μm
第八层:双组份的聚氨酯粘合剂,2μm
第九层:聚烯烃层,120μm
第十层:双组份的聚氨酯粘合剂,2μm
第十一层:拉伸的聚对苯二甲酸乙二酯薄膜,12μm
比较例f:(Aluthen P,Wolff-Walsrode):
第一层:聚烯烃层,50μm
第二层:双组份的聚氨酯粘合剂,2μm
第三层:拉伸的聚对苯二甲酸乙二酯薄膜,12μm
第四层:双组份的聚氨酯粘合剂,2μm
第五层:铝薄膜,12μm
第六层:双组份的聚氨酯粘合剂,2μm
第七层:拉伸的聚对苯二甲酸乙二酯薄膜,12μm
下面测定水蒸气、氧气、氮气和二氧化碳的渗透性:
实施例 | 渗透性[cm3/m2dbar](23℃,0%相对湿度) | 水蒸气渗透性[g/m2d](23℃,85%相对湿度) | ||
O2 | N2 | CO2 | ||
a | 0.01 | <0.01 | 0.02 | 0.015 |
b | 0.01 | <0.01 | 0.03 | 0.02 |
c | 0.01 | <0.01 | 0.02 | 0.015 |
d | 0.01 | <0.01 | 0.02 | 0.015 |
比较例 | ||||
e | 0.01 | <0.01 | 0.03 | 0.1 |
f | 太小无法测定 | 太小无法测定 |
2.)薄膜袋的说明
通过将50×50cm大小的薄膜片三侧熔接的方法来制备薄膜袋。袋子是由下面的材料制成的:
I.由商业上提供的含铝的多层薄膜(Wolff Walsrode公司的Aluthen-P,参见实施例1.f)对称制备的薄膜袋。
II.由商业上提供的无金属阻气层薄膜(Wolff Walsrode公司的Combithen PXX,参见实施例1.e)对称制备的薄膜袋。
III.由本发明多层薄膜对称制备的薄膜袋,该薄膜已经在实施例1.a中公开。
IV.由在2.III中描述的本发明多层薄膜和2.I中描述的含铝多层薄膜不对称制备的薄膜袋。
3.)芯层的说明-对应于W096/14207的回收硬质泡沫材料片材
在装配有双料喷嘴的Ldige-Pflugschar混合机中将由致冷设备回收厂来的1000gPUR硬质泡沫材料粉末与35g水和100g二苯甲烷二异氰酸酯和聚苯-聚亚甲基-聚异氰酸酯(DesmodurVP PU 1520A20;Bayer AG)的聚异氰酸酯混合物均匀混合。在模框中用这种混合物制成尺寸为400×400mm的模制件,并将其均匀地压实,然后用实验室压机在5bar的压力和120℃的温度下用时间测量程序加压8分钟直至将其厚度压成25mm。
由此获得了体密度为250kg/m3的多孔25mm片材。将该片材在120℃下加热约2小时以释放所有挥发性组分。
4.真空绝缘板的制备
将在3.中制备的板放入根据2.I和2.IV制成的薄膜袋中,将压力抽空到2×10-1torr然后熔接。充气后获得了相应的真空绝缘板。
已经发现用本发明厚薄膜制成的真空绝缘板具有比那些用薄的薄膜制成的板有光滑得多的表面。
仍然存在的低水蒸气渗透性能够通过测量经过储存测试后真空绝缘板的重量增量来测定。该重量增量是在储存时间达1年后测定的,并且外推至15年。这里,会想到由聚氨酯硬质泡沫材料构成的芯层具有为其本身重量约0.5-1%的吸水能力,因此板中的压力最初没有增加。因为它仅在毫克范围内波动,所以由氧气、氮气和二氧化碳渗透性产生的重量增量可以在比较中被忽略。
从水蒸气渗透性中计算和测量出的重量增量:
薄膜袋的真空绝缘板 | 重量增量[g] | ||
一年后(计算值) | 一年后(测定值) | 外推至15年 | |
2. I | 0 | 0.2 | 3 |
2.II | 11.68 | 5.34 | 80.1 |
2.III | 1.75 | 1.63 | 24.45 |
2.IV | 0.88 | 0.72 | 10.8 |
5.导热系数λ的测量
根据DIN18164 Teil 1和2,测量4.中所生产的具有2.I至2.IV的薄膜结构的真空绝缘板的导热性。这些片材均具有9.0-9.1mW/m°K的可比导热性。
6.在致冷设备中真空绝缘板的安装
如附图1中垂直切面所示,在台式致冷设备中,内部物上装入外壳(附图标记为(2))之前,将具有2.I至2.IV薄膜结构的真空绝缘板(附图标记为(1))结合起来,而其中真空绝缘板的尺寸为60×50×2.5和50×50×2.05。将另外的真空绝缘板结合到门的内侧和结合到后壁上(两者均未在表1中示出)。因此真空绝缘板占据了部分绝缘体积。在内壳(附图标记3)安装完成后,剩余的绝缘体积通常用PUR泡沫材料(附图标记4)来填充。
生产应用在各种场合中的具有不同真空绝缘板薄膜结构的四种致冷设备。
结合后,由本发明优选厚薄膜形成的真空绝缘板比用薄的薄膜制成的真空绝缘板好并且更耐用,例如根据结构2.I。在后者的情况下,在剩余空间体积填充泡沫材料后,在某些场合下没有真空绝缘板和外层之间的结合。
7.用不同真空绝缘板制成的致冷设备外壳指数的测量
下面来研究6.中所制备致冷设备的外壳指数:通过安装在致冷设备内部的可调节的电加热装置,将内部空间温度升至比环境温度高30℃至40℃。当内部温度达到固定状态时(通常在4天后),通过测量电加热效果和在24小时内测定内部和环境之间平均温差来测定外壳指数Z(W/°K),在内部的温度测量是通过应用共6个热电偶来完成的。得到了下面的结果:
真空绝缘板的薄膜结构 | 外壳指数(W/°K) |
2.I | 0.36 |
2.II | 0.30 |
2.III | 0.29 |
2.IV | 0.29 |
如我们所见到的那样,在应用2.I的情况下(在两侧均有铝复合薄膜),导热性比当应用塑料薄膜的大得多,甚至当仅在一侧应用塑料薄膜、另一侧应用铝复合薄膜(2.IV)时也是如此。
Claims (11)
1.真空绝缘板,具有作为芯层的微孔片材和塑料薄膜覆盖层,其中该塑料薄膜包括至少具有下面层顺序的7层
(1)聚烯烃热封层(I)
(2)粘结或粘合层(II)
(3)阻气层(III)
(4)粘结或粘合层(II)
(5)聚烯烃层(IV)
(6)粘结或粘合层(II)
(7)基本上包括用铝或SiOx或第2或第3主族金属氧化物蒸镀的聚酯和/或聚酰胺和/或聚丙烯的层(V)。
2.如权利要求1所述的真空绝缘板(VIP),其中聚烯烃热封层(I)为单层或多层的,并且基本上是由聚烯烃均聚物或聚烯烃共聚物组成。
3.如权利要求1或2所述的真空绝缘板(VIP),其中将双组份聚氨酯粘合剂或聚烯烃粘合剂用作粘结或粘合层(II)。
4.如权利要求1-3中任一权利要求所述的真空绝缘板(VIP),其中阻气层(III)基本上由聚乙烯醇(“PVOH”),乙烯/乙烯醇共聚物(“EVOH”)和/或由聚酰胺或由PA和EVOH的混合物组成,并且可任选为多层结构。
5.如权利要求1-4中任一权利要求所述的真空绝缘板(VIP),其中聚烯烃层(IV)基本上由聚乙烯、聚丙烯或聚乙烯共聚物组成,优选厚度为5-500μm。
6.如权利要求1-5中任一权利要求所述的真空绝缘板(VIP),其中层(V)是基本上由用铝蒸镀的聚酯或聚丙烯组成的层,优选厚度为30-80nm。
7.如权利要求1-6中任一权利要求所述的真空绝缘板(VIP),其中根据本发明应用聚氨酯或聚苯乙烯微孔、开孔泡沫材料作为芯层。
8.如权利要求1-6中任一权利要求所述的真空绝缘板(VIP),其中将任选添加合适的粘接剂来压制形成片材的研磨、闭孔发泡材料用作芯层。
9.如权利要求1-8中任一权利要求所述的真空绝缘板(VIP),其中仅在覆盖层一侧具有包括至少具有下面层顺序的7层的塑料薄膜
(1)聚烯烃热封层(I)
(2)粘结或粘合层(II)
(3)阻气层(III)
(4)粘结或粘合层(II)
(5)聚烯烃层(IV)
(6)粘结或粘合层(II)
(7)基本上包括用铝或SiOx或第2或第3主族金属氧化物蒸镀的聚酯和/或聚酰胺和/或聚丙烯的层(V)。
并且在其相对面上用铝阻气层来形成常见多层薄膜。
10.用于制造真空绝缘板(VIP)的塑料薄膜,至少具有下面层顺序的7层
(1)聚烯烃热封层(I)
(2)粘结或粘合层(II)
(3)阻气层(III)
(4)粘结或粘合层(II)
(5)聚烯烃层(IV)
(6)粘结或粘合层(II)
(7)基本上包括用铝或SiOx或第2或第3主族金属氧化物蒸镀的聚酯和/或聚酰胺和/或聚丙烯的层(V)。
11.如权利要求1-9中任一权利要求所述的真空绝缘板(VIP)在致冷设备绝缘中的用途。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102661648A (zh) * | 2010-10-14 | 2012-09-12 | 三菱电机株式会社 | 冰箱 |
CN103402754A (zh) * | 2011-03-04 | 2013-11-20 | 巴斯夫欧洲公司 | 复合元件 |
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-
1999
- 1999-04-03 DE DE19915311A patent/DE19915311A1/de not_active Withdrawn
-
2000
- 2000-03-22 PL PL00350763A patent/PL350763A1/xx not_active Application Discontinuation
- 2000-03-22 BR BR0009545-1A patent/BR0009545A/pt not_active Application Discontinuation
- 2000-03-22 AU AU32921/00A patent/AU3292100A/en not_active Abandoned
- 2000-03-22 JP JP2000609662A patent/JP2002541393A/ja active Pending
- 2000-03-22 HU HU0200652A patent/HUP0200652A2/hu unknown
- 2000-03-22 WO PCT/EP2000/002511 patent/WO2000060184A1/de not_active Application Discontinuation
- 2000-03-22 MX MXPA01009946A patent/MXPA01009946A/es unknown
- 2000-03-22 TR TR2001/02830T patent/TR200102830T2/xx unknown
- 2000-03-22 CA CA002367996A patent/CA2367996A1/en not_active Abandoned
- 2000-03-22 CN CN00805788A patent/CN1345394A/zh active Pending
- 2000-03-22 EP EP00910871A patent/EP1169525A1/de not_active Withdrawn
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102661648A (zh) * | 2010-10-14 | 2012-09-12 | 三菱电机株式会社 | 冰箱 |
CN103402754A (zh) * | 2011-03-04 | 2013-11-20 | 巴斯夫欧洲公司 | 复合元件 |
CN106163808A (zh) * | 2014-02-12 | 2016-11-23 | 哈钦森公司 | 包括有机气凝胶的真空绝缘板 |
CN104369506A (zh) * | 2014-11-19 | 2015-02-25 | 苏州北开生化设备有限公司 | 一种用于生化制药设备的绝缘片 |
CN104369506B (zh) * | 2014-11-19 | 2016-06-29 | 太仓弘杉环保科技有限公司 | 一种用于生化制药设备的绝缘片 |
CN111959075A (zh) * | 2020-08-26 | 2020-11-20 | 安徽省恳思惠新型材料有限责任公司 | 一种应用于真空绝热板包装的多层共挤高阻隔膜 |
Also Published As
Publication number | Publication date |
---|---|
EP1169525A1 (de) | 2002-01-09 |
TR200102830T2 (tr) | 2002-03-21 |
AU3292100A (en) | 2000-10-23 |
HUP0200652A2 (en) | 2002-07-29 |
CA2367996A1 (en) | 2000-10-12 |
BR0009545A (pt) | 2001-12-26 |
WO2000060184A1 (de) | 2000-10-12 |
DE19915311A1 (de) | 2000-10-05 |
JP2002541393A (ja) | 2002-12-03 |
PL350763A1 (en) | 2003-01-27 |
MXPA01009946A (es) | 2002-04-24 |
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