CN1331160C - 含有绝缘材料的电线或电缆 - Google Patents
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Abstract
含有绝缘材料的电线或电缆,该绝缘材料包括:层(ⅰ):至少一个第一层聚烯烃基材料层,它包含占全部材料组合物至少20wt%的含羰基聚合物,所述聚合物为均聚物或共聚物或三元共聚物,该聚合物的组成单体或至少一种组成单体为羧酸酯,使用时该单体本身构成至少5wt%的所述共聚或三元共聚聚合物,而该共聚或三元共聚聚合物的余下部分衍生自烯烃单体;与层(ⅰ)接触的层(ⅱ):至少一个第二层材料层,它包含以全部材料组合物为基准至少10wt%的聚偏氟乙烯或偏氟乙烯与部分或全部氟化的共聚单体的共聚物;其中所述层(ⅰ)和层(ⅱ)在彼此接触的情况下经历了交联反应以足以将所述层间的剥离粘结强度增加到至少5牛顿。
Description
技术领域
本发明涉及电线或电缆(此后统称“电线”)用绝缘材料,其中在聚烯烃基材料层和聚偏氟乙烯基材料层之间的界面处获得牢固的结合。本发明特别用于电线的多层绝缘材料,可以获得这种材料层之间的高性能结合并保持可接受的关系复杂的其它电线性能要求之间的均衡,这些性能要求是专门的,不同于其它种类制品如模塑制品或包装薄膜的标准。
背景技术
下文中将用到下列缩写符号:
PJ=基套(Primary Jacket);pro-rad=交联促进剂;TMPTM=三羟甲基丙烷三甲基丙烯酸酯;ASTM=美国试验与材料学会;PVDF=聚偏氟乙烯;VDF =偏氟乙烯;HFP=六氟丙烯;HDPE=高密度聚乙烯;EEA=乙烯/丙烯酸乙酯;EMA=乙烯/乙酸甲酯;EVA=乙烯/乙酸乙烯酯;EA=丙烯酸乙酯;MA=丙烯酸甲酯;VA=乙酸乙烯酯。
包括聚烯烃内层(芯层)和聚偏氟乙烯(PVDF)外层(基套或PJ)的双层电线绝缘材料已商品化30年以上,并且可由一些不同的生产商供应。这些产品的内(聚烯烃)外(PVDF)层间的粘结均是可忽略的,因此很容易分离。必须接受由这种缺乏结合而限制了结构坚固性所带来的某些缺陷。例如,如果受到机械应力、暴露在某些流体中、接触尖锐物品、或受到冲击,外面的绝缘层可能破裂并从内层剥离。绝缘材料的耐磨性和耐弯曲疲劳性、以及抗弯曲折皱性(这可引起将电线密封或将其插入绝缘垫圈或接头的困难)也受具有两层易分离绝缘层的不利影响。一直认为以工业上可接受的成本及生产效率将诸如聚烯烃和PVDF这样两种不相似类型的材料层粘结到电线上是不可能的。而且,已有的粘结技术令人不能接受地影响电线的性能特性。传统粘结聚烯烃和PVDF的方法是使用衔接层材料(例如US专利5,589,028),但它们昂贵并且当用于电线时损害其它性能,例如热老化性,并增加了形成外层的制造过程的复杂性。而且根据已增加的粘结强度的效力也是有限的。
发明内容
根据本发明已经发现不相似的绝缘材料聚烯烃基芯层和聚偏氟乙烯基PJ层可以以相当水平的粘着力共同粘结到电线或电缆上;这种粘结倾向于减少或消除电线上的上述坚固性问题;并且出乎意料的是获得这种粘结未对抗龟裂延伸性、成本或对电线性能特性的总体平衡产生不能令人接受的影响。
在本发明的电线或电缆绝缘材料中,通过联合使用所选择的聚烯烃基配制物层、与聚偏氟乙烯基层接触、以及交联反应,优选通过使用辐射,特别是离子辐射进行交联而出乎意料地获得了相当大的粘结强度。
因此本发明提供了含有绝缘材料的电线,该绝缘材料包括:
(i)至少一个第一层聚烯烃基材料层,它包含至少20wt%、优选至少40wt%、更优选至少60wt%或至少80wt%(占全部材料组合物)的具有非芳族骨架的含羰基聚合物(均聚物或共聚物或三元共聚物),该聚合物的组成单体或至少一种组成单体为羧酸酯,优选为丙烯酸酯或乙酸酯,特别是丙烯酸烷基酯(优选丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯或丙烯酸丁酯),使用时该单体本身构成至少5wt%、优选至少9wt%、更优选至少15wt%的所述共聚或三元共聚聚合物,而所述共聚或三元共聚聚合物的余下部分优选衍生自烯烃单体,优选乙烯,(i)与(ii)接触;
(ii)至少一个第二层材料层,它包含至少10wt%,更优选至少50wt%或至少90wt%聚偏氟乙烯(PVDF),或特别优选基于VDF与部分或全部氟化的共聚单体的共聚物,最优选VDF和六氟丙烯(HFP)的共聚物;其中所述层(i)和(ii)彼此接触的同时经历了交联反应,优选通过辐射,更优选通过电离性辐射进行交联以足以将所述层间的剥离粘结强度增加到至少5N,与未交联层间粘结强度相比,粘结强度优选增加了至少50%,更优选增加了至少100%,特别是增加了至少500%或1000%。
根据本发明的另一方面,我们提供了含有绝缘材料的电线,所述绝缘材料包括:
(i)至少一个第一层聚烯烃基材料层,该材料的聚合物部分的至少20wt%、优选至少40wt%、更优选至少60wt%或非常优选至少80wt%由含羰基聚合物(均聚物或共聚物或三元共聚物)组成,该聚合物的组成单体或至少一种组成单体为羧酸酯,优选为丙烯酸酯或乙酸酯,特别是丙烯酸烷基酯(优选丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯或丙烯酸丁酯),使用时该单体本身构成至少5wt%,优选至少9wt%,更优选至少15wt%的所述共聚或三元共聚聚合物,而共聚或三元共聚聚合物的余下部分或大部分余下部分优选衍生自烯烃单体,优选乙烯;(i)与(ii)接触,
(ii)至少一个第二层另一种材料材料层,它包含至少10wt%、更优选至少50wt%、非常优选至少90wt%、特别是100wt%聚偏氟乙烯(PVDF),或特别优选基于VDF与部分或全部氟化的共聚单体的共聚物,最优选VDF和六氟丙烯(HFP)的共聚物;
其中所述层(i)和(ii)在彼此接触的情况下经历了交联反应,优选通过辐射,更优选通过电离性辐射进行交联以足以防止两层在下述的丙酮浸泡试验中分层,或能够将根据下述ASTM B1876-95方法测定的所述层间的剥离粘结强度增加到至少5N,与未交联层间粘结强度相比,粘结强度优选增加了至少50%,更优选增加了至少100%,特别是增加了至少500%或1000%。
优选在至少一层中的聚合物材料的熔点或软化点之上的温度下使各层彼此接触,由此倾向于使其界面接触的紧密度最大并因此可以促进在随后的交联反应中形成增进粘结的界面交联键。
除了配制物的聚合物部分(对其要求已经在上面规定)外,
聚烯烃基层 (i)还可包含任何所需要的本身已知的添加剂如抗氧剂、颜料、填料、阻燃剂等以赋予聚合物所要求的机械、热、电等性能。
聚偏氟乙烯基层(ii)也可包含本身已知的其它添加剂以得到粘结性之外的所要求性能。
根据本发明
获得牢固粘结的优点包括:
-表层的耐磨性和绝缘作用整体提高,如果将其(表层)粘结到基底材料上;
-改进的抗剥离性,特别是如果一层被损坏/打孔时;
-改进的抗两层起泡性,如果加热时;
-改进的抗两层间分层/折痕/折皱性,例如由于机械应力或暴露于化学试剂如暴露于溶剂;
-获得降低了的电线弯曲折皱性和上述特性的改进,同时保持适当的抗切开和缺口扩展性,后者是出乎意料的,因为通常认为牢固粘结的层能相当容易地将切口或缺口从外层扩展至内层。
具体实施方案
本申请中所述的
粘结强度可用所研究的两种材料的粘结条带间的剥离强度来度量。可用于这种试验的一个标准方法是ASTM 1876-95。由该规定,有效粘结可以是剥离力超过5N者,而强粘结为剥离力大于10N者。测定所述层,即(i)和(ii)间粘结强度的一个便利方法是于23(+/-3)℃把总长度为60mm的样品电线(层(i)和(ii)已经被制作到该电线上)放入丙酮(例如Fisher Scientific UK,分析纯丙酮)中至在丙酮中的深度等于样品电线长度的70%,时间为1小时。与绝缘层具有可忽略粘结的电线沿电线轴向发生PVDF PJ扩展,这是与聚烯烃芯的任何扩展无关的,和/或发生PJ折皱以致在该位置与芯层分层。当发生时,上述PJ扩展一般在经过上述试验后的样品电线上产生一个长于芯切口端1mm或更多的PJ“管”。与绝缘层具有有效粘结的电线将发生芯和PJ的共同扩展而不分离,这种扩展延至导线的切割边缘之外并沿电线轴方向,和/或将发生芯及PJ层的共同起皱而不分层。可通过在显微镜下检测折皱的横截面来区分这种芯和PJ的共同起皱与单独PJ起皱。
制作电线的方法可以包括引起上述(i)和(ii)层间紧密接触的任何方法。实例包括将一种材料涂布到另一种的预成形的层上,进行双层或多层挤塑形成分别包含一种或另一种上述两种类型材料的绝缘层。烯烃基材料(i)优选为内层而PVDF基层(ii)优选为电线上的外层。由这两种不同材料制成的层可进行共挤塑、串联式挤塑、多程挤塑、或用其它方法涂布。可用已知的电线绝缘方法如软管牵伸挤塑来形成其中的一层或多层,但是本身已知的加压挤塑优选用于将另一层及任何后继的待施加绝缘层最佳粘结到预成形的基层上。
电线上的绝缘材料经受交联反应,这可引入化学试剂如过氧化物而进行,但优选通过辐射,特别是由能引发自由基形成并由此在聚合物中形成交联键的
电离性辐射源进行,有些交联键优选应该在两种材料间的界面区域形成。因此需要辐射至少能穿透材料到材料的界面,虽然这种穿透不是必需的,如果例如离子或自由基迁移率能够在辐射过程后在界面处或附近使分子反应继续进行的话。辐射源可以为例如放射性同位素、或X射线源、或可以是非电离性自由基生成源,例如UV源,但优选为电子束,更优选提供辐射入材料中的电子束剂量大于2Mrad,优选至少为5Mrad,更优选至少为10Mrad,非常优选至少为15Mrad者。
已经发现通过使用某些添加剂可获得界面粘结强度的增强。添加剂优选包括聚烯烃基材料和/或PVDF基材料中的交联促进剂(“pro-rad”)。可将已知的交联材料,优选甲基丙烯酸酯/丙烯酸酯基交联材料,且非常优选三羟甲基丙烷三甲基丙烯酸酯(TMPTM)型交联材料用于聚烯烃材料和/或PVDF基材料中。
实验结果:
下表中所引全部结果均是通过试验由本身为人熟知的通常聚合物处理技术制备的两种材料的压片而获得的。将样片压在一起使其面对面粘结并如表中所示辐照已粘结的组合片。由于片上的粘结强度较易测定,所以使用压片而不是电线来进行这些证实性实验。这些实验的条件如下:
压片尺寸:150mm×150mm×0.85mm
压制温度:200℃
压制时间:预热2min,加压1min
压制压力:在300mm×300mm金属板上施加20-40吨压力
冷却条件:在水冷却的300mm×300mm金属板间于上述压力下2min
实施例:辐射剂量对适当聚烯烃基和PVDF基材料间已建立的粘结强
度的影响
材料1 | 材料2 | 剂量(Mrad) | 剥离力(N) |
VA含量为25wt%的EVA共聚物 | HFP含量为10wt%的VDF/HFP共聚物+7.5wt%添加剂 | 0 | 0.5 |
同上 | 同上 | 15 | 40 |
EA含量为15wt%的EEA共聚物 | HFP含量为10wt%的VDF/HFP共聚物 | 0 | 1 |
EA含量为15wt%的EEA共聚物 | HFP含量为10wt%的VDF/HFP共聚物 | 8 | 24 |
EA含量为15wt%的EEA共聚物 | HFP含量为10wt%的VDF/HFP共聚物 | 20 | 52 |
丙烯酸酯含量为19wt%的乙烯/丙烯酸酯/马来酸酐三元共聚物 | HFP含量为10wt%的VDF/HFP共聚物 | 0 | 5 |
丙烯酸酯含量为19wt%的乙烯/丙烯酸酯/马来酸酐三元共聚物 | HFP含量为10wt%的VDF/HFP共聚物 | 20 | 21 |
实施例:乙烯共聚物材料中共聚单体百分比对电子束交联后该共聚
物材料与适当PVDF基材料间粘结强度的影响
材料1 | 材料2 | 剂量(Mrad) | 剥离力(N) |
MA含量为9wt%的EMA共聚物 | HFP含量为10wt%的VDF/HFP共聚物+7.5wt%添加剂 | 20 | 4 |
MA含量为28wt%的EMA共聚物 | 同上 | 20 | 45 |
实施例:聚烯烃聚合物共混物中共聚物百分比对电子束交联后该共
混物与适当PVDF基材料间粘结强度的影响
材料1 | 材料2 | 剂量(Mrad) | 剥离力(N) |
100%HDPE | HFP含量为10wt%的VDF/HFP共聚物+7.5wt%添加剂 | 20 | 0 |
20%HDPE+80%的EA含量为15wt%的EEA共聚物 | 同上 | 20 | 70 |
实施例:PVDF基材料类型对电子束交联后该PVDF基材料与适当聚
烯烃基材料间粘结强度的影响
材料1 | 材料2 | 剂量(Mrad) | 剥离力(N) |
VA含量为25wt%的EVA共聚物 | PVDF均聚物 | 15 | 4 |
同上 | HFP含量为10wt%的VDF/HFP共聚物 | 15 | 17.5 |
实施例:烯烃材料中加入Pro-rad对电子束交联后该烯烃材料与适
当PVDF基材料间粘结强度的影响
材料1 | 材料2 | 剂量(Mrad) | 剥离力(N) |
20%HDPE+80%的EA含量为15wt%的EEA共聚物 | HFP含量为10wt%的VDF/HFP共聚物+7.5wt%添加剂 | 20 | 70 |
19%HDPE+77%的EA含量为15wt%的EEA共聚物+4%TMPTM pro-rad | 同上 | 20 | >130 |
电线构造实施例
如下制备其中绝缘材料由根据本发明的粘结在一起的两层聚合物层组成的电线:
绝缘材料的内层(即离电线导体较近的层)为聚烯烃基材料,主要由(a)含有15wt%EA的EEA共聚物和(b)共聚物:HDPE重量比约为8∶2的HDPE组成,常规的其它添加剂包括交联促进剂、稳定剂、抗氧剂、颜料和加工助剂以总含量为24wt%的较小比例存在。该层被加压挤塑到金属电线导体上。
绝缘材料的外层主要由含有10wt%HFP的PVDF/HFP共聚物组成,在该实施例中包括总共为7.5wt%通常比例的交联促进剂和其它已知的添加剂如颜料、增塑剂、稳定剂、抗氧剂和加工助剂。在另一个单独操作中将该外层加压挤塑到预成形的内层上。随后使该已涂布电线产品通过电子束,并接受20Mrad的辐射剂量。
在第二个实施例中如上制备电线,其中内层中的交联促进剂为4%TMPTM,而绝缘材料外层仅包括含有10wt%HFP的PVDF/HFP共聚物。随后使该已涂布电线产品通过电子束,并接受20Mrad的辐射剂量。使该电线经历丙酮浸泡试验,以证明绝缘材料层有效粘结在一起。
在第三个实施例中,与第二个实施例相同构造的电线是通过串联式加压挤塑内和外绝缘材料层而制备的。随后使该已涂布电线产品通过电子束,并接受20Mrad的辐射剂量。使该电线经历丙酮浸泡试验,以证明绝缘材料层有效粘结在一起。
按上述第二个实施例构造的电线相对目前商品化的电线有性能改进
的证明
将根据上述构造和制备方法的电线(称作电线A)与相同尺寸的市场上的主导商品聚烯烃/PVDF双层电线(称作电线B)通过苛刻处理和最终使用环境下电线牢固性的一系列试验进行比较。获得下列结果。
耐刮磨性改进实施例
方法:设备=常规型电线刮磨机,电线尺寸0.75mm2(导线横截面面积),刀片型平板,厚度3.5mm,与导线垂直放置,每边半径边缘0.05mm,所用载荷1.8kg,冲程10cm,55循环/min
电线类型 | 在40℃磨损PJ的刮擦循环次数 |
A | >800 |
B | 272 |
电线类型 | 在5℃磨损PJ的刮擦循环次数 |
A | >1350 |
B | 212 |
耐冷冲击性改进的实施例
方法:电线尺寸6mm2(导线横截面面积),冲击重量800g,坠落到砧板的高度275mm,冲击在电线上的砧板面积尺寸7mm×2mm,沿每边45°锥角扩展到3.4mm,环境温度5℃。目视检测绝缘材料的裂纹扩展情况。
电线类型 | 冷冲击试验结果 |
A | PJ中无裂纹扩展到砧板冲击点之外 |
B | PJ中有一些长度>5mm的裂纹扩展到砧板冲击点之外。PJ开始从芯层剥离 |
耐溶剂性改进的实施例
方法:电线尺寸0.75mm2,电线长度60mm,丙酮中浸泡长度为电线长度的75%,浸泡时间1小时,温度23℃
电线类型 | 丙酮浸泡试验结果 |
A | 芯层和PJ不分离/不分层,两个绝缘材料层中均未观察到裂纹 |
B | 沿浸泡长度PJ折皱非常严重,两处同时开裂,并暴露出2-3mm芯层 |
Claims (16)
1.含有绝缘材料的电线或电缆,该绝缘材料包括:
层(i):至少一个第一层聚烯烃基材料层,它包含占全部材料组合物至少20wt%的含羰基聚合物,所述聚合物为均聚物或共聚物或三元共聚物,该聚合物的组成单体或至少一种组成单体为羧酸酯,使用时该单体本身构成至少5wt%的所述共聚或三元共聚聚合物,而该共聚或三元共聚聚合物的余下部分衍生自烯烃单体;
层(i)与层(ii)接触,
层(ii):至少一个第二层材料层,它包含以全部材料组合物为基准至少10wt%的聚偏氟乙烯或偏氟乙烯与部分或全部氟化的共聚单体的共聚物;
其中所述层(i)和层(ii)在彼此接触的情况下经历了交联反应以足以将所述层间的剥离粘结强度增加到至少5牛顿。
2.含有绝缘材料的电线或电缆,该绝缘材料包括:
层(i):至少一个第一层聚烯烃基材料层,该材料的聚合物部分的至少20wt%由含羰基聚合物组成,所述聚合物为均聚物或共聚物或三元共聚物,该聚合物的组成单体或至少一种组成单体为羧酸酯,使用时该单体本身构成至少5wt%的所述共聚或三元共聚聚合物,而共聚或三元共聚聚合物的余下部分或大于50wt%的余下部分衍生自烯烃单体;
层(i)与层(ii)接触,
层(ii):至少一个第二层另一种材料层,其包含至少10wt%聚偏氟乙烯,或偏氟乙烯与部分或全部氟化的共聚单体的共聚物;
其中所述层(i)和层(ii)在彼此接触的情况下经历了交联反应,以足以防止两层在23℃于丙酮中浸泡1小时的试验中分层,或能够将根据ASTMB1876-95方法测定的所述层间的剥离粘结强度增加到至少5牛顿,与未交联层间粘结强度相比,粘结强度增加了至少50%。
3.权利要求1的电线或电缆,其中所述层(i)和层(ii)在彼此接触的情况下经历了交联反应,以足以防止两层在23℃于丙酮中浸泡1小时的试验中分层。
4.权利要求1的电线或电缆,其中与未交联层间粘结强度相比,交联反应将粘结强度增加了至少50%。
5.权利要求1-3任一项的电线或电缆,其中在任一层交联前并在至少一层中的聚合物材料的熔点或软化点之上的温度下使各层彼此接触。
6.权利要求1-3任一项的电线或电缆,其中聚偏氟乙烯基层包括偏氟乙烯和六氟丙烯的共聚物,以重量计,该共聚物构成此层中的大于50wt%的材料。
7.权利要求1-3任一项的电线或电缆,其中聚偏氟乙烯基层包括六氟丙烯含量为8-12wt%的偏氟乙烯和六氟丙烯的共聚物。
8.权利要求1-3任一项的电线或电缆,其中聚烯烃基层包括聚乙烯和所述含羰基聚合物的混合物。
9.权利要求1-3任一项的电线或电缆,它包括所述聚烯烃基材料内层和所述聚偏氟乙烯基材料外层。
10.权利要求9的电线或电缆,其中所述外层被加压挤塑到所述内层上。
11.权利要求1-3任一项的电线或电缆,其中交联反应是通过辐射进行的。
12.权利要求1-3任一项的电线或电缆,它包括构成所述层(i)和层(ii)材料的多重交替层。
13.权利要求1-3任一项的电线或电缆,其在所述层(i)和层(ii)的任一层或两层的材料中包含至少一种交联促进剂。
14.权利要求13的电线或电缆,其中交联促进剂为多官能团丙烯酸酯或甲基丙烯酸酯。
15.权利要求14的电线或电缆,其中交联促进剂只加入到所述层(i)的材料中。
16.权利要求1-3任一项的电线或电缆,其中层(ii)为透明的,只含有聚偏氟乙烯或所述的偏氟乙烯共聚物。
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US5206459A (en) * | 1991-08-21 | 1993-04-27 | Champlain Cable Corporation | Conductive polymeric shielding materials and articles fabricated therefrom |
US5589028A (en) * | 1994-11-03 | 1996-12-31 | Elf Atochem North America, Inc. | Bonding method employing tie layers for adhering polyethylene to fluoropolymers |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3269862A (en) * | 1964-10-22 | 1966-08-30 | Raychem Corp | Crosslinked polyvinylidene fluoride over a crosslinked polyolefin |
US3650827A (en) * | 1969-11-17 | 1972-03-21 | Electronized Chem Corp | Fep cables |
-
1998
- 1998-09-17 GB GBGB9820214.6A patent/GB9820214D0/en not_active Ceased
-
1999
- 1999-09-17 PL PL346214A patent/PL192515B1/pl unknown
- 1999-09-17 RO ROA200100291A patent/RO121928B1/ro unknown
- 1999-09-17 WO PCT/GB1999/003116 patent/WO2000017889A1/en active IP Right Grant
- 1999-09-17 DE DE69930532T patent/DE69930532T2/de not_active Expired - Lifetime
- 1999-09-17 ES ES99947633T patent/ES2260937T3/es not_active Expired - Lifetime
- 1999-09-17 TR TR2001/00761T patent/TR200100761T2/xx unknown
- 1999-09-17 KR KR1020017002898A patent/KR100638181B1/ko active IP Right Grant
- 1999-09-17 CZ CZ20010482A patent/CZ299046B6/cs not_active IP Right Cessation
- 1999-09-17 BR BR9913843-3A patent/BR9913843A/pt not_active IP Right Cessation
- 1999-09-17 ID IDW20010554A patent/ID29877A/id unknown
- 1999-09-17 RU RU2001107973/09A patent/RU2231147C2/ru not_active IP Right Cessation
- 1999-09-17 JP JP2000571464A patent/JP2002525819A/ja active Pending
- 1999-09-17 EP EP99947633A patent/EP1116243B1/en not_active Expired - Lifetime
- 1999-09-17 CA CA002340386A patent/CA2340386C/en not_active Expired - Fee Related
- 1999-09-17 HU HU0103585A patent/HU226699B1/hu unknown
- 1999-09-17 CN CNB998110302A patent/CN1331160C/zh not_active Expired - Lifetime
- 1999-09-17 IL IL14133899A patent/IL141338A0/xx active IP Right Grant
- 1999-09-17 AU AU61019/99A patent/AU766430B2/en not_active Expired
- 1999-09-17 AT AT99947633T patent/ATE321345T1/de not_active IP Right Cessation
-
2001
- 2001-02-08 IL IL141338A patent/IL141338A/en not_active IP Right Cessation
- 2001-02-12 ZA ZA200101181A patent/ZA200101181B/en unknown
- 2001-03-15 NO NO20011307A patent/NO324458B1/no not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5206459A (en) * | 1991-08-21 | 1993-04-27 | Champlain Cable Corporation | Conductive polymeric shielding materials and articles fabricated therefrom |
US5589028A (en) * | 1994-11-03 | 1996-12-31 | Elf Atochem North America, Inc. | Bonding method employing tie layers for adhering polyethylene to fluoropolymers |
Also Published As
Publication number | Publication date |
---|---|
EP1116243A1 (en) | 2001-07-18 |
AU766430B2 (en) | 2003-10-16 |
HUP0103585A2 (hu) | 2002-01-28 |
NO324458B1 (no) | 2007-10-22 |
CN1318200A (zh) | 2001-10-17 |
JP2002525819A (ja) | 2002-08-13 |
ID29877A (id) | 2001-10-18 |
RO121928B1 (ro) | 2008-07-30 |
IL141338A0 (en) | 2002-03-10 |
CA2340386C (en) | 2009-04-14 |
TR200100761T2 (tr) | 2001-09-21 |
AU6101999A (en) | 2000-04-10 |
CA2340386A1 (en) | 2000-03-30 |
DE69930532D1 (de) | 2006-05-11 |
PL192515B1 (pl) | 2006-10-31 |
EP1116243B1 (en) | 2006-03-22 |
PL346214A1 (en) | 2002-01-28 |
RU2231147C2 (ru) | 2004-06-20 |
CZ2001482A3 (cs) | 2001-07-11 |
KR100638181B1 (ko) | 2006-10-26 |
IL141338A (en) | 2006-12-31 |
ES2260937T3 (es) | 2006-11-01 |
CZ299046B6 (cs) | 2008-04-09 |
DE69930532T2 (de) | 2007-03-08 |
NO20011307D0 (no) | 2001-03-15 |
WO2000017889A1 (en) | 2000-03-30 |
ZA200101181B (en) | 2002-05-13 |
HU226699B1 (en) | 2009-07-28 |
NO20011307L (no) | 2001-03-15 |
GB9820214D0 (en) | 1998-11-11 |
KR20010079751A (ko) | 2001-08-22 |
ATE321345T1 (de) | 2006-04-15 |
HUP0103585A3 (en) | 2002-04-29 |
BR9913843A (pt) | 2001-08-14 |
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