CN1496570A - 电线和电缆的绝缘材料 - Google Patents
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Abstract
电线或电缆的绝缘材料,按整个绝缘组合物的重量计,包括至少30%、优选的是至少40%的聚丙烯均聚物和/或共聚物,和至少2%,优选的是至少4%的硫化锌和/或至少5%、优选的是至少10%的氧化锌。优选地,该绝缘材料包括很少或基本不含水合的阻燃剂填充物和基本不含巯基苯并咪唑,并且按重量计,所存在的大部分或基本上全部丙烯共聚物都是丙烯与无卤素共聚单体的共聚物。
Description
技术领域
本发明涉及电线或电缆的绝缘,其中绝缘材料由聚合物部分以及附加的稳定剂、填料和其它添加剂组成,聚合物部分主要是聚丙烯或含丙烯的共聚物,这赋予了该材料出乎意料的有利的性能均衡。
背景技术
在线缆行业中,一直以生产一种基于聚丙烯的可行的高性能绝缘材料为目标。例如,这样的材料在汽车制造业中特别有用,在汽车制造业中,聚丙烯固有的韧性、低成本和可重复利用性是非常理想的特性。对于这种改变的附加强驱动力是由于环境的原因而希望消除PVC。尽管越来越多地在模塑等用途中采用聚丙烯,然而由于一些决定性的限制,迄今为止,作为汽车的电线绝缘,它还没有得到广泛应用。主要的限制是:(i)PVC的降解产物对聚丙烯的侵蚀,(ii)汽车环境中所用液体对聚丙烯的侵蚀;(iii)与聚丙烯直接接触的其它材料,特别是在电线配线制造过程中所使用的聚合材料从聚丙烯中提取抗氧化剂;和(iv)在高温下长期使用的热稳定性。
能够克服这些缺点将允许广泛采用聚丙烯在汽车配线中作为电线,特别的是在发动机支架中,其中,暴露在高温下相当长一段时间(例如公知的“等级3”要求在125℃能耐受3000个小时),以及暴露在机油、挡风玻璃雨刷液体和其它腐蚀性液体中是常见的。另外,对于这些用途必需的是电线能够承受与所有通用类型的绝缘胶带(粘性的和非粘性的)、套管、连接器、密封、以及可选择的电缆护套材料相接触,因为大规模生产不能使用这些部件的电线配线是很不经济的。
发明内容
在本发明中,聚丙烯相对于上述要求的局限性已经得到改善,获得了性能非常有利地均衡的绝缘材料。令人惊讶的是,除了传统的抗氧化剂以外,添加较高含量的某些无机材料实现了这一目的。这些添加剂是金属硫化物和/或金属氧化物,特别是硫化锌和/或氧化锌。根据本发明,其硫化物和/或金属氧化物可以使用的其它可能节约成本的金属包括镁、钙、铁、铝和锡。
硫化物和/或氧化物添加剂在整个配方中的加入量大于1%,优选的是至少2%,非常优选的是至少4%,按重量计。具体地,金属硫化物优选的是硫化锌,添加量是至少2%,优选的是至少4%,按重量计,和/或金属氧化物优选的是氧化锌,加入量是至少5%,优选的是至少10%,按重量计。这里所说的百分比组成都是按整个绝缘组合物的重量计。组合物的其余成分应当由聚丙烯均聚物或优选含有丙烯作为共聚单体之一的共聚物、以及根据需要加入的其它聚合物、传统的抗氧化剂、稳定剂和加工助剂、阻燃剂(卤化的或不含卤素的)和其它填充物组成,以获得所需要的性能均衡。
按整个绝缘组合物重量计,单独的聚丙烯(均聚物和/或共聚物)或它与其它聚合物(如果存在的话)的混合物,优选占至少30%,更优选的是占至少40%,通常占至少50%。在低卤素的和不含卤素的配方中,其中可能使用较高含量的阻燃剂水合填充物,如铝或镁的氢氧化物,聚丙烯聚合物或混合物优选占至少30%,例如30-50%,尽管可以得到更高的聚合物含量。在其中使用更少或没有水合填料的卤化配方中,上述聚合物优选占至少40%,更优选占至少50%,并且经常在绝缘组合物中含量更高。
优选配方包括很少或基本不含水合的阻燃剂填充物,并且基本不含巯基苯并咪唑,按重量计,存在的大部分或基本上全部丙烯共聚物都是丙烯与无卤素共聚单体的共聚物。
本发明的范围中进一步的优点是加入金属硫化物,特别是硫化锌,降低或消除了对传统的金属(铜)钝化剂的需要。还观察到,金属硫化物的加入降低或是消除了对加入的抗氧化剂的需要。通过向上述类型的绝缘材料配方中单独加入金属硫化物或是单独加入金属氧化物,获得了有利的性能,并且在同一配方中加入金属硫化物和金属氧化物的组合,可以获得进一步的优点,金属硫化物和金属氧化物的每一种都按以上建议的含量加入。
以下利用非限制性实施例描述根据本发明的具体绝缘材料配方。
具体实施方式
实施例A
按重量计,该配方包括市售聚丙烯(乙烯丙烯共聚物),其含有5%金属硫化物、6%的包括主抗氧化剂和辅助抗氧化剂的抗氧化剂组合、和21%的含卤素的阻燃剂组合,因此该组合物的溴含量约为(不超过)13%。该混合物可以用传统的处理设备如双螺杆混合机或内混式混合机混合。然后,该混合物可以以较薄的壁厚例如0.2mm-0.3mm挤出在一排裸铜导体上。
样品与一排在普通线缆配线应用中常用的PVC绝缘胶带相接触,在150℃加速老化240小时。当没有硫化锌加到该配方中时,样品(允许在离开加热老化环境后冷却)绕直径约等于绝缘线直径的四倍的卷筒弯曲时开裂。当添加的硫化锌含量为5%或更多时,将提高与PVC的相容性,即在绝缘材料如此弯曲而开裂前可以在150℃老化约600个小时(在某些情况下超过720个小时)。
在125℃与已知的PVC套管接触进行的类似测试显示:如果没有硫化锌,在加热老化大约1500-2000小时的时候(如果抗氧化剂的量降到低于6%,时间会更短),样品将在靠近PVC-聚丙烯的接触面处开裂。含硫化锌混合物的样品显示,在125℃老化超过3500小时后没有裂纹,表明硫化锌往往使与PVC接触的电线寿命增加一倍。
数据还显示,当含硫化锌的聚丙烯电线与其他配线元件密切接触时,如聚合物管道、粘合剂、聚合物连接器和金属连接器、电缆扎带和电缆夹具,往往重复加热老化方面的这种改进模式。
实施例B:
该配方包括含有20%的氧化锌和6%的上述抗氧化剂组合的聚丙烯共聚物,以及21重量%的含卤素的阻燃剂组合。
与PVC绝缘胶带接触的样品在150℃下经过240小时加速老化后显示出与上述实施例A中相似的PVC相容性/加热老化性能的改进。虽然氧化锌明显不如硫化锌有效,但是氧化锌在125℃与PVC套管接触时的性能也改进了,因为含氧化锌的样品在3000个小时之后才在与PVC的接触面上出现裂纹。
实施例C:
聚丙烯与EPR(乙丙橡胶)的共混物的检测是在EPR含量在10%和30%之间,聚丙烯含量在40%和70%之间进行的。聚丙烯与VAE(乙酸乙烯酯/乙烯共聚物)的类似共混物也进行了试验。结果显示:对于含有上述含量的硫化锌和/或氧化锌的配方具有类似的性能改进。
实施例D:
测试含有不同含量抗氧化剂和不同比例的主抗氧化剂和辅助抗氧化剂的配方。结果表明:根据存在的辅助抗氧化剂含量,主抗氧化剂的含量优选等于或大于2%,虽然4%或更多是理想的。在这些情况下,辅助抗氧化剂的含量可以降低到2%而不影响含5%硫化锌的混合物的结果。适合的主抗氧化剂和辅助抗氧化剂本身是公知的。
Claims (15)
1.电线或电缆的绝缘材料,按整个绝缘组合物的重量计,包括至少30%、优选至少40%的聚丙烯均聚物和/或聚丙烯共聚物,和至少2%、优选至少4%的硫化锌和/或至少5%、优选至少10%的氧化锌。
2.权利要求1的绝缘材料,其包括很少或基本不含水合的阻燃剂填充物和基本上不含巯基苯并咪唑,并且按重量计,存在的大部分或基本全部的任何丙烯共聚物都是丙烯与无卤素共聚单体的共聚物。
3.权利要求1或2的绝缘材料,其中硫化锌和/或氧化锌的含量足以使加热老化时间提高至少25%(优选的是至少50%,更优选的是至少75%),所述加热老化时间是电线上的绝缘材料与PVC绝缘胶带或PVC套管接触,能够耐受而在冷却到室温后弯曲而开裂的加热老化时间。
4.前述任一项权利要求的绝缘材料,其卤素含量低或基本为零,并且包含含量至少为30重量%,优选为30-50重量%的聚丙烯聚合物或混合物;或者其具有显著的卤素含量,并且包括含量至少为40%,优选的至少为50%的聚丙烯聚合物或混合物。
5.前述任一项权利要求的绝缘材料,包含至少为2%、优选至少为4%、更优选至少为6%的抗氧化剂组合。
6.前述任一项权利要求的绝缘材料,包含含有10-30%氧化锌的聚丙烯共聚物。
7.前述任一项权利要求的绝缘材料,包含氧化锌和硫化锌的混合物。
8.前述任一项权利要求的绝缘材料,包含聚丙烯共聚物和一种或多种聚合物成份的混合物,所述聚合物成分优选的是乙丙橡胶或VAE。
9.前述任一项权利要求的绝缘材料,其中抗氧化剂的含量大于2%。
10.前述任一项权利要求的绝缘材料,其中抗氧化剂包括主抗氧化剂和辅助抗氧化剂,其比例为1∶0到1∶10,优选1∶1到1∶4。
11.权利要求10的绝缘材料,其包含硫化锌,其中抗氧化剂的含量大于2%,并且省去辅助抗氧化剂(0%)。
12.前述任一项权利要求的绝缘材料,其包含硫化锌,其中没有附加的铜钝化剂。
13.前述任一项权利要求的绝缘材料,其包含小于7%的卤素,优选的是基本上不含卤素,并且包含含量在20%和60%之间的无卤素阻燃剂。
14.前述任一项权利要求的绝缘材料,其中聚丙烯是或者包括均聚物和/或丙烯/乙烯共聚物,优选的是嵌段共聚物。
15.电线或电缆绝缘材料,按整个绝缘组合物重量计,包括至少30%、优选至少40%的聚丙烯均聚物和/或共聚物,包括足够的金属硫化物和/或金属氧化物,优选的是硫化锌和/或氧化锌,使得加热老化时间增加至少25%(优选的是至少50%,更优选的是至少75%),所述加热老化时间是电线上的绝缘与PVC绝缘胶带或PVC套管接触,能够耐受加热老化而在冷却到室温后弯曲但不开裂的时间。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB0106739A GB0106739D0 (en) | 2001-03-14 | 2001-03-14 | Wire insulation |
GB0106739.6 | 2001-03-14 | ||
GB0114611.7 | 2001-06-15 | ||
GB0114611A GB0114611D0 (en) | 2001-06-15 | 2001-06-15 | Wire and cable insulation |
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CN1496570A true CN1496570A (zh) | 2004-05-12 |
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CNA028063244A Pending CN1496570A (zh) | 2001-03-14 | 2002-02-22 | 电线和电缆的绝缘材料 |
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US (1) | US20040079547A1 (zh) |
EP (1) | EP1371068A1 (zh) |
JP (1) | JP2004528681A (zh) |
KR (1) | KR20040030531A (zh) |
CN (1) | CN1496570A (zh) |
BR (1) | BR0208048A (zh) |
CA (1) | CA2439978A1 (zh) |
CZ (1) | CZ20032182A3 (zh) |
HU (1) | HUP0303476A2 (zh) |
IL (1) | IL157379A0 (zh) |
MX (1) | MXPA03008156A (zh) |
NO (1) | NO20034006D0 (zh) |
PL (1) | PL363623A1 (zh) |
RU (1) | RU2003127406A (zh) |
WO (1) | WO2002073631A1 (zh) |
YU (1) | YU72703A (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101006132B (zh) * | 2004-07-30 | 2010-05-05 | 沙特基础工业公司 | 高透明度的丙烯共聚物组合物 |
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JP4198039B2 (ja) | 2003-06-03 | 2008-12-17 | 株式会社オートネットワーク技術研究所 | 非架橋型難燃性樹脂組成物ならびにこれを用いた絶縁電線およびワイヤーハーネス |
JP4652845B2 (ja) * | 2005-02-28 | 2011-03-16 | 古河電気工業株式会社 | 絶縁樹脂組成物および絶縁電線 |
EP2035495B1 (de) * | 2006-06-21 | 2019-09-04 | Venator Germany GmbH | Zinksulfid enthaltender kunststoff |
GB2441158A (en) * | 2006-08-22 | 2008-02-27 | Tyco Electronics Ltd Uk | Zero-halogen wire or cable insulation |
CN101724188B (zh) * | 2008-10-29 | 2012-08-22 | 卢忠远 | 含有金属氧合物的膨胀阻燃材料及其制备方法 |
US8829349B2 (en) * | 2008-12-18 | 2014-09-09 | Exxonmobil Chemical Patents Inc. | Oxides for protection against electrochemical oxidation and ionic contamination in medium-voltage power-cable insulation |
JP5187269B2 (ja) * | 2009-04-28 | 2013-04-24 | 住友電装株式会社 | 絶縁組成物 |
CA2788403C (en) * | 2010-01-29 | 2017-08-08 | Prysmian S.P.A. | Energy cable |
EP2637178A4 (en) * | 2010-11-05 | 2017-11-01 | LS Cable Ltd. | Insulating composition and electric cable comprising same |
KR20170107326A (ko) * | 2016-03-15 | 2017-09-25 | 엘에스전선 주식회사 | 저유전율을 갖는 절연 조성물 및 이로부터 형성된 절연층을 포함하는 케이블 |
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BE597511A (zh) * | 1959-11-25 | 1900-01-01 | ||
AT253610B (de) * | 1963-05-17 | 1967-04-10 | Gen Electric | Elektrisches Isoliermaterial |
US3535257A (en) * | 1967-08-04 | 1970-10-20 | Hercules Inc | Stabilization of olefin polymers against copper-induced degradation |
US4069190A (en) * | 1975-05-12 | 1978-01-17 | General Electric Company | Heat resistant ethylene-propylene rubber and insulated conductor product thereof |
US4125509A (en) * | 1977-10-17 | 1978-11-14 | General Electric Company | Flame and heat resistant ethylene-propylene rubber |
US4204024A (en) * | 1978-06-15 | 1980-05-20 | Harvey Hubbell, Incorporated | Electrical insulation composition having low power factor |
US4459380A (en) * | 1979-02-12 | 1984-07-10 | General Electric Company | Heat resisting ethylene-propylene rubber and insulated conductor product thereof |
US4303574A (en) * | 1979-06-19 | 1981-12-01 | General Electric Company | Heat resistant ethylene-propylene rubber with improved tensile properties and insulated conductor product thereof |
US4419475A (en) * | 1980-11-20 | 1983-12-06 | General Electric Company | Heat resistant ethylene-propylene rubber with improved tensile properties and insulated conductor product thereof |
US4382112A (en) * | 1981-07-07 | 1983-05-03 | General Electric Company | Flexible insulation with improved discoloration and heat age resistance |
JP2767051B2 (ja) * | 1989-02-21 | 1998-06-18 | 住友化学工業株式会社 | ポリプロピレン樹脂組成物 |
KR970006388A (ko) * | 1995-07-19 | 1997-02-19 | 조규향 | 열가소성 에라스토머 (elastomer) 조성물 및 그의 제조방법 |
-
2002
- 2002-02-22 RU RU2003127406/09A patent/RU2003127406A/ru not_active Application Discontinuation
- 2002-02-22 CZ CZ20032182A patent/CZ20032182A3/cs unknown
- 2002-02-22 PL PL02363623A patent/PL363623A1/xx unknown
- 2002-02-22 BR BR0208048-6A patent/BR0208048A/pt not_active Application Discontinuation
- 2002-02-22 KR KR10-2003-7011743A patent/KR20040030531A/ko not_active Application Discontinuation
- 2002-02-22 EP EP02712111A patent/EP1371068A1/en not_active Withdrawn
- 2002-02-22 JP JP2002572591A patent/JP2004528681A/ja active Pending
- 2002-02-22 CN CNA028063244A patent/CN1496570A/zh active Pending
- 2002-02-22 MX MXPA03008156A patent/MXPA03008156A/es not_active Application Discontinuation
- 2002-02-22 CA CA002439978A patent/CA2439978A1/en not_active Abandoned
- 2002-02-22 HU HU0303476A patent/HUP0303476A2/hu unknown
- 2002-02-22 IL IL15737902A patent/IL157379A0/xx unknown
- 2002-02-22 US US10/469,565 patent/US20040079547A1/en not_active Abandoned
- 2002-02-22 YU YU72703A patent/YU72703A/sh unknown
- 2002-02-22 WO PCT/GB2002/000781 patent/WO2002073631A1/en not_active Application Discontinuation
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2003
- 2003-09-10 NO NO20034006A patent/NO20034006D0/no not_active Application Discontinuation
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101006132B (zh) * | 2004-07-30 | 2010-05-05 | 沙特基础工业公司 | 高透明度的丙烯共聚物组合物 |
TWI417904B (zh) * | 2007-03-15 | 2013-12-01 | Union Carbide Chem Plastic | 具有降低的電樹(electrical treeing)之電纜及用於降低電樹的方法 |
CN102884122A (zh) * | 2010-04-05 | 2013-01-16 | 株式会社自动网络技术研究所 | 电线包覆材料用组合物、绝缘电线以及线束 |
CN102884122B (zh) * | 2010-04-05 | 2014-12-17 | 株式会社自动网络技术研究所 | 电线包覆材料用组合物、绝缘电线以及线束 |
US9305678B2 (en) | 2010-04-05 | 2016-04-05 | Autonetworks Technologies, Ltd. | Composition for wire coating member, insulated wire, and wiring harness |
CN105419109A (zh) * | 2016-01-12 | 2016-03-23 | 芜湖航天特种电缆厂股份有限公司 | 一种耐寒高阻燃电缆保护套 |
CN110869429A (zh) * | 2017-07-07 | 2020-03-06 | Sabic环球技术有限责任公司 | 聚乙烯组合物 |
CN109306113A (zh) * | 2018-11-01 | 2019-02-05 | 中广核高新核材科技(苏州)有限公司 | 一种汽车线用辐照交联低烟无卤阻燃聚烯烃电缆料 |
Also Published As
Publication number | Publication date |
---|---|
CZ20032182A3 (cs) | 2003-11-12 |
YU72703A (sh) | 2006-03-03 |
EP1371068A1 (en) | 2003-12-17 |
PL363623A1 (en) | 2004-11-29 |
JP2004528681A (ja) | 2004-09-16 |
NO20034006L (no) | 2003-09-10 |
WO2002073631A1 (en) | 2002-09-19 |
BR0208048A (pt) | 2004-07-27 |
HUP0303476A2 (hu) | 2004-01-28 |
RU2003127406A (ru) | 2005-04-20 |
NO20034006D0 (no) | 2003-09-10 |
KR20040030531A (ko) | 2004-04-09 |
MXPA03008156A (es) | 2003-12-12 |
CA2439978A1 (en) | 2002-09-19 |
IL157379A0 (en) | 2004-02-19 |
US20040079547A1 (en) | 2004-04-29 |
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