CN104220511A - 无卤阻燃树脂组合物、以及使用该无卤阻燃树脂组合物的电线和电缆 - Google Patents

无卤阻燃树脂组合物、以及使用该无卤阻燃树脂组合物的电线和电缆 Download PDF

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CN104220511A
CN104220511A CN201280046230.0A CN201280046230A CN104220511A CN 104220511 A CN104220511 A CN 104220511A CN 201280046230 A CN201280046230 A CN 201280046230A CN 104220511 A CN104220511 A CN 104220511A
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mass parts
resin composition
flame retardant
halogen
electric wire
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真山裕平
西川信也
远藤仁
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Sumitomo Electric Industries Ltd
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Abstract

本发明提供一种无卤阻燃树脂组合物,以及使用所述阻燃树脂组合物作为其包覆层的电线和电缆,其中该无卤阻燃树脂组合物具有绝缘置换用电线所需的切通强度、耐磨性和阻燃性,并且具有满足UL标准的拉伸性能。相对于100质量份的树脂组分,该无卤阻燃树脂组合物包含60质量份至100质量份的金属氢氧化物和5质量份至20质量份的氮系阻燃剂,其中每100质量份的树脂组分中含有50质量份至80质量份的聚烯烃系树脂和20质量份至50质量份的苯乙烯系弹性体,以及2质量份至15质量份的含环氧基的乙烯系共聚物作为聚烯烃系树脂的一部分。

Description

无卤阻燃树脂组合物、以及使用该无卤阻燃树脂组合物的电线和电缆
技术领域
本发明涉及适合用作电线等的包覆层的无卤阻燃树脂组合物,以及使用该树脂组合物的电线和电缆。
背景技术
在办公自动化(OA)设备(如复印机与打印机)和电子装置的内部布线中,使用了多条线束,这些线束在印刷电路板之间或者在印刷电路板与电子元件(如传感器、执行器或马达)之间输送电力并电传输信号。
通过将多条电线或电缆捆扎在一起,并在所得的束末端连接诸如可插入/移除的连接器之类的端子从而制造线束。考虑到阻燃性、电绝缘性等,将包含聚氯乙烯(PVC)作为绝缘材料的PVC电线用作线束用电线。由于PVC电线具有良好的挠性,因此当这类电线被用于线束时可获得良好的易操作性。由于PVC电线具有足够的强度,因而在配线时不会发生绝缘体断裂或磨损的问题。另外,将待连接的绝缘置换连接器连接至PVC电线的末端时,PVC电线具有良好的可加工性。
然而,由于PVC电线含有卤元素,因此可能会有以下问题:当使用之后焚烧线束时会产生氯化氢有毒气体,或在一些焚烧条件下会产生二噁英。考虑到减轻环境负荷的要求,PVC作为绝缘材料不是优选的。
近年来,为了满足日益增长的降低环境负荷的需求,已经开发了这样的无卤素电线,这种无卤素电线中的包覆材料不含有PVC树脂或卤系阻燃剂。通常要求用于电子装置内部布线的绝缘电线和绝缘电缆的性能符合美国保险商实验室公司(Underwriters LaboratoriesInc.(UL))的标准。在UL标准中,详细规定了产品应当满足的各种性能,如阻燃性、热变形性、低温性能和包覆材料在初始状态以及热老化后的拉伸性能。
就用于绝缘置换或压接的电线而言,需要在电子装置内布置线束。在这个过程中,可能会产生电线的绝缘包覆层的擦伤和破裂,从而造成缺陷。因此,要求用于线束的绝缘电线具有高的切通强度(cut-through strength)。也要求具有耐磨性。
日本未审查专利申请公开No.2002-105255(专利文献1)公开了一种阻燃树脂组合物以及使用该阻燃树脂组合物的布线材料,其中该阻燃树脂组合物是通过将金属水合物和热塑性树脂组分在加热下捏合而制得的,该热塑性树脂组分是通过将弹性体(如乙烯丙烯橡胶或丁苯橡胶)与聚丙烯共混而制备的。通过混合弹性体可增强填料的可接受性。此外已经研究出,通过与弹性体交联从而平衡了诸如挠性与伸长率等机械性能、挤出性能和阻燃性。然而,与PVC相比,这种材料在耐磨性和耐刃性(edge resistance)(切通性能)方面较差。当这些性能得到改善时,则挠性降低,从而导致诸性能间失去平衡的问题。
日本未审查专利申请公开No.2006-36813(专利文献2)和2007-302907(专利文献3)公开了这样的树脂组合物,其通过在有机过氧化物的存在下对含有聚丙烯作为主要成分的树脂混合物进行动态交联而获得。因为聚丙烯不会通过电离辐射的照射而交联,所以通过动态交联提高了这些材料的强度。然而,关于这类动态交联的材料,挤出过程中的稳定性不足,并且在一些挤出条件下诸如伸长率和强度之类的拉伸性能可能不足。
当使用含有聚乙烯作为主要成分的树脂组合物时,可通过调节交联度来获得必要的强度,其中,该树脂组合物通过电离辐射的照射而交联。然而,为了在使用无卤阻燃树脂组合物时表现出阻燃性能,需要向该树脂组合物中添加大量的诸如金属氢氧化物之类的阻燃剂,因此不能满足绝缘置换或压接用电线所要求具备的切通强度和耐磨性。另外,因为伸长率降低,所以不能满足UL标准中所规定的拉伸性能。
引用列表
专利文献
专利文献1:日本未审查专利申请公开No.2002-105255
专利文献2:日本未审查专利申请公开No.2006-36813
专利文献3:日本未审查专利申请公开No.2007-302907
发明内容
技术问题
本发明的目的是提供一种无卤阻燃树脂组合物,以及使用该阻燃树脂组合物作为其包覆层的电线和电缆,其中该无卤阻燃树脂组合物具有绝缘置换用电线所要求具备的切通强度、耐磨性和阻燃性,并且具有满足UL标准的拉伸性能。
问题的解决方案
本发明提供了一种无卤阻燃树脂组合物,其包含:树脂组分;金属氢氧化物,相对于100质量份的所述树脂组分,所述金属氢氧化物的量为60质量份至100质量份;以及氮系阻燃剂,相对于100质量份的所述树脂组分,所述氮系阻燃剂的量为5质量份至20质量份,其中每100质量份的所述树脂组分中含有50质量份至80质量份的聚烯烃系树脂和20质量份至50质量份的苯乙烯系弹性体,所述聚烯烃系树脂含有2质量份至15质量份的含环氧基的乙烯系共聚物作为其一部分。
聚烯烃系树脂和苯乙烯系弹性体被组合用作树脂组分。聚烯烃系树脂被广泛用作电线的覆层并且具有良好的挤出性能。另外,聚烯烃系树脂可以通过电离辐射的照射而交联,并有助于同时实现高拉伸性能和高耐热性。因为苯乙烯系弹性体具有挠性,所以其不仅可以提供填料可接受性,而且还可以实现拉伸性能的进一步提高和稳定。通过组合聚烯烃系树脂和苯乙烯系弹性体,可以稳定地获得UL标准所要求的拉伸性能。此外,通过引入金属氢氧化物和氮系阻燃剂,可获得能够通过VW-1垂直试样燃烧试验的阻燃性。
将含环氧基的乙烯系共聚物用作聚烯烃系树脂的一部分。因为含环氧基的乙烯系共聚物为聚乙烯系树脂,所以其可通过电离辐射的照射而交联。与未引入含环氧基的乙烯系共聚物的情况相比,通过在100质量份的树脂组分中引入2质量份至15质量份的含环氧基的乙烯系共聚物,可以显著提高切通强度。
优选包含乙烯-醋酸乙烯酯共聚物作为聚烯烃系树脂,其中该乙烯-醋酸乙烯酯共聚物含有20质量份以上50质量份以下的醋酸乙烯酯。另外,优选含有高密度聚乙烯。因为乙烯-醋酸乙烯酯共聚物具有良好的挠性,因此其在氢氧化镁等阻燃剂的可接受性方面是良好的,并且还有助于伸长率的提高。高密度聚乙烯有助于切通强度和耐磨性的提高。如同上述的两种树脂,优选将可以通过电离辐射的照射而交联的乙烯系树脂用作聚烯烃系树脂。除这两种树脂以外,还可以将其他树脂(诸如低密度聚乙烯)用作聚烯烃系树脂。
优选地将苯乙烯和橡胶组分的嵌段共聚物弹性体用作苯乙烯系弹性体。因为苯乙烯和橡胶组分的嵌段共聚物弹性体具有高伸长率和高强度,所以可进一步提高阻燃树脂组合物的拉伸性能。
氮系阻燃剂优选为平均粒径为5μm以下的氰尿酸三聚氰胺。氰尿酸三聚氰胺在混合过程中具有良好的热稳定性。在氮系阻燃剂中,就阻燃性而言,氰尿酸三聚氰胺特别优异。此外,因为平均粒径为5μm以下,所以混合过程中的分散性提高。金属氢氧化物优选为平均粒径为0.1μm以上3μm以下的氢氧化镁。需要注意的是,术语“平均粒径”是指50%粒径(D50)。该平均粒径可以通过(例如)使用激光多普勒法的粒径分布分析仪(Nanotrac(注册商标)粒径分布分析仪UPA-EX150,由Nikkiso株式会社制造)来测定。
本发明的另一个实施方案提供了一种电线/电缆,其包括由无卤阻燃树脂组合物构成的包覆层。根据本发明,可获得具有切通强度、耐磨性和阻燃性、以及满足UL标准的拉伸性能的无卤绝缘电线/电缆。
在所述电线/电缆中,包覆层优选具有0.4mm以下的厚度。当该包覆层的厚度小至0.4mm以下时,其与相关领域中的电线在切通强度等性能方面的差异变得明显,并且实现了良好的效果。
在所述电线/电缆中,包覆层优选通过电离辐射的照射而交联。通过使该包覆层交联,提高了耐热性和拉伸性能。
本发明的有益效果
根据本发明,可提供具有切通强度、耐磨性和阻燃性、以及满足UL标准的拉伸性能的无卤阻燃树脂组合物,并提供使用该阻燃树脂组合物的电线和电缆。
附图简要说明
[图1]图1是示出测量切通强度的方法的示意图。
具体实施方式
首先,将描述无卤阻燃树脂组合物中所使用的各种材料。可使用的聚烯烃系树脂的例子包括聚乙烯(高密度聚乙烯、直链低密度聚乙烯、低密度聚乙烯和极低密度聚乙烯)、乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-甲基丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙丙橡胶、乙烯-丙烯酸橡胶、乙烯-甲基丙烯酸缩水甘油酯共聚物、乙烯-甲基丙烯酸共聚物、聚丙烯(均聚物、嵌段聚合物和无规聚合物)、以及聚丙烯系热塑性弹性体和离子键树脂。
将含环氧基的乙烯系共聚物用作聚烯烃系树脂的一部分。含环氧基的乙烯系共聚物是通过将诸如甲基丙烯酸缩水甘油酯之类的含环氧基的烯烃单体与乙烯系单体共聚而获得的。其具体例子包括乙烯-甲基丙烯酸缩水甘油酯共聚物、乙烯-丙烯-甲基丙烯酸缩水甘油酯共聚物、乙烯-丁烯-甲基丙烯酸-1-缩水甘油酯共聚物(ethylene-butene-1-glycidylmethacrylate copolymers)、乙烯-醋酸乙烯酯-甲基丙烯酸缩水甘油酯共聚物和乙烯-丙烯酸-甲基丙烯酸缩水甘油酯共聚物。在全部树脂组分中,含环氧基的乙烯系共聚物的含量为2质量份以上15质量份以下,更优选为5质量份以上10质量份以下。
优选含有乙烯-醋酸乙烯酯共聚物作为聚烯烃系树脂的一部分,该乙烯-醋酸乙烯酯共聚物含有20质量份以上50质量份以下的醋酸乙烯酯。当醋酸乙烯酯的含量低于20质量份时,阻燃性降低并且不能满足UL标准。当醋酸乙烯酯的含量超过50质量份时,阻燃性提高。然而,除了拉伸强度降低以外,切通强度和耐磨性也降低,由此不能满足所要求的特性。相对于全部树脂组分,乙烯-醋酸乙烯酯共聚物的含量优选为10质量份以上30质量份以下。
优选含有高密度聚乙烯作为聚烯烃系树脂的一部分。高密度聚乙烯为均聚乙烯或聚乙烯共聚物,并且为密度在0.942g/cm3以上的聚乙烯。优选的是使用熔体流动速率(以下简称为“MFR”,根据JIS K7210、在230℃×2.16kgf下测量,单位:g/10分钟)为0.80以下的高密度聚乙烯,其中MFR为分子量的指标。MFR越低,耐磨性越倾向于得到显著提高。相对于全部树脂组分,高密度聚乙烯的含量优选为10质量份以上30质量份以下。
苯乙烯系弹性体的例子包括苯乙烯/乙烯-丁烯/苯乙烯共聚物、苯乙烯/乙烯-丙烯/苯乙烯共聚物、苯乙烯/乙烯/乙烯-丙烯/苯乙烯共聚物和苯乙烯/丁烯/苯乙烯共聚物。其例子还包括上述共聚物的氢化聚合物和部分氢化聚合物。可根据需要混合这样的聚合物,该聚合物中引入有马来酸酐等羧酸。
其中,除了从改善挤出性能的角度考虑以外,从(例如)提高拉伸伸长率和耐冲击性的角度考虑,优选使用苯乙烯和橡胶组分的嵌段共聚物弹性体。作为所述嵌段共聚物,可使用诸如氢化苯乙烯/丁烯/苯乙烯嵌段共聚物和苯乙烯/异丁烯/苯乙烯系共聚物之类的三嵌段共聚物,以及诸如苯乙烯/乙烯共聚物和苯乙烯/乙烯-丙烯之类的二嵌段共聚物。优选在苯乙烯系弹性体中含有50质量%以上的三嵌段组分,因为可提高包覆层的强度和硬度。
从拉伸性能(强度和伸长率)和阻燃性的角度考虑,优选使用苯乙烯含量为20质量%以上的苯乙烯系弹性体。当苯乙烯的含量小于20质量%时,硬度和挤出性能降低。苯乙烯的含量高于60质量%是不优选的,这是因为拉伸伸长率会降低。此外,作为分子量指标的MFR优选在0.8g/10分钟至15g/10分钟的范围内。其原因是,当MFR小于0.8g/10分钟时,挤出性能降低,而当MFR超过15g/10分钟时,机械强度降低。
氮系阻燃剂的例子包括三聚氰胺树脂和氰尿酸三聚氰胺。即使在使用后将氮系阻燃剂焚烧,也不会产生诸如卤化氢之类的有毒气体,因此可降低环境负荷。从混合过程中的热稳定性和阻燃性改善效果的角度考虑,优选将氰尿酸三聚氰胺用作氮系阻燃剂。可以用硅烷偶联剂或钛酸酯偶联剂对氰尿酸三聚氰胺进行表面处理。氮系阻燃剂的平均粒径优选为5μm以下。相对于100质量份的树脂组分,氮系阻燃剂的含量为5质量份以上20质量份以下。当氮系阻燃剂的含量低于5质量份时,所得的绝缘电线的阻燃性不足。当氮系阻燃剂的含量超过20质量份时,伸长率和挤出性能降低。
金属氢氧化物的例子包括氢氧化铝、氢氧化镁和氢氧化钙。其中,从挤出性能的角度考虑,优选的是平均粒径为0.1μm以上3μm以下的氢氧化镁。相对于100质量份的树脂组分,金属氢氧化物的含量为60质量份以上100质量份以下。当金属氢氧化物的含量低于60质量份时,绝缘电线的阻燃性不足。当金属氢氧化物的含量超过100质量份时,伸长率和挤出性能降低。
该无卤阻燃树脂组合物还可含有交联助剂。优选将分子中含有多个碳-碳双键的多官能单体用作交联助剂,这种多官能单体为(例如)三羟甲基丙烷三甲基丙烯酸酯、氰尿酸三烯丙酯和异氰尿酸三烯丙酯。交联助剂在室温下优选为液体。其原因在于,这种为液体的交联助剂可容易地与聚烯烃系树脂和苯乙烯系弹性体混合。优选使用三羟甲基丙烷三甲基丙烯酸酯作为交联助剂,这是因为可提高与树脂的相容性。
此外,根据需要,可将抗氧化剂、防老化剂、加工稳定剂、着色剂、重金属钝化剂、发泡剂等与本发明的无卤阻燃树脂组合物混合。可通过使用诸如短螺杆挤出型混合器、压力捏合机或班伯里密炼机之类的已知熔融混合器来混合这些材料,从而制备无卤阻燃树脂组合物。
本发明的电线(也称为绝缘电线)包括由上述阻燃树脂组合物构成的包覆层,并且通过在导体上直接形成包覆层、或在两者之间存在另一个层的情况下形成包覆层来制造。可以使用已知的挤出机(如熔融挤出机)来形成包覆层。该包覆层优选通过电离辐射的照射而交联。电缆(也称为绝缘电缆)包括电线和位于该电线表面上的外部覆层(如屏蔽层)。
可将具有良好导电性的铜线、铝线等用作导体。可根据用途适当选择导体的直径。然而,为了在狭小的空间内实现布线,导体的直径优选为2mm以下。考虑到易于操作,导体的直径优选为0.1mm以上。该导体可以是单根导线或是通过绞合多根导线获得的绞合导线。
可根据导体的直径适当选择包覆层的厚度。即使当包覆层的厚度为0.4mm以下时,也能够通过使用本发明的阻燃树脂组合物而获得良好的机械强度。对于相关领域中的无卤素电线,当包覆层的厚度为0.4mm以下时,耐磨性和切通强度降低。相比之下,根据本发明,即使当包覆层的厚度为0.4mm以下时,也能获得良好的性能。因此,可明显观察到其与相关领域中的电线之间的区别。在用于绝缘置换的电线中,从与连接器间的嵌合性的角度考虑,优选使用包覆层的厚度为0.4mm以下的电线。
包覆层优选通过电离辐射的照射而交联,这是因为可提高机械强度。电离辐射源的例子包括加速电子束、伽马射线、X射线、α射线和紫外线。从使用辐射源的容易程度、电离辐射的传输厚度、交联处理速度等工业应用角度考虑,最优选使用加速电子束。
下面,将利用实施例对本发明进行更详细的描述。这些实施例并不限制本发明的范围。
实施例
[实施例1至14]
(无卤阻燃树脂组合物粒料的制备)
将组分混合以使其具有表1中所示的组成(单位:质量份)。使用直径φ为300mm的开炼机,在160℃至180℃的温度下进行熔融混合。利用造粒机对所得到的各带状树脂组合物进行切割以制备粒料。
(绝缘电线的制备)
使用单螺杆挤出机(直径φ:30mm,L/D=24)对导体(通过绞合七根镀锡软铜线而制造,导体直径:0.48mm)进行挤出包覆,从而使得覆层厚度为0.25mm。然后在2MeV的加速电压下,用60kGy的电子束对所得到的包覆层进行照射,从而制备绝缘电线。需要注意的是,使用以下样品来评价拉伸性能(初始状态和热老化后),该样品是通过将导体从所制备的绝缘导线中除去从而只留下包覆层而制得的。
(包覆层的评价:拉伸性能)
将导体从所制备的电线中抽出,并对包覆层进行拉伸试验。关于试验条件,拉伸速度为500mm/分钟、标线间距离为25mm、并且温度为23℃。拉伸强度和拉伸伸长率(断裂伸长率)分别用三个样品进行测定,然后确定其平均值。将拉伸强度为10.3Mpa以上并且拉伸伸长率为150%以上的样品评价为“合格”。
(包覆层的评价:割线模量)
使用与上述拉伸试验中所用相同的样品,在下述条件下进行拉伸试验:拉伸速度为50mm/分钟、标线间距离为25mm、并且温度为23℃。然后,从应力-伸长率曲线计算伸长率为2%的点处的弹性模量。
(包覆层的评价:耐热老化性)
将绝缘电线在设定为136℃的Geer烘箱中静置168小时(七日),然后如拉伸性能评价中那样进行拉伸试验。将测得的拉伸强度和拉伸伸长率与热处理之前的拉伸强度和拉伸伸长率相比。当相对于热处理前的拉伸强度,热处理之后的拉伸强度的残率为70%以上时,将该结果界定为合格水平。当相对于热处理前的拉伸伸长率,热处理之后的拉伸伸长率的残率为45%以上时,将该结果界定为合格水平。
(绝缘电线的评价:切通强度)
使用如图1所示的测量装置来测量切通强度。将具有90°锐边(边缘R=0.125mm,边缘角:90°)的刀片4施加于包括导体1和包覆层2的绝缘电线3上,并测量导体和锐边之间流过的电流。在初始状态下,在导体和锐边之间具有包覆层2,两者彼此绝缘,并且没有电流流过。当包覆层2被刀片4切断时,电流在导体和锐边之间流过。向刀片4施加负载,并测量包覆层2未被切断时所承受的最大负载。测试环境中,温度为23℃,并且湿度为50%RH。将35N以上的负载界定为合格水平。
(绝缘电线的评价:耐刮磨性(Scrape abrasion resistance))
将绝缘电线水平固定,并使直径为1.6mm的钢琴丝与绝缘电线接触。从该钢琴丝的上方施加408g的负载,并将该钢琴丝以50Hz至60Hz的速率往复运动。测量直至包覆层被破坏时的往复数以及导体和钢琴丝之间流过的电流。当往复数为650以上时,将该结果界定为合格水平。
(绝缘电线的评价:垂直试样燃烧试验)
使用五个样品进行UL标准1581第1080部分中所描述的VW-1垂直试样燃烧试验。将火焰施加至每个样品15秒,然后移除。将此过程重复五次。当火焰在60秒内熄灭,位于下部的脱脂棉未被燃烧的滴落物引燃,并且附着于样品上部的牛皮纸条未烧着或烧焦时,将该样品评价为合格。评价五个样品,并计算被评价为合格的样品数目。
(绝缘电线的评价:水平试样燃烧试验)
使用五个样品进行UL标准1581第1100部分中所述的水平试样燃烧试验,并计算被评价为合格的样品数目。
[比较例1至11]
除使用了具有表II中所示组成(单位:质量份)的树脂组合物以外,如实施例1至14中那样制备绝缘电线,并如实施例1至14中那样进行一系列的评价。
[比较例12]
使用单螺杆挤出机(直径φ:30mm、L/D=24)对导体(通过绞合七根镀锡软铜线而制造,导体直径:0.48mm)进行挤出包覆,以使得覆层厚度为0.25mm。由此,如实施例1至14中那样,对包括包覆层(由动态交联聚丙烯(INA-9968,Riken Technos公司制造)构成)的绝缘电线进行一系列评价。上述的评价结果在表I和II中示出。
(脚注)
EVA1:含有25质量%的醋酸乙烯酯的乙烯-醋酸乙烯酯共聚物:Evaflex EV360,由Du pont-Mitsui Polychemicals株式会社制造
EVA2:含有33质量%的醋酸乙烯酯的乙烯-醋酸乙烯酯共聚物:Evaflex EV170,由Du pont-Mitsui Polychemicals株式会社制造
HDPE1:MFR为0.8、密度为0.951g/cm3、且硬度为62D的高密度聚乙烯:HI-ZEX5305E,由Prime Polymer株式会社制造
HDPE2:MFR为0.55、密度为0.959g/cm3、且硬度为70D的高密度聚乙烯:NOVATEC HY530,由Japan Polyethylene株式会社制造
HDPE3:MFR为0.25、密度为0.961g/cm3、且硬度为65D的高密度聚乙烯:HI-ZEX520MB,由Prime Polymer株式会社制造
HDPE4:MFR为0.3、密度为0.964g/cm3、且硬度为71D的高密度聚乙烯:NOVATEC HB530,由Japan Polyethylene株式会社制造
E-GMA:BONDFAST E(含有12质量%的甲基丙烯酸缩水甘油酯的含环氧基的乙烯系共聚物),由Sumitomo Chemical株式会社制造
St系弹性体1:含有30质量%的苯乙烯的SEEPS(聚苯乙烯-聚(乙烯-乙烯/丙烯)嵌段-聚苯乙烯):SEPTON(注册商标)4033,由Kuraray株式会社制造
St系弹性体2:SEEPS-OH(末端具有OH基的SEEPS):SEPTON(注册商标)HG252,由Kuraray株式会社制造
St系弹性体3:SEBS(聚苯乙烯-聚(乙烯/丁烯)嵌段-聚苯乙烯):Tuftec1041,由Asahi Kasei株式会社制造
St系弹性体4:SEBS:Tuftec H1051,由Asahi Kasei株式会社制造
St系弹性体5:SEBS:SEPTON(注册商标)8104,由Kuraray株式会社制造
氢氧化镁:KISUMA5SDK,由Kyowa Chemical Industry株式会社制造
氰尿酸三聚氰胺:MC6000,由Nissan Chemical Industries株式会社制造
防老化剂:Irganox1010,由BASF Japan株式会社制造
铜抑制剂:ADK STAB CDA-1,由Adeka株式会社制造
润滑剂:硬脂酸
交联助剂:三羟甲基丙烷三甲基丙烯酸酯:TD1500S,由DIC株式会社制造
对于实施例1至14的各绝缘电线,切通强度为35N以上,并且耐刮磨性的往复数为650以上,因此该绝缘电线具有高强度。初始状态下的拉伸性能(伸长率和强度)以及热老化后的拉伸性能(伸长率和强度的残率)为合格水平,并且也满足阻燃性。
比较例1至6的绝缘电线中所使用的无卤阻燃树脂组合物不包含含环氧基的乙烯系共聚物。初始状态下的拉伸性能(伸长率和强度)、热老化后的拉伸性能(伸长率和强度的残率)、以及阻燃性都为合格水平,然而,其切通强度低。这些结果表明,通过在树脂组合物中混合适当量的含环氧基的乙烯系共聚物,提高了切通强度。一些树脂组合物的耐刮磨性没有达到合格水平(比较例3和比较例6)。
比较例7至11的绝缘电线中使用的无卤阻燃树脂组合物包含含环氧基的乙烯系共聚物。在比较例7中,由于苯乙烯系弹性体的含量过高,所以切通强度低。在比较例8至10中,由于金属氢氧化物(氢氧化镁)的含量过高,所以伸长率没有达到目标性能。在比较例11中,因为氮系阻燃剂(氰尿酸三聚氰胺)的含量过高,所以热老化后的伸长率和伸长率的残率没有达到目标性能。比较例12的绝缘电线中的包覆层由通过聚丙烯的动态交联获得的树脂组合物构成。虽然在此次评价中基本满足了目标性能,但是挤出过程中动态交联材料的稳定性不足,并且在一些挤出条件下,诸如伸长率和强度等拉伸性能可能不足。
参考符号列表
1.导体
2.包覆层
3.绝缘电线
4.刀片

Claims (9)

1.一种无卤阻燃树脂组合物,包含:树脂组分;金属氢氧化物,相对于100质量份的所述树脂组分,所述金属氢氧化物的量为60质量份至100质量份;以及氮系阻燃剂,相对于100质量份的所述树脂组分,所述氮系阻燃剂的量为5质量份至20质量份,其中每100质量份的所述树脂组分中含有50质量份至80质量份的聚烯烃系树脂和20质量份至50质量份的苯乙烯系弹性体,所述聚烯烃系树脂含有2质量份至15质量份的含环氧基的乙烯系共聚物作为其一部分。
2.根据权利要求1所述的无卤阻燃树脂组合物,其中含有乙烯-醋酸乙烯酯共聚物作为所述聚烯烃系树脂,该乙烯-醋酸乙烯酯共聚物含有20质量份以上50质量份以下的醋酸乙烯酯。
3.根据权利要求1或2所述的无卤阻燃树脂组合物,其中含有高密度聚乙烯作为所述聚烯烃系树脂。
4.根据权利要求1至3中任一项所述的无卤阻燃树脂组合物,其中所述苯乙烯系弹性体为苯乙烯和橡胶组分的嵌段共聚物弹性体。
5.根据权利要求1至4中任一项所述的无卤阻燃树脂组合物,其中所述氮系阻燃剂为平均粒径为5μm以下的氰尿酸三聚氰胺。
6.根据权利要求1至5中任一项所述的无卤阻燃树脂组合物,其中所述金属氢氧化物为平均粒径为0.1μm以上3μm以下的氢氧化镁。
7.一种电线/电缆,包括由根据权利要求1至6中任一项所述的无卤阻燃树脂组合物构成的包覆层。
8.根据权利要求7所述的电线/电缆,其中所述包覆层的厚度为0.4mm以下。
9.根据权利要求7或8所述的电线/电缆,其中所述包覆层通过利用电离辐射进行照射而交联。
CN201280046230.0A 2012-03-22 2012-12-25 无卤阻燃树脂组合物、以及使用该无卤阻燃树脂组合物的电线和电缆 Pending CN104220511A (zh)

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