CN112424273A - 具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物、其制备方法和其制备的注塑制品 - Google Patents
具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物、其制备方法和其制备的注塑制品 Download PDFInfo
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- CN112424273A CN112424273A CN201980047533.6A CN201980047533A CN112424273A CN 112424273 A CN112424273 A CN 112424273A CN 201980047533 A CN201980047533 A CN 201980047533A CN 112424273 A CN112424273 A CN 112424273A
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Abstract
本发明涉及一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物、该热塑性树脂组合物的制备方法以及使用该热塑性树脂组合物制备的注塑制品,所述热塑性树脂组合物包含:(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为1至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末。根据本发明,可以提供具有优异的例如冲击强度的机械性能、导电性、耐热性、外观和电磁波屏蔽能力,特别是对高频电磁波具有高屏蔽效率的热塑性树脂组合物,该热塑性树脂组合物的制备方法,以及使用该热塑性树脂组合物制备的注塑制品。由于具有这些优点,使用该热塑性树脂组合物制备的注塑制品可以用作汽车部件和电气与电子部件,并且该热塑性树脂组合物可以用作铝合金和镁合金的替代品。
Description
技术领域
对相关申请的交叉引用
本申请要求于2019年1月11日在韩国知识产权局提交的韩国专利申请No.10-2019-0004003的优先权,该专利申请的公开内容通过引用并入本说明书。
本发明涉及一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物、该热塑性树脂组合物的制备方法以及使用该热塑性树脂组合物制备的注塑制品。更具体而言,本发明涉及一种具有优异的例如冲击强度的机械性能、导电性、耐热性、外观和电磁波屏蔽能力,特别是对高频电磁波具有高屏蔽效率的热塑性树脂组合物,该热塑性树脂组合物的制备方法,以及使用该热塑性树脂组合物制备的注塑制品。由于具有这些优点,使用该热塑性树脂组合物制备的注塑制品可以用作汽车部件和电气与电子部件,并且可以用作铝合金和镁合金的替代品。
背景技术
为了响应当前的市场需求,对高性能电子产品的小型化和高集成化的研究正在进行。因此,需要具有提高的耐热性和电磁波屏蔽性能的材料。
金属材料例如铝、镁和铜由于其优异的散热能力和电磁波屏蔽性能而广泛地用于电子部件中。但是,金属材料具有不良的塑模性能和生产率,因此在使用金属材料时部件的设计可能受到限制。
为了解决这些问题,已经开发了碳纤维增强的热塑性树脂组合物。虽然该热塑性树脂组合物的导电性良好,但是电磁波屏蔽性能、外观和耐热性尚未达到所需的水平。
另外,已经开发了通过向例如聚碳酸酯树脂或聚苯乙烯树脂的热塑性树脂中加入多壁碳纳米管和基于碳的导电添加剂来制备树脂组合物的方法。但是,电磁波屏蔽性能和耐热性尚未达到所需的水平。
因此,对开发具有优异的机械性能、导电性、耐热性、电磁波屏蔽能力和外观的用于汽车部件和电气与电子部件的塑料材料的需求不断增长。
[相关技术文件]
[专利文件]KR 2013-0066973 A
发明内容
技术问题
因此,鉴于上述问题而完成了本发明,本发明的一个目的是提供一种具有优异的例如冲击强度的机械性能、导电性、耐热性、外观和电磁波屏蔽能力,特别是对高频电磁波具有高屏蔽效率的热塑性树脂组合物,该热塑性树脂组合物的制备方法,以及使用该热塑性树脂组合物制备的注塑制品。根据本发明,使用该热塑性树脂组合物制备的注塑制品可以用作汽车部件和电气与电子部件,并且可以用作铝合金和镁合金的替代品。
上述和其它目的可以通过下面描述的本公开内容而实现。
技术方案
根据本发明的一个方面,提供一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物,包含:(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为3至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末。
根据本发明的另一个方面,提供一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物的制备方法,该制备方法包括:采用挤出机在250℃至320℃和250至350rpm下,对(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为3至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末进行熔融捏合和挤出。
根据本发明的又一个方面,提供一种包含本发明的热塑性树脂组合物的具有电磁波屏蔽能力的注塑制品。
有益效果
根据本发明,可以提供具有优异的例如冲击强度的机械性能、导电性、耐热性、外观和电磁波屏蔽能力,特别是对高频电磁波具有高屏蔽效率的热塑性树脂组合物,该热塑性树脂组合物的制备方法,以及使用该热塑性树脂组合物制备的注塑制品。由于具有这些优点,使用该热塑性树脂组合物制备的注塑制品可以用作汽车部件和电气与电子部件,并且可以用作铝合金和镁合金的替代品。
附图说明
图1示出了配备有9个或更多个捏合区的挤出机,其用于制备根据本发明的热塑性树脂组合物。
具体实施方式
下文,将详细地描述根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物、其制备方法和使用该热塑性树脂组合物制备的注塑制品。
本发明人证实,当例如尼龙66等的热塑性树脂与线性碳纤维、碳纳米原纤、碳纳米片和金属粉末以预定重量比混合以制备热塑性树脂组合物时,所制得的热塑性树脂组合物的例如冲击强度等的机械性能优异,并且其耐热性和电磁波屏蔽性能大大地提高。基于这些结果,本发明人进行了进一步的研究以完成本发明。
根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物包含:(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为3至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末。在这种情况下,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
作为另一个实例,根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物包含:(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的线性碳纤维;(c)1至5重量份的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末。在这种情况下,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
在本说明书中,如果不另外定义,则使用透射电子显微镜(TEM)测量40个样品的长度、直径和/或厚度,其平均长度、平均直径和/或平均厚度是由测量值计算出的算术平均值。
下文,将详细地描述构成根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物的每一组分。
(a)基础树脂
例如,本发明的基础树脂可以包括选自聚酰胺树脂、聚碳酸酯树脂、聚芳硫醚树脂、聚苯乙烯树脂、聚烯烃树脂、聚酮树脂、聚苯醚树脂和聚酯树脂中的一种或多种。优选地,所述基础树脂包括选自聚酰胺树脂、聚碳酸酯树脂、聚苯醚树脂和聚酯树脂中的一种或多种。更优选地,所述基础树脂是聚酰胺树脂。在这种情况下,外观和电磁波屏蔽性能可以是优异的,并且机械性能和耐热性可以大大地改善。
例如,所述聚酰胺树脂可以包括选自尼龙4.6、尼龙6、尼龙6.6、尼龙6.10、尼龙7、尼龙8、尼龙9、尼龙11、尼龙12、尼龙46、MXD 6和共聚聚酰胺中的一种或多种。优选地,所述聚酰胺树脂是尼龙66。在这种情况下,导电性、冲击强度、耐热性和电磁波屏蔽性能可以是优异的。
例如,当在20℃下使用将1g聚酰胺溶解在100ml 96重量%的硫酸水溶液中制成的溶液测量相对粘度时,所述聚酰胺树脂的相对粘度为1.5至5,优选为2.0至4.5,更优选为2.1至2.8。在该范围内,导电性、冲击强度、耐热性和电磁波屏蔽性能可以是优异的。
例如,所述共聚聚酰胺是通过使两种或更多种聚酰胺作为单体聚合而制备的聚酰胺共聚物。
例如,所述聚碳酸酯树脂的熔体指数(MI;在300℃和1.2kg的条件下测量)可以为5至40g/10分钟或10至35g/10分钟,优选为15至30g/10分钟。在该范围内,导电性、冲击强度、耐热性和电磁波屏蔽性能可以是优异的。
例如,所述聚酯树脂可以包括选自聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚酯型氨基甲酸酯(poly(ester)urethanes)和聚醚酯中的一种或多种。优选地,所述聚酯树脂是聚对苯二甲酸丁二醇酯。在这种情况下,外观和电磁波屏蔽性能可以是优异的。
例如,所述聚酯树脂的熔体指数(MI;在250℃和2.16kg的条件下测量)可以为5至50g/10分钟或10至40g/10分钟,优选为15至30g/10分钟。在该范围内,导电性、冲击强度、耐热性和电磁波屏蔽性能可以是优异的。
例如,所述聚酮树脂可以包括聚芳醚酮、聚醚醚酮或其混合物。
例如,所述聚苯醚树脂可以包括选自如下中的一种或多种聚合物:聚(2,6-二甲基-1,4-亚苯基)醚、聚(2,6-二乙基-1,4-亚苯基)醚、聚(2,6-二丙基-1,4-亚苯基)醚、聚(2-甲基6-乙基-1,4-亚苯基)醚、聚(2-甲基-6-丙基-1,4-亚苯基)醚、聚(2-乙基-6-丙基-1,4-亚苯基)醚、聚(2,6-二苯基-1,4-亚苯基)醚、聚(2,3,6-三甲基-1,4-亚苯基)醚、聚(2,3,6-三乙基-1,4-亚苯基)醚,以及它们的改性聚合物,或者包含上述聚合物的共聚物。优选地,所述聚苯醚树脂是聚(2,6-二甲基-1,4-亚苯基)醚或其共聚物。
在本发明中,改性聚合物是指一种由聚合物与例如不饱和羧酸或其酸酐等的活性单体反应而制备的产物。
例如,所述聚苯乙烯树脂可以包括选自均聚苯乙烯、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物和苯乙烯-丁二烯共聚物中的一种或多种。
例如,所述聚芳硫醚树脂可以是聚苯硫醚树脂。
作为具体实例,所述聚烯烃树脂可以包括选自聚乙烯、聚丙烯、聚丁烯、聚甲基戊烯、乙烯-丙烯共聚物和丙烯-1-丁烯共聚物中的一种或多种,而不特别限制。
例如,根据本发明的增强树脂可以是抗冲增强树脂。优选地,所述增强树脂是用选自不饱和羧酸及其酸酐中的一种或多种(下文称为“变性剂”)接枝的改性聚烯烃树脂。在这种情况下,冲击强度可以大大地改善。
本发明所属领域中常用的改性方法可以用作上述接枝方法,即,改性方法,而不特别限制。例如,所述改性可以采用熔融捏合法、溶液法或淤浆法来进行。
例如,熔融捏合法可以是使用挤出机在自由基聚合用的催化剂存在下,在150℃至350℃的温度下熔融捏合聚烯烃树脂和变性剂的方法。
另外,溶液法或淤浆法可以是如下的方法:将聚烯烃树脂、变性剂和自由基聚合催化剂加入到例如甲苯和二甲苯等的有机溶剂中,以制备溶解或淤浆状态的混合物,然后在80℃至350℃的温度下进行接枝(改性)反应,同时搅拌该混合物。
在聚烯烃树脂改性中常用的不饱和羧酸可以用作上述不饱和羧酸而不特别限制。例如,所述不饱和羧酸可以包括选自丙烯酸、α-乙基丙烯酸、甲基丙烯酸、马来酸、富马酸、卤代马来酸、柠康酸、四氢邻苯二甲酸、甲基四氢邻苯二甲酸、卤代柠康酸、巴豆酸、卤代巴豆酸、衣康酸、卤代衣康酸和顺式-4-环己烯-1,2-二甲酸中的一种或多种。优选地,所述不饱和羧酸是马来酸。
例如,所述聚烯烃树脂可以包括选自聚乙烯、聚丙烯、聚丁烯、聚甲基戊烯、乙烯-丙烯共聚物和丙烯-1-丁烯共聚物中的一种或多种。优选地,所述聚烯烃树脂可以包括聚乙烯。在这种情况下,冲击强度和电磁波屏蔽性能可以得到改善。
例如,所述改性聚烯烃树脂可以是包含0.5重量%至4重量%、0.5重量%至3重量%、0.5重量%至2.5重量%或0.8重量%至2重量%的变性剂的改性聚合物或接枝聚合物。在此范围内,冲击强度可以得到大大地改善。
(b)线性碳纤维
根据本发明的线性碳纤维可以具有平均直径为3至15μm或者5至12μm,优选平均直径为6至12μm,更优选平均直径为5至10μm。在此范围内,产物强度和屏蔽性能可以是优异的。
例如,所述线性碳纤维的含量可以为2至60重量份或10至50重量份,优选为15至40重量份,更优选为20至35重量份,最优选为30至35重量份。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
在本说明书中,所述线性碳纤维是指在本发明所属技术领域中定义或分类为线性碳纤维的纤维,而不特别限制。通常,所述线性碳纤维是指整体上为直的形态的碳纤维。具体地,所述线性碳纤维是指在线性碳纤维的绳股中没有成螺旋或圆柱形卷曲的结构的直的形态的碳纤维。例如,所述线性碳纤维是指不包括以90°以上,优选30°以上,更优选10°以上的角度弯曲的绳股的直碳纤维。
例如,所述线性碳纤维的平均长度可以为0.1至12mm,0.2至9mm或0.3至6mm。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
例如,所述线性碳纤维可以是10至100k或40至60k的大丝束纤维。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。在此,1k表示1,000根短纤维。
(c)碳纳米原纤
根据本发明的碳纳米原纤可以具有BET比表面积为180至600m2/g,优选为200至500m2/g,更优选为200至400m2/g。在此范围内,导电性、耐热性和屏蔽性能可以是优异的。
在本说明书中,所述BET比表面积定义为根据BET方法测量的比表面积,并使用Brunauer-Emmett-Teller方法(根据ASTM 6556)使用氮吸附测量。
例如,所述碳纳米原纤的含量可以为1至5重量份,优选为1至4重量份,更优选为1至3重量份,最优选为1至2重量份。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
例如,所述碳纳米原纤可以具有平均直径为4至30nm或5至20nm,并且长宽比为80至500。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
在本说明书中,所述碳纳米原纤的长宽比是指在水平截面中的宽度与长度之间的比例,且由宽度和长度中较长的一个(2b)与宽度和长度中较短的一个(2a)的比值(b/a)来表示。
例如,所述碳纳米原纤可以具有平均长度为1至500μm或者2至200μm。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
在本说明书中,当确定所述碳纳米原纤的平均直径、平均长宽比和平均长度时,使用扫描电子显微镜(SEM)测量40个样品的直径、长宽比和长度,其平均直径、平均长宽比和平均长度是由测量值计算出的算术平均值。
(d)碳纳米片
例如,根据本发明的碳纳米片的含量可以为1至15重量份、1至10重量份或者2至10重量份,优选为3至10重量份,更优选为5至10重量份,最优选为3至5重量份。在此范围内,拉伸强度和冲击强度可以得到改善,并且耐热性可以是优异的。
例如,(d)碳纳米片可以是平均厚度为2至50nm的片状碳纳米材料。作为具体的实例,所述碳纳米片可以包括选自片状剥离的石墨、石墨烯纳米片和片状剥离与膨胀的石墨中的一种或多种。在这种情况下,拉伸强度和冲击强度可以得到改善,并且耐热性可以是优异的。
在本说明书中,当确定所述碳纳米片的平均厚度时,使用扫描电子显微镜(SEM)测量40个样品的厚度,其平均厚度是由测量值计算出的算术平均值。
(e)金属粉末
例如,根据本发明的金属粉末的含量可以为1至25重量份或者1至20重量份,优选为3至20重量份,更优选为5至20重量份,最优选为10至20重量份。在此范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
例如,(e)所述金属粉末可以是磁性金属粉末。优选地,该金属粉末包括由选自铁(Fe)、钴(Co)和镍(Ni)中的一种或多种得到的金属粉末,更优选包括镍(Ni)金属粉末。在这种情况下,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
例如,(e)所述金属粉末可以具有平均直径为1至100μm,优选为20至80μm,更优选为30至70μm,最优选为40至60μm。在该范围内,导电性、冲击强度、耐热性、外观和电磁波屏蔽性能可以是优异的。
在本说明书中,当确定所述金属粉末的平均直径时,使用透射电子显微镜(TEM)测量40个样品的直径,其平均直径是由测量结果计算出的算术平均值。
例如,(e)所述金属粉末可以是涂覆有有机粘合剂的金属粉末。在本发明所属领域中常用的有机粘合剂,例如硬脂酸,可以用作所述有机粘合剂而不特别限制。
例如,组分(b)、(c)、(d)和(e)的总重量可以为5至80重量份或20至70重量份,优选为30至60重量份,更优选为36至55重量份,最优选为48至55重量份。在此范围内,拉伸强度、冲击强度、导电性、耐热性、外观和电磁波屏蔽性能可以是优异的。
添加剂
例如,本发明的热塑性树脂组合物根据需要,可以还包含选自阻燃剂、成核剂、紫外线吸收剂、抗氧化剂、除尘剂、抗菌剂、驱虫剂、除臭剂、抗着色剂、热稳定剂、脱模剂、抗静电剂、增塑剂、润滑剂、着色剂、颜料、染料、发泡剂、消泡剂、偶联剂和无机填料中的一种或多种的添加剂。
例如,所述添加剂的含量可以为0.1至20重量份,优选为0.1至10%重量份。在该范围内,可以充分表现出添加剂的性质,而不会干扰树脂组合物的物理性质。
在本发明所属领域中常用的阻燃剂可以用作本发明的阻燃剂而不特别限制。作为具体实例,所述阻燃剂可以包括选自如下中的一种或多种:卤素类阻燃剂,例如四溴双酚A(TBBA);磷类阻燃剂,例如烷基磷酸酯和烯丙基磷酸酯(allyl phosphate);以及无机阻燃剂,例如氢氧化镁和氢氧化铝。
包含不含碳的无机成分的无机填料可以用作所述无机填料而不特别限制。
在本发明所属领域中常用的其它添加剂可以用于本发明而不特别限制。
对于本领域技术人员显而易见的是,在不脱离本发明的精神和范围的情况下可以进行各种变化和改变,且这些变化和改变也在所附权利要求的范围内。
热塑性树脂组合物
例如,根据本发明的热塑性树脂组合物可以具有150℃以上的热变形温度和47以上的电磁波屏蔽dB值(@1GHz)。优选地,当热变形温度为150℃至250℃时,电磁波屏蔽dB值为47至60。更优选地,当热变形温度为215℃至250℃时,电磁波屏蔽dB值为50至60。最优选地,当热变形温度为240℃至245℃时,电磁波屏蔽dB值为50至55。在此范围内,机械性能、导电性和外观可以是优异的。
例如,当根据ISO 180A方法在样品厚度为4mm的条件下测量缺口悬臂梁式冲击强度时,所述热塑性树脂组合物的缺口悬臂梁式冲击强度可以为70kJ/m2或更高,优选为70至120kJ/m2,更优选80至120kJ/m2。在此范围内,导电性、耐热性、外观和电磁波屏蔽性能可以是优异的。
热塑性树脂组合物的制备方法
根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物的制备方法包括:采用挤出机在250℃至320℃和250至350rpm下,对(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为3至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末进行熔融捏合和挤出的步骤。使用该方法制备的热塑性树脂组合物可以具有优异的导电性、冲击强度、耐热性、外观和电磁波屏蔽性能。
图1示出了配备有9个或更多个捏合区的挤出机,其用于制备根据本发明的热塑性树脂组合物。将参考图1来描述本发明。
挤出机的类型不受特别限制,并且可以适当选择和使用本领域中通常使用的挤出机。例如,可以使用配备有一个螺杆的单螺杆挤出机或配备有多个螺杆的多螺杆挤出机。考虑到材料的均匀捏合、易于加工和经济效率,优选使用配备有两个螺杆的双螺杆挤出机。
典型的挤出机包括:用于将材料进料到桶(也称为圆筒)中的原料进料器,用于输送和捏合所供入的材料的螺杆,以及用于挤出捏合好的材料的模具。在这种情况下,所述螺杆由用于各种功能的多个螺杆元件组成。
在典型的挤出机中,根据需要,可以设置一个或更多个原料进料器,且可以设置两个或更多个或者三个原料进料器。另外,可以设置主入口,并且可以可选择地设置两个或更多个或者三个辅助入口。
作为具体的实例,热塑性树脂、线性碳纤维、碳纳米原纤、碳纳米片和金属粉末可以分批供入主入口中。作为另一实例,热塑性树脂可以供入主入口中,然后线性碳纤维、碳纳米原纤、碳纳米片和金属粉末可以供入辅助入口。
作为另一实例,热塑性树脂可以供入主入口中,一些线性碳纤维、碳纳米原纤、碳纳米片和金属粉末可以供入辅助入口1,然后剩余物可以供入辅助入口2中。
作为另一实例,热塑性树脂可以供入主入口中,线性碳纤维、碳纳米原纤、碳纳米片和金属粉末可以供入辅助入口1中,添加剂例如抗氧化剂和热稳定剂等可以供入辅助入口2中。
本发明的捏合区对应于所述螺杆元件。具体地,每个捏合区由多个圆盘组成,优选由3至7个圆盘,5至7个圆盘,3至5个圆盘,或者4至5个圆盘组成,并且具有多边形截面或椭圆形截面。所述捏合区沿输送材料的方向连续地排列。另外,在所述捏合区中,圆盘的相位角(表示圆盘之间的行进角(travel angle))通常为45°至90°。
另外,所述捏合区包括:能够输送、分配和混合材料的正向捏合区,能够分配和混合材料而不具有输送能力的中性捏合区,以及能够沿与输送方向相反的方向输送材料的反向捏合区。
例如,根据本发明的热塑性树脂组合物可以采用如下方法来制备,该方法包括使用配备有9个以上、10个以上、10至18或者12至16个捏合区的挤出机进行捏合和挤出的步骤。在这种情况下,相对于树脂的流动方向以正向捏合区、中性捏合区和反向捏合区的顺序排列所述捏合区会是有效的。取决于组合方式,可以采用连续或分开的捏合区组合。在这种情况下,分散性和相容性可以得到进一步改善,因此可以提供高品质的热塑性树脂组合物。
9个以上的捏合区可以连续地设置,或者可以在螺杆间不连续地设置。作为具体实例,在主入口和辅助入口1之间可以连续地设置3至6个捏合区,在辅助入口1和辅助入口2之间可以连续地设置3至8个捏合区,在辅助入口2和出口(未示出)之间可以设置2至5个捏合区。由于这种结构,在熔融捏合期间的局部热生成可以得到控制以防止原料的热变形。另外,可以防止线状碳纤维和碳纳米原纤的过度切割,从而改善导电性和物理性质。
捏合和挤出步骤可以在250℃至320℃、280℃至310℃或290℃至310℃的桶温下进行。在这种情况下,每单位时间的处理量会是合适的,同时可以充分地进行熔融捏合。另外,可以防止例如树脂组分热分解等的问题。
另外,捏合和挤出步骤可以在250至350rpm或250至310rpm的螺杆旋转速率下进行。在这种情况下,每单位时间的处理量会是合适的。因此,加工效率可以是优异的,并且可以防止导电填料(碳纳米原纤等)的过度切割,从而改善了最终产品的导电性。
例如,所述热塑性树脂组合物的制备方法可以包括在挤出之后通过使用造粒机剪切挤出物而得到粒料的步骤。在这种情况下,操作容易,并且可以通过注塑成型容易地制备电磁波屏蔽注塑制品。
组分(a)至(e)的详情与上面的描述相同,因此将省略对它们的描述。
注塑制品
本发明的注塑制品包含上述热塑性树脂组合物。
例如,所述注塑制品可以通过在250℃至300℃的桶温和60℃至100℃的模塑温度下将根据本发明的具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物注塑成型来制备。所制备的注塑制品可以具有150℃以上的热变形温度和47以上或者47至60、优选50至60、更优选50至55的电磁波屏蔽dB(@1GHz)值。
例如,所述注塑制品可以包括汽车部件或者电气与电子部件。特别是,所述注塑制品可以用作用于制造电子部件罩面、电路部件、变换器罩面等的金属部件(例如铝合金和镁合金等)的替代品。
下文,将参考下面优选的实施例更详细地描述本发明。然而,提供这些实施例仅为了举例说明的目的,且这些实施例不应解释为限制本发明的范围和精神。另外,对于本领域技术人员显而易见的是,在不脱离本发明的精神和范围的情况下可以进行各种变化和改变,且这些变化和改变也在所附权利要求的范围内。
[实施例]
在下面实施例和比较例中使用的组分如下。
(a1)使用尼龙66树脂(产品编号:3600;相对粘度:2.4;数均分子量:14,000g/mol;Invista Co.)。
(a2)使用聚碳酸酯树脂(产品编号:1330;熔体指数(300℃;1.2kg):30g/10分钟;LG Chemical Co.)。
(a3)使用聚对苯二甲酸丁二醇酯树脂(产品编号:GP2000;熔体指数(250℃;2.16kg):30g/10分钟;LG Chemical Co.)。
(a4)使用用0.5重量%至2重量%的马来酸酐改性的聚乙烯树脂。
(a5)聚(2,6-二甲基-1,4-亚苯基)醚(产品编号:201A;Asahi Chemical Co.)用作聚苯醚树脂。
(b)Pyrofil(平均直径:7μm;50k大丝束产品;Zoltek Co.)用作碳纤维。
(c)CP1002M(BET比表面积:200至300m2/g;平均直径:10至15nm,碳纯度:95重量%;LG Chemical Co.)用作碳纳米原纤。
(d)CB-100(片状石墨产品;Japan Graphite Co.,Ltd.)用作碳纳米片。
(e)平均直径为50μm的镍金属粉末用作金属粉末。
实施例1至实施例6和比较例1至比较例4
根据下面表1所示的组成,将各组分供入双螺杆挤出机中,在250℃至320℃的温度和300转/分钟的旋转速率下进行熔融捏合和挤出,所排出的挤出物采用制粒机进行剪切而得到粒料。然后,采用注射机(80吨;Engel Co.)在250℃至300℃的注射温度(桶温)和70℃至100℃的模塑温度下将得到的粒料注塑成型,以制备用于测量物理性质的样品。
[试验性实施例]
采用下面的方法测量实施例1至实施例6和比较例1至比较例4中制备的样品的性质,其结果示于表1中。
1)拉伸强度和伸长率:根据ASTM D638测量拉伸强度和伸长率。在这种情况下,样品厚度为3.2mm,测量速度为5mm/min,测量单位为MPa。
2)冲击强度:对厚度为4mm的样品进行切口,在室温(23℃)下根据ISO 180A测量该样品的切口悬臂梁式冲击强度。在这种情况下,测量单位为kJ/m2。
3)热变形温度:根据ISO 75-2在0.45MPa的应力下测量热变形温度。在这种情况下,样品厚度为4mm,测量单位为℃。
4)表面电阻:使用PRS-801(Prostat Co.)测量表面电阻。
5)电磁波屏蔽:使用EM2107A(Electro-metrics Co.)在1GHz下测量屏蔽度。
6)外观:通过目测评价注塑样品的外观。在这种情况下,将成型性和外观优异的情况标记为○,将外观良好的情况标记为△,将外观差的情况标记为X,将外观很差的情况标记为XX。
[表1]
如表1所示,可以确认,与其中不含组分(b)至(e)的某些的热塑性树脂组合物(参见比较例1至比较例4)相比,包含所有根据本发明的组分(b)至(e)的根据本发明的热塑性树脂组合物(参见实施例1至实施例6)具有提高的拉伸强度、冲击强度、热变形温度(耐热性)和导电性以及优异的外观和电磁波屏蔽性能。特别是,可以确认,在实施例1至3的情况下,其中包含尼龙66且组分(b)至(e)的总重量在48至55重量份的范围内,拉伸强度、耐热性和电磁波屏蔽性能大大地提高。
Claims (14)
1.一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物,包含:
(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;
(b)2至60重量份的平均直径为3至15μm的线性碳纤维;
(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;
(d)1至15重量份的碳纳米片;和
(e)1至25重量份的金属粉末。
2.根据权利要求1所述的热塑性树脂组合物,其中,组分(b)、(c)、(d)和(e)的总重量是5至80重量份。
3.根据权利要求1所述的热塑性树脂组合物,其中,所述基础树脂包括选自聚酰胺树脂、聚碳酸酯树脂、聚芳硫醚树脂、聚苯乙烯树脂、聚烯烃树脂、聚酮树脂和聚酯树脂中的一种或多种。
4.根据权利要求1所述的热塑性树脂组合物,其中,所述增强树脂是抗冲增强树脂。
5.根据权利要求1所述的热塑性树脂组合物,其中,(d)所述碳纳米片的平均厚度为2至50nm。
6.根据权利要求1所述的热塑性树脂组合物,其中,(e)所述金属粉末是磁性金属粉末。
7.根据权利要求6所述的热塑性树脂组合物,其中,所述磁性金属粉末包括选自铁粉、钴粉和镍粉中的一种或多种。
8.根据权利要求1所述的热塑性树脂组合物,其中,(e)所述金属粉末的平均直径为1至100μm。
9.根据权利要求1所述的热塑性树脂组合物,还包含选自阻燃剂、成核剂、紫外线吸收剂、抗氧化剂、除尘剂、抗菌剂、驱虫剂、除臭剂、抗着色剂、热稳定剂、脱模剂、抗静电剂、增塑剂、润滑剂、着色剂、颜料、染料、发泡剂、消泡剂、偶联剂和无机填料中的一种或多种的添加剂。
10.根据权利要求1所述的热塑性树脂组合物,其中,所述热塑性树脂组合物的热变形温度为150℃以上,电磁波屏蔽dB值为47以上。
11.根据权利要求1所述的热塑性树脂组合物,其中,当根据ISO 180A方法在样品厚度为4mm的条件下测量缺口悬臂梁式冲击强度时,所述热塑性树脂组合物的缺口悬臂梁式冲击强度为70kJ/m2以上。
12.一种具有优异的耐热性和电磁波屏蔽能力的热塑性树脂组合物的制备方法,该制备方法包括:采用挤出机在250℃至320℃和250至350rpm下,对(a)100重量份的热塑性树脂,该热塑性树脂包含80重量%至100重量%的基础树脂和0至20重量%的增强树脂;(b)2至60重量份的平均直径为3至15μm的线性碳纤维;(c)1至5重量份的BET比表面积为200至400m2/g的碳纳米原纤;(d)1至15重量份的碳纳米片;和(e)1至25重量份的金属粉末进行熔融捏合和挤出。
13.根据权利要求12所述的制备方法,包括在所述熔融捏合和挤出之后,通过使用造粒机剪切挤出物而得到粒料。
14.一种具有电磁波屏蔽能力的注塑制品,包含根据权利要求1至11中任一项所述的热塑性树脂组合物。
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Publication number | Publication date |
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WO2020145500A1 (ko) | 2020-07-16 |
KR102125262B1 (ko) | 2020-06-22 |
US11993695B2 (en) | 2024-05-28 |
CN112424273B (zh) | 2023-03-10 |
EP3808803A1 (en) | 2021-04-21 |
US20210269617A1 (en) | 2021-09-02 |
JP7055931B2 (ja) | 2022-04-18 |
JP2021532214A (ja) | 2021-11-25 |
EP3808803A4 (en) | 2021-08-18 |
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