CN113910703A - 一种碳氢树脂基柔性高频覆铜板材料及其制备方法 - Google Patents

一种碳氢树脂基柔性高频覆铜板材料及其制备方法 Download PDF

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CN113910703A
CN113910703A CN202111075509.9A CN202111075509A CN113910703A CN 113910703 A CN113910703 A CN 113910703A CN 202111075509 A CN202111075509 A CN 202111075509A CN 113910703 A CN113910703 A CN 113910703A
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hydrocarbon resin
hot pressing
copper
clad plate
copolymer
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CN113910703B (zh
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张启龙
王浩
董娇娇
杨辉
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Zhejiang University ZJU
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Abstract

本发明涉及材料科学与工程领域,旨在提供一种碳氢树脂基柔性高频覆铜板材料及其制备方法。该覆铜板材料具有五层的层状结构,包括:位于最外侧表面的两个铜箔层,位于中央的碳氢树脂/填充粉料复合薄膜层,以及位于铜箔层和碳氢树脂/填充粉料复合薄膜层之间的两个烯烃类共聚物薄膜层。本发明具有低介电常数、低介电损耗、低吸水率、高热分解温度以及良好的体积电阻率。充分满足了高频高速条件下的热量传输需求,并且其吸水率、热分解温度、体积电阻率与其他柔性覆铜板相当。本发明创新性地采用两种碳氢树脂作为基体,设计了包夹叠层结构来提高覆铜板的综合性能;产品具有良好的尺寸稳定性和耐折性,在柔性高频覆铜板材料领域有很大的应用前景。

Description

一种碳氢树脂基柔性高频覆铜板材料及其制备方法
技术领域
本发明涉及一种柔性高频覆铜板材料及其制备方法,属于材料科学与工程领域。
背景技术
柔性印制电路板(Flexible Printing Circuit,FPC)是由柔性的绝缘基材制备而成,具有集成密度高、轻薄、可弯折等特点,在产品的造型设计和可靠性设计方面具有明显的优势。柔性基板适合当今社会电子产品小型化、轻薄化的发展趋势,在智能手机、平板电脑、柔性电子、可穿戴设备等消费电子以及其他通信领域具有重要价值。随着电子信息技术的快速发展,柔性电子设备也面临高频化高速化信号传输的需求。随着设备使用频率的不断提高,柔性覆铜板材料(FCCL)不断朝着低介电损耗的方向发展,目前市场上使用的高频FPC绝缘基体主要为改性聚酰亚胺(MPI)和液晶聚合物LCP。毫米波频段对于能够控制传输损耗且介电性能更优异的材料有进一步的需求,但由于上述树脂基体的分子结构及固有物理性能的局限性,MPI与LCP材料仍具有相对较高的介电损耗,可能无法满足更高频率的要求。为了满足更高性能需求,具有更低介电损耗的树脂材料也纷纷被开发为FCCL。
碳氢树脂种类繁多,因其高频条件下优异的介电性能、低吸水率及优良的耐腐蚀性、耐热性而广泛应用于高频刚性覆铜板中,而且其中部分树脂也具有优异的柔韧性及耐折性,因此其有望应用于柔性高频覆铜板材料当中。但目前由于单一碳氢树脂综合性能很难满足柔性覆铜板材料需求以及填充材料的加入会损害板材柔韧性的原因,目前尚未见到有将此类树脂用作加工柔性高频覆铜板原材料的研究成果或相关报道。
发明内容
本发明要解决的技术问题是,克服现有技术中的不足,提供一种碳氢树脂基柔性高频覆铜板材料及其制备方法。
为解决技术问题,本发明的解决方案是:
提供一种碳氢树脂基柔性高频覆铜板材料,该覆铜板材料具有五层的层状结构,包括:位于最外侧表面的两个铜箔层,位于中央的碳氢树脂/填充粉料复合薄膜层,以及位于铜箔层和碳氢树脂/填充粉料复合薄膜层之间的两个烯烃类共聚物薄膜层。
作为本发明的优选方案,在所述碳氢树脂/填充粉料复合薄膜层中,碳氢树脂是氢化苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯嵌段共聚物、聚苯乙烯丁二烯共聚物、丁腈聚合物、三元乙丙橡胶或聚二甲基硅氧烷中的一种;填充粉料是二氧化硅、氧化铝、氮化铝、氮化硅、氮化硼、碳化硅、钛酸钙或二氧化钛中的一种;碳氢树脂与填充粉料的质量比为1∶1~4。
作为本发明的优选方案,在所述烯烃类共聚物薄膜层中,烯烃类共聚物是聚乙烯、聚苯乙烯、聚丁烯、环烯烃共聚物或聚4-甲基-1-戊烯中的一种。
本发明进一步提高了前述碳氢树脂基柔性高频覆铜板材料的制备方法,包括以下步骤:
(1)将碳氢树脂置于环己烷中,搅拌直至溶液澄清透明;然后加入填充粉料,超声搅拌1h,得到分散均匀的悬浮液;
(2)将悬浮液倒入等体积的无水乙醇中,搅拌直至产生白色沉淀;将白色沉淀过滤、烘干,得到碳氢树脂/填充粉料复合粉末;
(3)将复合粉末作为真空热压机的进料,经热压得到碳氢树脂/填充粉料复合薄膜;
(4)取烯烃类共聚物置于二甲苯中,在60℃水浴锅中搅拌直至溶液澄清透明;将透明溶液均匀滴涂在玻璃板上,然后置于真空烘箱中烘干溶剂,得到烃类共聚物薄膜;
(5)按照铜箔、烃类共聚物薄膜、碳氢树脂/填充粉料复合薄膜、烃类共聚物薄膜、铜箔的顺序依次叠放各层材料,然后置于真空热压机中热压,得到碳氢树脂基柔性高频覆铜板材料。
作为本发明的优选方案,所述步骤(1)中,碳氢树脂是氢化苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯嵌段共聚物、聚苯乙烯丁二烯共聚物、丁腈聚合物、三元乙丙橡胶或聚二甲基硅氧烷中的一种;填充粉料是二氧化硅、氧化铝、氮化铝、氮化硅、氮化硼、碳化硅、钛酸钙或二氧化钛中的一种;碳氢树脂与填充粉料的质量比为1∶1~4,碳氢树脂和填充粉料的总质量与环己烷的质量比为1∶8。
作为本发明的优选方案,所述步骤(2)中,烘干温度为80℃,烘干时间为12h;所述步骤(4)中,烘干温度为60℃,烘干时间为12h。
作为本发明的优选方案,所述步骤(3)中,热压过程中的参数设定为:热压压力1~10MPa,热压温度100~190℃,真空度-0.085MPa,热压时间30~180min。
作为本发明的优选方案,所述步骤(4)中,烯烃类共聚物薄膜层中,烯烃类共聚物是聚乙烯、聚苯乙烯、聚丁烯、环烯烃共聚物或聚4-甲基-1-戊烯中的一种,烯烃类共聚物与二甲苯的质量比为1∶10~18。
作为本发明的优选方案,所述步骤(5)中,热压过程中的参数设定为:热压压力1~3MPa,热压温度150~200℃,热压时间为10~30min,真空度为-0.085MPa。
作为本发明的优选方案,所述碳氢树脂/填充粉料复合薄膜的厚度为100微米,烃类共聚物薄膜的厚度为30微米,铜箔的厚度为12微米,最终碳氢树脂基柔性高频覆铜板材料的厚度为180微米。
发明原理描述:
本发明基于碳氢树脂高频条件下优异的介电性能、低吸水率及优良的耐腐蚀性、耐热性、柔韧性和耐折性等特点采用烯烃类碳氢树脂薄膜包夹高弹性树脂/填充粉料复合薄膜制备了柔性覆铜板。采用高弹性树脂作为中间层有效保证了覆铜板的柔韧性,控制填充粉料的加入能够在不破坏其柔韧性的同时降低尺寸变化率和提高覆铜板的导热性能。烯烃类碳氢树脂薄膜具有低介电常数、低介电损耗和低吸水率的特点,采用包夹的形式能够避免中间层高弹性树脂/填充粉料复合薄膜与外界的接触,有效降低了整体的吸水率,同时还降低了整体的介电常数及介电损耗。烯烃类碳氢树脂薄膜同样也具有优异的柔韧性,能够保证整体的柔韧性及耐折性。
与现有技术相比,本发明的有益效果是:
1、本发明的覆铜板材料是由两种碳氢树脂材料和填充粉料经叠层覆铜箔真空热压而成,具有低介电常数、低介电损耗、低吸水率、高热分解温度以及良好的体积电阻率。
本发明所制备的柔性高频覆铜板材料介电常数为2.7~3.5(10GHz),介电损耗为4.0×10-4~8.8×10-4(10GHz),热导率为4~17.64W/(mK),吸水率为0.04%~0.12%,热分解温度大于400℃,体积电阻率为1×1013Ω·cm~3.45×1013Ω·cm,
与目前应用较多的MPI和LCP(介电损耗2.5×10-3 10GHz)柔性覆铜板相比,本发明覆铜板材料的介电损耗具有极大的优势(<1×10-3 10GHz),并且可以实现介电常数在2.7~3.5之间调节,同时还实现了覆铜板热导率的大幅提高,充分满足了高频高速条件下的热量传输需求,并且其吸水率、热分解温度、体积电阻率与其他柔性覆铜板相当。
2、本发明创新性地采用两种碳氢树脂作为基体,设计了包夹叠层结构来提高覆铜板的综合性能。具有良好的尺寸稳定性和耐折性,综合性能优异,在柔性高频覆铜板材料领域有很大的应用前景。
具体实施方式
本发明将参照下述的实施例进一步详细说明,但这些实施例并不是为了限制本发明的范围。
实施例1:
步骤(1):将氢化苯乙烯-丁二烯嵌段共聚物置于环己烷中搅拌直至溶液澄清透明,加入二氧化硅粉末超声搅拌1h得到分散均匀的悬浮液,其中氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的质量比为1:1,氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力1MPa,热压温度100℃,真空度-0.085MPa,热压时间30min;
步骤(4):取环烯烃共聚物置于二甲苯中,环烯烃共聚物与二甲苯的质量比为1:10,在60℃水浴锅中搅拌直至溶液澄清透明,然后将所得透明溶液均匀滴涂在玻璃板上,而后置于60℃真空烘箱中12h烘干溶剂得到环烯烃共聚物薄膜,通过控制溶液浓度控制薄膜厚度为30微米;
步骤(5):将步骤(3)所得复合薄膜上下表面分别覆盖步骤(4)所得环烯烃共聚物薄膜,再置于双面覆铜箔之间后转置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力1MPa,热压温度150℃,热压时间为10min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数2.7(10GHz),介电损耗8.8×10-4(10GHz),热导率4.0W/(mK),吸水率0.12%,热分解温度412℃,体积电阻率1×1013Ω·cm,尺寸稳定性-0.59%,耐折性大于2000次,柔性覆铜板材料的最终厚度为180微米。
实施例2:
步骤(1):将苯乙烯-丁二烯嵌段共聚物置于环己烷中搅拌直至溶液澄清透明,加入氮化硼粉末超声搅拌1h得到分散均匀的悬浮液,其中苯乙烯-丁二烯嵌段共聚物与氮化硼粉末的质量比为1:4,苯乙烯-丁二烯嵌段共聚物和氮化硼粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力10MPa,热压温度190℃,真空度-0.085MPa,热压时间180min;
步骤(4):取聚乙烯置于二甲苯中,聚乙烯与二甲苯的质量比为1:18,在60℃水浴锅中搅拌直至溶液澄清透明,然后将所得透明溶液均匀滴涂在玻璃板上,而后置于60℃真空烘箱中12h烘干溶剂得到聚乙烯薄膜,通过控制溶液浓度控制薄膜厚度为30微米;
步骤(5):将步骤(3)所得复合薄膜上下表面覆盖步骤(4)所得聚乙烯薄膜,再置于双面覆铜箔之间后转置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力3MPa,热压温度200℃,热压时间为30min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数3.5(10GHz),介电损耗4.0×10-4(10GHz),热导率17.64W/(mK),吸水率0.04%,热分解温度442℃,体积电阻率3.45×1013Ω·cm,尺寸稳定性-0.084%,耐折性大于2000次,柔性覆铜板材料的最终厚度为180微米。
实施例3:
步骤(1):将聚苯乙烯丁二烯共聚物置于环己烷中搅拌直至溶液澄清透明,加入碳化硅粉末超声搅拌1h得到分散均匀的悬浮液,其中聚苯乙烯丁二烯共聚物与碳化硅粉末的质量比为1:2,聚苯乙烯丁二烯共聚物和碳化硅粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力5MPa,热压温度150℃,真空度-0.085MPa,热压时间100min;
步骤(4):取聚苯乙烯置于二甲苯中,聚苯乙烯与二甲苯的质量比为1:15,在60℃水浴锅中搅拌直至溶液澄清透明,然后将所得透明溶液均匀滴涂在玻璃板上,而后置于60℃真空烘箱中12h烘干溶剂得到聚苯乙烯薄膜,通过控制溶液浓度控制薄膜厚度为30微米;
步骤(5):将步骤(3)所得复合薄膜上下表面覆盖步骤(4)所得聚苯乙烯薄膜,再置于双面覆铜箔之间后转置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力2MPa,热压温度180℃,热压时间为20min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数3.0(10GHz),介电损耗5.2×10-4(10GHz),热导率10.1W/(mK),吸水率0.05%,热分解温度422℃,体积电阻率1.3×1013Ω·cm,尺寸稳定性-0.034%,耐折性大于2000次,柔性覆铜板材料的最终厚度为180微米。
实施例4:
步骤(1):将聚二甲基硅氧烷置于环己烷中搅拌直至溶液澄清透明,加入氮化铝粉末超声搅拌1h得到分散均匀的悬浮液,其中聚二甲基硅氧烷与氮化铝粉末的质量比为1:3,聚二甲基硅氧烷和氮化铝粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力7MPa,热压温度180℃,真空度-0.085MPa,热压时间120min;
步骤(4):取聚丁烯置于二甲苯中,聚丁烯与二甲苯的质量比为1:12,在60℃水浴锅中搅拌直至溶液澄清透明,然后将所得透明溶液均匀滴涂在玻璃板上,而后置于60℃真空烘箱中12h烘干溶剂得到聚丁烯薄膜,通过控制溶液浓度控制薄膜厚度为30微米;
步骤(5):将步骤(3)所得复合薄膜上下表面覆盖步骤(4)所得聚丁烯薄膜,再置于双面覆铜箔之间后转置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力3MPa,热压温度170℃,热压时间为25min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数3.2(10GHz),介电损耗4.5×10-4(10GHz),热导率11.2W/(mK),吸水率0.07%,热分解温度432℃,体积电阻率2.4×1013Ω·cm,尺寸稳定性0.014%,耐折性大于2000次,柔性覆铜板材料的最终厚度为180微米。
实施例5:
步骤(1):将三元乙丙橡胶置于环己烷中搅拌直至溶液澄清透明,加入二氧化钛粉末超声搅拌1h得到分散均匀的悬浮液,其中三元乙丙橡胶与二氧化钛粉末的质量比为1:1,三元乙丙橡胶和二氧化钛粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力3MPa,热压温度140℃,真空度-0.085MPa,热压时间50min;
步骤(4):取聚4-甲基-1-戊烯置于二甲苯中,聚4-甲基-1-戊烯与二甲苯的质量比为1:16,在60℃水浴锅中搅拌直至溶液澄清透明,然后将所得透明溶液均匀滴涂在玻璃板上,而后置于60℃真空烘箱中12h烘干溶剂得到聚丁烯薄膜,通过控制溶液浓度控制薄膜厚度为30微米;
步骤(5):将步骤(3)所得复合薄膜上下表面覆盖步骤(4)所得聚4-甲基-1-戊烯薄膜,再置于双面覆铜箔之间后转置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力3MPa,热压温度190℃,热压时间为28min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数3.1(10GHz),介电损耗6.3×10-4(10GHz),热导率8.6W/(mK),吸水率0.09%,热分解温度412℃,体积电阻率2.1×1013Ω·cm,尺寸稳定性-0.024%,耐折性大于2000次,柔性覆铜板材料的最终厚度为180微米。
对比例1:
步骤(1):将氢化苯乙烯-丁二烯嵌段共聚物置于环己烷中搅拌直至溶液澄清透明,加入二氧化硅粉末超声搅拌1h得到分散均匀的悬浮液,其中氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的质量比为1:1,氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的总质量与环己烷的质量比为1:8;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力1MPa,热压温度100℃,真空度-0.085MPa,热压时间30min;
步骤(4):将步骤(3)所得复合薄膜双面覆铜箔置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力1MPa,热压温度150℃,热压时间为10min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数3.6(10GHz),介电损耗2.24×10-3(10GHz),热导率4.0W/(mK),吸水率0.52%,热分解温度398℃,体积电阻率4×1012Ω·cm,尺寸稳定性-1.2%,耐折性大于2000次,柔性覆铜板材料的最终厚度为120微米。
与本发明实施例相比,该对比例1的产品中未使用烃类共聚物薄膜层,最终产品是传统技术所应用的三层包夹结构。
对比例2:
步骤(1):将氢化苯乙烯-丁二烯嵌段共聚物、环烯烃共聚物置于环己烷中搅拌直至溶液澄清透明,加入二氧化硅粉末超声搅拌1h得到分散均匀的悬浮液,其中氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的质量比为1:1,氢化苯乙烯-丁二烯嵌段共聚物与二氧化硅粉末的总质量与环己烷的质量比为1:8,环烯烃共聚物在覆铜板中的质量分数与实施例1相同;
步骤(2):将步骤(1)中悬浮液倒入等体积的无水乙醇当中搅拌30min直至产生白色沉淀,将白色沉淀过滤烘干得到复合粉末,烘干的温度为80℃,烘干时间为12h;
步骤(3):将步骤(2)所得复合粉末置于真空热压机中热压得到柔性薄膜,通过控制压力和温度控制柔性薄膜厚度为100微米,热压过程中的参数设定为热压压力1MPa,热压温度100℃,真空度-0.085MPa,热压时间30min;
步骤(4):将步骤(3)所得复合薄膜双面覆铜箔置于真空热压机中热压得到柔性高频覆铜板材料,其中铜箔厚度为12微米,热压过程中的参数为,热压压力1MPa,热压温度150℃,热压时间为10min,真空度为-0.085MPa。
按照前述配方和工艺制备得到的柔性覆铜板材料,各项性能指标为:介电常数2.7(10GHz),介电损耗8.8×10-4(10GHz),热导率2.3W/(mK),吸水率0.42%,热分解温度400℃,体积电阻率3×1012Ω·cm,尺寸稳定性-1.47%,弯折2000次后断裂,柔性覆铜板材料的最终厚度为120微米。
与本发明实施例相比,该对比例1的产品中虽然使用了烯烃类共聚物成分,但未将该烯烃类共聚物单独制成烯烃类共聚物薄膜层,最终产品仍是传统的三层包夹结构。
通过实施例1与对比例1的产品性能指标可以看出,本发明产品中五层包夹结构相比传统的三层包夹结构而言,具有更低的介电常数、介电损耗、吸水率和更高的体积电阻率、热分解温度和尺寸稳定性。通过实施例1与对比例2的产品性能指标可以看出,即便是使用完全相同的制备原料,本发明的五层包夹结构设计相对比于传统的三层结构产品,仍然具有更高的热导率、尺寸稳定性、耐折性和更低的吸水率。以上结果充分证明,本发明所述多层设计的包夹结构,在提高柔性覆铜板材料综合性能方面具有显著作用。

Claims (10)

1.一种碳氢树脂基柔性高频覆铜板材料,其特征在于,该覆铜板材料具有五层的层状结构,包括:位于最外侧表面的两个铜箔层,位于中央的碳氢树脂/填充粉料复合薄膜层,以及位于铜箔层和碳氢树脂/填充粉料复合薄膜层之间的两个烯烃类共聚物薄膜层。
2.根据权利要求1所述的碳氢树脂基柔性高频覆铜板材料,其特征在于,在所述碳氢树脂/填充粉料复合薄膜层中,碳氢树脂是氢化苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯嵌段共聚物、聚苯乙烯丁二烯共聚物、丁腈聚合物、三元乙丙橡胶或聚二甲基硅氧烷中的一种;填充粉料是二氧化硅、氧化铝、氮化铝、氮化硅、氮化硼、碳化硅、钛酸钙或二氧化钛中的一种;碳氢树脂与填充粉料的质量比为1∶1~4。
3.根据权利要求1所述的碳氢树脂基柔性高频覆铜板材料,其特征在于,在所述烯烃类共聚物薄膜层中,烯烃类共聚物是聚乙烯、聚苯乙烯、聚丁烯、环烯烃共聚物或聚4-甲基-1-戊烯中的一种。
4.权利要求1所述碳氢树脂基柔性高频覆铜板材料的制备方法,其特征在于,包括以下步骤:
(1)将碳氢树脂置于环己烷中,搅拌直至溶液澄清透明;然后加入填充粉料,超声搅拌1h,得到分散均匀的悬浮液;
(2)将悬浮液倒入等体积的无水乙醇中,搅拌直至产生白色沉淀;将白色沉淀过滤、烘干,得到碳氢树脂/填充粉料复合粉末;
(3)将复合粉末作为真空热压机的进料,经热压得到碳氢树脂/填充粉料复合薄膜;
(4)取烯烃类共聚物置于二甲苯中,在60℃水浴锅中搅拌直至溶液澄清透明;将透明溶液均匀滴涂在玻璃板上,然后置于真空烘箱中烘干溶剂,得到烃类共聚物薄膜;
(5)按照铜箔、烃类共聚物薄膜、碳氢树脂/填充粉料复合薄膜、烃类共聚物薄膜、铜箔的顺序依次叠放各层材料,然后置于真空热压机中热压,得到碳氢树脂基柔性高频覆铜板材料。
5.根据权利要求4所述的方法,其特征在于,所述步骤(1)中,碳氢树脂是氢化苯乙烯-丁二烯嵌段共聚物、苯乙烯-丁二烯嵌段共聚物、聚苯乙烯丁二烯共聚物、丁腈聚合物、三元乙丙橡胶或聚二甲基硅氧烷中的一种;填充粉料是二氧化硅、氧化铝、氮化铝、氮化硅、氮化硼、碳化硅、钛酸钙或二氧化钛中的一种;碳氢树脂与填充粉料的质量比为1∶1~4,碳氢树脂和填充粉料的总质量与环己烷的质量比为1∶8。
6.根据权利要求4所述的方法,其特征在于,所述步骤(2)中,烘干温度为80℃,烘干时间为12h;所述步骤(4)中,烘干温度为60℃,烘干时间为12h。
7.根据权利要求4所述的方法,其特征在于,所述步骤(3)中,热压过程中的参数设定为:热压压力1~10MPa,热压温度100~190℃,真空度-0.085MPa,热压时间30~180min。
8.根据权利要求4所述的方法,其特征在于,所述步骤(4)中,烯烃类共聚物薄膜层中,烯烃类共聚物是聚乙烯、聚苯乙烯、聚丁烯、环烯烃共聚物或聚4-甲基-1-戊烯中的一种,烯烃类共聚物与二甲苯的质量比为1∶10~18。
9.根据权利要求4所述的方法,其特征在于,所述步骤(5)中,热压过程中的参数设定为:热压压力1~3MPa,热压温度150~200℃,热压时间为10~30min,真空度为-0.085MPa。
10.根据权利要求4所述的方法,其特征在于,所述碳氢树脂/填充粉料复合薄膜的厚度为100微米,烃类共聚物薄膜的厚度为30微米,铜箔的厚度为12微米,最终碳氢树脂基柔性高频覆铜板材料的厚度为180微米。
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