CN112795169B - 一种树脂组合物及包含其的树脂膜、预浸料、层压板、覆铜板和印刷电路板 - Google Patents
一种树脂组合物及包含其的树脂膜、预浸料、层压板、覆铜板和印刷电路板 Download PDFInfo
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Abstract
本发明涉及一种树脂组合物及包含其的树脂膜、预浸料、层压板、覆铜板和印刷电路板,所述树脂组合物包括:热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物的组合;以所述热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物添加量之和为100重量份计,所述完全氢化的弹性体聚合物的添加量为20‑50重量份。本发明提供的树脂组合物制备得到的覆铜板具有低介电常数和低介电损耗,还具有优异的抗热氧老化性能,同时兼具高玻璃化转变温度、高耐热性能、高剥离强度和低吸水率等特性,可应用于汽车雷达等使用环境更加恶劣的场景。
Description
技术领域
本发明涉及通信材料技术领域,尤其涉及一种树脂组合物及包含其的树脂膜、预浸料、层压板、覆铜板和印刷电路板。
背景技术
对于高频电子电路基材,在长期的使用过程中,保持基材的介质常数和介质损耗的稳定性,对基材的特性阻抗的变化以及信号完整性产生重大影响。在基材树脂固化体系中,树脂在长期的使用过程中,会发生热氧老化,基材的介质常数和介质损耗都会升高,从而影响其稳定性,最终使基材的信号完整性能恶化。因此,基材树脂固化体系良好的抗热氧老化性能是高速电子电路基材的重要性能要求。
改性热固性聚苯醚树脂分子结构中含有大量的苯环结构,且无强极性基团,赋予了聚苯醚树脂优异的性能,如玻璃化转变温度高、尺寸稳定性好、热膨胀系数小、吸水率低,尤其是出色的低介质常数、低介电损耗,成为制备高速电路基板的理想树脂材料。
CN105086417A公开了一种树脂组合物,所述树脂组合物包括:不饱和热固性改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的由单官能度硅氧烷单元(M单元)与四官能度硅氧单元(Q单元)水解缩合而成的MQ有机硅树脂。该发明所述高频电路基板具有高的玻璃化转变温度,高的热分解温度,高的层间粘合力,低介电常数及低介质损耗正切,非常适合作为高频电子设备的电路基板。该树脂组合物同样存在容易被热氧老化的问题。
因此,本领域亟待开发一种具有低介电常数、低介电损耗,以及优异的热氧老化性能的树脂组合物。
发明内容
本发明的目的之一在于提供一种树脂组合物,尤其在于提供一种用于覆铜板的热固性树脂组合物,所述树脂组合物制备得到的板材既具有低的介质常数(Dk)和介质损耗(Df),又具有优异的抗热氧老化性能,使基材的介质常数和介质损耗在长期高温使用环境中保持稳定。
为达此目的,本发明采用以下技术方案:
本发明提供一种树脂组合物,所述树脂组合物包括:热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物;以所述热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物添加量之和为100重量份计,所述完全氢化的弹性体聚合物的添加量为20-50重量份,例如22重量份、24重量份、26重量份、28重量份、30重量份、32重量份、34重量份、36重量份、38重量份、40重量份、42重量份、44重量份、46重量份、48重量份等。
本发明在热固性聚苯醚树脂和乙烯基有机硅树脂体系中加入完全氢化的弹性体聚合物,完全氢化的弹性体聚合物具有优异的低介质常数和低介质损耗性能,特别是具有优异的热氧老化性能,从而能够有效降低树脂体系的Dk和Df,同时提高Dk、Df热氧老化性能,使基材的Dk和Df在长期高温使用环境中保持稳定,同时兼具高玻璃化转变温度、高耐热性能、高剥离强度和低吸水率等特性。
本发明提供的树脂组合物中,完全氢化的弹性体聚合物添加量对树脂组合物制备的基材热氧老化性能产生显著影响,以热固性聚苯醚树脂、乙烯基有机硅树脂体系和完全氢化的弹性体聚合物添加量之和为100份计算,完全氢化的弹性体聚合物的添加量为20-50份。当完全氢化的弹性体聚合物添加量不足20份时,树脂组合物制备的基材Df偏高且热氧老化性能改善不显著。当完全氢化的弹性体聚合物添加量超过50份时,树脂组合物制备的基材玻璃化转变温度过低,给尺寸稳定性和耐热可靠性能带来隐患。
本发明选择完全氢化的弹性体聚合物的添加量在上述特定范围之内的,使树脂组合物具有低介质常数和低介质损耗,以及优异介质常数和介质损耗的热氧老化稳定性能,同时兼具高玻璃化转变温度、高耐热性能、高剥离强度和低吸水率等特性,使覆铜板具有优异的综合性能。
优选地,所述热固性聚苯醚树脂为改性热固性聚苯醚树脂,优选乙烯类基团改性热固性聚苯醚树脂,进一步优选甲基丙烯酸酯基改性热固性聚苯醚树脂。本发明中,“乙烯类基团”指的是含有乙烯基的基团。
优选地,所述甲基丙烯酸酯基改性热固性聚苯醚树脂的数均分子量为500-10000g/mol,例如1000g/mol、2000g/mol、3000g/mol、4000g/mol、5000g/mol、6000g/mol、7000g/mol、8000g/mol、9000g/mol等,优选800~8000g/mol,进一步优选1000~4000g/mol。
如无特殊说明,则本发明中所述数均分子量均是指通过凝胶渗透色谱法测得的数均分子量。
优选地,以所述热固性聚苯醚树脂和乙烯基有机硅树脂的添加量之和为100重量份计,所述乙烯基有机硅树脂的添加量为20-60重量份,例如22重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、58重量份等。
优选地,所述乙烯基有机硅树脂包括环形结构乙烯基有机硅树脂、线性结构乙烯基有机硅树脂或三维网状结构乙烯基有机硅树脂中的任意一种或至少两种组合。
优选地,所述完全氢化的弹性体聚合物包括完全氢化的嵌段弹性体聚合物。
优选地,所述完全氢化的嵌段弹性体聚合物的制备原料包括乙烯基芳香族化合物和共轭二烯的组合。
优选地,所述乙烯基芳香族化合物包括苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、3,5-二乙基苯乙烯、4-正丙基苯乙烯、α-甲基苯乙烯,α-甲基乙烯基甲苯、α-氯苯乙烯,α-溴苯乙烯、二氯苯乙烯、二溴苯乙烯或四氯苯乙烯中的任意一种或至少两种组合。
优选地,所述共轭二烯包括1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)、2,3-二甲基-1,3-丁二烯或1,3-戊二烯中的任意一种或至少两种组合。
优选地,所述完全氢化的嵌段弹性体聚合物为线型嵌段结构或星型嵌段结构。
优选地,所述线型嵌段结构为二嵌段结构(A-B)、三嵌段结构(A-B-A或B-A-B)、四嵌段结构(A-B-A-B)、五嵌段结构(A-B-A-B-A或B-A-B-A-B)或至少六嵌段结构。
优选地,所述完全氢化的弹性体聚合物包括完全氢化的苯乙烯-丁二烯二嵌段共聚物、完全氢化的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、完全氢化的苯乙烯-异戊二烯二嵌段共聚物或完全氢化的苯乙烯-异戊二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种组合。
优选地,所述完全氢化的弹性体聚合物为马来酸酐改性的完全氢化的弹性体聚合物,优选马来酸酐改性的完全氢化的苯乙烯-丁二烯二嵌段共聚物、马来酸酐改性的完全氢化的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、马来酸酐改性的完全氢化的苯乙烯-异戊二烯二嵌段共聚物或马来酸酐改性的完全氢化的苯乙烯-异戊二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种组合。
本发明进一步优选马来酸酐改性的完全氢化的弹性体聚合物,由于马来酸酐基团属于富氧基团,用于热固性聚苯醚树脂、乙烯基有机硅树脂体系中,能够进一步提高热氧老化性能。
本发明中,马来酸酐改性的完全氢化的弹性体聚合物为本领域公知的物质,可以通过商购获得,包括但不限于科腾的KIC1-023。示例性地,马来酸酐改性的完全氢化的弹性体聚合物的合成工艺之一为:乙烯基芳香族化合物和共轭二烯单体中加入一定比例的单体马来酸酐单体及进行聚合反应,再经过催化加氢工艺实现完全氢化。
优选地,所述马来酸酐改性的完全氢化的弹性体聚合物中,马来酸酐基团的含量为≤5%,例如1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%等。本发明中,所述“马来酸酐基团的含量”指的是马来酸酐单体占马来酸酐改性的完全氢化的弹性体聚合物的质量百分比。
本发明优选马来酸酐基团的含量为≤5%,在该范围内,能够使得到的树脂组合物具有最佳的Df以及热氧老化性能。马来酸酐基团的含量过高,会导致树脂组合物制备的基材Df偏高。
优选地,所述树脂组合物还包括引发剂,优选自由基引发剂。
优选地,所述自由基引发剂包括有机过氧化物引发剂,优选过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3,5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊基过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的任意一种或至少两种组合。
优选地,以所述热固性聚苯醚树脂和乙烯基有机硅树脂的添加量之和为100重量份计,所述引发剂的添加量为1~3重量份,例如1.5重量份、2重量份、2.5重量份、2.8重量份等。
优选地,所述树脂组合物还包括阻燃剂。
优选地,所述阻燃剂包括含溴阻燃剂和/或含磷阻燃剂。
优选地,以所述热固性聚苯醚树脂、乙烯基有机硅树脂、完全氢化的弹性体聚合物和阻燃剂添加量之和为100重量份计,所述阻燃剂的添加量为10-30重量份,例如12重量份、15重量份、18重量份、20重量份、22重量份、24重量份、26重量份、28重量份等。
优选地,所述树脂组合物还包括粉末填料。
优选地,所述粉末填料包括有机填料和/或无机填料。
优选地,所述无机填料包括结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、碳化硅铝、氢氧化铝、氢氧化镁、二氧化钛、钛酸锶、钛酸钡、氧化锌、氧化锆、氧化铝、氧化铍、氧化镁、硫酸钡、滑石粉、粘土、硅酸钙、碳酸钙或云母中的任意一种或至少两种组合。
优选地,所述有机填料包括聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的任意一种或至少两种组合。
以所述热固性聚苯醚树脂、乙烯基有机硅树脂、完全氢化的弹性体聚合物、阻燃剂和粉末填料的添加量之和为100重量份计,所述粉末填料的添加量为10-70重量份,例如15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份等。
本发明的目的之二在于提供一种树脂膜,所述树脂膜是将目的之一所述的树脂组合物涂覆在离型材料上,经过干燥和/或半固化工艺后,除去所述离型材料后制得。
本发明的目的之三在于提供一种预浸料,所述预浸料包括增强材料以及通过浸渍干燥后附着其上的目的之一所述的树脂组合物。
在本发明中,所述增强材料可以为有机纤维布、无机纤维编织布或无纺布;其中,所述有机纤维为芳纶无纺布;所述无机纤维编织布为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度为0.01-0.2mm,例如0.02mm、0.05mm、0.08mm、0.1mm、0.12mm、0.15mm、0.18mm等。且所述增强材料最好经过开纤处理及硅烷偶联剂表面处理;所述硅烷偶联剂为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。
本发明的目的之四在于提供一种层压板,所述层压板包括至少一张目的之三所述的预浸料。
优选地,所述层压板的制备方法为通过加热和加压,使一片或两片以上的预浸料粘合在一起而制成的层压板。
本发明的目的之五在于提供一种覆铜板,所述覆铜板含有至少一张目的之三所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
优选地,所述金属箔为铜箔、镍箔、铝箔或SUS箔等。
本发明的目的之六在于提供一种印刷电路板,所述印刷电路板包括目的之四所述的层压板或目的之五所述的覆铜板。
相对于现有技术,本发明具有以下有益效果:
(1)本发明在热固性聚苯醚树脂和乙烯基有机硅树脂体系中加入特定添加量的完全氢化的弹性体聚合物,能够有效降低树脂体系的Dk和Df,同时提高Dk、Df热氧老化稳定性能,使基材的Dk和Df在长期高温环境使用中保持稳定。所制备的基材具有低的Dk/Df以及优异的Dk/Df热氧老化稳定性能,同时兼具高玻璃化转变温度、高耐热性、高剥离强度以及较低的吸水率。
(2)在本发明的优选技术方案中,采用马来酸酐改性完全氢化的弹性体聚合物,可进一步提高基材Dk/Df热氧老化性能的稳定性,通过进一步优选马来酸酐基团含量为≤5%,能够在保证优异热氧老化性能的前提下进一步降低Df。
(3)本发明提供的覆铜板的Dk(10GHz)为2.5-3.5,Df(10GHz)为0.0018-0.0023,玻璃化转变温度为180-208℃,T300>60min,吸水率为0.09%,125℃/30天Dk变化绝对值为0.02-0.04,125℃/30天Df变化绝对值为0.0003-0.0006。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
本发明实施例制备高速电子电路基材所选取的原料如下表所示:
表1
上表中,马来酸酐改性完全氢化SBS-A树脂的制备(马来酸酐含量4.8%):
将100g的SBS嵌段共聚物G1726树脂颗粒添加5.04g的马来酸酐,在0.5g引发剂BPO作用下进行挤出改性,得到马来酸酐改性的完全氢化SBS-A树脂,其中马来酸酐含量4.8%。
上表中,马来酸酐改性完全氢化SBS-B树脂的制备(马来酸酐含量6.0%):
将100g的SBS嵌段共聚物G1726树脂颗粒添加6.38g的马来酸酐,在0.5g引发剂BPO作用下进行挤出改性,得到马来酸酐改性的完全氢化SBS-B树脂,其中马来酸酐含量6.0%。
实施例1-10:
按表2所示组分配制树脂组合物,并按照如下覆铜板的制作方法制作覆铜板样品:
(1)将树脂组合物中配方量的各组分在甲苯中混合均匀,室温下分散均匀,得到树脂胶液;
(2)使用增强材料(Low Dk1035玻纤布)浸渍步骤(1)得到的树脂胶液,过夹轴控制适合单重,并在烘箱中烘片,除去甲苯溶剂,制得1035半固化片。将2张1035半固化片重叠,上下两面配以HOZ厚度的铜箔,在压机中真空层压固化120min,固化压力25Kg/cm2,固化温度200℃,制得覆铜板。
比较例1-8:
按表3所示组分配制树脂组合物,并按照如下覆铜板的制作方法制作覆铜板样品:
(1)将树脂组合物中配方量的各组分在甲苯中混合均匀,室温下分散均匀,得到树脂胶液;
(2)使用增强材料(Low Dk1035玻纤布)浸渍步骤(1)得到的树脂胶液,过夹轴控制适合单重,并在烘箱中烘片,除去甲苯溶剂,制得1035半固化片。将2张1035半固化片重叠,上下两面配以HOZ厚度的铜箔,在压机中真空层压固化120min,固化压力25Kg/cm2,固化温度200℃,制得覆铜板。
性能测试:
针对上述实施例和比较例得到的覆铜板进行如下性能测试:
(1)介电常数和介电损耗测试:采用SPDR(splite post dielectric resonator)法进行测试,测试条件为A态,频率为10GHz。
(2)玻璃化转变温度(Tg)测试:按照IPC-TM-650 2.4.24所规定的DMA方法进行测定。
(3)T300(带铜):参照IPC-TM-650 2.4.24.1,采用带铜箔板材在温度300℃下测试。
(4)铜箔剥离强度(PS)测试:IPC-TM-650 2.4.8;铜箔抗剥仪。
(5)吸水率测试:按照IPC-TM-650 2.6.2.1方法进行测定。
(6)抗老化性能测试:125℃烘箱烘板30天,测试烘板前后的Dk/Df。
上述性能测试结果如表2和表3所示。
表2
表3
由表2和表3的数据可知,本发明提供的包含热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物的树脂组合物所制备的覆铜层压板除了具有低介质常数和低介质损耗,还具有优异的介质常数和介质损耗的热氧老化稳定性能,同时兼具高玻璃化转变温度,高耐热性能,高剥离强度,低吸水率综合性能。
将比较例1-3与实施例1-3对比可知,树脂体系为改性聚苯醚和乙烯基有机硅树脂,不含完全氢化的弹性体树脂(比较例1-3),基材介质损耗偏高,高达0.0028-0.0029,且基材介质损耗热氧老化性能欠佳,125℃热氧老化30天,介质损耗升高0.0015-0.0016,不能满足市场的需求。
将比较例4与实施例3对比可知,使用未氢化的弹性体聚合物(比较例4),基材介质损耗热氧老化性能欠佳,125℃热氧老化30天,基材介质损耗升高0.003,不能满足市场的需求。
将比较例5-6与实施例2、5、6对比可知,比较例5-6中完全氢化的弹性体聚合物的添加量不足20重量份(以所述热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物添加量之和为100重量份计),基材介质损耗偏高,高达0.0027-0.0028,且基材介质损耗热氧老化性能欠佳,125℃热氧老化30天,介质损耗升高0.0014-0.0015,不能满足市场的需求。
比较例7-8与实施例2、5、6对比可知,比较例7-8中完全氢化的弹性体聚合物的添加量超过50重量份(以所述热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物添加量之和为100重量份计),基材玻璃化转变温度偏低,低至143-150℃,给尺寸稳定性和耐热可靠性能带来隐患,不能满足市场的需求。
将实施例10与实施例4对比可知,马来酸酐改性的完全氢化的弹性体树脂中马来酸酐含量为6.0%时(实施例10),基材介质损耗偏高,Df值为0.0024,由此证明,本发明通过优选马来酸酐的含量≤5%,能够在保证优异热氧老化性能的前提下进一步降低基材介质损耗,以提高板材的综合性能。
申请人声明,本发明通过上述实施例来说明本发明的详细方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (28)
1.一种树脂组合物,其特征在于,所述树脂组合物包括:热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物;以所述热固性聚苯醚树脂、乙烯基有机硅树脂和完全氢化的弹性体聚合物添加量之和为100重量份计,所述完全氢化的弹性体聚合物的添加量为20-50重量份;
以所述热固性聚苯醚树脂和乙烯基有机硅树脂添加量之和为100重量份计,所述乙烯基有机硅树脂的添加量为20-60重量份;
所述树脂组合物还包括自由基引发剂;
所述完全氢化的弹性体聚合物包括完全氢化的嵌段弹性体聚合物;
所述热固性聚苯醚树脂为甲基丙烯酸酯基改性热固性聚苯醚树脂。
2.根据权利要求1所述的树脂组合物,其特征在于,所述甲基丙烯酸酯基改性热固性聚苯醚树脂的数均分子量为500-10000g/mol。
3.根据权利要求2所述的树脂组合物,其特征在于,所述甲基丙烯酸酯基改性热固性聚苯醚树脂的数均分子量为800~8000g/mol。
4.根据权利要求3所述的树脂组合物,其特征在于,所述甲基丙烯酸酯基改性热固性聚苯醚树脂的数均分子量为1000~4000g/mol。
5.根据权利要求1所述的树脂组合物,其特征在于,所述乙烯基有机硅树脂包括环形结构乙烯基有机硅树脂、线性结构乙烯基有机硅树脂或三维网状结构乙烯基有机硅树脂中的任意一种或至少两种组合。
6.根据权利要求1所述的树脂组合物,其特征在于,所述完全氢化的嵌段弹性体聚合物的制备原料包括乙烯基芳香族化合物和共轭二烯的组合。
7.根据权利要求6所述的树脂组合物,其特征在于,所述乙烯基芳香族化合物包括苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、3,5-二乙基苯乙烯、4-正丙基苯乙烯、α-甲基苯乙烯,α-甲基乙烯基甲苯、α-氯苯乙烯,α-溴苯乙烯、二氯苯乙烯、二溴苯乙烯或四氯苯乙烯中的任意一种或至少两种组合。
8.根据权利要求6所述的树脂组合物,其特征在于,所述共轭二烯包括1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)、2,3-二甲基-1,3-丁二烯或1,3-戊二烯中的任意一种或至少两种组合。
9.根据权利要求1所述的树脂组合物,其特征在于,所述完全氢化的弹性体聚合物包括完全氢化的苯乙烯-丁二烯二嵌段共聚物、完全氢化的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、完全氢化的苯乙烯-异戊二烯二嵌段共聚物或完全氢化的苯乙烯-异戊二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种组合。
10.根据权利要求9所述的树脂组合物,其特征在于,所述完全氢化的弹性体聚合物为马来酸酐改性的完全氢化的弹性体聚合物。
11.根据权利要求10所述的树脂组合物,其特征在于,所述完全氢化的弹性体聚合物为马来酸酐改性的完全氢化的苯乙烯-丁二烯二嵌段共聚物、马来酸酐改性的完全氢化的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、马来酸酐改性的完全氢化的苯乙烯-异戊二烯二嵌段共聚物或马来酸酐改性的完全氢化的苯乙烯-异戊二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种组合。
12.根据权利要求10所述的树脂组合物,其特征在于,所述马来酸酐改性的完全氢化的弹性体聚合物中,马来酸酐基团的含量为≤5%。
13.根据权利要求1所述的树脂组合物,其特征在于,所述自由基引发剂包括有机过氧化物引发剂。
14.根据权利要求13所述的树脂组合物,其特征在于,所述自由基引发剂包括过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸特戊酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3,5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊基过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的任意一种或至少两种组合。
15.根据权利要求1所述的树脂组合物,其特征在于,以所述热固性聚苯醚树脂和乙烯基有机硅树脂的添加量之和为100重量份计,所述自由基引发剂的添加量为1~3重量份。
16.根据权利要求1所述的树脂组合物,其特征在于,所述树脂组合物还包括阻燃剂。
17.根据权利要求16所述的树脂组合物,其特征在于,所述阻燃剂包括含溴阻燃剂和/或含磷阻燃剂。
18.根据权利要求16所述的树脂组合物,其特征在于,以所述热固性聚苯醚树脂、乙烯基有机硅树脂、完全氢化的弹性体聚合物和阻燃剂添加量之和为100重量份计,所述阻燃剂的添加量为10-30重量份。
19.根据权利要求1所述的树脂组合物,其特征在于,所述树脂组合物还包括粉末填料。
20.根据权利要求19所述的树脂组合物,其特征在于,所述粉末填料包括有机填料和/或无机填料。
21.根据权利要求20所述的树脂组合物,其特征在于,所述无机填料包括结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、角形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、碳化硅铝、氢氧化铝、氢氧化镁、二氧化钛、钛酸锶、钛酸钡、氧化锌、氧化锆、氧化铝、氧化铍、氧化镁、硫酸钡、滑石粉、粘土、硅酸钙、碳酸钙或云母中的任意一种或至少两种组合。
22.根据权利要求20所述的树脂组合物,其特征在于,所述有机填料包括聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的任意一种或至少两种组合。
23.根据权利要求19所述的树脂组合物,其特征在于,以所述热固性聚苯醚树脂、乙烯基有机硅树脂、完全氢化的弹性体聚合物、阻燃剂和粉末填料的添加量之和为100重量份计,所述粉末填料的添加量为10-70重量份。
24.一种树脂膜,其特征在于,所述树脂膜是将如权利要求1-23中任一项所述的树脂组合物涂覆在离型材料上,经过干燥和/或半固化工艺后,除去所述离型材料后制得。
25.一种预浸料,其特征在于,所述预浸料包括增强材料以及通过浸渍干燥后附着其上的权利要求1-23中任一项所述的树脂组合物。
26.一种层压板,其特征在于,所述层压板包括至少一张权利要求25所述的预浸料。
27.一种覆铜板,其特征在于,所述覆铜板含有至少一张权利要求25所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
28.一种印刷电路板,其特征在于,所述印刷电路板包括权利要求26所述的层压板或权利要求27所述的覆铜板。
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