CN111253702B - 一种树脂组合物及使用其的预浸料和电路材料 - Google Patents

一种树脂组合物及使用其的预浸料和电路材料 Download PDF

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CN111253702B
CN111253702B CN202010239472.8A CN202010239472A CN111253702B CN 111253702 B CN111253702 B CN 111253702B CN 202010239472 A CN202010239472 A CN 202010239472A CN 111253702 B CN111253702 B CN 111253702B
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resin
resin composition
weight
parts
unsaturated
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CN111253702A (zh
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师剑英
殷卫峰
许永静
颜善银
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN202010239472.8A priority Critical patent/CN111253702B/zh
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Priority to EP21153736.0A priority patent/EP3889209A1/en
Priority to US17/160,011 priority patent/US11584851B2/en
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Abstract

本发明提供了一种树脂组合物及使用其的预浸料和电路材料。所述树脂组合物包括不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂和引发剂;以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述萜烯树脂的含量为3‑40重量份;所述聚烯烃树脂选自不饱和聚丁二烯树脂、SBS树脂和丁苯树脂中的一种或至少两种的组合。本发明通过不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂三者之间的相互配合,使得到的树脂组合物具有良好的成膜性、粘结性和介电性能,采用其的电路板材具有较高的层间剥离强度和较低的介电损耗。

Description

一种树脂组合物及使用其的预浸料和电路材料
技术领域
本发明属于印制电路板技术领域,具体涉及一种树脂组合物及使用其的预浸料和电路材料。
背景技术
电路板材是手机、电脑、通信基站、智能机器人等电子设备的关键组成部件,对信息传输的速率和准确性影响重大。近年来,随着通讯设备高性能化、高功能化以及网络化的发展,为了高速传输及处理大容量信息,操作信号正在进行高频化。
电路绝缘材料的介电常数越小,信号的传输速率越快,因此为了信号的高高速传输,必须开发低介电常数的电路基板。同时,高频信号会增加信号传输过程中的介电损失,这会使信号失真的风险增大,因此还需要降低电路基板的介电损耗因子。
US 5223568A公开了一种使用聚丁二烯、聚异戊二烯、热塑性弹性体制备的板材。US 5571609A公开了一种使用不饱和的聚丁二烯树脂、不饱和化的烯烃树脂和填料制备的板材,该板材不黏手、工艺制造性好,但是该板材含有大量填料,板材的剥离强度低,介电损耗高。上述板材使用了非极性的聚烯烃类材料,板材具有良好的介电性能。但是,聚烯烃材料的可反应基团较少,固化后分子间作用力较弱,因此制备的板材存在剥离强度低、耐热性不足的缺点。而高剥离强度和高耐热性同样是高性能通讯设备的电路基板所需要的。
此外,传统的覆铜板是通过增强材料浸润树脂组合物的方法制备得到,但是对于由粘结性薄膜粘合得到的电路板材,则还需要考虑到基体材料成膜性能。
因此,研究一种兼具较高剥离强度、较低介电损耗的电路板材,对于电子信息通讯行业具有重要意义。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种树脂组合物及使用其的预浸料和电路材料。本发明提供的树脂组合物具有良好的成膜性、粘结性和介电性能,采用其的电路板材具有较高的层间剥离强度和较低的介电损耗。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供一种树脂组合物,所述树脂组合物包括不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂和引发剂;以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述萜烯树脂的含量为3-40重量份;所述聚烯烃树脂选自聚丁二烯树脂、SBS树脂和丁苯树脂中的一种或至少两种的组合。
本发明中萜烯树脂能够与不饱和聚苯醚树脂、聚烯烃树脂相互反应,通过三者相互配合,使得到的树脂组合物具有良好的成膜性、粘结性和介电性能,该树脂组合物可以用作电路材料的粘合剂层材料,或用于浸渍增强材料制备预浸料,使得到的电路板材达到较高的层间剥离强度和较低的介电损耗。
作为本发明的优选技术方案,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的重量为100重量份计,所述树脂组合物包括不饱和聚苯醚树脂40-80重量份、聚烯烃树脂10-50重量份和萜烯树脂3-40重量份。
其中,不饱和聚苯醚树脂的含量可以是40重量份、42重量份、45重量份、48重量份、50重量份、52重量份、55重量份、58重量份、60重量份、62重量份、65重量份、68重量份、70重量份、72重量份、75重量份、78重量份或80重量份等。
聚烯烃树脂的含量可以是10重量份、12重量份、15重量份、18重量份、20重量份、22重量份、25重量份、28重量份、30重量份、32重量份、35重量份、38重量份、40重量份、42重量份、45重量份、48重量份或50重量份等。
萜烯树脂的含量可以是3重量份、5重量份、8重量份、10重量份、12重量份、15重量份、18重量份、20重量份、22重量份、25重量份、28重量份、30重量份、32重量份、35重量份、38重量份或40重量份等。
作为本发明的优选技术方案,所述不饱和聚苯醚树脂的结构式如式(1)所示:
Figure BDA0002432079120000031
式(1)中,a、b各自独立地为1-30的整数(例如1、3、5、8、10、12、15、18、20、22、25、28或30等),Z具有式(2)或式(3)所示结构,
Figure BDA0002432079120000033
具有式(4)所示结构,/>
Figure BDA0002432079120000034
具有式(5)所示结构;
Figure BDA0002432079120000032
式(3)中,A选自亚芳基、羰基和碳原子数为1-10(例如可以是1、2、3、4、5、6、7、8、9或10)的亚烷基中的任意一种,m为0-10的整数(例如可以是0、1、2、3、4、5、6、7、8、9或10),R1-R3各自独立地为氢原子或碳原子数为1-10(例如可以是1、2、3、4、5、6、7、8、9或10)的烷基;
式(4)中,R4和R6各自独立地选自氢原子、卤素原子、苯基和碳原子数为1-8(例如可以是1、2、3、4、5、6、7或8)的烷基中的任意一种;R5和R7各自独立地选自卤素原子、苯基和碳原子数为1-8(例如可以是1、2、3、4、5、6、7或8)的烷基中的任意一种;
式(5)中,R8-R15各自独立地选自氢原子、卤素原子、苯基和碳原子数为1-8(例如可以是1、2、3、4、5、6、7或8)的烷基中的任意一种,B为碳原子数为20以下(例如可以是1、2、3、4、5、6、7、8、10、12、15、18或20等)的亚烃基、-O-、
Figure BDA0002432079120000041
n为0或1;R16为氢原子或碳原子数为1~10的烃基。
作为本发明的优选技术方案,所述聚烯烃树脂为不饱和聚丁二烯树脂。不饱和聚丁二烯树脂相比其他材料能够使树脂组合物的交联密度更高、耐热性更好。
优选地,所述不饱和聚丁二烯树脂的数均分子量为1000-50000,例如可以是1000、1500、2000、2500、3000、3500、4000、4500、5000、5500、6000、6500、7000、8000、9000、10000、15000、20000、25000、30000、35000、40000、45000或50000等;进一步优选为2000-40000,更优选为3000-30000。若其分子量过小,树脂组合物形成的胶膜粘手性强、无法连续操作;若其分子量过大,无法溶解,难以制备胶膜。
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,所述聚丁二烯树脂的乙烯基含量为60-99mol%,例如可以是60mol%、62mol%、65mol%、68mol%、70mol%、72mol%、75mol%、78mol%、80mol%、82mol%、85mol%、88mol%、90mol%、92mol%、95mol%或99mol%等;进一步优选为70-95mol%,更优选为75-93mol%。若乙烯基含量小于60%,会导致树脂组合物的交联密度小,耐热性差。
需要说明的是,本发明中所述不饱和聚丁二烯树脂的乙烯基含量是指含乙烯基的单元的摩尔量占不饱和聚丁二烯树脂所有单元摩尔量的百分比。
优选地,所述不饱和聚丁二烯树脂为极性基团改性的不饱和聚丁二烯树脂。使用极性基团改性,更有利于提高树脂组合物的粘结性,提高层压板、电路材料的剥离强度。
优选地,所述极性基团改性的不饱和聚丁二烯树脂中极性基团的接枝率为5-10%。
优选地,所述极性基团改性的不饱和聚丁二烯树脂选自环氧改性不饱和聚丁二烯树脂、马来酸酐改性不饱和聚丁二烯树脂、丙烯酸改性不饱和聚丁二烯树脂、羟基封端的不饱和聚丁二烯树脂、羧基封端的不饱和聚丁二烯树脂和胺改性的不饱和聚丁二烯树脂中的一种或至少两种的组合。
作为本发明的优选技术方案,所述萜烯树脂的数均分子量400-4000,例如可以是400、500、600、700、800、900、1000、1200、1500、1800、2000、2200、2500、2800、3000、3200、3500、3800或4000等;进一步优选为500-3000,更优选为600-2000。若其分子量小于400,树脂组合物形成的胶膜的黏手性大、难以连续化生产;若其分子量大于4000,则溶解性差,无法制备胶膜。
优选地,所述萜烯树脂包含松节油、α-蒎烯、β-蒎烯、苧烯、β-水芹烯、柠檬烯中的一种单体或多种单体的聚合物。
优选地,所述萜烯树脂选自多萜树脂、萜烯-酚树脂、苯乙烯化的萜烯树脂、萜烯-烃树脂和萜烯-乙烯基芳香化合物树脂中一种或至少两种的组合。
作为本发明的优选技术方案,优选地,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述引发剂的含量为0.1-7重量份;例如可以是0.1重量份、0.2重量份、0.5重量份、0.8重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、5.5重量份、6重量份、6.5重量份或7重量份等。
优选地,所述引发剂为第一引发剂、第二引发剂或第一引发剂与第二引发剂的组合;所述第一引发剂的1min半衰期温度为50-160℃(例如可以是50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃或160℃等),所述第二种引发剂的1min半衰期温度为160-300℃(例如可以是160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃或300℃等)。
优选地,所述第一引发剂选自叔丁基过氧化乙酸酯、2,2-双(叔丁基过氧化)辛烷、叔丁基过氧化异丙基碳酸酯、1,1-双(叔丁基过氧基)环己酮、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己酮、叔丁基过氧化辛酸酯、叔丁基过氧化异丁酸酯、二琥珀酸过氧化物、二间甲苯酰过氧化物、二甲苯酰过氧化物、二乙酰过氧化物、异丙苯基过氧化辛酸酯、二葵酰过氧化物、二辛酰过氧化物、双十二烷酰过氧化物、双(3,5,5-三甲基乙酰过氧化物)、叔丁基过氧化新戊酸酯、叔己基过氧化三甲基乙酸酯、叔丁基过氧化新己酸酯、叔己基过氧化新己酸酯、双(3-甲基-3-甲氧基丁基过氧化碳酸氢酯)、叔己基过氧化新葵酸酯、叔丁基过氧化新葵酸酯、异丙苯基过氧化新己酸酯、双甲氧基异丙基过氧化碳酸氢酯、双十四烷基过氧化碳酸氢酯、双烯丙基过氧化碳酸氢酯、异丙苯基过氧化新葵酸酯、二正丙级过氧化碳酸氢酯、双(2-羟乙基己基过氧化碳酸氢酯)、双(2-乙基己基过氧化碳酸氢酯)、二正丁基过氧化碳酸氢酯、二异丁基过氧化碳酸氢酯、二异丁烯过氧化物、二异丙基过氧化碳酸氢酯和乙酰基环己基磺酰基过氧化物中的一种或至少两种的组合。
优选地,所述第二引发剂选自叔丁基过氧化氢、四甲基丁烷过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己炔、二叔丁基过氧化物、a,a双(叔丁基过氧化-间-异丙苯基)、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、叔丁基异丙苯基过氧化物、叔丁基过氧化烯丙基碳酸氢酯、二异丙苯基过氧化物(DCP)、叔丁基过氧化苯甲酸酯、二叔丁过氧化异酞酸酯、正丁基-4,4-双(叔丁基过氧化)戊酸酯、叔丁基过氧化(3,5,5-三甲基乙酸酯)、叔丁基过氧化月桂酸酯、2,5-二甲-2,5-二(二苯甲酰过氧化)己烷和2,2-双(叔丁基过氧化)丁烷中的一种或至少两种的组合。
作为本发明的优选技术方案,所述树脂组合物还包括阻燃剂。
优选地,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述阻燃剂的含量为10-40重量份;例如可以是10重量份、12重量份、15重量份、18重量份、20重量份、22重量份、25重量份、28重量份、30重量份、32重量份、35重量份、38重量份或40重量份等。
优选地,所述阻燃剂选自十溴二苯醚、乙基-双(四溴苯邻二甲酰亚胺)、十溴二苯乙烷、三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧化-10膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯和10-苯基-9,10-二氢-9-氧化-10-膦菲-10-氧化物中的一种或至少两种的组合。
优选地,所述树脂组合物还包括硅烷偶联剂。
优选地,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述硅烷偶联剂的含量为0.1-5重量份;例如可以是0.1重量份、0.3重量份、0.5重量份、0.8重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份等。
优选地,所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三叔丁基过氧硅烷、乙烯基三异丙氧基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三硅烷、乙烯基三异丙氧基硅烷、丙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基三异丙氧基硅烷、三苯氧基乙烯基硅烷和乙烯基三异丙氧基硅烷中的一种或至少两种的组合。
通过添加硅烷偶联剂,有助于进一步提高树脂组合物的粘结性,提高电路层压板的剥离强度。
优选地,所述树脂组合物还包括填料。
优选地,所述填料占树脂组合物总重量的20-90%;例如可以是20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%或90%等。
优选地,所述填料选自结晶型二氧化硅、无定型二氧化硅、球型二氧化硅、角形二氧化硅、中空微球、二氧化钛、氮化硼、氮化铝、碳化硅、氧化铝、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜和钛酸铅-铌镁酸铅中的一种或至少两种的组合。
优选地,所述填料的中位粒径为0.5-20μm,例如可以是0.5μm、1μm、3μm、5μm、8μm、10μm、12μm、15μm、18μm或20μm等;进一步优选为1-15μm,更优选为4-10μm。
如无特殊说明,本发明中位粒径均是指用激光粒度分析仪方法测得的中位粒径。
第二方面,本发明提供一种预浸料,所述预浸料包括增强材料,和通过含浸干燥后附着在所述增强材料上的第一方面所述的树脂组合物。
第三方面,本发明提供一种树脂膜,所述树脂膜由第一方面所述的树脂组合物经烘烤加热后半固化而成。具体地,树脂膜可以由第一方面所述的树脂组合物涂在离型材料上经烘烤加热半固化后除去离型材料获得。
第四方面,本发明提供一种涂树脂铜箔,所述涂树脂铜箔由第一方面所述的树脂组合物涂在铜箔上经烘烤加热后半固化而成。
第五方面,本发明提供一种层压板,所述层压板包括一张或至少两张叠合的如第二方面所述的预浸料。
第六方面,本发明提供一种电路材料,包括:导电金属层和电介质基板层;以及设置在所述导电金属层和所述电介质基板层之间的粘合剂层,所述粘合剂层是通过将溶解在溶剂中的第一方面所述的树脂组合物以溶液形式施用到所述导电金属层或所述电介质基板层的表面上获得,或施用到离型材料上部分固化或完全固化后除去离型材料获得。
优选地,所述导电金属层为铜箔。
优选地,所述铜箔的表面粗糙度在2μm以下,例如可以是2μm、1.8μm、1.6μm、1.5μm、1.3μm、1.2μm、1μm、0.8μm、0.7μm、0.5μm、0.4μm、0.3μm或0.2μm等;进一步优选在0.7μm以下。
第七方面,本发明提供一种多层电路,包括第五方面所述的层压板或第六方面所述的电路材料。
与现有技术相比,本发明具有以下有益效果:
本发明通过不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂三者之间的相互配合,使得到的树脂组合物具有良好的成膜性、粘结性和介电性能,其可以用作电路材料的粘合剂层材料,或用于浸渍增强材料制备预浸料,得到的电路板材具有较高的层间剥离强度和较低的介电损耗,满足高频板材的性能要求。
具体实施方式
下面通过具体实施例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。
本发明实施例中采用的原料来源如下:
不饱和聚苯醚树脂:
聚苯醚树脂MMA-PPE(SA9000,SABIC公司);
聚苯醚树脂St-PPE-2(三菱化学公司制);
聚苯醚树脂St-PPE-1(三菱化学公司制)。
不饱和聚丁二烯树脂:
B1000:日本曹达株式会社;
B3000:日本曹达株式会社;
R810:日本JSR株式会社。
SBS树脂:
D1118:科腾高性能聚合物公司。
萜烯树脂:
KT90,广东科茂林产化工股份有限公司
KT100,广东科茂林产化工股份有限公司
KT5090广东科茂林产化工股份有限公司
萜烯类溶剂:
GP00007(α-蒎烯单体),福建青松股份有限公司
引发剂:
BPO:大河油脂株式会社;
DCP:上海方锐达化工。
实施例1-3和比较例1-6
实施例1-3和比较例1-6各提供一种电路材料,其制备方法如下:
提供半固化片:Synamic6半固化片,热固性烃基基板材料,广东生益科技自制;
粘合剂层的制备:将不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂、引发剂、阻燃剂、填料等按照比例溶解在二甲苯中,在室温下混合得到胶液;使用涂覆机将该胶液涂覆在铜箔上,然后在155℃的烘箱中烘烤5分钟,得到带有粘合剂层的铜箔(粘合剂层单位克重为20g/m2)。
电路材料的制备:将4张Synamic6半固化片和带有粘合剂层的铜箔叠合整齐(粘合剂层在半固化片和铜箔之间),在压机中于210℃层压并固化,得到电路材料。
实施例4
本实施例提供一种覆铜箔层压板,其制备方法如下:
将不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂、引发剂、阻燃剂、填料等按照比例溶解在二甲苯中,在室温下混合得到胶液;用胶液浸渍增强材料2116玻纤布,干燥半固化,得到半固化片;
将上述半固化片和一张铜箔叠合整齐,在压机中于210℃层压并固化,得到覆铜箔层压板。
实施例5
本实施例提供一种电路材料,其制备方法如下:
提供半固化片:S7136半固化片,热固性烃基基板材料,广东生益科技自制;
粘合剂层的制备:将不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂、引发剂、阻燃剂、填料等按照比例溶解在二甲苯中,在室温下混合得到胶液;使用涂覆机将该胶液涂覆在离型膜上,然后在155℃的烘箱中烘烤5分钟,除去离型膜得到粘合剂层(粘合剂层单位克重为20g/m2);
电路材料的制备:将4张S7136半固化片、粘合剂层和铜箔按顺序叠合整齐,在压机中于210℃层压并固化,得到电路材料。
比较例7
提供一种电路材料,与实施例1的区别在于,将树脂组合物的制备原料萜烯树脂替换为萜烯溶剂。
上述实施例1-5和比较例1-7中原料种类和用量如下表1和表2所示。
对上述实施例1-5和比较例1-7提供的覆铜箔层压板、电路材料的介电常数、介电损耗因子、剥离强度和耐浮焊性进行测试,测试方法如下:
(1)介电常数(Dk)和介电损耗因子(Df):按照SPDR方法测试,测试条件为A态,10GHz;
(2)剥离强度:按照IPC-TM-650,2.4.8方法进行测试;
(3)耐浮焊性:按照IPC-TM-650中规定的方法进行测定。
上述测试的结果如下表1和表2所示:
表1
Figure BDA0002432079120000131
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表2
Figure BDA0002432079120000132
由表1和表2的测试结果可以看出,采用本发明实施例提供的树脂组合物制备的覆铜箔层压板和电路材料的剥离强度达到1.04-1.37N/mm,介电常数(10GHz)为3.35-3.67,介电损耗因子(10GHz)为0.0029-0.0037,具有良好的介电性能、剥离强度和耐浮焊性。
其中,比较例1中使用不饱和PPO树脂的含量小于40wt%,与实施例1相比,板材的剥离强度下降,只有0.71N/mm;
比较例2中使用不饱和PPO树脂含量大于80wt%,与实施例2相比,胶液成膜性差,无法制备出合格胶膜;
比较例3中使用烯萜树脂含量小于3wt%,与实施例4相比,板材的剥离强度下降,只有0.75N/mm;
比较例4中使用烯萜树脂含量大于40wt%,与实施例3相比,胶膜成膜性差,无法制备出合格胶膜;
比较例5中使用聚烯烃树脂含量小于10wt%,与实施例3相比,板材的介电损耗高,介电性能变差;
比较例6中使用聚烯烃树脂含量大于50wt%,与实施例1相比,板材的剥离强度下降,只有0.71N/mm;
与实施例1相比,比较例7用萜烯溶剂代替烯萜树脂,板材的剥离强度下降,只有0.71N/mm;浮焊小于10s,耐热性下降。
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。

Claims (31)

1.一种由树脂组合物经烘烤加热后半固化而成的树脂膜或由树脂组合物涂在铜箔上经烘烤加热后半固化而成涂树脂铜箔,其特征在于,所述树脂组合物由不饱和聚苯醚树脂、聚烯烃树脂、萜烯树脂、引发剂以及任选的阻燃剂、任选的硅烷偶联剂和任选的填料组成;
以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述树脂组合物包括不饱和聚苯醚树脂40-80重量份、聚烯烃树脂10-50重量份和萜烯树脂3-40重量份;
所述聚烯烃树脂选自不饱和聚丁二烯树脂或SBS树脂中的一种或至少两种的组合;
所述萜烯树脂的数均分子量400-4000。
2.根据权利要求1所述的树脂组合物,其特征在于,所述不饱和聚苯醚树脂的结构式如式(1)所示:
Figure QLYQS_1
式(1)中,a、b各自独立地为1-30的整数,Z具有式(2)或式(3)所示结构,
Figure QLYQS_2
具有式(4)所示结构,/>
Figure QLYQS_3
具有式(5)所示结构;
Figure QLYQS_4
Figure QLYQS_5
式(3)中,A选自亚芳基、羰基和碳原子数为1-10的亚烷基中的任意一种,m为0-10的整数,R1-R3各自独立地为氢原子或碳原子数为1-10的烷基;
式(4)中,R4和R6各自独立地选自氢原子、卤素原子、苯基和碳原子数为1-8的烷基中的任意一种;R5和R7各自独立地选自卤素原子、苯基和碳原子数为1-8的烷基中的任意一种;
式(5)中,R8-R15各自独立地选自氢原子、卤素原子、苯基和碳原子数为1-8的烷基中的任意一种,B为碳原子数为20以下的亚烃基、-O-、
Figure QLYQS_6
n为0或1,R16为氢原子或碳原子数为1~10的烃基。
3.根据权利要求1所述的树脂组合物,其特征在于,所述聚烯烃树脂为不饱和聚丁二烯树脂。
4.根据权利要求3所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的数均分子量为1000-50000。
5.根据权利要求4所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的数均分子量为2000-40000。
6.根据权利要求5所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的数均分子量为3000-30000。
7.根据权利要求3所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的乙烯基含量为60-99mol%。
8.根据权利要求7所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的乙烯基含量为70-95mol%。
9.根据权利要求8所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂的乙烯基含量为75-93mol%。
10.根据权利要求3所述的树脂组合物,其特征在于,所述不饱和聚丁二烯树脂为极性基团改性的不饱和聚丁二烯树脂。
11.根据权利要求10所述的树脂组合物,其特征在于,所述极性基团改性的不饱和聚丁二烯树脂中极性基团的接枝率为5-10%。
12.根据权利要求10所述的树脂组合物,其特征在于,所述极性基团改性的不饱和聚丁二烯树脂选自环氧改性不饱和聚丁二烯树脂、马来酸酐改性不饱和聚丁二烯树脂、丙烯酸改性不饱和聚丁二烯树脂、羟基封端的不饱和聚丁二烯树脂、羧基封端的不饱和聚丁二烯树脂和胺改性的不饱和聚丁二烯树脂中的一种或至少两种的组合。
13.根据权利要求1所述的树脂组合物,其特征在于,所述萜烯树脂的数均分子量500-3000。
14.根据权利要求13所述的树脂组合物,其特征在于,所述萜烯树脂的数均分子量600-2000。
15.根据权利要求1所述的树脂组合物,其特征在于,所述萜烯树脂包含松节油、α-蒎烯、β-蒎烯、苧烯、β-水芹烯、柠檬烯中的一种单体或多种单体的聚合物。
16.根据权利要求1所述的树脂组合物,其特征在于,所述萜烯树脂选自多萜树脂、萜烯-酚树脂、苯乙烯化的萜烯树脂、萜烯-烃树脂和萜烯-乙烯基芳香化合物树脂中一种或至少两种的组合。
17.根据权利要求1所述的树脂组合物,其特征在于,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述引发剂的含量为0.1-7重量份。
18.根据权利要求1所述的树脂组合物,其特征在于,所述引发剂为第一引发剂、第二引发剂或第一引发剂与第二引发剂的组合;所述第一引发剂的1min半衰期温度为50-160℃,所述第二种引发剂的1min半衰期温度为160-300℃。
19.根据权利要求18所述的树脂组合物,其特征在于,所述第一引发剂选自叔丁基过氧化乙酸酯、2,2-双(叔丁基过氧化)辛烷、叔丁基过氧化异丙基碳酸酯、1,1-双(叔丁基过氧基)环己酮、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己酮、叔丁基过氧化辛酸酯、叔丁基过氧化异丁酸酯、二琥珀酸过氧化物、二间甲苯酰过氧化物、二甲苯酰过氧化物、二乙酰过氧化物、异丙苯基过氧化辛酸酯、二葵酰过氧化物、二辛酰过氧化物、双十二烷酰过氧化物、双(3,5,5-三甲基乙酰过氧化物)、叔丁基过氧化新戊酸酯、叔己基过氧化三甲基乙酸酯、叔丁基过氧化新己酸酯、叔己基过氧化新己酸酯、双(3-甲基-3-甲氧基丁基过氧化碳酸氢酯)、叔己基过氧化新葵酸酯、叔丁基过氧化新葵酸酯、异丙苯基过氧化新己酸酯、双甲氧基异丙基过氧化碳酸氢酯、双十四烷基过氧化碳酸氢酯、双烯丙基过氧化碳酸氢酯、异丙苯基过氧化新葵酸酯、二正丙级过氧化碳酸氢酯、双(2-羟乙基己基过氧化碳酸氢酯)、双(2-乙基己基过氧化碳酸氢酯)、二正丁基过氧化碳酸氢酯、二异丁基过氧化碳酸氢酯、二异丁烯过氧化物、二异丙基过氧化碳酸氢酯和乙酰基环己基磺酰基过氧化物中的一种或至少两种的组合。
20.根据权利要求18所述的树脂组合物,其特征在于,所述第二引发剂选自叔丁基过氧化氢、四甲基丁烷过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己炔、二叔丁基过氧化物、a,a双(叔丁基过氧化-间-异丙苯基)、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、叔丁基异丙苯基过氧化物、叔丁基过氧化烯丙基碳酸氢酯、二异丙苯基过氧化物(DCP)、叔丁基过氧化苯甲酸酯、二叔丁过氧化异酞酸酯、正丁基-4,4-双(叔丁基过氧化)戊酸酯、叔丁基过氧化(3,5,5-三甲基乙酸酯)、叔丁基过氧化月桂酸酯、2,5-二甲-2,5-二(二苯甲酰过氧化)己烷和2,2-双(叔丁基过氧化)丁烷中的一种或至少两种的组合。
21.根据权利要求1所述的树脂组合物,其特征在于,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述阻燃剂的含量为10-40重量份。
22.根据权利要求1所述的树脂组合物,其特征在于,所述阻燃剂选自十溴二苯醚、乙基-双(四溴苯邻二甲酰亚胺)、十溴二苯乙烷、三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧化-10膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯和10-苯基-9,10-二氢-9-氧化-10-膦菲-10-氧化物中的一种或至少两种的组合。
23.根据权利要求1所述的树脂组合物,其特征在于,以所述不饱和聚苯醚树脂、聚烯烃树脂和萜烯树脂的总重量为100重量份计,所述硅烷偶联剂的含量为0.1-5重量份。
24.根据权利要求1所述的树脂组合物,其特征在于,所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三叔丁基过氧硅烷、乙烯基三异丙氧基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三硅烷、丙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基三异丙氧基硅烷、三苯氧基乙烯基硅烷和乙烯基三异丙氧基硅烷中的一种或至少两种的组合。
25.根据权利要求1所述的树脂组合物,其特征在于,所述填料占所述树脂组合物总重量的20-90%。
26.根据权利要求1所述的树脂组合物,其特征在于,所述填料选自结晶型二氧化硅、无定型二氧化硅、球型二氧化硅、角形二氧化硅、中空微球、二氧化钛、氮化硼、氮化铝、碳化硅、氧化铝、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜和钛酸铅-铌镁酸铅中的一种或至少两种的组合。
27.根据权利要求1所述的树脂组合物,其特征在于,所述填料的中位粒径为0.5-20μm。
28.根据权利要求27所述的树脂组合物,其特征在于,所述填料的中位粒径为1-15μm。
29.根据权利要求28所述的树脂组合物,其特征在于,所述填料的中位粒径为4-10μm。
30.一种电路材料,其特征在于,所述电路材料包括:
导电金属层和电介质基板层;以及
设置在所述导电金属层和所述电介质基板层之间的粘合剂层;
所述粘合剂层是通过将溶解在溶剂中的如权利要求1-29任一项所述的树脂组合物以溶液形式施用到所述导电金属层或所述电介质基板层的表面上获得,或施用到离型材料上部分固化或完全固化后除去离型材料获得。
31.一种多层电路,其特征在于,所述多层电路包括权利要求30所述的电路材料。
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