CN112280329B - 印刷电路板用树脂组成物、覆金属基板及印刷电路板 - Google Patents
印刷电路板用树脂组成物、覆金属基板及印刷电路板 Download PDFInfo
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- CN112280329B CN112280329B CN201910717344.7A CN201910717344A CN112280329B CN 112280329 B CN112280329 B CN 112280329B CN 201910717344 A CN201910717344 A CN 201910717344A CN 112280329 B CN112280329 B CN 112280329B
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Abstract
本发明公开一种印刷电路板用树脂组成物、覆金属基板及印刷电路板,其中印刷电路板用树脂组成物包含100重量份的液晶高分子、20至150重量份的双马来酰亚胺树脂以及20至150重量份的氰酸酯树脂。本发明的树脂组成物通过特定的组成成分和用量比例,可达到低介电常数、低介电损耗及高耐热性等特性。
Description
技术领域
本发明涉及一种树脂组成物,特别是涉及一种印刷电路板用树脂组成物及其应用,例如预浸材、覆金属基板及印刷电路板。
背景技术
随着信息科技的蓬勃发展,为了处理大量信息,印刷电路板被要求能够适应高频信号的传输,而印刷电路板的绝缘材料对于其高频应用是非常重要的。
目前,印刷电路板的绝缘材料较常使用环氧树脂及聚苯醚树脂。环氧树脂系绝缘材料虽于固化后具有良好的绝缘性,且在原料成本上有优势,然而所形成的印刷电路板其电气特性不佳,而无法满足高频信号的传输需求。聚苯醚树脂(PPE)因为具有优异的介电特性,例如低介电常数(dielectric constant)和低介电损耗(dielectric dissipationfactor),所以被业界广泛使用,然而聚苯醚树脂不利于印刷电路板的制作工艺,可能影响印刷电路板的可靠性。
因此,业界需要一种创新的印刷电路板的绝缘材料,以改善印刷电路板的电气特性和可靠性,确保高频信号的传输质量和稳定性。
发明内容
本发明所要解决的技术问题在于,针对现有技术的不足提供一种印刷电路板用树脂组成物;并且,提供应用此树脂组成物的预浸材、覆金属基板及印刷电路板。
为了解决上述的技术问题,本发明所采用的其中一技术方案是,提供一种印刷电路板用树脂组成物,所述印刷电路板用树脂组成物包含:100重量份的液晶高分子、20至150重量份的双马来酰亚胺树脂以及20至160重量份的氰酸酯树脂。
在本发明的一实施例中,所述液晶高分子的分子量为3,000至50,000。
在本发明的一实施例中,所述液晶高分子的至少一末端基被改性为乙烯基。
在本发明的一实施例中,所述液晶高分子的乙烯基含量为10%至70%。
在本发明的一实施例中,所述液晶高分子的结构如下式(1)所示:
其中,R1及R2各表示乙烯基、异氰酸酯基、双马来酰亚胺基、羟基或环氧基;x表示10至500之间的正整数;y表示10至300之间的正整数;z表示10至400之间的正整数。
在本发明的一实施例中,所述液晶高分子的结构如下式(2)所示:
其中,R1及R2各表示乙烯基、异氰酸酯基、双马来酰亚胺基、羟基或环氧基;x表示10至500之间的正整数;y表示10至300之间的正整数。
在本发明的一实施例中,所述液晶高分子的结构如下式(3)所示:
其中,R1及R2各表示乙烯基、异氰酸酯基、双马来酰亚胺基、羟基或环氧基;x表示10至300之间的正整数;y表示10至500之间的正整数。
在本发明的一实施例中,所述印刷电路板用树脂组成物还进一步包含至少一功能性添加剂,所述功能性添加剂选自阻燃剂、溶剂、填充剂以及硬化促进剂中的至少一种。
为了解决上述的技术问题,本发明所采用的另外一技术方案是,提供一种预浸材,所述预浸材是将具有前述组成的印刷电路板用树脂组成物施加于一基材上,并经干燥而形成。
为了解决上述的技术问题,本发明所采用的另外再一技术方案是,提供一种覆金属基板,所述覆金属基板包括至少一基于具有前述组成的印刷电路板用树脂组成物的预浸材以及一形成于所述预浸材上的金属层。
为了解决上述的技术问题,本发明所采用的另外再一技术方案是,提供一种印刷电路板,所述印刷电路板是将具有前述构造的覆金属基板的所述金属层图案化而形成。
本发明的其中一有益效果在于,本发明的印刷电路板用树脂组成物,其包含100重量份的液晶高分子、20至150重量份的双马来酰亚胺树脂以及20至160重量份的氰酸酯树脂,以提供良好的工艺加工性,且能满足高频传输系统对印刷电路板的要求。
为使能更进一步了解本发明的特征及技术内容,请参阅以下有关本发明的详细说明与附图,然而所提供的附图仅用于提供参考与说明,并非用来对本发明加以限制。
附图说明
图1为本发明的预浸材的制造过程示意图。
图2为本发明的预浸材的结构示意图。
图3为本发明的覆金属基板的制造过程示意图。
图4为本发明的印刷电路板的结构示意图。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开有关“印刷电路板用树脂组成物、预浸材、覆金属基板及印刷电路板”的实施方式,本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节也可基于不同观点与应用,在不悖离本发明的构思下进行各种修改与变更。另外,本发明的附图仅为简单示意说明,并非依实际尺寸的描绘,事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容,但所公开的内容并非用以限制本发明的保护范围。
应当可以理解的是,虽然本文中可能会使用到“第一”、“第二”、“第三”等术语来描述各种组件或者信号,但这些组件或者信号不应受这些术语的限制。这些术语主要是用以区分一组件与另一组件,或者一信号与另一信号。另外,本文中所使用的术语“或”,应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
除非另外定义,否则本文中使用的所有技术及科学术语,都具有与本领域技术人员通常所理解含义相同的含义。当术语以单数形式出现时,涵盖此术语的复数形式。当提供一系列上、下限范围时,涵盖所提到的范围的所有组合,如同明确列出各组合。
为了满足高频传输系统对印刷电路板的要求,本发明提供一种印刷电路板用树脂组成物,其能取代聚苯醚树脂系绝缘材料。本发明的树脂组成物主要包含100重量份的液晶高分子、20至150重量份的双马来酰亚胺树脂及20至160重量份的氰酸酯树脂;双马来酰亚胺树脂的含量,相对于100重量份的液晶高分子,可为30、40、50、60、70、80、90、100、110、120、130或140重量份;氰酸酯树脂的含量,相对于100重量份的液晶高分子,可为30、40、50、60、70、80、90、100、110、120、130、140或150重量份。
本发明的树脂组成物中,液晶高分子具有特殊的化学结构,且与双马来酰亚胺树脂之间可形成良好的配合,以提升树脂组合物的耐候性和介电特性,而氰酸酯树脂可作为硬化剂。
进一步而言,液晶高分子的结构具有高度规律性,而具有优异的介电特性,液晶高分子的分子量可为3,000至50,000。根据实际应用,液晶高分子的结构组成中可修饰有至少一种功能性分子团,以达到目标应用所需的功能性(如耐热性、耐湿性等);功能性分子团可为含有不饱和双键的官能基团,但不限于此。优选地,液晶高分子的至少一末端基可被修饰为乙烯基,其中液晶高分子的乙烯基含量可为10%至70%,例如15%、20%、25%、30%、35%、40%、45%、50%、55%、60%或65%;或者,液晶高分子的至少一末端基可被修饰为双马来酰亚胺基,其中液晶高分子的双马来酰亚胺基含量可为10%至70%,例如15%、20%、25%、30%、35%、40%、45%、50%、55%、60%或65%。然而,本发明不以上述所举的例子为限。
在本实施例中,液晶高分子的结构如下式(1)、式(2)或式(3)所示:
式(1)至(3)中,R1及R2各表示乙烯基、异氰酸酯基、双马来酰亚胺基、羟基或环氧基。式(1)中,x表示10至500之间的正整数;y表示10至300之间的正整数;z表示10至400之间的正整数。式(2)中,x表示10至500之间的正整数;y表示10至300之间的正整数。式(3)中,x表示10至300之间的正整数;y表示10至500之间的正整数。
本发明的树脂组成物可进一步包含功能性添加剂,以提高实际应用时所需的各种特性,功能性添加剂可选自阻燃剂、溶剂、填充剂及硬化促进剂中的至少一种。进一步而言,在适当的阻燃剂的存在下,树脂组成物可具有良好的阻燃性;阻燃剂可为溴系阻燃剂、磷系阻燃剂、金属水合物系阻燃剂或它们的任意组合,阻燃剂的含量,相对于100重量份的液晶高分子,可为2至40重量份。
溴系阻燃剂可举出:溴化双酚A型环氧树脂及溴化酚系酚醛清漆型环氧树脂等溴化环氧树脂;六溴苯、五溴甲苯、双(五溴苯基)乙烷、伸乙基双(四溴邻苯二甲酰亚胺)、1,2-二溴-4-(1,2-二溴乙基)环己烷、四溴环辛烷、六溴环十二烷、双(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯、2,4,6-三(三溴苯氧基)-1,3,5-三嗪(2,4,6-tris(tribromophenoxy)-1,3,5-triazine)等溴化添加型阻燃剂;三溴苯基马来酰亚胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴双酚A型二甲基丙烯酸酯、丙烯酸五溴苯甲酯、溴化苯乙烯等含不饱和双键的溴化反应型阻燃剂等。
磷系阻燃剂可举出:磷酸三苯酯、磷酸三(甲苯)酯、磷酸三(二甲苯)酯、磷酸甲苯酯二苯酯、磷酸甲苯酯二(2,6-二甲苯)酯、间苯二酚双(磷酸二苯酯)、1,3-伸苯基双(磷酸二(2,6-二甲苯)酯)、双酚A双(磷酸二苯酯)、1,3-伸苯基双(磷酸二苯酯)等芳香族磷酸酯化合物;苯膦酸二乙烯酯、苯膦酸二烯丙酯、苯膦酸二(1-丁烯)酯等膦酸酯;二苯基次膦酸苯酯、二苯基次膦酸甲酯等次膦酸酯;双(2-烯丙基苯氧基)磷腈、二(甲苯基)磷腈等磷腈(phosphazene)化合物;9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物及其衍生物(如10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物);磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸铵、含磷乙烯基苯甲基化合物、次膦酸化合物的金属盐、红磷等其他含磷物质。
金属水合物系阻燃剂可举出氢氧化镁及氢氧化铝。
溶剂用以将树脂组成物中的成分溶解或分散,溶剂可使用有机溶剂;有机溶剂可举出:甲醇、乙醇、丁醇、丁基赛璐苏、乙二醇单甲基醚、丙二醇单甲基醚等醇类;丙酮、甲基乙基酮、甲基异丁基酮、环己酮等酮类;甲苯、二甲苯、三甲苯等芳香族烃类;乙酸甲氧基乙酯、乙酸乙氧基乙酯、乙酸丁氧基乙酯、乙酸乙酯等酯类;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯啶酮等含氮类等。
在适当适量的填充剂的存在下,树脂组成物的一些特性可以获得改善,例如热膨胀特性、弹性模数、耐热性和阻燃性等;填充剂可使用无机填充剂,填充剂的含量,相对于100重量份的液晶高分子,可为5至100重量份,填充剂的平均外径可为0.2微米至30微米,优选为1微米至10微米。填充剂可举出:氧化硅、氧化铝、氧化钛、云母、氧化铍、钛酸钡、钛酸钾、钛酸锶、钛酸钙、碳酸铝、氢氧化镁、氢氧化铝、硅酸铝、碳酸钙、硅酸钙、硅酸镁、氮化硅、氮化硼、煅烧黏土、滑石、硼酸铝、硼酸铝、碳化硅等。
硬化促进剂可以提升树脂组成物的硬化性,进而树脂组成物可以发挥预期的效果;硬化促进剂可为钴盐、过氧化物或其组合,填充剂的含量,相对于100重量份的液晶高分子,可为5至100重量份。
参阅图1及图2所示,本发明的树脂组成物12可应用于制作预浸材1;预浸材1可以是将具有前述组成的树脂组成物12施加于一基材11上,并经干燥而形成。进一步而言,树脂组成物12可以树脂清漆的形式存在,且施加树脂组成物12的方式可为涂布或含浸;带有树脂组成物12的基材11可用150℃至210℃的温度加热干燥2至10分钟,以形成半硬化状态的预浸材1。在本实施例中,基材11可为一绝缘纸、玻璃纤维布或其他纤维材料,但不限于此。
参阅图3所示,本发明的预浸材1可应用于覆金属基板C;覆金属基板C可以是在至少一片预浸材1的单片或双面层迭金属层2,然后进行热压合而形成。在本实施例中,金属层2可为金属箔(如铜箔)所形成;热压合的条件包括:压力为350psi、温度为190℃及时间为90分钟。然而,上述所举的例子只是其中一可行的实施例而并非用以限定本发明。
参阅图4所示,本发明的覆金属基板C可应用于印刷电路板P’;印刷电路板P’可以是将覆金属基板C的金属层2图案化而形成。在本实施例中,可通过微影蚀刻制程将覆金属基板C的金属层2图案化,即将金属层2形成线路层2’,但不限于此。
表1中显示根据比较例1-3与实验例的树脂组成物的覆铜基板的特性;比较例1的树脂组成物不含液晶高分子,比较例2的树脂组成物的液晶高分子与双马来酰亚胺树脂的用量低于实施例,比较例3的树脂组成物的液晶高分子与双马来酰亚胺树脂的用量高于实施例。
表1(单位:重量份)
实施例的有益效果
本发明的其中一有益效果在于,本发明的印刷电路板用树脂组成物,其包含100重量份的液晶高分子、20至150重量份的双马来酰亚胺树脂以及20至160重量份的氰酸酯树脂,以提供良好的工艺加工性,且能满足高频传输系统对印刷电路板的要求。
以上所公开的内容仅为本发明的优选可行实施例,并非因此局限本发明的申请专利范围,所以凡是运用本发明说明书及附图内容所做的等效技术变化,均包含于本发明的申请专利范围内。
Claims (8)
2.如权利要求1所述的印刷电路板用树脂组成物,其特征在于,所述液晶高分子的分子量为3,000至50,000。
3.如权利要求2所述的印刷电路板用树脂组成物,其特征在于,所述液晶高分子的至少一末端基被改性为乙烯基。
4.如权利要求3所述的印刷电路板用树脂组成物,其特征在于,所述液晶高分子的乙烯基含量为10%至70%。
5.如权利要求1所述的印刷电路板用树脂组成物,其特征在于,所述印刷电路板用树脂组成物还进一步包含至少一功能性添加剂,所述功能性添加剂选自阻燃剂、溶剂、填充剂以及硬化促进剂中的至少一种。
6.一种预浸材,其特征在于,所述预浸材是将如权利要求1所述的印刷电路板用树脂组成物施加于一基材上,并经干燥而形成。
7.一种覆金属基板,其特征在于,所述覆金属基板包括至少一如权利要求6所述的预浸材以及一形成于所述预浸材上的金属层。
8.一种印刷电路板,其特征在于,所述印刷电路板是将如权利要求7所述的覆金属基板的所述金属层图案化而形成。
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