CN106832226B - 一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 - Google Patents

一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板 Download PDF

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Publication number
CN106832226B
CN106832226B CN201510888817.1A CN201510888817A CN106832226B CN 106832226 B CN106832226 B CN 106832226B CN 201510888817 A CN201510888817 A CN 201510888817A CN 106832226 B CN106832226 B CN 106832226B
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epoxy resin
halogen
resin composition
free
free epoxy
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CN106832226A (zh
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李辉
方克洪
许永静
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201510888817.1A priority Critical patent/CN106832226B/zh
Priority to TW105115622A priority patent/TWI598402B/zh
Priority to PCT/CN2016/098480 priority patent/WO2017092472A1/zh
Priority to US15/318,787 priority patent/US10400099B2/en
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Abstract

本发明涉及一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板。所述无卤环氧树脂组合物，其包括环氧树脂和固化剂，以环氧树脂的环氧基总当量数为1，固化剂中与环氧基团发生反应的活性基团的当量数为0.5～0.95。本发明通过控制环氧树脂中环氧基和固化剂中活性基团的当量比为0.5～0.95，在保持低介电常数和低介质损耗的同时，保证了预浸料在不同固化温度条件下Df值的稳定性。此外，使用该树脂组合物制备的预浸料及层压板，具有低介电常数、低介质损耗、优异的阻燃性、耐热性、粘结性、低的吸水率及优异的耐湿性等综合性能，适合在无卤高多层电路板中使用。

Description

一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印 制电路板
技术领域
本发明属于覆铜板技术领域，具体涉及一种无卤环氧树脂组合物以及含有它的预浸料、层压板和印制电路板。
背景技术
目前，含卤阻燃剂(特别是溴系阻燃剂)被广泛用于高分子阻燃材料，并起到了较好的阻燃作用。随着人们环保意识的提高及欧盟一系列指令的颁布，无卤阻燃印制线路板的开发成为了业内开发工作的重点，各覆铜箔层压板的厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。
目前工业上普遍使用含磷树脂来实现阻燃效果，但过多磷的引入会使基材吸水性高和耐化学性差等诸多问题。
近年来，以苯并噁嗪作为基体树脂用于无卤基材的开发越来越受到重视。苯并噁嗪是一类由氧原子和氮原子构成的苯并六元杂环体系，具有开环聚合的特点，聚合时无小分子释放，聚合后形成类似酚醛树脂的网状结构，制品的固化收缩小，孔隙率低，有优良的力学、电学和阻燃性能。
另一方面，随着电子工业的飞速发展，电子产品向轻、薄、短小、高密度化、安全化和高功能化发展，要求电子元件有更高的信号传播速度和传输效率，这样就对作为载体的印刷电路板提出了更高的性能要求。电子产品信息处理的高速化和多功能化，应用频率不断提高，除了保持对层压板材料的耐热性有更高的要求外，对其介电常数和介质损耗值要求会越来越低。
现有的传统FR-4很难满足电子产品的高频及高速发展的使用需求，同时基板材料不再是扮演传统意义下的机械支撑角色，而将与电子组件一起成为PCB和终端厂商设计者提升产品性能的一个重要途径。因为高Dk会使信号传递速率变慢，高Df会使信号部分转化为热能损耗在基板材料中，因此具有低介电常数和低介质损耗的高频传输，尤其是无卤高频板材的开发已成为覆铜箔层压板行业的重点。
为了解决上述问题，CN101684191B提出了使用苯并噁嗪、苯乙烯-马来酸酐(SMA)、含磷固化剂复合固化环氧树脂可以得到一种较低介电常数及介质损耗的固化物，SMA用量过多，虽然可以降低材料的介电常数值，但不可避免的会出现很多其他方面的问题，对粘结性影响尤为显著，因为SMA分子结构中非极性的苯乙烯结构单元含量降低了改性基体树脂的极性，削弱了树脂与铜箔之间相互作用力；同时，因为SMA中大量的苯环结构增大了树脂交联网络的脆性，也对动态条件下粘结性能产生不利影响，从而降低了基材之间及基材与铜箔的粘结强度，且随着电子工业的发展，对基材的耐热性提出了更高的要求。
CN100523081C提出了使用苯并噁嗪、苯乙烯-马来酸酐和其他固化剂复合固化含磷及无卤无磷环氧组合物可以得到一种较低介电常数及介质损耗的固化物，但以含磷环氧作为主体树脂，虽然可以达到优异的阻燃性，但磷的过多引入，必然对基材的吸水性产生极大影响，这势必会对基材的很多性能有负面影响。
CN103131131A提出了使用苯并噁嗪、苯乙烯-马来酸酐和胺类固化剂复合固化环氧树脂，可以得到一种较低介电常数及介质损耗的固化物，胺类固化剂的引入虽然可以提升基材的粘结性，但是势必会造成基材耐热性的下降，难以满足高多层应用的需求。
CN 103881302A提供了一种树脂组合物及应用其的铜箔基板及印刷电路板。所述树脂组合物包含环氧树脂、苯并噁嗪树脂、苯乙烯马来酸酐共聚物以及聚酯，使用聚酯虽然具有较好的介电性能，但聚酯价格贵，且所述树脂组合物使用了较多的苯并噁嗪，会使基材的脆性增加。
而且，以上苯并噁嗪和苯乙烯-马来酸酐复合固化环氧树脂的已有技术均没有考虑苯并噁嗪及苯乙烯马来酸酐的用量对预浸料在不同固化温度条件下介质损耗值(Df)稳定性的影响，而稳定的Df值对与基材在终端的应用中信号的稳定性传输具有重要意义。
发明内容
针对现有技术的不足，本发明的目的之一在于提供一种无卤环氧树脂组合物，通过控制环氧树脂环氧基和固化剂活性基团的当量比，在保持低介电常数和低介质损耗的同时，保证了预浸料在不同固化温度条件下Df值的稳定性。
为了实现上述目的，本发明采用了如下技术方案：
一种无卤环氧树脂组合物，其包括环氧树脂和固化剂，以环氧树脂的环氧基总当量数为1，固化剂中与环氧基团发生反应的活性基团的当量数为0.5～0.95。
本发明通过控制环氧树脂环氧基和固化剂活性基团的当量比为0.5～0.95，在保持低介电常数和低介质损耗的同时，保证了预浸料在不同固化温度条件下Df值的稳定性。
在本发明中，所述固化剂中与环氧基团发生反应的活性基团即为在环氧树脂固化过程中，固化剂中可以与环氧基团发生固化反应的基团。
在本发明中，以环氧树脂的环氧基总当量数为1，固化剂中与环氧基团发生反应的活性基团的当量数例如为0.53、0.56、0.58、0.61、0.64、0.67、0.7、0.73、0.76、0.79、0.82、0.85、0.88、0.91或0.94，优选0.7～0.85。
优选地，在本发明中，所述固化剂为苯乙烯-马来酸酐和苯并噁嗪树脂。采用苯乙烯-马来酸酐和苯并噁嗪树脂复合固化环氧树脂，在保持低介电常数和低介质损耗的同时，可以保证预浸料在不同固化温度条件下Df值的稳定性，同时，可以使得到的预浸料及层压板具有低介电常数、低介质损耗、优异的阻燃性、耐热性、低吸水率以及优异的耐湿性等综合性能。
优选地，在本发明中，以环氧树脂的环氧基总当量数为1，苯并噁嗪树脂的当量数为0.3～0.55，苯乙烯-马来酸酐当量数为0.2～0.4，而且，苯并噁嗪树脂当量数和苯乙烯-马来酸酐当量数之和小于环氧基总当量数。
本发明通过将环氧树脂、苯并噁嗪和苯乙烯-马来酸酐(SMA)的当量数控制在合适的范围，在保持低介电常数和低介质损耗的同时，保证了预浸料在不同固化温度条件下Df值的稳定性，克服了目前苯并噁嗪和苯乙烯-马来酸酐固化环氧树脂体系Df随固化温度发生变化的缺点。
在本发明中，苯并噁嗪树脂有利于提高固化后树脂及其制成的基材所需的阻燃性能、吸湿性、耐热性、力学性能及介电性能。本发明通过对其添加量的选择，使所得基材具有上述性能的前提下，还保证了预浸料在不同固化温度条件下Df值的稳定性，克服了目前苯并噁嗪和苯乙烯-马来酸酐固化环氧树脂体系Df随固化温度发生变化的缺点。在本发明中，所述苯并噁嗪树脂的当量数例如为0.32、0.34、0.36、0.38、0.4、0.42、0.44、0.46、0.48、0.5、0.52或0.54。苯并噁嗪树脂当量数低于0.3，则阻燃和介电性能不佳，高于0.55则基材脆性增加且Df值会随固化温度而发生变化，Df值稳定性降低。优选地，苯并噁嗪树脂当量数为0.4～0.5。
本发明中的苯乙烯-马来酸酐有利于改善基材的介电性能，以环氧树脂的环氧基总当量数为1，苯乙烯-马来酸酐的当量数为0.2～0.4，例如0.22、0.24、0.26、0.28、0.3、0.32、0.34、0.36或0.38。在此添加范围内的苯乙烯-马来酸酐含量，可使该无卤环氧树脂组成物具有较好的综合性能，若低于0.2，则工艺性差、Tg不足且达不到改善介电性能的作用，若高于0.4，一方面会使基材的粘结性变差，另一方面也会使基材Df值随固化温度而发生变化，降低Df值的稳定性。优选地，苯乙烯-马来酸酐当量数为0.3～0.35。
优选地，在本发明中，以环氧树脂的环氧基总当量数为1，苯并噁嗪树脂的当量数为0.4～0.5，苯乙烯-马来酸酐当量数为0.3～0.35，而且，苯并噁嗪当量数和苯乙烯-马来酸酐当量数之和小于环氧基总当量数。
采用该优选的无卤环氧树脂组合物得到的基材除具有上述性能外，还具有更低的Df值以及更高的Tg。
在本发明中，优选地，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂、烷基酚醛环氧树脂、双环戊二烯环氧树脂、双酚A型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、苯酚型酚醛环氧树脂、四官能环氧树脂、异氰酸酯改性环氧树脂、萘型环氧树脂或含磷环氧树脂中的任意一种或者至少两种的混合物。
优选地，所述苯并噁嗪树脂选自具有如下结构的苯并噁嗪树脂中的任意一种或者至少两种的组合：
其中，R2和R3为单取代或多取代，R2和R3各自独立地为氢、甲基、烯丙基或醛基，R1为—CH2—、—O—、—C(CH3)2—、—SO2—、—C(CF3)2—、—CH2CH2—或双环戊二烯基中的任意一种或者至少两种的组合，R4和R5各自独立地为烯丙基、未取代或取代的苯基、未取代或取代的碳原子数为1～8的烷基或未取代或取代的环烷基中的任意一种或者至少两种的组合。
优选地，所述苯乙烯-马来酸酐结构式为：
其中，x:n＝0.8～19:1，优选1～15:1，进一步优选1～12:1。
优选地，所述苯乙烯马来酸酐共聚物的数均分子量为1000～50000，优选1500～45000，进一步优选2000～40000。
示例性的苯乙烯-马来酸酐如商品名SMA-1000、SMA-2000、SMA-3000、EF-30、EF-40、EF-60和EF-80等的马来酸酐。
优选地，所述无卤环氧树脂组合物可以包含选自下列群组中的一种或多种：聚苯醚树脂、氰酸酯树脂、双马来酰亚胺、活性酯、苯乙烯树脂、丁二烯树脂、苯氧树脂、橡胶树脂、核壳树脂、聚酰胺和聚酰亚胺。
优选地，所述无卤环氧树脂组合物还包括无卤阻燃剂。
优选地，所述无卤阻燃剂为含磷酚醛、磷氮基化合物、聚磷酸铵、三(2-羧乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯或三-羟乙基异氰尿酸酯中的任意一种或者至少两种的组合。
优选地，所述含磷酚醛选自9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)改性酚醛树脂、10-(2,5-二羟基苯基)9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)改性酚醛树脂或10-(2,9-二羟基萘基)9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO-NQ)改性酚醛树脂中的任意一种或者至少两种的混合物。
优选地，所述无卤阻燃剂为含磷酚醛和磷氮基化合物，所述含磷酚醛的重量为环氧树脂重量的1/6～2/3，所述磷氮基化合物的重量为环氧树脂重量的1/6～5/6。
含磷酚醛在低于环氧树脂重量的1/6时，阻燃性能达不到V-0等级，而高于2/3时，虽然能保证阻燃，但基材吸水率增加、Tg降低，且会影响基材的PCT性能。
磷氮基化合物的添加量不足环氧树脂重量的1/6时，则阻燃性不佳，超过5/6则成本增加，而且，基材玻璃化转变温度降低。
优选地，所述无卤环氧树脂组合物还包括填料。
优选地，所述填料为有机或/和无机填料，主要起改善介电性能、降低热膨胀系数、改善导热性及降低成本的作用。
优选地，所述无机填料选自氢氧化铝、氧化铝、氢氧化镁、氧化镁、三氧化二铝、二氧化硅(包括结晶型、熔融型、球形二氧化硅)、碳酸钙、氮化铝、氮化硼、碳化硅、二氧化钛、氧化锌、氧化锆、云母、勃姆石、煅烧滑石、滑石粉、氮化硅或煅烧高岭土中的任意一种或者至少两种的混合物。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。
优选地，在本发明中，填料的粒径为0.01～50μm。
为使所述填料在无卤环氧树脂组合物中分散均匀，还可以添加分散剂，使用的分散剂为氨基硅烷偶联剂或/和环氧基硅烷偶联剂，用来改善无机以及织造玻璃布等增强材料间的结合性能，而达到分散均匀的目的。而且，这类偶联剂无重金属存在，不会对人体产生不良影响，其使用量为填料重量的0.5-2％。若使用量太高，则加快反应，影响储存时间，用量太小，则无显著改善结合稳定性的效果。
优选地，所述无卤环氧树脂组合物进一步包含固化促进剂，该固化促进剂选自咪唑类促进剂，优选自2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑中的任意一种或者至少两种的组合。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述环氧树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述环氧树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
在本发明中，优选地，所述环氧树脂组合物不包括胺类固化剂。这主要是由于，胺类固化剂的引入虽然可以提升基材的粘结性，但是会造成基材耐热性的下降，难以满足高多层应用的需求。
本发明的目的之二在于提供一种使用所述的无卤环氧树脂组合物制作的预浸料，所述预浸料包括增强材料及通过含浸干燥后附着在增强材料上的如上所述的无卤环氧树脂组合物。
所述增强材料为无纺或有纺玻璃纤维布等。
本发明的目的之三在于提供一种使用所述的预浸料制作的层压板，所述层压板包括至少一张如上所述的预浸料。
本发明的目的之四在于提供一种印制电路板，其包括至少一张如上所述的预浸料。
此外，采用如上所述的预浸料还可以得到覆铜箔层压板，其包括至少一张叠合的如上所述的预浸料以及压覆在叠合后的预浸料一侧或两侧的铜箔。
与已有技术相比，本发明具有如下有益效果：
①本发明通过控制环氧树脂环氧基和固化剂活性基团的当量比为0.5～0.95，在保持低介电常数和低介质损耗的同时，保证了预浸料在不同固化温度条件下Df值的稳定性。
②本发明采用苯乙烯-马来酸酐和苯并噁嗪树脂复合固化环氧树脂，在保持低介电常数和低介质损耗的同时，可以保证预浸料在不同固化温度条件下Df值的稳定性，同时，可以使得到的预浸料及层压板具有低介电常数、低介质损耗、优异的阻燃性、耐热性、低吸水率以及优异的耐湿性等综合性能。
③本发明以具有阻燃作用苯并噁嗪作为固化剂，可以与含磷阻燃剂实现磷氮协同阻燃效应，在大大减少组分磷含量的同时提高了基材的阻燃性，且使基材具有较好的耐湿性。
④使用该树脂组合物制备的预浸料及层压板，具有低介电常数(1GHZ，≤3.9)、低介质损耗、优异的阻燃性(V-0或V-1)、耐热性(Tg，DSC，≥178℃)、粘结性(剥离强度≥1.25N/mm)、低的吸水率(≤0.36％)及优异的耐湿性等综合性能，克服了目前无卤层压板介电常数偏高、耐热性不足以及耐湿性差等缺点，适合在无卤高多层电路板中使用。
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。
针对上述发明的预浸料及层压板用树脂组合物，测试200℃固化120min程序下的固化基材的剥离强度、玻璃化转变温度、阻燃性、PCT两小时后耐浸焊极限、吸水率以及介电常数，测试不同固化温度条件下的介质损耗性能，如下述实施例进一步给予说明与描述。
将含有环氧树脂、苯并噁嗪、苯乙烯-马来酸酐、无卤阻燃剂、填料及其他助剂放入容器中，搅拌使其混合均匀，制成胶水，用溶剂调整溶液固体含量至60％-70％而制成胶液，即得到本发明树脂组合物胶液。用2116电子级玻纤布浸渍胶水，经烘箱烘烤成预浸料，取6张2116预浸料，双面再覆上35μm厚电解铜箔，在热压机作真空层压，选择的固化程序分别为190℃、200℃和210℃条件下固化120min，制成覆铜板。
实施例及比较例中所用各组分详述如下：
(A)环氧树脂
(A-1)NC-3000-H(日本化药商品名)
(A-2)HP-7200H(大日本油墨商品名)
(B)苯并噁嗪树脂
(B-1)D-125(四川东材科技集团股份有限公司商品名)
(B-2)LZ8280(亨斯曼先进材料)
(C)苯乙烯-马来酸酐低聚物：SMA-EF40(美国Sartomer商品名)
(D-1)双氰胺：DICY(宁夏大荣商品名)
(D-2)聚酯：EXB-9460
(E)含磷酚醛树脂
(E-1)XZ92741(DOW化学商品名)
(E-2)LC-950(SHIN-A公司商品名)
(F)磷氮基化合物：SPB-100(大塚化学商品名)
(G)填料：熔融二氧化硅
表1
表2
表3
表4
从表1～表4可以看出以下几点：
通过实施例1和实施例2、7、8可知，固化剂优化后的配方具有更低的Df值及更高的Tg，通过实施例2、7、8和实施例3可知，固化剂优化后的配方虽然Tg稍低但具有更高的剥离强度和更低的吸水率，即从实施例1-3、7、8可看出固化剂优化后的配方具有更好的综合性能。
通过对比实施例2和实施例4、9可知，虽然添加含磷酚醛和磷氮基化合物后Tg稍降，但可以保证阻燃可达V-0而对其他性能影响不大，而添加填料对基材性能影响不大。
通过实施例4和比较例1-2可看出，苯并噁嗪当量数在低于0.3时Tg偏低，且介电性能较差，而高于0.55时虽然具有较高的Tg，但加工性差且Df不稳定，随固化温度的升高而升高。
通过实施例5和对比例3-4可知，苯乙烯-马来酸酐当量数在低于0.2时Tg不足，介质损耗性能较差，还会影响基材的加工性，而高于0.4时虽然能提高Tg但阻燃不足，吸水率增加且Df不稳定，随固化温度的升高而升高。
通过实施例6和对比例5-6可知，含磷酚醛在低于环氧树脂重量的1/6时阻燃性能达不到V-0等级，而高于2/3时虽然能保证阻燃，但会是基材吸水率增加、Tg降低，且会影响基材的PCT性能。
通过实施例5和对比例7-8可知，磷氮基化合物在低于环氧树脂重量的1/6时阻燃性能达不到V-0等级，而高于5/6时虽然能保证阻燃，但会是基材Tg降低，且会影响基材的PCT性能及加工性。
对比例9
对比例9为CN 101684191B公开的实施例4。
对比例10
对比例10为CN103131131A公开的实施例1。
对比例11
对比例11为CN 103881302A公开的实施例2。
表5
表6
通过实施例1-9可以得出，采用本发明的无卤树脂组合物制备得到的层压板，其介电性能较好，介质损耗值不随固化温度的升高而发生变化，达到阻燃性试验UL-94中的V-0标准，因而，该层压板在保证无卤阻燃的同时，还具有低介电常数、低介质损耗、优异的耐热性、粘结性及耐湿性等综合性能，适合在无卤高多层电路板中使用。即使用本发明树脂组合物制备的预浸料及层压板，具有低介电常数、低介质损耗、优异的阻燃性、耐热性、粘结性及耐湿性等综合性能，克服了目前无卤层压板介电常数偏高，耐热性不足，耐湿性差等缺点，适合在无卤高多层电路板中使用。
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 (26)

1.一种无卤环氧树脂组合物，其包括环氧树脂和固化剂，以环氧树脂的环氧基总当量数为1，固化剂中与环氧基团发生反应的活性基团的当量数为0.5～0.95；
所述固化剂为苯乙烯-马来酸酐和苯并噁嗪树脂，以环氧树脂的环氧基总当量数为1，苯并噁嗪树脂的当量数为0.3～0.55，苯乙烯-马来酸酐当量数为0.2～0.4；
所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、联苯环氧树脂、烷基酚醛环氧树脂、双环戊二烯环氧树脂、双酚A型酚醛环氧树脂、邻甲酚型酚醛环氧树脂、苯酚型酚醛环氧树脂、四官能环氧树脂、异氰酸酯改性环氧树脂、萘型环氧树脂或含磷环氧树脂中的任意一种。
2.如权利要求1所述的无卤环氧树脂组合物，其特征在于，以环氧树脂的环氧基总当量数为1，苯并噁嗪树脂当量数为0.4～0.5。
3.如权利要求1所述的无卤环氧树脂组合物，其特征在于，以环氧树脂的环氧基总当量数为1，苯乙烯-马来酸酐当量数为0.3～0.35。
4.如权利要求1所述的无卤环氧树脂组合物，其特征在于，以环氧树脂的环氧基总当量数为1，苯并噁嗪树脂的当量数为0.4～0.5，苯乙烯-马来酸酐当量数为0.3～0.35。
5.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述苯并噁嗪树脂选自具有如下结构的苯并噁嗪树脂中的任意一种或者至少两种的组合：
其中，R2和R3为单取代或多取代，R2和R3各自独立地为氢、甲基、烯丙基或醛基，R1为—CH2—、—O—、—C(CH3)2—、—SO2—、—C(CF3)2—、—CH2CH2—或双环戊二烯基中的任意一种或者至少两种的组合，R4和R5各自独立地为烯丙基、未取代或取代的苯基、未取代或取代的碳原子数为1～8的烷基或未取代或取代的环烷基中的任意一种或者至少两种的组合。
6.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述苯乙烯-马来酸酐结构式为：
其中，x:n＝0.8～19:1。
7.如权利要求6所述的无卤环氧树脂组合物，其特征在于，x:n＝1～15:1。
8.如权利要求6所述的无卤环氧树脂组合物，其特征在于，x:n＝1～12:1。
9.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述苯乙烯马来酸酐共聚物的数均分子量为1000～50000。
10.如权利要求9所述的无卤环氧树脂组合物，其特征在于，所述苯乙烯马来酸酐共聚物的数均分子量为1500～45000。
11.如权利要求9所述的无卤环氧树脂组合物，其特征在于，所述苯乙烯马来酸酐共聚物的数均分子量为2000～40000。
12.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包含选自下列群组中的一种或多种：聚苯醚树脂、氰酸酯树脂、双马来酰亚胺、活性酯、苯乙烯树脂、丁二烯树脂、苯氧树脂、橡胶树脂、核壳树脂、聚酰胺和聚酰亚胺。
13.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包括无卤阻燃剂。
14.如权利要求13所述的无卤环氧树脂组合物，其特征在于，所述无卤阻燃剂为含磷酚醛、磷氮基化合物、聚磷酸铵、三(2-羧乙基)膦、三(异丙基氯)磷酸盐、三甲基磷酸盐、二甲基-甲基磷酸盐、间苯二酚双二甲苯基磷酸盐、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯或三-羟乙基异氰尿酸酯中的任意一种或者至少两种的组合。
15.如权利要求14所述的无卤环氧树脂组合物，其特征在于，所述含磷酚醛选自9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物改性酚醛树脂、10-(2,5-二羟基苯基)9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物改性酚醛树脂或10-(2,9-二羟基萘基)9,10-二氢-9-氧杂-10-膦菲-10-氧化物改性酚醛树脂中的任意一种或者至少两种的混合物。
16.如权利要求14所述的无卤环氧树脂组合物，其特征在于，所述无卤阻燃剂为含磷酚醛和磷氮基化合物，所述含磷酚醛的重量为环氧树脂重量的1/6～2/3，所述磷氮基化合物的重量为环氧树脂重量的1/6～5/6。
17.如权利要求1无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包括填料。
18.如权利要求17无卤环氧树脂组合物，其特征在于，所述填料为有机或/和无机填料。
19.如权利要求18无卤环氧树脂组合物，其特征在于，所述无机填料选自氢氧化铝、氢氧化镁、氧化镁、三氧化二铝、二氧化硅、碳酸钙、氮化铝、氮化硼、碳化硅、二氧化钛、氧化锌、氧化锆、云母、勃姆石、煅烧滑石、滑石粉、氮化硅或煅烧高岭土中的任意一种或者至少两种的混合物。
20.如权利要求18无卤环氧树脂组合物，其特征在于，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物。
21.如权利要求17无卤环氧树脂组合物，其特征在于，所述填料的粒径为0.01～50μm。
22.如权利要求1所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包含固化促进剂，该固化促进剂选自咪唑类促进剂。
23.如权利要求22所述的无卤环氧树脂组合物，其特征在于，所述咪唑类促进剂选自2-甲基咪唑、十一烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或1-氰乙基取代咪唑中的任意一种或者至少两种的组合。
24.一种预浸料，其包括增强材料及通过含浸干燥后附着在增强材料上的如权利要求1-23之一所述的无卤环氧树脂组合物。
25.一种层压板，其包括至少一张如权利要求24所述的预浸料。
26.一种印制电路板，其包括至少一张如权利要求24所述的预浸料。
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