CN104448702A - 一种无卤树脂组合物及用其制作的预浸料与层压板 - Google Patents

一种无卤树脂组合物及用其制作的预浸料与层压板 Download PDF

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CN104448702A
CN104448702A CN201410631941.5A CN201410631941A CN104448702A CN 104448702 A CN104448702 A CN 104448702A CN 201410631941 A CN201410631941 A CN 201410631941A CN 104448702 A CN104448702 A CN 104448702A
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halogen
resin composition
parts
epoxy resin
free
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CN104448702B (zh
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李辉
方克洪
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to US15/313,669 priority patent/US10144824B2/en
Priority to KR1020167022070A priority patent/KR101798809B1/ko
Priority to EP14905721.8A priority patent/EP3133122B1/en
Priority to JP2016528902A priority patent/JP6271008B2/ja
Priority to PCT/CN2014/092841 priority patent/WO2016074290A1/zh
Priority to AU2014411039A priority patent/AU2014411039B2/en
Priority to TW104101385A priority patent/TWI555792B/zh
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Abstract

本发明涉及一种无卤树脂组合物及用其制作的预浸料与层压板，所述的无卤树脂组合物按重量份包括如下组分：环氧树脂50-100份；苯并噁嗪20-70份；聚苯醚5-40份；苯丙烯-马来酸酐5-40份；无卤阻燃剂10-60份；固化促进剂0.2-5份；填料20-100份。用所述无卤树脂组合物制作的预浸料与层压板，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，适合在无卤高多层电路板中使用。

Description

一种无卤树脂组合物及用其制作的预浸料与层压板
技术领域
本发明涉及层压板技术领域，具体涉及一种树脂组合物，尤其涉及一种无卤树脂组合物及用其制作的预浸料，层压板与印刷电路板。
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。然而人们对火灾现场深入研究后得出结论：虽然含卤阻燃剂的阻燃效果好，且添加量少，但是采用含卤阻燃剂的高分子材料在燃烧过程中会产生大量的有毒且具有腐蚀性的气体和烟雾，容易使人窒息而死，其危害性比大火本身更为严重。因此，随着欧盟《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用有害物质指令》于2006年7月1日的正式实施，无卤阻燃印刷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得基材的吸水性变高，耐化学性变差。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，具有优良的力学、电学和阻燃性能等。
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、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，3GHz以上将逐渐成为主流，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的要求会越来越低。
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，而是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。因为高介电常数(Dk)会使信号传递速率变慢，高介质损耗(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，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、含磷固化剂复合固化环氧树脂可以得到一种具有较低介电常数及介质损耗的固化物，但是仅仅以苯乙烯-马来酸酐来降低材料的介电性能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，因为苯乙烯-马来酸酐(SMA)分子结构中非极性的苯乙烯结构单元降低了改性基体树脂的极性，削弱了树脂与铜箔之间的相互作用力；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，也对动态条件下的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。
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具有较低介电常数及介质损耗的固化物，但以含磷环氧树脂作为主体树脂，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，这势必会对板材的其它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，可以得到一种具有较低介电常数及介质损耗的固化物，但使用普通的苯并噁嗪虽然可以达到固化环氧树脂及阻燃的目的，但由于普通苯并噁嗪的介电常数较高，往往难以满足高频高速传输，且胺类固化剂的引入虽然可以提升粘结性，但其存在吸湿性较大及用其固化环氧树脂耐热性不足的缺陷，必然会对其在高多层电路板中的使用产生负面影响。
因此，如何生产一种具有低介电常数、低介质损耗，同时保证其耐化学性优良的预浸料及层压板是目前亟待解决的问题。
发明内容
本发明的目的在于提供一种树脂组合物，特别是一种无卤树脂组合物及用其制作的预浸料，层压板与印刷电路板。
为达到此发明目的，本发明采用以下技术方案：
第一方面，本发明提供了一种无卤树脂组合物，该组合物按重量份包括如下组分：环氧树脂50-100份；苯并噁嗪20-70份；聚苯醚5-40份；苯丙烯-马来酸酐5-40份；无卤阻燃剂10-60份；固化促进剂0.2-5份；填料20-100份。
本发明的苯丙烯-马来酸酐的化学结构式为：
其中，x为1-4，6，8；n为1-12；x，n均为整数。
本发明的苯丙烯-马来酸酐含量为5-40份，例如可以是5份、10份、15份、17份、20份、22份、25份、30份、35份、40份，优选为15-22份，进一步优选为15份。
本发明采用苯丙烯-马来酸酐与苯并噁嗪复合固化环氧组合物，不仅使基材具有低的介电常数及介质损耗，而且由于苯丙烯-马来酸酐中甲基的存在使空间位阻增大，分子链内旋转位阻和聚合物的分子链刚性增大，从而使基材的耐热性提高，同时由于甲基具有憎水性，还能显著提升基材的耐湿性。
本发明的环氧树脂可以为双酚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、三官能环氧树脂、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至少两种的混合物。
本发明的环氧树脂含量为50-100份，例如可以是50份、55份、60份、65份、70份、75份、80份、85份、90份、95份、100份，优选为60份。
本发明的苯并噁嗪可以为氟化苯并噁嗪树脂、脂肪族苯并噁嗪树脂或双环戊二烯型苯并噁嗪树脂中的任意一种或至少两种的混合物。
优选地，本发明的苯并噁嗪可以为氟化苯并噁嗪树脂或脂肪族苯并噁嗪树脂中的任意一种或至少两种的混合物。
本发明的氟化苯并噁嗪树脂为下述化学结构式中的任意一种或至少两种的混合物：
本发明的脂肪族苯并噁嗪树脂的化学结构式为：
其中，n为2或3。
本发明的双环戊二烯型苯并噁嗪树脂的化学结构式为：
本发明的苯并噁嗪含量为20-70份，例如可以是20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份，优选为40-50份，进一步优选为40份。
本发明的聚苯醚为低分子量聚苯醚，数均分子量在1000-4000。
本发明的聚苯醚含量为5-40份，例如可以是5份、10份、15份、20份、25份、30份、35份、40份，优选为20份。
本发明的无卤阻燃剂可以为磷腈、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、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羟乙基异氰尿酸酯、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或含DOPO酚醛树脂中的任意一种或至少两种的混合物。
本发明的无卤阻燃剂含量为10-60份，例如可以是10份、15份、20份、22份、25份、30份、40份、50份、60份，优选为20-22份，进一步优选为20份。
本发明以具有阻燃作用的低介电苯并噁嗪为主要固化剂，同时添加少量含磷阻燃剂，实现了磷氮协同阻燃效应，在大大减少磷含量的同时提高了基材的阻燃性，并且使基材具有较好的耐湿性。
本发明的固化促进剂可以为咪唑类促进剂，所述的咪唑类促进剂为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至少两种的混合物。
本发明的固化促进剂含量为0.2-5份，例如可以是0.2份、0.5份、1份、2份、3份、4份、5份。
本发明的填料可以为无机或有机填料；当所述填料为无机填料时，可以为氢氧化铝、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至少两种的混合物；当所述填料为有机填料时，可以为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。
本发明的二氧化硅可以选择结晶型、熔融型或球形二氧化硅。
本发明填料的粒径为0.01-50μm，例如可以是0.01μm、0.05μm、1μm、5μm、10μm、15μm、20μm、25μm、30μm、40μm、50μm，优选为1-15μm。
本发明的填料含量为20-100份，例如可以是20份、30份、40份、50份、60份、70份、80份、90份、100份，优选为50份。
为使所述的填料在本发明的树脂组合物中分散均匀，还可以添加入分散剂，使用的分散剂为氨基硅烷偶联剂或环氧基硅烷偶联剂，用来改善无机以及织造玻璃布间的结合性能，从而达到分散均匀的目的，且这类偶联剂无重金属存在，不会对人体产生不良影响，使用量为填料的0.5-2％重量份，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。
第二方面，本发明还提供了一种使用如本发明第一方面所述的无卤树脂组合物制作的预浸料，该预浸料包括基体材料；和通过浸渍干燥后附着在其上的无卤树脂组合物。
本发明的基体材料为无纺或有纺玻璃纤维布。
第三方面，本发明还提供了一种层压板，该层压板包括如本发明第二方面所述的预浸料。
第四方面，本发明还提供了一种印刷电路板，其包含如本发明第三方面所述的层压板。
与现有技术相比，本发明具有以下有益效果：
采用本发明的无卤树脂组合物制备得到的层压板，其介电常数可控制在3.7及以下，介质损耗最高值仅为0.0060，可达到阻燃性试验UL-94中的V-0标准，PCT吸水率为0.34-0.36；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。
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。
制备例、聚丙烯-马来酸酐的合成
在氮气保护和搅拌的条件下，将单体马来酸酐和引发剂加入到介质中溶解，并加热至60-80℃时，滴加单体苯丙烯和分子量调节剂，滴加完毕后继续搅拌反应1-8h，得到低分子量苯丙烯/马来酸酐聚合物粒子的分散体系，将分散体系离心分离、干燥，得到低分子量苯丙烯/马来酸酐交替共聚物；其中，所述的引发剂为有机过氧化物或偶氮化合物；所述的介质为有机酸烷基酯与烷烃的混合溶液；所述的分子量调节剂为乙酸乙烯酯；马来酸酐和苯丙烯的用量关系，按摩尔比为1:0.90-0.96；反应体系中马来酸酐和苯丙烯两种单体的质量浓度之和为2.0-7.5％；引发剂的质量浓度为0.05-0.35％；分子量调节剂的质量浓度为0.10-0.45％；有机酸烷基酯与烷烃的混合溶液中有机酸烷基酯的体积分数为20-80％。
得到如下结构式的苯丙烯-马来酸酐：
其中，x为1-4，6，8；n为1-12；x，n均为整数。
实施例、覆铜箔层压板的制备方法
将环氧树脂、苯并噁嗪、聚苯醚、苯丙烯-马来酸酐、无卤阻燃剂、固化促进剂、填料及溶剂等，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，即得到本发明的无卤树脂组合物胶液，用2116电子级玻璃纤维布浸渍胶液，经烘箱烘烤成半固化片，取6张2116半固化片，双面再覆上35μm厚的电解铜箔，在热压机作真空层压，固化190℃/120min，制成覆铜箔层压板。
实施例1-8以及对比例1-5中所用的各组分及其含量(按重量份计)如表1所示，各组分代号及其对应的组分名称如下所示：
A环氧树脂
A-1联苯型环氧树脂：NC-3000-H(日本化药商品名)
A-2双环戊二烯型环氧树脂：HP-7200H(大日本油墨商品名)
B苯并噁嗪
B-1脂肪族苯并噁嗪：KAH-F5404(韩国Kolon商品名)
B-2氟化苯并噁嗪KAH-F5301(韩国Kolon商品名)
B-3双酚F型苯并噁嗪：LZ8280(亨斯曼先进材料)
B-4双环戊二烯苯并噁嗪：LZ8260(亨斯曼先进材料)
C-1低分子量聚苯醚：MX90(SABIC Innovative Plastics商品名)，数均分子量1000-4000
C-2高分子量聚苯醚：Sabic640-111(SABIC Innovative Plastics商品名)数均分子量15000-20000
D-1制备例中的苯丙烯-马来酸酐低聚物
D-2苯乙烯-马来酸酐低聚物：SMA-EF40(美国Sartomer商品名)
E无卤阻燃剂：含磷酚醛树脂：XZ92741(DOW化学商品名)
F固化促进剂：2E4MZ(四国化成商品名)
G填料：熔融二氧化硅
实施例1-8和对比例1-5采用的覆铜箔层压板的制备方法与实施例相同。
采用以下方法对实施例1-8和对比例1-5制备的覆铜箔层压板的玻璃化转变温度(Tg)、剥离强度(PS)、介电常数(Dk)与介质损耗角正切值(Df)、阻燃性和PCT 2小时后耐浸焊性及吸水率进行测试，测试结果如表2所示。
各性能参数的测试方法如下：
A玻璃化转变温度(Tg)
根据差示扫描量热法(DSC)，按照IPC-TM-650 2.4.25所规定的DSC方法进行测定；
B剥离强度(PS)
按照IPC-TM-650 2.4.8方法中的“热应力后”实验条件，测试金属盖层的剥离强度；
C介电常数(Dk)与介质损耗角正切值(Df)
使用条状线的共振法，按照IPC-TM-650 2.5.5.5测定1GHz下的介电常数(Dk)与介质损耗角正切值(Df)；
D阻燃性
按照UL-94标准进行测试；
E PCT 2小时后耐浸焊性及吸水率
将覆铜箔层压板浸渍在铜蚀刻液中，除去表面铜箔评价基板；将基板放置在压力锅中，在121℃，2atm下处理2h，测试吸水率后，浸渍在温度为288℃的锡炉中，当基材出现起泡或分裂时记录相应的时间。当基材在锡炉中超过5min还没有出现起泡或分层时结束评价。
表1
表2
从表1和表2可以看出以下几点：
(1)通过将实施例2-3与对比例1-2相比可知，实施例2-3的层压板比对比例1-2的介电常数、介质损耗和PCT吸水率都要低，说明实施例2-3采用苯丙烯-马来酸酐比对比例1使用苯乙烯-马来酸酐低聚物可以获得更低的介电常数、介质损耗和PCT吸水率；
(2)通过将实施例3和5与对比例3相比可知，实施例3和5的层压板比对比例3的玻璃化转化温度要高，而其介电常数、介质损耗以及PCT吸水率比对比例3的都要低，阻燃性可达到V-0级，说明实施例3和5分别采用脂肪族苯并噁嗪及氟化苯并噁嗪比对比例3使用双酚F苯并噁嗪可以获得更高的玻璃化转化温度，更低的介电常数、介质损耗以及PCT吸水率，且阻燃性更高；由实施例7和8可知，使用双环戊二烯苯并噁嗪与脂肪族苯并噁嗪均可实现较高的玻璃化转变温度、较低的介电常数，其中使用脂肪族苯并噁嗪具有更高的玻璃化转变温度及更低的介电常数。
(3)通过将实施例5与对比例4相比可知，实施例5的层压板比对比例4的介电常数、介质损耗和PCT吸水率都要低，说明实施例5采用低分子量聚苯醚树脂比对比例4未使用上述组分可以获得更低的介电常数、介质损耗和PCT吸水率；将实施例5与对比例5相比可知，虽然两者的综合性能相当，但使用高分子量的聚苯醚导致加工性变差。
(4)通过将实施例1-4相比可知，实施例1的玻璃化转化温度最低，介电常数、介质损耗最高，实施例4的玻璃化转化温度最高，介电常数、介质损耗最低，说明随着苯丙烯-马来酸酐含量的增加，可以提升玻璃化转变温度，使介电常数、介质损耗降低。
通过实施例1-8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，其介电常数可控制在3.7及以下，介质损耗最高值仅为0.0060，可达到阻燃性试验UL-94中的V-0标准，PCT吸水率为0.34-0.36，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。
当然，以上所述之实施例，只是本发明的较佳实例而已，并非用来限制本发明的实施范围，故凡依本发明申请专利范围所述的原理所做的等效变化或修饰，均包括于本发明申请专利范围内。

Claims (10)

1.一种无卤树脂组合物，其特征在于，按重量份包括如下组分：环氧树脂50-100份；苯并噁嗪20-70份；聚苯醚5-40份；苯丙烯-马来酸酐5-40份；无卤阻燃剂10-60份；固化促进剂0.2-5份；填料20-100份。
所述的苯丙烯-马来酸酐的化学结构式为：
其中，x为1-4，6，8；n为1-12；x，n均为整数。
2.如权利要求1所述的无卤树脂组合物，其特征在于，所述的环氧树脂为双酚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、三官能环氧树脂、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至少两种的混合物。
3.如权利要求1所述的无卤树脂组合物，其特征在于，所述的苯并噁嗪为氟化苯并噁嗪树脂、脂肪族苯并噁嗪树脂或双环戊二烯型苯并噁嗪树脂中的任意一种或至少两种的混合物；
优选地，所述苯并噁嗪为氟化苯并噁嗪树脂或脂肪族苯并噁嗪树脂中的任意一种或至少两种的混合物；
优选地，所述氟化苯并噁嗪树脂为下述化学结构式中的任意一种或至少两种的混合物：
优选地，所述脂肪族苯并噁嗪树脂的化学结构式为：
其中，n为2或3；
优选地，所述双环戊二烯型苯并噁嗪树脂的化学结构式为：
4.如权利要求1所述的无卤树脂组合物，其特征在于，所述的聚苯醚数均分子量在1000-4000。
5.如权利要求1所述的无卤树脂组合物，其特征在于，所述的无卤阻燃剂为磷腈、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、磷氮基化合物、聚磷酸三聚氰胺、三聚氰胺氰尿酸酯、三-羟乙基异氰尿酸酯、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物或含DOPO酚醛树脂中的任意一种或至少两种的混合物。
6.如权利要求1所述的无卤树脂组合物，其特征在于，所述的固化促进剂为咪唑类促进剂；
优选地，所述的固化促进剂为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至少两种的混合物。
7.如权利要求1所述的无卤树脂组合物，其特征在于，所述的填料为无机或有机填料；
优选地，所述的填料为无机填料，所述的无机填料为氢氧化铝、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至少两种的混合物；
优选地，所述的填料为有机填料，所述的有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物；
优选地，所述填料的粒径为0.01-50μm，优选为1-15μm，进一步优选为1-5μm。
8.一种使用如权利要求1-7之一所述的无卤树脂组合物制作的预浸料，其特征在于，所述预浸料包括基体材料；和通过浸渍干燥后附着在其上的无卤树脂组合物；
优选地，所述基体材料为无纺或有纺玻璃纤维布。
9.一种层压板，其特征在于，包含如权利要求8所述的预浸料。
10.一种印刷电路板，其特征在于，其包含如权利要求9所述的层压板。
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