CN105348744A - 热固性树脂组合物、包含其的预浸料、层压板和印制电路板 - Google Patents

热固性树脂组合物、包含其的预浸料、层压板和印制电路板 Download PDF

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CN105348744A
CN105348744A CN201510895451.0A CN201510895451A CN105348744A CN 105348744 A CN105348744 A CN 105348744A CN 201510895451 A CN201510895451 A CN 201510895451A CN 105348744 A CN105348744 A CN 105348744A
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pore
resin
thermosetting resin
composition
creating agent
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CN105348744B (zh
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陈文欣
杜翠鸣
柴颂刚
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201510895451.0A priority Critical patent/CN105348744B/zh
Publication of CN105348744A publication Critical patent/CN105348744A/zh
Priority to PCT/CN2016/099122 priority patent/WO2017097000A1/zh
Priority to US15/780,621 priority patent/US20180346675A1/en
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Abstract

热固性树脂组合物、包含其的预浸料、层压板和印制电路板。本发明涉及一种热固性树脂组合物，所述组合物包括热固性树脂、交联剂、促进剂和致孔剂，所述致孔剂为能够溶解于有机溶剂的致孔剂；所述有机溶剂为能够溶解热固性树脂的有机溶剂。本发明采用直接往树脂体系中添加可溶性致孔剂的方式，可以通过简单的工艺与低廉的成本使树脂基体均匀地布满孔径均一的微小孔洞，获得具有低介电常数、低介电损耗的高性能组合物，且该方法对众多的树脂体系均具有良好的适用性；由于体系中的孔洞尺寸达到纳米级别，该技术方案不会牺牲最终体系的力学强度、热学性能、吸水率等性能。

Description

热固性树脂组合物、包含其的预浸料、层压板和印制电路板
技术领域
本发明涉及一种热固性树脂组合物及其用途，具体涉及一种热固性树脂组合物及由该热固性树脂组合物得到的树脂胶液、预浸料、层压板以及印制电路板。
背景技术
随着电子产品向小型化、多功能化、高性能化及高可靠性方面的迅速发展，印制电路板开始朝着高精度、高密度、高性能、微孔化、薄型化和多层化方向迅猛发展，其应用范围越来越广泛，已从工业用大型电子计算机、通讯仪表、电气测量、国防及航空、航天等部门迅速进入到民用电器及其相关产品。随着电路集成密度的进一步提高，信号传输的速度及精度对于基体材料的介电性能提出了更高的要求。
为降低印制电路用基体材料的介电常数，目前常用的主要手段包括如下三种：
(1)如专利CN102206399A所采取的利用中空无机填料，通过往体系中引入一定份数的空气以达到降低介电常数的作用，但该技术路线因限于无机粉体与高分子树脂的界面结合能力较差，需要进行一定的表面化学修饰，从而增加了生产工序与生产成本；
(2)如专利CN103992620A所采取的添加微孔发泡剂的方法，虽然该方案可以通过较为廉价的技术路线较大幅度地降低体系的介电常数，但由于其采用的发泡剂不溶于常见的有机溶剂，在实际制备过程中容易聚集成团，从而树脂体系产生的微孔的粒径与分布均不可控，且其微孔粒径较大而易造成力学强度的大幅下降，并易造成CAF风险，无法满足印制电路的生产与应用要求；
(3)如专利CN1802407A所述的通过将易分解的二碳酸酯基团接枝于环氧树脂上，以达到对发泡区域及孔洞尺寸的精细控制，但是该技术路线对于树脂体系具有较高的选择性，且树脂的制备成本相应提升。
因此，开发出一种技术先进、工艺简单、成本低廉、空隙均一且微小的具有低介电常数、低介电损耗的高性能树脂组合物具有重要的现实意义。
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具有低介电常数及低介电损耗的热固性树脂组合物。
本发明所述热固性树脂组合物，包括热固性树脂、交联剂、促进剂和致孔剂，所述致孔剂为能够溶解于有机溶剂的致孔剂；
所述有机溶剂为能够溶解热固性树脂的有机溶剂。
通过加入能够溶解于有机溶剂的致孔剂，使其以分子水平分散到热固性树脂基体中而与高聚物形成均相体系，使得致孔剂以分子状态均匀分散于树脂体系中，当热固性树脂组合物在100℃以上发生交联固化反应时，致孔剂原位分解产生氮气、二氧化碳等小分子气体，最终使得热固性树脂体系中均匀分布有孔洞，且孔洞尺寸可至纳米级别而不影响材料的热学、力学性能。
本发明对有机溶剂的选择不做具体限定，能够溶解热固性树脂的有机溶剂均可用于本发明。
与常见的热塑性树脂用致孔剂如偶氮二甲酰胺相比，本发明所述的能够溶解于特定有机溶剂的致孔剂能够提高致孔剂的加工性，便于其在热固性树脂基体中达到分子级分散，达到区域分布均匀、孔径均一的致孔效果。
本发明所述有机溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、二氯甲烷、环己酮、丁酮、丙酮、乙醇、甲苯、二甲苯中的任意1种或至少2种的混合物。
本发明所述能够溶解致孔剂的有机溶剂典型但非限制性的组合包括N,N-二甲基甲酰胺和二甲基亚砜的组合，N-甲基-2-吡咯烷酮和丙酮的组合，丙二醇甲醚醋酸酯、乙酸乙酯和二甲苯的组合，N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和丁酮的组合，环己酮、丁酮、丙酮和N-甲基-2-吡咯烷酮的组合，和的组合，和的组合，丙二醇甲醚、丙二醇甲醚醋酸酯和环己酮的组合，N-甲基-2-吡咯烷酮、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸乙酯和二甲基亚砜的组合，乙酸乙酯、二氯甲烷、环己酮、丁酮和N,N-二甲基甲酰胺的组合等。
优选地，所述致孔剂选自偶氮类化合物、亚硝基类化合物、二碳酸酯类化合物、叠氮类化合物、肼类化合物、三唑类化合物、脲氨基类化合物中的任意1种或至少2种的组合。
本发明偶氮类化合物典型但非限制性的实例有偶氮苯、对羟基偶氮苯、4-甲胺基偶氮苯中的任意1种或至少2种的组合，所述组合典型但非限制性的实例有对羟基偶氮苯和4-甲胺基偶氮苯的组合，偶氮苯、对羟基偶氮苯和4-甲胺基偶氮苯的组合等。
本发明所述亚硝基类化合物典型但非限制性的实例有甲基苄基亚硝胺、二乙基亚硝胺吡咯烷亚硝胺、二丁基亚硝胺、二戊基亚硝胺、乙基二羟乙基亚硝胺、N,N-二亚硝基五亚甲基四胺中的任意1种或至少2种的组合，所述组合典型但非限制性的实例有N,N-二亚硝基五亚甲基四胺和二乙基亚硝胺的组合，吡咯烷亚硝胺和二戊基亚硝胺的组合，甲基苄基亚硝胺、二乙基亚硝胺和吡咯烷亚硝胺的组合，甲基苄基亚硝胺、二乙基亚硝胺和N,N-二亚硝基五亚甲基四胺的组合等。
本发明所述二碳酸酯类化合物典型但非限制性的实例有二碳酸辛酯、二碳酸二环己酯、二碳酸甲乙酯中的任意1种或至少2种的组合，所述组合典型但非限制性的实例有二碳酸二环己酯和二碳酸甲乙酯的组合，二碳酸辛酯、二碳酸二环己酯和二碳酸甲乙酯的组合等
本发明所述叠氮类化合物典型但非限制性的实例有芳基叠氮化合物、烷基叠氮化合物、酰基叠氮化合物、磺酰基叠氮化合物、磷酰基叠氮化合物。
本发明所述肼类化合物典型但非限制性的实例有磺酰肼类化合物，如苯磺酰肼(BSH)、对甲苯磺酰肼(TSH)、2,4-甲苯二磺酰肼、对(N-甲氧基甲酰氨基)苯磺酰肼中的任意1种或至少2种的组合，所述组合典型但非限制性的实例有苯磺酰肼和2,4-甲苯二磺酰肼的组合，对(N-甲氧基甲酰氨基)苯磺酰肼和2,4-甲苯二磺酰肼的组合，苯磺酰肼(BSH)、对甲苯磺酰肼(TSH)和对(N-甲氧基甲酰氨基)苯磺酰肼的组合等。
优选地，本发明所述致孔剂在100～190℃时能够分解放出气体。
选择100～190℃时分解放出气体的致孔剂，能够有效控制致孔的周期，起到稳定孔径的作用，进而获得孔径更加均一，分布更加均匀的孔洞。
本发明所述致孔剂分解放出气体的温度典型但非限制性的实例有110℃、120℃、130℃、142℃、148℃、155℃、163℃、168℃、175℃、182℃、188℃等。
优选亚硝基类化合物和/或叠氮类化合物，进一步优选叠氮类化合物，特别优选磺酰基叠氮化合物，最优选4-甲基苯磺酰叠氮。
优选地，所述的致孔剂为液体状的叠氮类化合物，叠氮类化合物的分解温度区间较宽，在覆铜板的整个层压加热过程中均可缓慢分解，可避免前期分解导致的孔洞坍塌和后期分解产生的内应力过大；另外，与偶氮类、亚硝基类等致孔剂相比，叠氮类化合物的分解键能低，分解过程中产生的热量较少，对基体树脂的反应历程影响较小，热性能影响不大。
当所述致孔剂为固态的亚硝基类化合物时，所述亚硝基类化合物为平均粒径为0.1～20μm，优选0.5μm、2μm、4μm、5μm、7μm、10μm、15μm等，的粉末状，优选为平均粒径为0.5～10μm的粉末状。
优选地，所述致孔剂在热固性树脂组合物的含量≤10wt％，例如1wt％、3wt％、4wt％、6wt％、7wt％、8wt％、9wt％等，优选2～8wt％，进一步优选2～5wt％。致孔剂含量过高影响热固性树脂的力学性能，导致机械性能降低。
作为优选技术方案，本发明所述热固性树脂组合物按重量百分数包括如下组分：
50～90wt％的热固性树脂、低于30wt％的交联剂、0～10wt％的促进剂和低于10wt％的致孔剂；所述组合物中各组分之和为100wt％。
优选地，所述热固性树脂组合物按重量百分数包括：50～70wt％的热固性树脂、10～30wt％的交联剂、3～10wt％的促进剂和3～10wt％的致孔剂；所述组合物中各组分之和为100wt％。
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”。不管所述热固性树脂组合物包含何种成分，所述热固性组合物的各组分占热固性树脂组合物的质量百分比之和为100％。
例如，所述热固性树脂组合物还可以含有各种添加剂和功能性填料，作为具体例，添加剂可以举出阻燃剂、偶联剂、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，功能性填料可以举出硅微粉、勃姆石、水滑石、氧化铝、炭黑、核壳橡胶等。这些各种添加剂或填料可以单独使用，也可以两种或者两种以上混合使用。
本发明所述的热固性树脂为可交联形成网状结构的聚合物中的任意1种或至少2种的组合，优选环氧树脂、酚醛树脂、氰酸酯树脂、聚酰胺树脂、聚酰亚胺树脂、聚醚树脂、聚酯树脂、烃树脂或有机硅树脂中的任意1种或至少2种的组合；进一步优选环氧树脂或酚醛树脂。
所述热固性树脂的组合的具体例可以是环氧树脂和聚酰胺树脂的组合，聚酰亚胺树脂和烃树脂的组合，氰酸酯树脂、聚酰胺树脂和聚醚树脂的组合，氰酸酯树脂、聚酰胺树脂、聚酰亚胺树脂和环氧树脂的组合等。
对于环氧树脂及其与其他树脂的组合，所述固化剂可为酚醛树脂、酸酐化合物、活性酯类化合物、双氰胺、二氨基二苯甲烷、二氨基二苯砜、二氨基二苯醚、以及马来酰亚胺中的一种或两种以上的混合物；所述固化促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、以及2-甲基-4-苯基咪唑中的一种或两种以上的混合物；
对于酚醛树脂及其与其他树脂的组合，所述的固化剂可为有机酸酐、有机胺、路易斯酸、有机酰胺、咪唑类化合物、有机膦化合物及其按任意比例混合而成的混合物。
对于烯烃树脂、含有两个或两个以上不饱和双键的可反应性聚苯醚树脂、聚酰胺树脂及其与其他树脂组合，所述的固化剂选自有机过氧化物交联剂，优选为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化二乙酰、过氧化特戊酸特丁酯和过氧化二碳酸二苯氧化酯中的一种或多种。所述促进剂为烯丙基类有机化合物，优选为三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、三羟甲基丙烷三甲基丙烯酸酯和三羟甲基丙烷三丙烯酸酯中的一种或多种。
对于有机硅树脂，所述的促进剂选自有机铂类化合物。
作为本发明热固性树脂组合物之一的制备方法，可以通过公知的方法配合、搅拌、混合所述的热固性树脂、交联剂、促进剂、致孔剂，以及各种添加剂及填料，来制备。
本发明目的之二是提供一种树脂胶液，所述树脂胶液通过将目的之一所述的热固性树脂组合物分散在溶剂中获得。
优选地，所述树脂胶液通过将权利要求1～6之一所述的热固性树脂组合物溶解在溶剂中获得。
优选地，所述溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、二氯甲烷、环己酮、丁酮、丙酮、乙醇、甲苯、二甲苯中的任意1种或至少2种的组合。
上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类溶剂混合使用。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
本发明目的之三是提供一种预浸料，所述预浸料包括增强材料，及通过浸渍干燥后附着在其上的如目的之一所述的热固性树脂组合物。
本发明目的之四是提供一种层压板，所述层压板含有至少一张如目的之三所述的预浸料。
本发明的目的之五是提供一种印制电路板，所述印制电路板含有至少一张如目的之四所述的层压板。
为达到此发明目的，本发明采用以下技术方案：
与现有技术相比，本发明具有以下有益效果：
(1)本发明采用直接往树脂体系中添加可溶性致孔剂的方式，可以通过简单的工艺与低廉的成本使树脂基体均匀地布满孔径均一的微小孔洞，获得具有低介电常数、低介电损耗高性能组合物，且该方法对众多的树脂体系均具有良好的适用性；由于体系中的孔洞尺寸达到纳米级别，该技术方案不会牺牲最终体系的力学强度、热学性能、吸水率等性能；
(2)作为优选的技术方案，选择100～190℃时分解放出气体的致孔剂，能够有效控制致孔的周期，起到稳定孔径的作用，进而获得孔径更加均一，分布更加均匀的孔洞。
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。
以下实施例及对比例中使用的各产品型号如下：
(1)DER530为陶氏化学产品，环氧当量为435；
(2)双氰胺为业内通用的环氧固化剂；
(3)2-甲基咪唑、2-苯基咪唑为业内通用的促进剂；
(4)4-甲基苯磺酰叠氮，阿拉丁试剂，液体状，溶于常见有机溶剂，分解温度为140℃；
(5)N,N-二亚硝基五亚甲基四胺，阿拉丁试剂，溶于丙酮，分解温度为170～190℃，平均粒径为2～4μm；
(6)偶氮二甲酰胺，阿拉丁试剂，不溶于常见有机溶剂，分解温度为160～195℃，平均粒径为2～4μm；
(7)碳酸氢铵，阿拉丁试剂，溶于水及常见有机溶剂，分解温度为36～60℃；
(8)PT-30为龙沙集团的苯酚酚醛型氰酸酯；
(9)溴化苯乙烯为雅宝生产；
(10)MX9000为Sabic公司的甲基丙烯酸甲酯改性聚苯醚；
(11)双官能团马来酰亚胺为K-Ichemical产；
(12)R100为苯乙烯-丁二烯共聚物，Samtomer产品；
(13)DCP为上海高桥产的过氧化二异丙苯；
(14)HP7200-H为DIC公司的双环戊二烯环氧；
(15)D125为四川东材产的苯并噁嗪树脂；
(16)EPONOL6635M65，线性酚醛树脂，韩国momentive公司产品。
实验组A(表1)
实施例1～3：将100份环氧树脂DER530、3份双氰胺、0.05份2-甲基咪唑、4-甲基苯磺酰叠氮(质量份数分别为1、5、10)溶于有机溶剂中，机械搅拌，配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料(prepreg)，两面放置铜箔，加压加热制成铜箔基板。
对比例1～2：实施方式与实施例1相同，区别点在于对比例1中致孔剂的用量为0份，对比例2中致孔剂的用量为12份。
实验组B(表2)
实施例4：将100份环氧树脂DER530、3份双氰胺、0.05份2-甲基咪唑、5份N,N-二亚硝基五亚甲基四胺溶于有机溶剂中，机械搅拌，配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料，两面放置铜箔，加压加热制成铜箔基板。
对比例3～4：各组分质量配比与加料方式等同实施例4，区别在于对比例3使用的致孔剂为偶氮二甲酰胺，对比例4使用的致孔剂为碳酸氢铵。
实验组C(表3)
实施例5：将100份环氧树脂DER530、24份酚醛树脂TD2090、0.05份2-甲基咪唑、5份可溶性致孔剂(4-甲基苯磺酰叠氮)溶于有机溶剂中，机械搅拌乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料，两面放置铜箔，加压加热制成铜箔基板。
实施例6：将20份苯酚酚醛型氰酸酯PT30、40份邻甲基苯酚酚醛型环氧树脂N695、20份溴化苯乙烯及适量的催化剂辛酸锌、2-苯基咪唑、5份可溶性致孔剂(4-甲基苯磺酰叠氮)溶于有机溶剂中，机械搅拌乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料，两面放置铜箔，加压加热制成铜箔基板。
实施例7：将溶于甲苯的70g重量份的乙烯基热固性聚苯醚MX9000、溶于N,N-二甲基甲酰胺的5重量份的K-Ichemical的双官能马来酰亚胺、25重量份的丁二烯-苯乙烯共聚物R100、3重量份的固化引发剂DCP、5份可溶性致孔剂(4-甲基苯磺酰叠氮)溶于有机溶剂，机械搅拌乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料，两面放置铜箔，加压加热制成铜箔基板。
实施例8：将30份双环戊二烯环氧HP-7200H、60份苯并噁嗪树脂D125、5份线性酚醛树脂EPONOL6635M65、5份双氰胺、5份可溶性致孔剂(4-甲基苯磺酰叠氮)溶于有机溶剂，机械搅拌乳化配制成65wt％的胶水，然后含浸玻璃纤维布，经过加热干燥后形成预浸料，两面放置铜箔，加压加热制成铜箔基板。
对比例5～8：对比例5～8的实施方式分别于实施例5～8对应，区别在与对比例5～8的配方体系中不含有可溶性发泡剂。
表1.致孔剂用量的影响
表2.致孔剂种类的影响
表3.热固性树脂体系的影响
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。
从表1的性能测试结果中可以看出，添加可溶性致孔剂的实施例由于体系内部形成了均匀分布的微孔与纳孔，其介电常数下降较为明显，且形成的微小孔洞能够阻止板材受压时裂纹的扩展而使弯曲强度、弯曲模量等性能有了一定的提升，拉伸性能、剥离强度及玻璃化转变温度基本不受影响。其中，可溶性致孔剂添加量为5wt％时，该体系具有较低的介电常数及损耗，最好的弯曲性能；随着致孔剂用量的进一步增加(对比例2)，板材的介电常数下降并不明显，但其玻璃化转变温度及机械性能下降较为严重，同时其分解产生的气泡使板材的剥离强度大幅下降，因此致孔剂的用量在1～10wt％为宜。
从表2性能测试结果看出，实施例2具有最好的综合性能，这主要是由于4-甲基苯磺酰叠氮的分解温度位于常见覆铜板的生产工艺温度区间，且在常温下为液体，能够与环氧树脂形成均相体系，致孔剂得以以分子级分散到整个配方体系中，其孔径达到纳米级别且具有整板均匀性；实施例5使用的致孔剂为N,N-二亚硝基五亚甲基四胺，其分解温度在170℃以上，在室温下能够溶于丙酮等溶剂，亦能良好地分散于整个环氧配方体系，致孔效果较好；对比例3使用的致孔剂为偶氮二甲酰胺，其分解温度为160℃以上，但不溶于常见的有机溶剂，无法良好地分散于整个配方体系，实验考察发现其致孔的区域分布不均匀，且孔径尺度达到20微米以上，其板材的玻璃化转变温度、剥离强度、机械强度下降十分严重，无法满足覆铜板的可靠性及PCB加工要求；对比例4使用的致孔剂为碳酸氢铵，其分解温度为40℃左右，在上胶工艺过程中，该致孔剂已经完全分解，无法达到降低介电常数的作用。
另一方面，从表3性能测试结果看出，可溶性的高温致孔剂在不同的热固性树脂体系(实施例5与对比例5为酚醛固化环氧体系、实施例6与对比例6为氰酸酯-环氧体系、实施例7与对比例7为聚苯醚体系、实施例8与对比例8为环氧-苯并噁嗪体系)均具有降低介电常数，同时不降低玻璃化转变温度、剥离强度及拉伸强度等性能，且可使板材的弯曲性能得到一定提升。
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用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 (10)

1.一种热固性树脂组合物，所述组合物包括热固性树脂、交联剂、促进剂和致孔剂，其特征在于，所述致孔剂为能够溶解于有机溶剂的致孔剂。
2.如权利要求1所述的组合物，其特征在于，所述有机溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、二氯甲烷、环己酮、丁酮、丙酮、乙醇、甲苯、二甲苯中的任意1种或至少2种的混合物。
3.如权利要求1或2所述的组合物，其特征在于，所述致孔剂选自偶氮类化合物、亚硝基类化合物、二碳酸酯类化合物、叠氮类化合物、肼类化合物化合物中的任意1种或至少2种的组合；
优选地，所述亚硝基类化合物为平均粒径为0.1～50μm的粉末状，优选为平均粒径为0.5～20μm的粉末状；
优选地，所述致孔剂在热固性树脂组合物的含量≤10wt％，优选2～8wt％，进一步优选3～5wt％。
4.如权利要求1～3之一所述的组合物，其特征在于，所述致孔剂在100～190℃时能够分解放出气体；
优选地，所述致孔剂为亚硝基类化合物和/或叠氮类化合物，进一步优选叠氮类化合物，特别优选磺酰基叠氮化合物，最优选4-甲基苯磺酰叠氮。
5.如权利要求1～4之一所述的组合物，其特征在于，所述组合物按重量百分数包括如下组分：
50～90wt％的热固性树脂、低于30wt％的交联剂、0.1～10wt％的促进剂和低于10wt％的致孔剂；所述组合物中各组分之和为100wt％；
优选地，所述组合物按重量百分数包括：50～70wt％的热固性树脂、10～30wt％的交联剂、3～10wt％的促进剂和3～10wt％的致孔剂；所述组合物中各组分之和为100wt％。
6.如权利要求1～5之一所述的组合物，其特征在于，所述的热固性树脂为可交联形成网状结构的聚合物中的任意1种或至少2种的组合，优选环氧树脂、酚醛树脂、氰酸酯树脂、聚酰胺树脂、聚酰亚胺树脂、聚醚树脂、聚酯树脂、烃树脂、苯并噁嗪树脂或有机硅树脂中的任意1种或至少2种的组合；进一步优选环氧树脂或酚醛树脂。
7.一种树脂胶液，其特征在于，所述树脂胶液通过将权利要求1～6之一所述的热固性树脂组合物分散在溶剂中获得；
优选地，所述树脂胶液通过将权利要求1～6之一所述的热固性树脂组合物溶解在溶剂中获得；
优选地，所述溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、二氯甲烷、环己酮、丁酮、丙酮、乙醇、甲苯、二甲苯中的任意1种或至少2种的组合。
8.一种预浸料，其特征在于，所述预浸料包括增强材料，及通过浸渍干燥后附着在其上的如权利要求1-8之一所述的热固性树脂组合物。
9.一种层压板，其特征在于，所述层压板含有至少一张如权利要求8所述的预浸料。
10.一种印制电路板，其特征在于，所述印制电路板含有至少一张如权利要求9所述的层压板。
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CN106674602A (zh) * 2016-12-20 2017-05-17 广东生益科技股份有限公司 一种包覆型填料浆料组合物的制备方法、包含该浆料组合物的预浸料、层压板和印刷电路板
WO2017097000A1 (zh) * 2015-12-07 2017-06-15 广东生益科技股份有限公司 热固性树脂组合物、包含其的预浸料、层压板和印制电路板
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