CN106854361A - 一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板 - Google Patents

一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板 Download PDF

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Publication number
CN106854361A
CN106854361A CN201611262943.7A CN201611262943A CN106854361A CN 106854361 A CN106854361 A CN 106854361A CN 201611262943 A CN201611262943 A CN 201611262943A CN 106854361 A CN106854361 A CN 106854361A
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China
Prior art keywords
epoxy resin
benzoxazine
resin
weight portions
resin combination
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CN201611262943.7A
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CN106854361B (zh
Inventor
奚龙
李江
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 CN201611262943.7A priority Critical patent/CN106854361B/zh
Priority to KR1020177023341A priority patent/KR101963070B1/ko
Priority to PCT/CN2017/078496 priority patent/WO2018120471A1/zh
Priority to US15/736,887 priority patent/US10513608B2/en
Priority to TW106116372A priority patent/TWI628223B/zh
Publication of CN106854361A publication Critical patent/CN106854361A/zh
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Abstract

本发明涉及一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板，所述含有苯并噁嗪的树脂组合物的制备方法为：向含有苯并噁嗪的树脂组合物中添加酸性填料；所述含有苯并噁嗪的树脂组合物中含有苯并噁嗪树脂以及环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。

Description

一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预 浸料和层压板
技术领域
本发明涉及覆铜板技术领域，尤其涉及一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板。
背景技术
在电子材料行业，为实现无溴阻燃，业内通常采用含磷的树脂或阻燃剂，配合含氮的树脂或阻燃剂实现磷-溴协同高效阻燃。苯并噁嗪树脂中含有氮元素，与磷元素复配使用时，可以较低的磷含量实现UL 94的V-0等级。加之固化收缩率低，耐湿热性能佳，得到了广泛使用。然而，由于苯并噁嗪树脂结构特点，苯并噁嗪的开环聚合需要较高的温度，为工业化批量生产带来了困难，成为了其应用的难点。
业内学者对上述难题进行了很多研究，其工作主要集中在胺类固化剂，酚醛树脂，有机酸等物质对苯并噁嗪反应的影响和机理探讨。对于印制电路基板(覆铜板，copperclad laminate)行业而言，这些研究成果很难直接进行转化应用。原因在于：胺类固化剂耐热性不佳，制成的半成品储存期限较短；酚醛树脂虽然耐热性较好，介电性能较差，剥离强度较低；有机酸对苯并噁嗪的开环作用明显，在覆铜板生产过程中，最高超过200℃的烘箱温度促使低沸点酸挥发完毕，在压合制程无法催化苯并噁嗪的开环和聚合。而高沸点有机酸则会在树脂组合物中残留，在制作过程中增加了PCB板受热分层爆板的风险。因此，对于苯并噁嗪树脂的应用，一直存在难题。
发明内容
基于此，本发明的目的之一在于提供含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板。通过在含有苯并噁嗪的树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；使用该添加有酸性填料的组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过将酸性填料与含有苯并噁嗪的树脂组合物适当混合从而进行树脂组合物的制备，可达到上述目的。
为了实现上述目的，本发明采用了如下技术方案：
一种含有苯并噁嗪的树脂组合物的制备方法，所述方法为：
向含有苯并噁嗪的树脂组合物中添加酸性填料，酸性填料的pH值在2～6之间；
所述含有苯并噁嗪的树脂组合物中含有环氧树脂和苯并噁嗪树脂；
所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本发明中通过向含有苯并噁嗪的树脂组合物中添加酸性填料，可以催化苯并噁嗪和环氧树脂的开环聚合反应，又能促进苯并噁嗪自身交联聚合，极大地降低了苯并噁嗪和环氧聚合所需的温度；另外，酸性填料的熔点可高达1000℃以上，在覆铜板生产过程中受热不会挥发，在PCB加工中也不会分解，解决了有机酸和普通无机酸在树脂中的弱点；再有，酸性填料在树脂组合物中还能降低制品的CTE，其在树脂组合物中保留下来对制品的可靠性有益。
本发明还采用了不同结构和不同环氧当量的环氧树脂进行配合使用，其在保证树脂组合物具有较高玻璃化转变温度，较好的力学性能，较低吸水率的同时，还改善了树脂组合物机械加工性差的难题。
根据本发明，所述酸性填料的pH值在2～6之间，例如2、2.5、3、3.5、4、5或6，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述酸性填料的特征是：将该填料与去离子水按1:9的质量比配制成水溶液，对其进行测定从而得到该填料的pH值在2～6之间。
优选地，所述酸性填料的pH值在4～6之间。
根据本发明，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为硅微粉和石英粉、黏土和草酸钙、炭黑和云母粉。
本发明中，所述酸性填料的粒径在50nm～50μm之间，例如50nm、60nm、70nm、80nm、90nm、100nm、300nm、500nm、800nm、5μm、10μm、30μm、40μm、45μm或50μm，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
对于所述酸性填料的物理形态，本发明不做特殊限定，例如可以是片材、棒状、球形、空心球形、粒状、纤维状或板状等；也可以选择性以硅烷偶联剂对酸性填料进行处理。
根据本发明，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，例如0.05重量份、0.1重量份、1重量份、10重量份、20重量份、30重量份、40重量份、55重量份、60重量份、65重量份、70重量份、80重量份、90重量份或100重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～60重量份。
本发明采用酸性填料的添加量为5～60作为优选方式，经发明人研究发现，若所述填料使用量超过60重量份，树脂组合物整体酸性较强，苯并噁嗪-环氧体系的开环聚合反应明显加快，会使得树脂组合物的加工工艺窗口变窄；若所述酸性填料使用量低于5份，树脂组合物整体酸性较弱，对苯并噁嗪-环氧体系的催化作用不明显。
根据本发明，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
(A)环氧树脂：5～80重量份；
(B)苯并噁嗪树脂：10～80重量份；
(C)阻燃剂：1～30重量份；
所述环氧树脂中，环氧树脂A1和A2的重量比为10:1～1:10，例如10:1、10:2、10:3、10:4、10:5、10:6、10:7、10:8、10:9、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9或1:10，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选4:1～1:4。
本发明中，所述环氧树脂的添加量为5～80重量份，例如5重量份、7重量份、10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为20～80重量份。
根据本发明，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本发明通过采用不同环氧当量的环氧树脂进行组合，其不仅保证了树脂组合物具有较高的玻璃化转变温度、较好的力学性能和较低的吸水率，同时还改善了树脂组合物机械性差的问题。
本发明中，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于150～450之间；其中典型但非限制性的混合物为：联苯环氧树脂和双环戊二烯环氧树脂、双环戊二烯环氧树脂和含萘环氧树脂、含萘环氧树脂和含蒽环氧树脂；所述环氧当量例如可以是150、180、192、200、210、250、315、380、400或450，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间；其中典型但非限制性的混合物为：双酚A环氧树脂和羧基丁腈橡胶改性环氧树脂、羧基丁腈橡胶改性环氧树脂和含有噁唑烷酮环的环氧树脂；所述环氧当量例如可以是451、455、480、492、500、610、720、810、861、900或1000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中通过环氧树脂的选择搭配，以及酸性填料对苯并噁嗪开环聚合反应的引导和控制，其相互之间产生协同作用，有助于实现较稳定的剥离强度，提升树脂组合物的可靠性。
根据本发明，所述苯并噁嗪树脂的添加量为10～80重量份，例如10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为30～65重量份。
本发明中，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：双酚A型苯并噁嗪树脂和双环戊二烯型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂和双酚F型苯并噁嗪树脂、双酚F型苯并噁嗪树脂和酚酞型苯并噁嗪树脂。
所述双酚A型苯并噁嗪树脂单体和双酚F型苯并噁嗪树脂单体、酚酞型苯并噁嗪树脂单体的结构如式(α)所示：
其中，R3为R4为-CH2-或中的任意1种。
当R4为时，结构式(α)为双酚A型苯并噁嗪树脂单体；当R4为-CH2-时，结构式(α)为双酚F型苯并噁嗪树脂单体；当R4为时，结构式(α)为酚酞型苯并噁嗪树脂单体。
所述MDA型苯并噁嗪树脂，又称(4,4’-二胺基二苯甲烷)型苯并噁嗪树脂，其结构如式(β)所示：
所述双环戊二烯苯并噁嗪树脂单体的结构式如(γ)所示：
根据本发明，所述阻燃剂的添加量为1～30重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份或30重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为3～20重量份。
本发明中，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：间苯二酚-双(磷酸二苯酯)和双酚A-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)和间苯二酚-双(2,6-二甲苯基磷酸酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)和甲基磷酸二甲酯、甲基磷酸二甲酯和磷腈化合物。
本发明中，所述含有苯并噁嗪的树脂组合物中还含有环氧当量大于1000的环氧树脂，其具体种类在此不做特殊限定。
优选地，所述含有苯并噁嗪的树脂组合物中还可以含有非酸性填料。
优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：碳酸钙和硫酸钙、氧化铝和硫酸钡、陶瓷粉和水滑石。
优选地，以有机固形物为100重量份计，所述非酸性填料的添加量为0～100重量份，例如1重量份、5重量份、12重量份、15重量份、24重量份、35重量份、48重量份、56重量份、78重量份、89份或100重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有(D)固化促进剂，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份，例如0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、0.9重量份或1重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述固化促进剂选自咪唑类促进剂及其衍生物，吡啶类促进剂，路易斯酸类促进剂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为咪唑类促进金和吡啶类促进剂、吡啶类促进剂和路易斯酸类促进剂、咪唑类促进剂和路易斯酸类促进剂。
优选地，所述咪唑类促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
所述固化促进剂有益于环氧树脂和苯并噁嗪树脂以及固化剂进行固化反应，形成均匀的三维网状分子结构，达到较佳的物性。并能促进羟基(-OH)和环氧基等基团浓度的下降，帮助树脂组合物实现较佳的介电性能，降低介电常数和介电损耗。
本发明的目的之二在于提供了一种含有苯并噁嗪的树脂组合物，其含有环氧树脂、苯并噁嗪树脂和酸性填料，所述酸性填料的pH值在2～6之间，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本领域技术人员可以明了，所述含有苯并噁嗪的树脂组合物中除了包含环氧树脂、苯并噁嗪树脂和酸性填料外，还可以任选地含有本发明目的之一所述的阻燃剂、环氧当量大于1000的环氧树脂、非酸性填料、固化促进剂等组分，且所述树脂组合物中含有的各个组分和含量均可示例性地参考本发明目的之一所述的范围。
本发明所述的“含有”，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“含有”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述含有苯并噁嗪的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。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。
对于本发明中未进一步限定的含有苯并噁嗪的树脂组合物的制备步骤，本领域技术人员可以参考现有的树脂组合物的制备方法，结合实际情况进行选择，本发明不做特殊限定。
本发明还提供了一种预浸料，其含有根据本发明目的之一所述方法制备得到的树脂组合物或目的之二所述的树脂组合物，以及增强材料；所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。将增强材料通过含浸上述的复合材料，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印刷电路板用覆铜箔层压板包括通过加热和加压，使两片或两片以上的预浸料粘合在一起而制成的层压板、粘合在层压板的一面或两面以上的铜箔；所述的覆铜箔层压需满足以下要求：1、层压的升温速率通常在料温80-160℃时的升温速度应控制在1.0～3.0℃/min；2、层压的压力设置，外层料温在80～100℃时施加满压，满压压力为300psi左右；3、固化时，控制料温在185℃，并保温90min；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；
(2)本发明通过使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数；
(3)本发明通过采用不同结构和不同环氧当量的环氧树脂进行配合，不仅保证了树脂组合物具有较高玻璃化转变温度，较好的力学性能和较低吸水率，还进一步改善了树脂组合物机械加工性差的难题；
(4)本发明通过对环氧树脂的选择搭配以及酸性填料的添加，其相互间可产生协同增效作用，从而有助于实现较稳定的剥离强度，提升树脂组合物的可靠性。
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。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
下文中如无特别说明，其份代表重量份，其％代表“重量％”。
实施例和对比例涉及的材料及牌号信息如下：
(A)环氧树脂：
A1：购于日本化药的型号为NC-3000H的联苯型环氧树脂，环氧当量288；
A2：购于日本化药的型号为EPPN-501H的酚醛环氧树脂，环氧当量166；
A3：购于上海势越的型号为KF21的双酚F型环氧树脂，环氧当量540；
A4：购于长春树脂的型号为BE504ELM65的双酚A型环氧树脂，环氧当量890；
A5：选自新日铁化学型号为YDF-2004的环氧树脂，环氧当量1005；
(B)苯并噁嗪树脂：
B1：购于亨斯迈的型号为LZ8290H62的产品；
B2：购于东材科技型号为D125的产品；
(C)阻燃剂
C1：购于日本大塚化学株式会社的型号为SPB-100的产品；
C2：购于日本大八化学的型号为PX-200的产品；
(D)填料
D1：购于江苏联瑞的球形二氧化硅DQ-1030，pH＝4.0；
D2：购于江苏联瑞的球形二氧化硅DQ-1028L，pH＝5.8；
D3：购于梧州颖丰矿业型号为3000目气流石英粉，pH＝3.0；
D4：购于安徽格锐云母粉GD-2，pH＝5.0；
D5：购于天津星龙泰化工产品科技有限公司的炭黑，pH＝3.0；
D6：购于蚌埠鑫源的勃姆石BG-615，pH＝6.8；
D7：购于矽比科的二氧化硅MEGASIL525，pH＝6.5；
D8：购于日本admatechs球形硅微粉SC2500-SEJ，pH＝8.0；
(E)固化促进剂
E1：购于日本四国化成的2-苯基咪唑。
将实施例和对比例提供的树脂组合物，按照如下方法制备印制电路用层压板，并对制备得到的层压板进行性能测试。
所述印制电路用层压板的制备方法包括：
①通过加热和加压作用使一张或一张以上的预浸料粘合在一起，制成的层压板；
②在步骤①制得的层压板的一面或两面上粘合金属箔；
③在层压机中进行层压；
在步骤②的过程中，使用8片预浸料和2片一盎司(35μm厚)的金属箔叠合在一起；
在步骤③的过程中，层压的操作条件为：料温80～140℃时，控制升温速率为1.5～2.5℃/min；外层料温80-100℃时，施加满压，满压压力为350psi左右；固化时，控制料温在195℃，并保温60min以上。
实施例和对比例提供的树脂组合物的配方及性能测试结果见表1～4。
表1
表2
表3
表4
性能测试的项目及具体方法为：
(a)玻璃化转变温度：
根据差示扫描量热法，按照IPC-TM-650中2.4.25所规定的DSC方法进行测定。
(b)耐燃烧性：
依据UL94法测定。
(c)吸水性：
按照IPC-TM-650中的2.6.2.1所规定的方法进行测定。
(d)胶水GT
测试温度174℃。
(e)树脂DSC反应曲线测试：
仪器商：美国TA。N2环境，升温速率10℃/min。
(f)剥离强度：
按照IPC-TM-650中的2.4.8所规定的方法进行测定。
(g)热膨胀系数：
按照IPC-TM-650中的2.4.24所规定的方法进行测定。
物性分析：
(1)从表1～4可以看出，将实施例1与对比例1进行比较，实施例1中添加酸性填料后，相比对比例1中未添加酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，剥离强度更高。
将实施例2与对比例2-4进行比较，实施例2中添加pH值在4.0的酸性填料后，相比对比例2-3中添加pH值大于6.0的酸性填料以及对比例4中添加非酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，剥离强度更高。
将实施例2与对比例7进行比较，实施例2中添加酸性填料后，相比对比例7未添加酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，剥离强度更高。
通过上述实施例1-2和对比例1-4和7可以看出，本发明通过添加pH在2～6之间的酸性填料，相比其他pH值范围的填料，可以使树脂DSC起始温度和峰值温度都较低，并使板材具有更优异的性能。
(2)从表1～4还可以看出，将实施例2与对比例8-10进行比较，实施例2中添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比例8和10仅添加环氧当量介于150～450之间的环氧树脂时，其吸水率更低，具有更优异的剥离强度；相比对比例9中仅添加环氧当量介于451～1000之间的环氧树脂时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，能达到V-0级阻燃，耐浸焊时间较长，吸水率较低，具有更优异的剥离强度。
将实施例4与对比例5-6进行比较，实施例4中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比例5中添加两种环氧当量介于150～450之间的环氧树脂，其具有更优异的耐浸焊性，吸水率低并且剥离强度更高；相比对比例6中添加两种环氧当量介于451～1000之间的环氧树脂，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，具有更优异的剥离强度。
将实施例8与对比例11-13进行比较，实施例8中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比例11中添加环氧当量大于1000的环氧树脂，其树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，吸水率较低；相比对比例12采用环氧当量介于150～450之间的环氧树脂和环氧当量大于1000的环氧树脂以及对比例13采用环氧当量介于451～1000之间的环氧树脂和环氧当量大于1000的环氧树脂，其树脂DSC起始温度和峰值温度都较低，玻璃化转变温度较高，吸水率较低。
通过上述实施例2、4和8与对比例5-6和对比例8-13可以看出，本发明中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，这两种环氧树脂之间具有协同增效作用，其共同作用使得板材具有更优异的性能。
(3)通过实施例1和3与实施例6和9进行比较可以看出，当实施例1和3中将环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂的重量比控制在4:1～1:4范围内时，相比实施例6和9中将两者范围控制在该范围之外时，其制得的板材具有更高的玻璃化转变温度。
通过上述实施例可以看出，本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；本发明通过使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数；同时，本发明通过采用不同结构和不同环氧当量的环氧树脂进行配合，不仅保证了树脂组合物具有较高玻璃化转变温度，较好的力学性能和较低吸水率，还进一步改善了树脂组合物机械加工性差的难题；本发明通过对环氧树脂的选择搭配以及酸性填料的添加，其相互间可产生协同增效作用，从而有助于实现较稳定的剥离强度，提升树脂组合物的可靠性。
应该注意到并理解，在不脱离后附的权利要求所要求的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案的范围不受所给出的任何特定示范教导的限制。
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 (10)

1.一种含有苯并噁嗪的树脂组合物的制备方法，其特征在于，所述方法为：
向含有苯并噁嗪的树脂组合物中添加酸性填料，酸性填料的pH值在2～6之间；
所述含有苯并噁嗪的树脂组合物中含有环氧树脂和苯并噁嗪树脂；
所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
2.如权利要求1所述的方法，其特征在于，所述酸性填料的pH值在4～6之间；
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，优选5～60重量份；
优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
优选地，所述酸性填料的粒径为50nm～50μm。
3.如权利要求1或2所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
(A)环氧树脂：5～80重量份；
(B)苯并噁嗪树脂：10～80重量份；
(C)阻燃剂：1～30重量份；
所述环氧树脂中，环氧树脂A1和A2的重量比为10:1～1:10，优选4:1～1:4。
4.如权利要求3所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，环氧树脂的含量为20～80重量份；
优选地，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于150～450之间；
优选地，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间。
5.如权利要求3或4所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，苯并噁嗪树脂的含量为30～65重量份；
优选地，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物。
6.如权利要求3-5之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，阻燃剂的含量为3～20重量份；
优选地，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物。
7.如权利要求3-6之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中还含有环氧当量大于1000的环氧树脂；
优选地，所述含有苯并噁嗪的树脂组合物中还含有非酸性填料；
优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
优选地，以有机固形物为100重量份计，所述非酸性填料的添加量为0～100重量份；
优选地，所述含有苯并噁嗪的树脂组合物中还含有(D)固化促进剂；
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份；
优选地，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物。
8.一种如权利要求1-7之一所述的方法制备的含有苯并噁嗪的树脂组合物，其特征在于，
所述含有苯并噁嗪的树脂组合物中含有环氧树脂、苯并噁嗪树脂和酸性填料，所述酸性填料的pH值在2～6之间，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2；
优选地，所述酸性填料的pH值在4～6之间；
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，优选5～60重量份；
优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
优选地，所述酸性填料的粒径为50nm～50μm；
优选地，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
(A)环氧树脂：5～80重量份；
(B)苯并噁嗪树脂：10～80重量份；
(C)阻燃剂：1～30重量份；
以及，酸性填料的添加量为0.05～100重量份；
所述环氧树脂中，环氧树脂A1和A2的重量比为10:1～1:10，优选为4:1～1:4；
优选地，所述环氧树脂的含量为20～80重量份；
优选地，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于150～450之间；
优选地，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间；
优选地，所述苯并噁嗪树脂的含量为30～65重量份；
优选地，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA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，所述阻燃剂的含量为3～20重量份；
优选地，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物；
优选地，所述含有苯并噁嗪的树脂组合物还包含环氧当量大于1000的环氧树脂；
优选地，所述含有苯并噁嗪的树脂组合物中还含有非酸性填料；
优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
优选地，以有机固形物为100重量份计，非酸性填料的添加量为0～100重量份；
优选地，所述含有苯并噁嗪的树脂组合物中还含有(D)固化促进剂；
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份；
优选地，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物。
9.一种预浸料，其含有根据权利要求1-7之一所述的方法制得的树脂组合物或含有根据权利要求8所述的树脂组合物。
10.一种层压板或印制电路板，其包括至少1张如权利要求9所述的预浸料。
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CN105542394A (zh) * 2015-12-23 2016-05-04 陕西生益科技有限公司 一种无卤树脂组合物及其应用

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CN107353594A (zh) * 2017-07-24 2017-11-17 无锡南理工科技发展有限公司 一种可固化树脂共混组合物及其应用
US10246588B1 (en) 2017-09-18 2019-04-02 Taiwan Union Technology Corporation Solvent-free resin composition and uses of the same
TWI656172B (zh) * 2017-09-18 2019-04-11 台燿科技股份有限公司 無溶劑之樹脂組合物及其應用
CN109161194A (zh) * 2018-08-17 2019-01-08 巢湖市翔宇渔具有限公司 一种钓竿用高强韧性复合材料
CN110845823A (zh) * 2018-08-21 2020-02-28 平高集团有限公司 一种苯并噁嗪改性环氧树脂绝缘材料、环氧浇注绝缘部件及其制备方法
CN110845823B (zh) * 2018-08-21 2022-06-14 平高集团有限公司 一种苯并噁嗪改性环氧树脂绝缘材料、环氧浇注绝缘部件及其制备方法
CN113248865A (zh) * 2021-05-10 2021-08-13 泰安市中研复合材料科技有限公司 一种可快速固化的苯并噁嗪树脂体系和一种复合材料
CN113248865B (zh) * 2021-05-10 2023-10-27 泰安市中研复合材料科技有限公司 一种可快速固化的苯并噁嗪树脂体系和一种复合材料

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