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CN111138636A - 一种树脂组合物、预浸料及层压板 - Google Patents

一种树脂组合物、预浸料及层压板 Download PDF

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CN111138636A
CN111138636A CN201911403407.8A CN201911403407A CN111138636A CN 111138636 A CN111138636 A CN 111138636A CN 201911403407 A CN201911403407 A CN 201911403407A CN 111138636 A CN111138636 A CN 111138636A
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curing agent
parts
resin composition
epoxy resin
bisphenol
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洪机剑
陈华刚
沈泉锦
何小玲
陈文泉
傅楚娴
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Hangzhou juehao Technology Co.,Ltd.
HANGZHOU LESON INSULATION Co.,Ltd.
ZHEJIANG HUAZHENG NEW MATERIAL GROUP Co.,Ltd.
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Hangzhou Leson Insulation Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Abstract

本发明公开了一种树脂组合物、预浸料及层压板。本发明的树脂组合物包括环氧树脂、第一固化剂、第二固化剂和第三固化剂，其中，所述第一固化剂为潜伏性固化剂，所述第二固化剂为咪唑类固化剂，所述第三固化剂为叔胺类固化剂。本发明的树脂组合物制备的预浸料具有中高温快速固化，常温贮存时间长等优点。本发明的层压板力学和热学性能较好，且提高了整个工艺的生产效率，节约了工艺成本。

Description

一种树脂组合物、预浸料及层压板
技术领域
本发明属于高分子树脂组合物技术领域，特别是涉及一种树脂组合物、预浸料及层压板。
背景技术
环氧树脂具备力学性能高、粘接性能优异、固化收缩率小、工艺性能优以及稳定性好等特点，是复合材料领域主要运用的热固性塑料之一。利用玻璃纤维布浸渍环氧树脂胶液制备高强度复合材料的工艺过程一般包括树脂组合物调配、涂覆胶水烘干制成预浸料、预浸料叠配热压。因此要求制成的预浸料具备适中的加工温度，较快的固化速率，常温贮存稳定性好，适应加工成型工艺。
但目前市场上环氧树脂组合物/预浸料产品一般需要高温固化，并且固化时间长，需要消耗大量资源成本的同时无法提升生产效率；而已有的满足快速固化的产品常温下反应过快，保质期一般在1周内，无法长期存放，或者需要另进行冰库存放。目前，几乎没有可以同时满足快固化速率和贮存稳定性要求的相关产品。如CN110256812A公开的中温快速固化无卤阻燃配方可满足130-150℃小于30min固化完全，但常温操作期只能7天。CN106589823A公开的液体环氧树脂组合物可以在120℃条件下15min完全固化，但只能在冷藏(4℃)条件下才能贮存一周。
因此，基于现有技术存在的缺陷，本发明开发了一种树脂组合物、预浸料及层压板。本发明的树脂组合物制备的预浸料满足中高温快速固化(具体150-160℃，小于20min)，并且常温贮存在1个月以上。
发明内容
本发明的目的是弥补现有技术的不足，提供一种树脂组合物、预浸料及层压板。本发明的树脂组合物添加了三种不同性质的固化剂，其制备的预浸料具有中高温快速固化，常温贮存时间长，生产效率高，成本低等优点。
本发明提供一种树脂组合物，所述树脂组合物包括环氧树脂、第一固化剂、第二固化剂和第三固化剂，其中，所述第一固化剂为潜伏性固化剂，所述第二固化剂为咪唑类固化剂，所述第三固化剂为叔胺类固化剂。
优选的，所述树脂组合物中各组分重量配比如下：环氧树脂100重量份，第一固化剂1-60重量份，第二固化剂0.1-3重量份，第三固化剂0.1-3重量份，且第二固化剂+第三固化剂0.2-5重量份。
本发明树脂组合物各组分的配比对树脂组合物在层压板中的应用具有重要影响，尤其是三种固化剂的重量配比，如果三种固化剂的重量配比超过上述记载的范围，会导致层压板在成型有缺陷或不能成型，如果三种固化剂的种类配比低于上述记载的范围，会导致层压板的力学和热学性能下降。
优选的，所述环氧树脂选自双酚A型环氧树脂，双酚F型环氧树脂、双酚S型环氧树脂和酚醛环氧树脂中的一种或多种；更优选的，所述环氧树脂选自双酚A性环氧树脂、双酚F型环氧树脂和酚醛环氧树脂中的一种或多种。
优选的，所述第一固化剂选自胺类固化剂、酚醛类固化剂、酸酐类固化剂和三氟化硼-胺络合物中的一种或多种；更优选的，所述第一固化剂选自双氰胺、二氨基二苯砜、二氨基二苯胺、有机酸酰肼、线性苯酚甲醛树脂、线性双酚A甲醛树脂、线性邻甲酚甲醛树脂、四氢苯二甲酸酐和六氢苯二甲酸酐中的一种或多种。
优选的，所述第二固化剂选自咪唑及其改性物质，且其分子结构中叔胺当量在80-500之间；更优选的，所述第二固化剂为咪唑类固化剂，包括咪唑及其改性物质，其要求为分子结构中叔胺当量在80-500之间，其中优选2-甲基咪唑(2MZ)，2一乙基咪唑(2-EI)，2-乙基-4甲基咪唑(2E4MZ)，2-十一烷基咪唑(C11Z)，2-十七烷基咪唑(C17Z)，2-苯基咪唑(2PZ)，1-苄基-2甲基咪唑(1B2MZ)中的一种或多种。
优选的，所述第三固化剂为叔胺类固化剂，包括改性咪唑和其他类叔胺物质，其要求为分子结构中叔胺当量在25-78之间，其中优选咪唑，1,2-二甲基咪唑，N-酰基咪唑，吡啶，4-二甲氨基吡啶，四甲基乙二胺中的一种或多种。
优选的，所述树脂组合物还包括有机溶剂，所述有机溶剂20-120重量份；所述有机溶剂选自醇类、酮类、醚类、酰胺类和苯类溶剂中的一种或多种；更优选的，所述有机溶剂选自N,N-二甲基甲酰胺、丁酮、乙醇、丙二醇甲醚、乙二醇单甲醚和甲苯中的一种或多种。
优选的，所述树脂组合物还包括无机填料、分散剂和偶联剂，所述无机填料10-80重量份，分散剂0.01-1重量份，偶联剂0.1-2重量份。
优选的，所述无机填料选自含硅类、含钛类、含钙类、含铝类、含镁类无机化合物中的一种或多种；更优选的，所述无机填料选自二氧化硅、钛白粉、氧化铝、滑石粉、高岭土和氢氧化铝中的一种或多种。
优选的，所述分散剂选自脂肪酸类、脂肪族酰胺类和脂类分散剂中的一种或多种；更优选的，所述分散剂选自脂肪酸类和脂类分散剂的一种或两种。
优选的，所述偶联剂包括硅烷偶联剂，所述硅烷偶联剂的化学通式为RSiX3，式中R代表氨基、巯基、乙烯基、环氧基、氰基或甲基丙烯酰氧基，X代表能够水解的烷氧基；更优选的，所述X代表甲氧基、乙氧基。
本发明还提供一种预浸料，所述预浸料包括增强材料以及通过涂覆干燥后附着在其上的上述树脂组合物。
本发明还提供一种层压板，其包括将叠置的预浸料置于两片不锈钢板之间，还包括在所述预浸料与不锈钢板接触的表面覆一层离型膜。
本发明具有以下技术特点：
1)本发明在树脂组合物中同时添加三种固化剂，潜伏性固化剂，咪唑类固化剂和叔胺类固化剂，通过三种固化剂的复配使用，不仅能够使树脂组合物制备的预浸料能够在中高温条件(150-160℃)下快速固化(小于20min)，而且在常温下能够贮存1个月以上。
2)本发明的层压板力学和热学性能较好(弯曲强度为500-700MPa，弯曲模量为27.0-29.5GPa，Tg为130-145℃)，且提高了整个工艺的生产效率，节约了工艺成本10-20％。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例的技术方案进行清楚、完整的描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所属领域内有一般技能的人士所理解的通常意义。
实施例1
步骤1：将3.5份双氰胺，0.9份二甲基咪唑，1.8份N-酰基咪唑加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
步骤2：将环氧树脂组合物均匀涂覆于电子级玻纤布上并120--180℃高温烘烤2-5min，后冷却至室温制成预浸料；
步骤3：将预浸料1至多层半固化片叠配好，两面附上离型膜，上下叠配不锈钢板，送进叠合式热压机，140-160℃/0.5-5MPa高温高压成型15-30min，制成热固性层压板①。
步骤4：将预浸料室温存放1个月，按照步骤3工艺过程进行热压成型，制成热固性层压板②。
观察层压板成型情况并用DSC测试玻璃化转变温度(Tg和△Tg，△Tg＞3℃则板材未固化完全)和万能拉力机测试弯曲性能。
实施例2
步骤1：将10.3份二氨基二苯砜，1.9份2-乙基-4甲基咪唑，1.3份四甲基乙二胺加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
实施例3
步骤1：39.5份线性苯酚甲醛树脂，1.4份2-十一烷基咪唑(C11Z)咪唑，2.3份1,2-二甲基咪唑加入到80份N,N-二甲基甲酰胺和丙二醇甲醚有机溶剂中，溶解完全后加入100份双酚A环氧树脂混合均匀，并加入二氧化硅20份，钛白粉10份，滑石粉5份，硅烷偶联剂0.8份，脂肪酸类分散剂0.5份，充分搅拌制备成环氧树脂组合物。
按照实施例1步骤工艺进行制备和测试。
实施例4
步骤1：将58份六氢苯二甲酸酐，1.6份2一乙基咪唑(2-EI)，2.6份吡啶加入到100份丁酮和丙二醇甲醚混合有机溶剂中，溶解完全后加入100份双酚A环氧树脂混合均匀，并加入二氧化硅40份，氢氧化铝15份，滑石粉5份，硅烷偶联剂1.5份，脂类分散剂0.8份，充分搅拌制备成环氧树脂组合物。
按照实施例1步骤工艺进行制备和测试。
实施例5
步骤1：将25.4份有机酸酰肼，0.4份2-苯基咪唑，2.8份4-二甲氨基吡啶加入到100份丁酮和丙二醇甲醚混合有机溶剂中，溶解完全后加入100份双酚A环氧树脂混合均匀，并加入钛白粉15份，氢氧化铝10份，硅烷偶联剂0.5份，脂类分散剂0.5份，充分搅拌制备成环氧树脂组合物。
按照实施例1步骤工艺进行制备和测试。
对比例1
将3.5份双氰胺，1.5份二甲基咪唑，3.2份，N-酰基咪唑加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
对比例2
将10.3份二氨基二苯砜，3.2份2-乙基-4甲基咪唑，1.5份四甲基乙二胺加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
对比例3
将39.5份线性苯酚甲醛树脂，3.5份2-十一烷基咪唑(C11Z)咪唑，3.5份1,2-二甲基咪唑加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100双酚A份环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
对比例4
将3.5份双氰胺，1份二甲基咪唑，加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
对比例5
将10.3份二氨基二苯砜，2.0份四甲基乙二胺加入到60份N,N-二甲基甲酰胺和丙酮有机溶剂中，溶解完全后加入100份双酚A环氧树脂制备成环氧树脂组合物。
按照实施例1工艺步骤进行制备和测试。
实施例1-5和对比例1-5的检测结果如下表所示。
Figure BDA0002348010600000071
注：DSC测试热固性材料Tg显示Tg1/Tg2，△Tg＝丨Tg1-Tg2丨表征固化程度，若△Tg＞3℃，则材料未在要求工艺条件内完全固化，性能出现不同程度降低。
通过实施例1-5可以看出，通过第一固化剂、第二固化剂和第三固化剂按要求组合，在预浸料制备完成和常温贮存一个月后都可以成型，并且完全固化，力学性能高。解决了中高温快速成型并且要求常温长时间贮存的问题。同时不同的固化体系表现出一定的热学和力学性能差异。
通过对比例1和实施例1，对比例2和实施例2，对比例3和实施例3看出，若第二固化剂、第三固化剂某一组分超过范围或者都超过范围，则板材成型有缺陷或不能成型，性能影响大。
通过对比例4和5可以看出，若只是用第一固化剂+第二固化剂或第一固化剂+第三固化剂，则板材虽然能够成型，但无法固化完全，热学和力学性能都不同程度降低。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求保护范围内。

Claims (10)

1.一种树脂组合物，其特征在于，所述树脂组合物包括环氧树脂、第一固化剂、第二固化剂和第三固化剂，其中，所述第一固化剂为潜伏性固化剂，所述第二固化剂为咪唑类固化剂，所述第三固化剂为叔胺类固化剂。
2.根据权利要求1所述的树脂组合物，其特征在于，所述树脂组合物中各组分重量配比如下：环氧树脂100重量份，第一固化剂1-60重量份，第二固化剂0.1-3重量份，第三固化剂0.1-3重量份，且第二固化剂+第三固化剂0.2-5重量份。
3.根据权利要求1所述的树脂组合物，其特征在于，所述环氧树脂选自双酚A型环氧树脂，双酚F型环氧树脂、双酚S型环氧树脂和酚醛环氧树脂中的一种或多种；更优选的，所述环氧树脂选自双酚A性环氧树脂、双酚F型环氧树脂和酚醛环氧树脂中的一种或多种。
4.根据权利要求1所述的树脂组合物，其特征在于，所述第一固化剂选自胺类固化剂、酚醛类固化剂、酸酐类固化剂和三氟化硼-胺络合物中的一种或多种；更优选的，所述第一固化剂选自双氰胺、二氨基二苯砜、二氨基二苯胺、有机酸酰肼、线性苯酚甲醛树脂、线性双酚A甲醛树脂、线性邻甲酚甲醛树脂、四氢苯二甲酸酐和六氢苯二甲酸酐中的一种或多种。
5.根据权利要求1所述的树脂组合物，其特征在于，所述第二固化剂为咪唑类固化剂，包括咪唑及其改性物质，其要求为分子结构中叔胺当量在80-500之间，其中优选2-甲基咪唑(2MZ)，2-乙基咪唑(2-EI)，2-乙基-4甲基咪唑(2E4MZ)，2-十一烷基咪唑(C11Z)，2-十七烷基咪唑(C17Z)，2-苯基咪唑(2PZ)，1-苄基-2甲基咪唑(1B2MZ)中的一种或多种。
6.根据权利要求1所述的树脂组合物，其特征在于，所述第三固化剂为叔胺类固化剂，包括改性咪唑和其他类叔胺物质，其要求为分子结构中叔胺当量在25-78之间，其中优选咪唑，1,2-二甲基咪唑，N-酰基咪唑，吡啶，4-二甲氨基吡啶，四甲基乙二胺中的一种或多种。
7.根据权利要求1所述的树脂组合物，其特征在于，所述树脂组合物还包括有机溶剂，所述有机溶剂20-120重量份；所述有机溶剂选自醇类、酮类、醚类、酰胺类和苯类溶剂中的一种或多种；优选的，所述有机溶剂选自N,N-二甲基甲酰胺、丁酮、乙醇、丙二醇甲醚、乙二醇单甲醚和甲苯中的一种或多种。
8.根据权利要求1所述的树脂组合物，其特征在于，所述树脂组合物还包括无机填料、分散剂和偶联剂，所述无机填料10-80重量份，分散剂0.01-1重量份，偶联剂0.1-2重量份。
9.一种预浸料，其特征在于，所述预浸料包括增强材料以及通过涂覆干燥后附着在其上的如权利要求1-8任一项所述的树脂组合物。
10.一种层压板，其特征在于，其包括将叠置的如权利要求9所述的预浸料置于两片不锈钢板之间，还包括在所述预浸料与不锈钢板接触的表面覆一层离型膜。
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