CN111801376B - 树脂组合物、包含其的预浸料、包含其的层合板、包括其的涂覆有树脂的金属箔 - Google Patents

树脂组合物、包含其的预浸料、包含其的层合板、包括其的涂覆有树脂的金属箔 Download PDF

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CN111801376B
CN111801376B CN201980015523.4A CN201980015523A CN111801376B CN 111801376 B CN111801376 B CN 111801376B CN 201980015523 A CN201980015523 A CN 201980015523A CN 111801376 B CN111801376 B CN 111801376B
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resin composition
resin
resins
organic
filler
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CN111801376A (zh
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黄勇善
沈昌补
闵铉盛
朴惠林
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LG Chem Ltd
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LG Chem Ltd
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Abstract

本发明涉及树脂组合物、包含其的预浸料、包含其的层合板、和包括其的涂覆有树脂的金属箔，所述树脂组合物包含粘合剂树脂和有机‑无机复合填料。

Description

树脂组合物、包含其的预浸料、包含其的层合板、包括其的涂 覆有树脂的金属箔
技术领域
相关申请的交叉引用
本申请要求于2018年11月23日向韩国知识产权局提交的韩国专利申请第10-2018-0146306号的申请日的权益，其全部公开内容通过引用并入本文。
本发明涉及树脂化合物、包含其的预浸料、包含其的层合板、和包括其的涂覆有树脂的金属箔。
背景技术
近来，诸如半导体基底、印刷电路板和环氧模制化合物(EMC，epoxy moldingcompound)的电子部件以及信息和通信设备的信号带趋于增加。电信号的传输损耗与介电损耗角正切和频率成比例。因此，较高的频率使传输损耗增加并引起信号衰减，从而导致信号传输的可靠性劣化。此外，传输损耗被转换成热，因此，还可能引起发热的问题。为此，对在高频区中具有非常低的介电损耗角正切的绝缘材料的需求正在增长。
此外，随着近来在半导体器件和PCB领域中对高集成度、高精细度、高性能等的需求增加，情况逐渐变为需要半导体器件的集成、印刷电路板的高密度以及同时配线间隔的简化的形势。为了满足这些特征，优选使用具有使传输速率能够增加的低介电常数和用于减小传输损耗的低介电损耗特征的材料。
常规地，为了开发这样的绝缘材料，已经开发出基于聚苯醚(PPE)树脂(其为具有优异介电特性的热固性树脂)的绝缘材料，但是它们具有熔体粘度高、预浸料的可操作性、模制可加工性困难等的问题。此外，向聚苯醚树脂中引入有利于低介电特性的填料例如多孔填料，但是填料的分散性低，这导致了可加工性和耐热性方面的问题，并且存在难以以高含量应用填料的问题。
发明内容
技术问题
本发明的一个目的是提供树脂组合物，其改善粘合剂树脂与填料之间的相容性，并因此表现出优异的可加工性和耐热性，并且还同时满足低热膨胀系数(CTE)、低介电特性和低介电损耗。
本发明的另一个目的是提供使用上述树脂组合物的预浸料、层合板和涂覆有树脂的金属箔。
技术方案
在一个方面中，提供了树脂组合物，其包含粘合剂树脂和有机-无机复合填料，其中有机-无机复合填料为其中形成有涂覆层的有机填料，所述涂覆层包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒。
在另一个方面中，提供了预浸料，其包含：纤维基底；和浸渍到纤维基底中的树脂组合物。
在又一个方面中，提供了其中层合有两个或更多个层的上述预浸料的层合板。
在再一个方面中，提供了涂覆有树脂的金属箔，其包括：金属箔，和位于金属箔上并且其中树脂组合物被固化的树脂层。
在下文中，将更详细地描述根据本发明的具体实施方案的树脂组合物、包含其的预浸料、包含其的层合板、和包括其的涂覆有树脂的金属箔。
在本说明书中，基于氟的有机填料意指有机填料中包含至少一个或更多个氟元素的有机填料。
此外，包含含有双键的官能团的硅烷意指包含含有一个或更多个双键的官能团作为硅烷的取代基的硅烷。
此外，(甲基)丙烯酸酯基意指包括丙烯酸酯基和甲基丙烯酸酯基二者。
此外，预浸料意指通过用树脂组合物涂覆或浸渍纤维基底，然后通过加热固化至半固化状态(B阶段)而获得的片状材料。
在本发明的一个实施方案中，提供了树脂组合物，其包含：粘合剂树脂和有机-无机复合填料，其中有机-无机复合填料为其中形成有涂覆层的有机填料，所述涂覆层包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒。
本发明人对用于预浸料、层合板、涂覆有树脂的金属箔等的树脂组合物进行了研究，并且通过实验发现，使用具有由有机填料(核)和涂覆层(壳)构成的核-壳结构的有机-无机复合填料的树脂组合物表现出低热膨胀系数(CTE)、低介电特性和低介电损耗，并且还同时满足优异的耐热性和可加工性，所述涂覆层包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒。
常规的树脂组合物中包含的有机或无机填料在粘合剂树脂中具有低分散性并因此导致可加工性、耐热性等方面的问题，从而难以以高含量应用填料。
然而，由于有机-无机复合填料在涂覆层中包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒，因此其具有显著优异的分散性和与粘合剂树脂的相容性，并因此，复合填料不仅防止可加工性、耐热性等方面的问题，而且还在降低介电特性的同时改善诸如吸湿后耐热性的效果。
对应于具有核-壳结构的有机-无机复合填料的核的有机填料没有特别限制，只要其是本领域已知的有机填料即可，但是其可以为例如包含氟元素的基于氟的有机填料。更具体地，基于氟的有机填料可以为选自以下的一者或更多者：聚四氟乙烯粉末、四氟乙烯-全氟烷氧基乙烯共聚物(PFA)、乙烯-氯三氟乙烯共聚物(PCTFE)和聚偏氟乙烯(PVDF)。
对应于具有核-壳结构的有机-无机复合填料的壳的涂覆层包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒。
包含含有双键的官能团的硅烷偶联剂用于改善与粘合剂树脂的相容性，并且其中经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒位于最外部的有机-无机复合填料与粘合剂树脂具有优异的相容性。
包含含有双键的官能团的硅烷偶联剂意指包含含有一个或更多个双键的官能团作为硅烷偶联剂的取代基的硅烷偶联剂。硅烷偶联剂中包含的含有双键的官能团可以为乙烯基或(甲基)丙烯酸酯基。
包含含有双键的官能团的硅烷偶联剂没有特别限制，只要其为本领域已知的包含含有双键的官能团的硅烷偶联剂即可，并且其可以为例如选自以下的一者或更多者：乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、对苯乙烯基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷和3-丙烯酰氧基丙基三甲氧基硅烷。
此外，无机颗粒没有特别限制，只要它们是本领域已知的无机颗粒并且是其表面经包含含有双键的官能团的硅烷偶联剂处理的那些即可。其实例包括二氧化硅，例如天然二氧化硅、熔融二氧化硅、无定形二氧化硅和结晶二氧化硅；勃姆石；氧化铝；滑石；球形玻璃；碳酸钙；碳酸镁；氧化镁；粘土；硅酸钙；钛氧化物；锑氧化物；玻璃纤维；硼酸铝；钛酸钡；钛酸锶；钛酸钙；钛酸镁；钛酸铋；钛氧化物；锆酸钡；锆酸钙；氮化硼；氮化硅；滑石；云母等。它们的表面经包含含有双键的官能团的硅烷偶联剂处理。这些无机颗粒可以单独使用或者以其两者或更多者的混合物使用。其中，可以使用显示出低热膨胀系数的熔融二氧化硅。
用包含含有双键的官能团的硅烷偶联剂处理无机颗粒的表面的方法可以通过本领域已知的常规方法来制备。作为一个实例，其可以通过将无机颗粒添加到含有包含含有双键的官能团的硅烷偶联剂的溶液中，然后干燥来制备。
经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒的平均颗粒尺寸没有特别限制，但是例如，平均颗粒直径可以为200nm或更小、50nm至200nm、50nm至100nm、或50nm至70nm。
用于制备有机-无机复合填料的方法没有特别限制，但是有机-无机复合填料可以通过将有机填料和经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒混合或者通过在混合之后施加振动来制备。将经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒涂覆在有机填料的表面上的方法可以在干燥状态下进行。
同时，有机填料与经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒的混合比不限于此。例如，在有机-无机复合填料中，基于100重量份的有机填料，经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒的含量可以为0.001重量份至10重量份、0.005重量份至5重量份、或0.01重量份至2重量份。
有机-无机复合填料的平均颗粒尺寸没有特别限制，但是例如，平均颗粒尺寸可以为0.3μm至5μm、0.4μm至4μm、或0.5μm至3μm。如果平均颗粒尺寸小于0.3μm，则存在内聚力变高的问题。如果平均颗粒尺寸大于5μm，则可能由于高体积/体积比而难以在生产薄膜时应用。
在树脂组合物中，基于100重量份的粘合剂树脂，有机-无机复合填料的含量可以为20重量份至90重量份、25重量份至85重量份、或30重量份至80重量份。
根据一个实施方案的树脂组合物还可以包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机填料。
在树脂组合物中，基于100重量份的粘合剂树脂，无机填料的含量可以为80重量份或更小、5重量份至80重量份、10重量份至70重量份、15重量份至60重量份、20重量份至50重量份、或25重量份至40重量份。如果无机填料的含量太高，则存在介电常数变高的问题。
无机填料是其表面经包含含有双键的官能团的硅烷偶联剂处理的无机填料，并且无机填料可以减小树脂层与另一层之间的热膨胀系数(CTE)差异，从而有效地改善最终产品的弯曲特性、低膨胀性、机械强度(韧性)和较低应力。
无机填料没有特别限制，只要它们是本领域已知的无机填料并且是其表面经包含含有双键的官能团的硅烷偶联剂处理的那些即可。其实例包括二氧化硅，例如天然二氧化硅、熔融二氧化硅、无定形二氧化硅和结晶二氧化硅；勃姆石；氧化铝；滑石；球形玻璃；碳酸钙；碳酸镁；氧化镁；粘土；硅酸钙；钛氧化物；锑氧化物；玻璃纤维；硼酸铝；钛酸钡；钛酸锶；钛酸钙；钛酸镁；钛酸铋；钛氧化物；锆酸钡；锆酸钙；氮化硼；氮化硅；滑石；云母等。它们的表面经包含含有双键的官能团的硅烷偶联剂处理。这些无机填料可以单独使用或者以其两者或更多者的混合物使用。其中，可以使用显示出低热膨胀系数的熔融二氧化硅。
用于制备经包含含有双键的官能团的硅烷偶联剂表面处理的无机填料的方法没有特别限制，并且可以通过本领域已知的常规方法制备。作为一个实例，其可以通过将无机填料添加到含有包含含有双键的官能团的硅烷偶联剂的溶液中，然后干燥来制备。
根据一个实施方案的树脂组合物可以包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机填料、以及有机-无机复合填料。由此，填料与粘合剂树脂之间的相容性得到改善，并因此可以在降低介电特性的同时改善诸如吸湿后耐热性、可加工性和耐热性的效果。此外，其可以减小树脂层与另一层之间的热膨胀系数(CTE)差异，从而有效地改善最终产品的弯曲特性、低膨胀性、机械强度(韧性)、较低应力。
根据一个实施方案的树脂组合物中包含的粘合剂树脂可以没有限制地使用，只要其是本领域已知的常规粘合剂树脂即可，并且例如，其可以包括选自以下的一者或更多者：聚苯醚树脂、氰酸酯树脂、双马来酰亚胺树脂、丁二烯树脂、苯氧基树脂、聚酰胺酰亚胺树脂、聚醚酰亚胺树脂、聚砜树脂、聚醚砜树脂、聚碳酸酯树脂和聚醚醚酮树脂。
更具体地，粘合剂树脂可以包括聚苯醚树脂(a)、双马来酰亚胺树脂(b)、氰酸酯树脂(c)和/或苯乙烯-丁二烯树脂(d)。由于这些树脂与有机-无机复合填料具有更优异的相容性，因此可以在降低介电特性的同时进一步改善吸湿后耐热性和可加工性。
聚苯醚树脂(a)可以包括两端经烯键式不饱和基团官能化的改性苯醚(phenyleneether)低聚物或改性聚(苯醚)。组分(a)的两端官能化的两个烯键式不饱和基团可以相同或不同。
烯键式不饱和基团可以为例如烯基，如乙烯基、烯丙基、甲代烯丙基、丙烯基、丁烯基、己烯基和辛烯基；环烯基，如环戊烯基和环己烯基；丙烯酰基；甲基丙烯酰基；或者烯基芳基，如乙烯基苄基和乙烯基萘基。
用于制备组分(a)的方法没有特别限制，但是例如，经乙烯基苄基官能化的那些可以通过将双官能苯醚低聚物和乙烯基苯氯化物溶解在溶剂中，在加热和搅拌下向其中添加碱以进行反应，然后使树脂硬化来制备。
通过GPC法以聚苯乙烯换算的组分(a)的数均分子量可以在500g/mol至3000g/mol、或1000g/mol至2500g/mol的范围内。当组分(a)的数均分子量小于500g/mol时，存在使用所述树脂组合物形成的预浸料充分粘附的问题。当其超过3000g/mol时，在溶剂中的溶解度可能降低。
作为双马来酰亚胺树脂(b)和氰酸酯树脂(c)，可以没有特别限制地使用本发明所属技术领域公知的那些。
例如，双马来酰亚胺树脂(b)可以为选自以下的一种或更多种化合物：二苯基甲烷双马来酰亚胺例如4,4'-二苯基甲烷双马来酰亚胺、苯基甲烷马来酰亚胺的低聚物、亚苯基双马来酰亚胺例如间亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷双马来酰亚胺、4-甲基-1,3-亚苯基双马来酰亚胺、和1,6-双马来酰亚胺-(2,2,4-三甲基)己烷。
此外，例如，氰酸酯树脂(c)可以为选自以下的一种或更多种化合物：酚醛清漆型氰酸酯树脂、二环戊二烯型氰酸酯树脂、双酚型氰酸酯树脂、及其部分三嗪化的预聚物。
苯乙烯-丁二烯树脂(d)为苯乙烯和丁二烯的共聚物树脂，在室温下为液体，并且可以具有约5％至50％的苯乙烯含量。此外，苯乙烯-丁二烯树脂(d)的玻璃化转变温度(Tg)可以为-35℃至0℃或-30℃至-5℃；以及数均分子量可以为1000g/mol至50000g/mol或2000g/mol至10000g/mol。
根据一个实施方案的树脂组合物还可以包含选自以下的一种或更多种添加剂：固化剂、阻燃剂、UV屏蔽剂、流平剂、增稠剂、颜料、分散剂和抗氧化剂。
作为固化剂，可以没有限制地使用本领域已知的常规固化剂，并且例如，其可以为选自以下的一种或更多种固化剂：基于酰胺的固化剂、基于聚胺的固化剂、酸酐固化剂、苯酚酚醛清漆型固化剂、聚硫醇固化剂、叔胺固化剂、咪唑固化剂和金属配位催化剂。具体地，金属配位催化剂可以为乙酸钴(II)，其可以促进可以包含在粘合剂树脂中的氰酸酯的三嗪键合。
基于树脂组合物的总重量，树脂组合物中的固化剂的含量可以为0.1重量％至10重量％、0.2重量％至8重量％、或0.5重量％至5重量％。
作为阻燃剂，可以没有限制地使用本领域已知的常规阻燃剂，并且其实例可以为包含溴或氯的卤素阻燃剂；基于磷的阻燃剂，例如磷酸三苯酯、磷酸三甲苯酯(tricrecylphosphate)、磷酸三二氯丙基酯和磷腈；基于锑的阻燃剂，例如三氧化锑；无机物质的阻燃剂，例如氢氧化铝和氢氧化镁等。
基于树脂组合物的总重量，树脂组合物中的阻燃剂的含量可以为0.1重量％至10重量％、0.2重量％至8重量％、或0.5重量％至5重量％。如果阻燃剂的含量小于0.1重量％，则其无法具有耐燃性，而如果其超过10重量％，则电特性可能劣化。
在本发明的另一个实施方案中，提供了预浸料，其包含：纤维基底；和浸渍到纤维基底中的树脂组合物。
纤维基底没有特别限制，但其实例可以包括选自以下的一者或更多者：玻璃纤维、玻璃纸、玻璃纤维非织造织物(玻璃网)、玻璃布、芳族聚酰胺纤维、芳族聚酰胺纸、聚酯纤维、碳纤维、无机纤维和有机纤维。
纤维基底可以经包含含有双键的官能团的硅烷偶联剂表面处理。
当将树脂组合物浸渍到经包含含有双键的官能团的硅烷偶联剂表面处理的纤维基底中时，由于纤维基底以及树脂组合物中包含的无机填料和有机-无机复合填料二者均包含含有双键的官能团，因此它们之间的相容性优异，从而使介电特性得到改善，吸湿后耐热性和可加工性得到进一步改善，并因此可以开发出用于高频的材料。
用包含含有双键的官能团的硅烷偶联剂处理纤维基底的表面的方法可以通过本领域已知的常规方法来制备，用包含含有双键的官能团的硅烷偶联剂处理纤维基底的表面的方法可以通过本领域已知的常用方法来生产。作为一个实例，其可以通过将纤维基底添加到含有包含含有双键的官能团的硅烷偶联剂的溶液中，然后干燥来准备。
纤维基底的厚度没有特别限制，并且可以例如在0.01mm至0.3mm的范围内。
用于生产预浸料的方法没有特别限制，并且可以根据本领域已知的生产方法来制备。
预浸料是指通过将树脂组合物涂覆或浸渍到经包含含有双键的官能团的硅烷偶联剂表面处理的纤维基底上，然后通过加热固化至半固化状态(B-阶段)而获得的片状材料。此时，加热温度和时间没有特别限制，并且例如，加热温度可以为约20℃至200℃、或70℃至170℃，以及加热时间可以在约1分钟至10分钟的范围内。
除了上述方法之外，预浸料可以通过本领域已知的已知热熔法、溶剂法等来生产。溶剂法是这样的方法：将树脂基底浸渍到通过将用于预浸料形成的树脂组合物溶解在有机溶剂中而形成的清漆中，然后将其干燥。当采用这样的溶剂法时，通常使用清漆。将树脂组合物浸渍到纤维基底中的方法的实例可以包括将纤维基底浸没在清漆中的方法、通过各种涂覆机将清漆施加至基底的方法、通过喷洒将清漆喷洒到基底上的方法等。此时，当将纤维基底浸没在树脂清漆中时，可以改善树脂组合物对纤维基底的可浸渍性，并因此其是优选的。
当制备清漆时，有机溶剂的实例可以包括酮，例如丙酮、甲基乙基酮和环己酮；乙酸酯，例如乙酸乙酯、乙酸丁酯、溶纤剂乙酸酯、丙二醇单甲醚乙酸酯和卡必醇乙酸酯；溶纤剂；卡必醇，例如丁基卡必醇；芳族烃，例如甲苯和二甲苯；二甲基甲酰胺；二甲基乙酰胺；N-甲基吡咯烷酮；四氢呋喃等。作为有机溶剂，可以单独使用一种类型的有机溶剂，或者可以以组合使用两种或更多种类型的有机溶剂。
此外，热熔法可以是这样的方法：其中将树脂组合物涂覆在相对于树脂组合物具有优异可离型性的离型纸上而不将树脂组合物溶解在有机溶剂中，然后层合在片状纤维基底上；或者通过模头涂覆机直接涂覆。此外，其可以通过在加热和压制条件下从片状增强基底的两侧对层合在支撑体上的包含热固性树脂组合物的粘合膜进行连续热层合来生产。
在又一个实施方案中，提供了层合板，其中层合有两个或更多个层的上述一个实施方案的上述预浸料。
根据本发明的层合板可以在其中层合有两个或更多个层的预浸料的状态下被加热和压制。
例如，层合板可以通过以下过程来生产：层合一个或复数个上述实施方案的预浸料，任选地，在其一侧或两侧上重叠金属箔，然后对所得产品进行加热和压制。
在层合板生产期间的加热和压制条件没有特别限制，但是可以在140℃至220℃的温度范围内施加70psi至800psi的压力。在该范围内，可以有利于层合板的层间粘合、耐热性、可靠性等。
此外，作为在层合板生产期间用于加热和压制的装置，可以使用多级压机、多级真空压机、连续模制机、高压釜模制机等，但是上述实施方案的层合板不限于此。
当在层合板生产期间使用金属箔时，虽然没有特别限制，但是可以使用由铜、铝、镍、镍磷、镍锡合金、镍铁合金、铅和铅锡合金中的一种或更多种金属制成的金属箔作为一个片或复数个片。
在本发明的另一个实施方案中，提供了涂覆有树脂的金属箔，其包括：金属箔；和位于金属箔上并且其中上述实施方案的树脂组合物被固化的树脂层。
例如，涂覆有树脂的金属箔可以通过制备未加工成预浸料的树脂组合物作为清漆，将其涂覆至金属箔，然后干燥来生产。
与用于制备预浸料的清漆组合物相似，用于用树脂生产金属箔的清漆包含溶剂，但是还可以包含固化剂、固化催化剂等。
作为金属箔，可以没有限制地使用由本领域已知的常规金属或合金制成的那些。在这种情况下，金属箔可以为铜箔，并且可以使用的铜箔的实例包括CFL(TZA_B、HFZ_B)、Mitsui(HSVSP、MLS-G)、Nikko(RTCHP)、Furukawa、ILSIN等。
铜箔包括通过轧制法和电解法生产的所有铜箔。在此，可以使铜箔经受防锈处理以防止其表面被氧化和腐蚀。
在金属箔中，还可以在树脂组合物与经固化的树脂层接触的一个表面上形成预定的表面粗糙度(Rz)。在这种情况下，表面粗糙度(Rz)没有特别限制，但是可以例如在0.6μm至3.0μm的范围内。
此外，金属箔的厚度没有特别限制，但是考虑到最终产品的厚度和机械特性，可以小于5μm或为1μm至3μm。
有益效果
由于根据本发明的树脂组合物同时满足低热膨胀系数(CTE)、低介电特性、低介电损耗、高耐热性和优异的可加工性，因此可以容易地提供使用其的预浸料、层合板、涂覆有树脂的金属箔等以用于诸如汽车、大型计算机和服务器的组件中。
具体实施方式
在下文中，将参照实施例更详细地描述本发明。然而，这些实施例仅用于说明目的，并且本发明的范围不受这些实施例限制。
实施例1至4和比较例1至4
根据下表1所示的组成将粘合剂树脂、无机填料和有机-无机复合填料混合，并搅拌4小时以制备实施例和比较例的树脂组合物。
[表1]
Figure GDA0003449672080000111
-聚苯醚：OPE-2st-1200，可由MGC(Mitsubishi Gas Chemical Company,Inc.)获得
-双马来酰亚胺树脂：可从DAIWAKasei获得的BMI-5100
-氰酸酯树脂：可从Lonza Ltd.获得的ULL-950S
-苯乙烯-丁二烯橡胶：可从Cray Valley获得的Ricon181
-无机填料：经乙烯基硅烷(乙烯基三甲氧基硅烷)表面处理的浆料型(固体含量为70％)的填料(二氧化硅)，平均颗粒尺寸为0.5μm，SC2050，可从Admatechs获得
-有机-无机复合填料：涂覆有二氧化硅*的聚四氟乙烯**，平均颗粒尺寸为3μm，比表面积为1.5m2/g，可从Admatechs获得
*二氧化硅：经乙烯基硅烷(乙烯基三甲氧基硅烷)表面处理的二氧化硅，平均颗粒尺寸为150nm，可从Admatechs获得
**聚四氟乙烯，平均颗粒尺寸为3μm，TFW-3000FK，可从Seishin Corporation获得
-phr：其为“每百份树脂的份数(parts per hundred resin)”的缩写并且是无机填料和有机-无机复合填料的使用单位。具体地，其是相对于100重量份的粘合剂树脂，无机填料和有机-无机复合填料各自的含量(重量份)。
评估
通过以下方法评估实施例和比较例的物理特性，并且评估结果示于下表2中。
(1)用于评估的预浸料和层合板的生产
将实施例和比较例的树脂组合物浸渍到经乙烯基硅烷表面处理的玻璃纤维(15μm的厚度，Asahi Kasei，1017，L-玻璃)中，然后在130℃至160℃的温度下干燥约3分钟至10分钟以制备厚度为30μm的预浸料。
随后，将两个预浸料层合，然后在两侧上压制铜箔(12μm的厚度，由Mitsui制造)以制备覆铜层合板(copper-clad laminated plate)。
(2)树脂流动性(Resin flow)
在预浸料状态下使用盖压机(cover press)根据IPC-TM-650 2.3.17测试方法手册测量和评估树脂流动性(％)。(基于在170℃下干燥3分钟)
(3)耐热性(焊料浮动)
通过以下过程评估耐热性：根据IPC-TM-650 2.4.13测试方法手册在288℃下使层合板在焊料上浮动以测量绝缘层与铜箔之间和绝缘层与金属芯或绝缘层之间发生分离现象时的时间点。
(4)相对介电常数和介电损耗角正切的测量
使用移除了铜箔的层合板，使用相对介电常数测量装置(RF Impedence，Agilent)在1GHz的频率下测量相对介电常数和介电损耗角正切。
(5)热膨胀系数(CTE)
使用移除了铜箔的层合板测量热膨胀系数。具体地，根据IPC-TM-650.2.4.24测试方法手册通过TMA Q400(TA Instruments)测量和评估热膨胀系数(ppm/℃)。
[表2]
Figure GDA0003449672080000131
根据表2确定，由于实施例1至4同时应用无机填料和有机-无机复合填料，因此它们由于其优异的耐热性和低的热膨胀系数而在作为绝缘材料的可靠性方面是优异的，并且表现出低介电常数。
另一方面，确定单独使用30phr含量的无机填料的比较例1与包含相同量的无机填料的实施例1和2相比具有较高的介电损耗和较高的热膨胀系数，并且使用75phr含量的无机填料的比较例2与包含相同量的无机填料的实施例3和4相比具有较高的介电常数。此外，确定其中仅应用有机-无机复合填料的比较例3和4与实施例相比具有较低的耐热性和较高的热膨胀系数。

Claims (12)

1.一种树脂组合物，包含：粘合剂树脂和有机-无机复合填料，
其中所述有机-无机复合填料为其中形成有涂覆层的有机填料，所述涂覆层包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒，
其中所述树脂组合物还包含经包含含有双键的官能团的硅烷偶联剂表面处理的无机填料。
2.根据权利要求1所述的树脂组合物，其中
所述粘合剂树脂包括选自以下的一者或更多者：聚苯醚树脂、氰酸酯树脂、双马来酰亚胺树脂、丁二烯树脂、苯氧基树脂、聚酰胺酰亚胺树脂、聚醚酰亚胺树脂、聚砜树脂、聚醚砜树脂、聚碳酸酯树脂和聚醚醚酮树脂。
3.根据权利要求1所述的树脂组合物，其中
所述有机填料为包含氟元素的基于氟的有机填料。
4.根据权利要求1所述的树脂组合物，其中
基于100重量份的所述粘合剂树脂，所述有机-无机复合填料的含量为20重量份至90重量份。
5.根据权利要求1所述的树脂组合物，其中
在所述有机-无机复合填料中，基于100重量份的所述有机填料，所述经包含含有双键的官能团的硅烷偶联剂表面处理的无机颗粒的含量为0.001重量份至10重量份。
6.根据权利要求1所述的树脂组合物，其中
所述含有双键的官能团为乙烯基或(甲基)丙烯酸酯基。
7.根据权利要求1所述的树脂组合物，其中
所述树脂组合物还包含选自以下的一者或更多者：固化剂、阻燃剂、UV屏蔽剂、流平剂、增稠剂、颜料、分散剂和抗氧化剂。
8.一种预浸料，包含：
纤维基底；和
浸渍到所述纤维基底中的根据权利要求1所述的树脂组合物。
9.根据权利要求8所述的预浸料，其中
所述纤维基底经包含含有双键的官能团的硅烷偶联剂表面处理。
10.一种层合板，其中层合有两个或更多个层的根据权利要求8所述的预浸料。
11.根据权利要求10所述的层合板，其中
所述层合板在其中层合有两个或更多个层的所述预浸料的状态下被加热和压制。
12.一种涂覆有树脂的金属箔，包括：
金属箔；和
位于所述金属箔上并且其中根据权利要求1所述的树脂组合物被固化的树脂层。
CN201980015523.4A 2018-11-23 2019-11-13 树脂组合物、包含其的预浸料、包含其的层合板、包括其的涂覆有树脂的金属箔 Active CN111801376B (zh)

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