CN110016206B - 一种树脂组合物、包含其的预浸料以及层压板和印制电路板 - Google Patents

一种树脂组合物、包含其的预浸料以及层压板和印制电路板 Download PDF

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CN110016206B
CN110016206B CN201910205606.1A CN201910205606A CN110016206B CN 110016206 B CN110016206 B CN 110016206B CN 201910205606 A CN201910205606 A CN 201910205606A CN 110016206 B CN110016206 B CN 110016206B
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weight
resin composition
parts
resin
cyanate ester
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CN110016206A (zh
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何烈相
曾耀德
杨中强
杨宇
潘华林
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 FIEP19920384.5T priority patent/FI3943548T3/fi
Priority to JP2021552166A priority patent/JP7270057B2/ja
Priority to KR1020217028463A priority patent/KR102623336B1/ko
Priority to EP19920384.5A priority patent/EP3943548B1/en
Priority to US17/437,564 priority patent/US20220135788A1/en
Priority to PCT/CN2019/081744 priority patent/WO2020186572A1/zh
Priority to TW108119832A priority patent/TWI710596B/zh
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Abstract

本公开提供了一种树脂组合物以及包含其的预浸料、层压板和印制电路板。该树脂组合物包含：48‑54重量份的无卤环氧树脂；16‑31重量份的由式(I)表示的化合物，其中n为2‑15，Ac表示乙酰基；和15‑32重量份的氰酸酯树脂。采用该树脂组合物制成的预浸料、层压板和印制电路板具有低热膨胀系数。

Description

一种树脂组合物、包含其的预浸料以及层压板和印制电路板
技术领域
本公开属于印制电路板技术领域，具体涉及一种树脂组合物和包含其的预浸料以及层压板和印制电路板。
背景技术
近年来，信息通讯设备变得具有更高性能、更多功能并且可以在网络中工作。为了高速传输及处理大容量信息，操作信号趋向于高频化。同时，为了满足各类电子产品的发展要求，电路板向着更多层、更高布线密度的方向发展。这就要求基板材料不仅具有良好的介电常数和介质损耗因子来满足信号高频传输的需要，而且要求其具有良好的耐热性来满足多层印制电路板可靠性的需求。特别地，基板材料需要有尽量低的热膨胀系数。
树脂预浸料常在印制电路板中作为基板材料。为此，已经开发了一些树脂组合物，其中采用氰酸酯和活性酯作为复合固化剂固化联苯型酚醛环氧树脂、亚芳烷基环氧树脂或萘酚环氧树脂。不过，上述树脂组合物的热膨胀系数(CTE)仍有待提高。
发明内容
在一个方面，本公开提供一种树脂组合物，其特征在于，所述树脂组合物包含：
无卤环氧树脂：48-54重量份；
由式(I)表示的化合物：16-31重量份，
Figure BDA0001998377790000011
其中n为2-15，Ac表示乙酰基；和
氰酸酯树脂：15-32重量份。
可选地，所述无卤环氧树脂选自由以下各项组成的组：联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、和它们的组合。
可选地，所述树脂组合物包含16-22重量份的所述由式(I)表示的化合物，25-32重量份的所述氰酸酯树脂。
可选地，所述氰酸酯树脂选自由以下各项组成的组：双酚A型氰酸酯树脂、双酚F型氰酸酯树脂、双环戊二烯型氰酸酯树脂、苯酚酚醛型氰酸酯树脂、和它们的组合。
可选地，所述树脂组合物还包括固化促进剂。
可选地，所述树脂组合物还包括无卤阻燃剂。
可选地，所述树脂组合物还包含填料。
在另一个方面，本公开提供一种预浸料，所述预浸料是通过对增强材料浸渍或涂布根据上述树脂组合物并将其半固化得到的。
在另一个方面，本公开提供一种层压板，其包含至少一张如上述的预浸料。
在另一个方面，本公开提供一种印制电路板，其包含至少一张如上所述的预浸料或层压板。
具体实施方式
本公开的目的在于提供一种树脂组合物。使用该树脂组合物制备的预浸料、层压板和印制电路板，具有低热膨胀系数。
本公开的发明人出人意料地发现，使用由式(I)表示的化合物代替活性酯树脂与氰酸酯一起作为复合固化剂，与无卤环氧树脂组合，可以得到具有低的热膨胀系数的环氧树脂体系。
一种环氧树脂组合物，其包括如下组分：
无卤环氧树脂：48-54重量份；
由式(I)表示的化合物：16-31重量份，
Figure BDA0001998377790000031
其中n为2-15，Ac表示乙酰基；和
氰酸酯树脂：15-32重量份。
本公开利用上述三种必要组分之间的相互配合以及相互协同促进作用，得到了如上的树脂组合物。采用该树脂组合物制成的预浸料、层压板以及印制电路板，具有低热膨胀系数。
无卤环氧树脂成分中是不含卤素的环氧树脂。本公开对无卤环氧树脂的种类没有特别的限定。
无卤环氧树脂的量为48-54重量份，例如48重量份、49重量份、50重量份、51重量份、53重量份或54重量份。
优选地，所述无卤环氧树脂选自由以下各项组成的组：联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、和它们的组合。这些无卤环氧树脂的优点在于具有低的热膨胀系数。
优选地，由式(I)表示的化合物可以为16-22重量份，例如16重量份、18重量份、20重量份或22重量份；所述氰酸酯树脂可以为25-32重量份，例如25重量份、26重量份、28重量份、30重量份或32重量份。选用以上组分可以很好地降低无卤环氧树脂组合物的热膨胀系数。
由式(I)表示的化合物的聚合度n为2-15，n可以为例如3、7、11或15。在本发明中，组合物中由式(I)表示的化合物中n可以不为整数，其表示由式(I)表示的化合物的平均聚合度。例如，当组合物中的由式(I)表示的化合物中的一半数量具有3个重复单元且另一半数量具有4个重复单元时，可以认为n＝3.5。当平均聚合度小于2时，组合物固化后热学性能差。而当平均聚合度大于15时，组合物的浸润性差，影响层压板或印制电路板的性能。式(I)表示的化合物的数均分子量相应地为约1300至7800。
优选地，所述氰酸酯树脂选自由以下各项组成的组：双酚A型氰酸酯树脂、双酚F型氰酸酯树脂、双环戊二烯型氰酸酯树脂、苯酚酚醛型氰酸酯树脂、和它们的组合。选用这些氰酸酯树脂的优点在于具有更低的热膨胀系数。
优选地，所述树脂组合物还可进一步包括固化促进剂，其使树脂固化并加快树脂固化速度。以无卤环氧树脂、由式(I)表示的化合物和氰酸酯树脂的总量为100重量份计，所述固化促进剂的量为0.05-1重量份，例如0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或0.95重量份。
优选地，所述固化促进剂选自由以下各项组成的组：异辛酸锌、4-二甲氨基吡啶、2-甲基咪唑、2-乙基4-甲基咪唑、2-苯基咪唑、和它们的组合。
优选地，如有需要，所述环氧树脂组合物还包括阻燃剂，使环氧树脂树脂组合物具有阻燃特性，符合UL94V-0要求。对视需要而添加的阻燃剂并无特别限定。优选地，该阻燃剂为无卤阻燃剂。
阻燃剂的量根据固化产物达到UL 94V-0级别要求而定，并无特别的限定。优选地，以无卤环氧树脂、由式(I)表示的化合物和氰酸酯树脂的总量为100重量份计，所述阻燃剂的量为5-50重量份，例如5重量份、10重量份、15重量份、25重量份、30重量份、35重量份、40重量份或45重量份。
优选地，所述无卤阻燃剂选自由以下各项组成的组：三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸锌、氮磷系膨胀型、有机聚合物无卤阻燃剂、含磷酚醛树脂、和它们的组合。
优选地，如有需要，所述树脂组合物还包含填料，所述填料为有机填料和/或无机填料，其主要用来调整环氧树脂组合物的一些物性效果，如进一步降低热膨胀系数(CTE)、降低吸水率和提高热导率等。
填料的添加量并无特别限定。优选地，以无卤环氧树脂、由式(I)表示的化合物和氰酸酯树脂的总量为100重量份计，所述填料的量为100重量份以下，优选50重量份以下。所述填料的量例如为0.5重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份。
优选地，所述无机填料选自由以下各项组成的组：熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉、和它们的组合。它们的组合例如熔融二氧化硅和结晶型二氧化硅的混合物，球型二氧化硅和空心二氧化硅的混合物，氢氧化铝和氧化铝的混合物，滑石粉和氮化铝的混合物，氮化硼和碳化硅的混合物，硫酸钡和钛酸钡的混合物，钛酸锶和碳酸钙的混合物，硅酸钙、云母和玻璃纤维粉的混合物，熔融二氧化硅、结晶型二氧化硅和球型二氧化硅的混合物，空心二氧化硅、氢氧化铝和氧化铝的混合物，滑石粉、氮化铝和氮化硼的混合物，碳化硅、硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙、硅酸钙、云母和玻璃纤维粉的混合物。
优选地，所述有机填料选自由以下各项组成的组：聚四氟乙烯粉末、聚苯硫醚、聚醚砜粉末、和它们的组合。它们的组合例如聚四氟乙烯粉末和聚苯硫醚的混合物，聚醚砜粉末和聚四氟乙烯粉末的混合物，聚苯硫醚和聚醚砜粉末的混合物，聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末的混合物。
优选地，所述填料为二氧化硅，填料的粒径中度值为0.1-15μm，优选填料的粒径中度值为0.1-10μm。
本公开所述的“包含”，意指其除所述组份外，还可以包含其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本公开所述的“包含”，还可以替换为封闭式的“为”或“由......组成”。
例如，所述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。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本公开的树脂组合物的常规制作方法是：取一容器，先将固体组分放入，然后加入溶剂，搅拌直至完全溶解后，再加入液体树脂、填料、阻燃剂和固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至60％-80％而制成胶液。
本公开的目的之二在于提供一种预浸料，其包含增强材料及通过含浸干燥后附着其上的如上所述的环氧树脂组合物。
示例性的增强材料如无纺织物和/或其他织物，例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物，将含浸好的增强材料在155-170℃的烘箱中加热干燥5-10分钟即可得到预浸料。
本公开的目的之三在于提供一种层压板，其包含至少一张如上所述的预浸料。
本公开的目的之四在于提供一种印制电路板，其包含至少一张如上所述的预浸料或层压板。
本公开利用上述三种必要组分之间的相互配合以及相互协同促进作用，得到了如上的树脂组合物。采用该树脂组合物制成的预浸料、层压板以及印制电路板，具有低热膨胀系数。
下面通过具体实施例来进一步说明本公开的技术方案。
根据上述所制成的树脂组合物覆金属箔层压板，测试其热膨胀系数，如下述实施例加于详细说明与描述，其中有机树脂的重量份按有机固形物重量份计。
本公开实施例中所用列举的材料具体如下：
KES-7695M75： 含有DCPD结构的环氧树脂(得自KOLON)。
NC-3000H： 联苯型酚醛环氧树脂(得自日本化药)。
E15-152T： 由式(I)表示的化合物(得自ICL)，其中n为约3.0。
HM1100： 膦酸酯聚合物(得自FRX Polymers公司)。
HPC-8000-65T： 活性酯树脂(得自日本DIC)。
CE01PS： 双酚A型氰酸酯树脂(得自扬州天启)。
PT60S： 酚醛型氰酸酯树脂(得自LONZA)。
DMAP： 固化促进剂，4-二甲氨基吡啶(得自广荣化学)。
异辛酸锌： 固化促进剂(得自阿法埃莎)。
热膨胀系数(CTE)的测试方法如下：根据热机械分析仪(TMA)，按照IPC-TM-6502.4.24.6所规定的TMA方法进行测定。
实施例1
取一容器，加入54重量份的环氧树脂KES-7695M75和31重量份的由式(I)表示的化合物E15-152T，加入适量的甲基乙基酮(MEK)和二甲基甲酰胺(DMF)搅拌至完全溶解，随后加入15重量份的氰酸酯树脂CE01PS、提前溶解好的固化促进剂DMAP和异辛酸锌，继续搅拌均匀，最后用溶剂调整液体固含量至70％，从而制成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用6张所制得的预浸料相互叠合，在其两侧分别压覆一张铜箔，放进热压机中固化制成所述的环氧树脂覆铜箔层压板。物性数据如表1所示。
实施列2-7
制作工艺和实施例1相同，配方组成及其物性指标如表1所示。
比较例1-7
制作工艺与实施例1相同，配方组成及其物性指标如表1所示。
表1.各实施例的配方组成及其物性数据
Figure BDA0001998377790000071
注：表中皆以固体组分重量份计。
实施例1-7相比于比较例1-3，其各组分含量均在本发明限定的范围内，特定含量比例的环氧树脂、氰酸酯与由式(I)表示的化合物具有协同作用，具有更优的热膨胀系数。实施例4-7的组分含量均在本发明优选的范围内，相比于其他实施例具有更低的热膨胀系数。
比较例4-7不使用具有式(I)表示的化合物，也能实现固化和阻燃的作用，但其热膨胀系数最高可达到3.7％。
因此，本公开的树脂组合物提供了具有低热膨胀系数的包含氰酸酯的环氧树脂。相应地，本公开的预浸料、层压板和印制电路板也具有低热膨胀系数。
显然，本领域的技术人员可以对本公开实施例进行各种改动和变型而不脱离本公开的精神和范围。这样，倘若本公开的这些修改和变型属于本公开权利要求及其等同技术的范围之内，则本公开也意图包含这些改动和变型在内。

Claims (9)

1.一种树脂组合物，其特征在于，所述树脂组合物包含：
无卤环氧树脂：48-54重量份；
由式(I)表示的化合物：16-31重量份，
Figure FDA0002526556150000011
其中n为2-15，Ac表示乙酰基；和
氰酸酯树脂：15-32重量份，其中所述氰酸酯树脂选自由以下各项组成的组：双酚A型氰酸酯树脂、双酚F型氰酸酯树脂、双环戊二烯型氰酸酯树脂、苯酚酚醛型氰酸酯树脂、和它们的组合。
2.如权利要求1所述的树脂组合物，其特征在于，所述无卤环氧树脂选自由以下各项组成的组：联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、和它们的组合。
3.如权利要求1所述的树脂组合物，其特征在于，所述树脂组合物包含16-22重量份的所述由式(I)表示的化合物，25-32重量份的所述氰酸酯树脂。
4.如权利要求1所述的树脂组合物，其特征在于，所述树脂组合物还包括固化促进剂。
5.如权利要求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卤阻燃剂。
6.如权利要求1所述的树脂组合物，其特征在于，所述树脂组合物还包含填料。
7.一种预浸料，所述预浸料是通过对增强材料浸渍或涂布根据权利要求1所述的树脂组合物并将其半固化得到的。
8.一种层压板，所述层压板包含至少一张如权利要求7所述的预浸料。
9.一种印制电路板，所述印制电路板包含：至少一张如权利要求7所述的预浸料，或至少一张如权利要求8所述的层压板。
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JP7270057B2 (ja) 2023-05-09
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CN110016206A (zh) 2019-07-16

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