CN112088187A - 用于半导体封装的热固性树脂组合物、使用其的预浸料和金属包层层合体 - Google Patents
用于半导体封装的热固性树脂组合物、使用其的预浸料和金属包层层合体 Download PDFInfo
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- CN112088187A CN112088187A CN202080002641.4A CN202080002641A CN112088187A CN 112088187 A CN112088187 A CN 112088187A CN 202080002641 A CN202080002641 A CN 202080002641A CN 112088187 A CN112088187 A CN 112088187A
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- thermosetting resin
- semiconductor encapsulation
- resin composition
- phenylene ether
- oligomer
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Abstract
本公开内容涉及用于半导体封装的热固性树脂组合物以及包含其的预浸料和金属包层层合体,所述热固性树脂组合物包含在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚);热固性树脂;预定的弹性(共聚)聚合物;和无机填料。
Description
技术领域
相关申请的交叉引用
本申请要求基于于2019年2月8日向韩国知识产权局提交的韩国专利申请第10-2019-0015098号的优先权的权益,其公开内容通过引用整体并入本文。
本公开内容涉及用于半导体封装的热固性树脂组合物、预浸料和金属包层层合体。
背景技术
近来,电子部件例如半导体基底、印刷电路板和环氧模制化合物(EMC,epoxymolding compound)以及信息和通信装置的信号带趋于增加。电信号的传输损耗与介电损耗因子和频率成比例。因此,较高的频率使传输损耗增加并引起信号的衰减,从而导致信号传输的可靠性降低。此外,传输损耗被转换为热,因此还可能引起热产生的问题。为此,对在高频区中具有非常低的介电损耗因子的绝缘材料的需求正在增长。
此外,随着目前在半导体装置和PCB领域中对高集成度、高精细度、高性能等的需求增加,情况逐渐变为同时需要半导体装置的集成、印刷电路板的高密度和配线间隔的简化的形势。为了满足这些特性,优选使用具有使传输速率增加的低介电常数和用于减小传输损耗的低介电损耗特性的材料。
常规地,为了开发这样的绝缘材料,已经开发了基于聚亚苯基醚(PPE)树脂(其为具有优异的介电特性的热固性树脂)的绝缘材料,但存在诸如高熔体粘度、难以处理、预浸料的可模制性、和低的对金属箔的粘合性的问题。此外,向聚亚苯基醚树脂中引入有利于低介电特性的填料例如多孔填料,但填料的分散性低,这引起可加工性和耐热性方面的问题,并且难以以高含量应用填料。
发明内容
技术问题
本公开内容的一个目的是提供用于半导体封装的热固性树脂组合物,其在表现出优异的可加工性和耐热性的同时同时满足低介电特性和低介电损耗。
本公开内容的另一个目的是提供包含用于半导体封装的热固性树脂组合物的预浸料。
本公开内容的另外的目的是提供包括预浸料的金属包层层合体。
技术方案
在本公开内容的一个方面中,提供了用于半导体封装的热固性树脂组合物,其包含:在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚);热固性树脂;选自以下的一种或更多种弹性(共聚)聚合物:a)数均分子量为1,500至10,000的基于丁二烯的橡胶、b)数均分子量为1,500至10,000且苯乙烯含量为10重量%至40重量%的基于苯乙烯-丁二烯的橡胶、c)以10重量%至70重量%的量包含苯乙烯的热塑性弹性体、和d)分子中包含聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的氰酸酯;以及无机填料。
在本公开内容的另一个方面中,提供了通过将用于半导体封装的树脂组合物浸渍到纤维基底中而制备的预浸料。
在本公开内容的另外的方面中,提供了金属包层层合体,其包括预浸料;以及通过加热和加压与预浸料一体化的金属箔。
在下文中,将更详细地描述根据本发明的具体实施方案的用于半导体封装的热固性树脂组合物以及使用其的预浸料和金属包层层合体。
如本文所用,(共聚)聚合物意指包括共聚物和均聚物二者。
根据本公开内容的一个实施方案,可以提供用于半导体封装的热固性树脂组合物,其包含:在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚);热固性树脂;选自以下的一种或更多种弹性(共聚)聚合物:a)数均分子量为1,500至10,000的基于丁二烯的橡胶,b)数均分子量为1,500至10,000且苯乙烯含量为10重量%至40重量%的基于苯乙烯-丁二烯的橡胶,c)以10重量%至70重量%的量包含苯乙烯的热塑性弹性体,和d)分子中包含聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的氰酸酯;以及无机填料。
本发明人对用于半导体封装的材料进行了研究,通过实验发现包含上述组分的组合物可以在表现出优异的可加工性和耐热性的同时同时满足低介电特性和低介电损耗,从而完成了本公开内容。
由于用于半导体封装的热固性树脂组合物包含在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚),因此可以在确保优异的可加工性和耐热性的同时显著降低固化之后的相对介电常数或介电损耗。
在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)是其中亚苯基醚低聚物或聚(亚苯基醚)的两端经烯键式不饱和基团官能化的那些。
烯键式不饱和基团包括:烯基,例如乙烯基、烯丙基、甲代烯丙基、丙烯基、丁烯基、己烯基和辛烯基;环烯基,例如环戊烯基和环己烯基;丙烯酰基、甲基丙烯酰基;以及烯基芳基,例如乙烯基苄基和乙烯基萘基。
在两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)的两端处的两个烯键式不饱和基团可以相同或不同。
用于制备在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)的方法没有特别限制。例如,乙烯基苄基官能化的产物可以通过如下来制备:将双官能亚苯基醚低聚物和乙烯基苯氯化物溶解在溶剂中,在加热和搅拌下添加碱以进行反应,然后使树脂凝固。
在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)的数均分子量(通过GPC方法以聚苯乙烯换算确定的)可以为500g/mol至3000g/mol、或1000g/mol至2500g/mol以确保由上述实施方案的用于半导体封装的热固性树脂组合物形成的预浸料的处理特性、优异的介电特性、可模制性等。
同时,用于半导体封装的热固性树脂组合物可以包含上述预定的弹性(共聚)聚合物,以及热固性树脂和在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)。由此,在具有低介电常数和低介电损耗因子的同时,可以防止在制造预浸料时出现裂纹的现象,并且可以实现高的铜箔粘合性和激光通孔可加工性(laser via-holeprocessability)。
弹性(共聚)聚合物的具体实例包括:a)数均分子量为1,500至10,000的基于丁二烯的橡胶;b)数均分子量为1,500至10,000且苯乙烯含量为10重量%至40重量%的基于苯乙烯-丁二烯的橡胶;c)苯乙烯含量为10重量%至70重量%的热塑性弹性体;和d)分子中包含聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的氰酸酯;或者其两者或更多者的混合物、或者其两者或更多者的共聚物。
数均分子量为1,500至10,000且苯乙烯含量为10重量%至40重量%的基于苯乙烯-丁二烯的橡胶的玻璃化转变温度可以为-100℃至-20℃。
苯乙烯含量为10重量%至70重量%的热塑性弹性体的实例包括苯乙烯-丁二烯/丁烯-苯乙烯嵌段共聚物,例如苯乙烯含量为10重量%至70重量%的Tuftec P系列。
苯乙烯-丁二烯/丁烯-苯乙烯嵌段共聚物的如根据ISO 1133在190℃和2.16kg负载下测量的熔体流动速率(melt flow rate,MFR)可以为3.0至5.0。
分子中包含聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的氰酸酯中包含的聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的物理特性没有特别限制,但例如,各化合物的重均分子量可以为100至10,000。
同时,热固性树脂可以包括选自双马来酰亚胺树脂、氰酸酯树脂和双马来酰亚胺-三嗪树脂中的至少一种树脂。
作为双马来酰亚胺树脂,可以没有限制地使用常规用于半导体封装用热固性树脂组合物的任何双马来酰亚胺树脂,并且其类型没有限制。作为优选的实例,双马来酰亚胺树脂可以为选自以下的至少一者:由以下化学式13表示的二苯基甲烷型双马来酰亚胺树脂、由以下化学式14表示的亚苯基双马来酰亚胺树脂、由以下化学式15表示的双酚A二苯基醚双马来酰亚胺树脂、和由以下化学式16表示的由二苯基甲烷型双马来酰亚胺和苯基甲烷型马来酰亚胺的低聚物构成的双马来酰亚胺树脂。
[化学式13]
在化学式13中,
R1和R2各自独立地为H、CH3或C2H5。
[化学式14]
[化学式15]
[化学式16]
在化学式16中,
n为0或1至50的整数。
此外,基于氰酸酯的树脂的具体实例可以包括氰酸酯树脂,并且可以没有限制地使用任意常规地通常用于半导体封装用热固性树脂组合物的那些,并且其类型没有限制。
作为优选的实例,氰酸酯树脂可以包括由以下化学式17表示的酚醛清漆型氰酸酯树脂、由以下化学式18表示的二环戊二烯型氰酸酯树脂、由以下化学式19表示的双酚型氰酸酯树脂及其部分三嗪化的预聚物。这些树脂可以单独使用或者以两者或更多者的组合使用。
[化学式17]
在化学式17中,
n为0或1至50的整数。
[化学式18]
在化学式18中,
n为0或1至50的整数。
[化学式19]
在化学式19中,
更具体地,根据R的类型,化学式19的氰酸酯树脂可以分别为双酚A氰酸酯树脂、双酚E型氰酸酯树脂、双酚F型氰酸酯树脂、或双酚M型氰酸酯树脂。
此外,双马来酰亚胺树脂可以包括双马来酰亚胺-三嗪树脂等,并且作为双马来酰亚胺-三嗪树脂,可以没有限制地使用常规用于半导体封装用热固性树脂组合物的任何双马来酰亚胺-三嗪树脂,并且其类型没有限制。
同时,热固性树脂还可以包括选自以下的至少一种环氧树脂:双酚A型环氧树脂、苯酚酚醛清漆环氧树脂、四苯基乙烷环氧树脂、基于萘的环氧树脂、基于联苯的环氧树脂、二环戊二烯环氧树脂、以及基于二环戊二烯的环氧树脂和基于萘的环氧树脂的混合物。
具体地,环氧树脂可以为由以下化学式5表示的双酚型环氧树脂、由以下化学式6表示的酚醛清漆型环氧树脂、由以下化学式7表示的苯基芳烷基型环氧树脂、由以下化学式8表示的四苯基乙烷型环氧树脂、由以下化学式9和10表示的萘型环氧树脂、由以下化学式11表示的联苯型环氧树脂、和由以下化学式12表示的二环戊二烯型环氧树脂。
[化学式5]
在化学式5中,
n为0或1至50的整数。
更具体地,根据R的类型,化学式5的环氧树脂可以分别为双酚A型环氧树脂、双酚F型环氧树脂、双酚M型环氧树脂、或双酚S型环氧树脂。
[化学式6]
在化学式6中,
R为H或CH3,以及
n为0或1至50的整数。
更具体地,根据R的类型,化学式6的酚醛清漆型环氧树脂可以分别为苯酚酚醛清漆型环氧树脂或甲酚酚醛清漆型环氧树脂。
[化学式7]
[化学式8]
[化学式9]
[化学式10]
[化学式11]
在化学式11中,
n为0或1至50的整数。
[化学式12]
在化学式12中,n为0或1至50的整数。
此外,一个实施方案的用于半导体封装的热固性树脂组合物可以包含无机填料。
作为无机填料,可以没有特别限制地使用常规用于半导体封装用热固性树脂组合物的任何无机填料,并且其具体实例可以为选自以下的至少一者:二氧化硅、三氢氧化铝、氢氧化镁、氧化钼、钼酸锌、硼酸锌、锡酸锌、氧化铝、粘土、高岭土、滑石、煅烧高岭土、煅烧滑石、云母、短玻璃纤维、玻璃细粉、和中空玻璃。
基于总计100重量份的在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、热固性树脂和弹性(共聚)聚合物,用于半导体封装的热固性树脂组合物可以包含30重量份至200重量份的无机填料。如果无机填料的含量太小,则热膨胀系数增加,这可能引起问题,例如,在回流过程或EMC(环氧模制化合物)模制过程期间翘曲现象加剧,或者由于吸湿速率的增加,半导体封装的可靠性降低并且印刷电路板的刚度降低。
作为无机填料,从改善耐湿性和分散性的角度来看,可以使用经硅烷偶联剂表面处理的二氧化硅。
作为对无机填料进行表面处理的方法,可以使用如下方法:使用硅烷偶联剂作为表面处理剂通过干法或湿法对二氧化硅颗粒进行处理。例如,基于100重量份的二氧化硅颗粒,可以使用0.01重量份至1重量份的硅烷偶联剂通过湿法对二氧化硅进行表面处理,并使用。
具体地,硅烷偶联剂可以包括氨基硅烷偶联剂,例如3-氨基丙基三乙氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷和N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷;环氧硅烷偶联剂,例如3-缩水甘油氧基丙基三甲氧基硅烷;乙烯基硅烷偶联剂,例如3-甲基丙烯酰氧基丙基三甲氧基硅烷和乙烯基三甲氧基硅烷;阳离子硅烷偶联剂,例如N-2-(N-乙烯基苄基氨基乙基)-3-氨基丙基三甲氧基硅烷盐酸盐;和苯基硅烷偶联剂。硅烷偶联剂可以单独使用,或者如有必要,可以以至少两种硅烷偶联剂的组合使用。
用于半导体封装的热固性树脂组合物中包含的组分的含量等可以考虑最终制造的产品的物理特性和特性来选择。
例如,基于总计100重量份的在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、热固性树脂和弹性(共聚)聚合物,用于半导体封装的热固性树脂组合物可以包含5重量份至70重量份的在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、10重量份至50重量份的热固性树脂、和5重量份至70重量份的弹性(共聚)聚合物。
同时,用于半导体封装的树脂组合物还可以包含热塑性树脂。热塑性树脂具有在预浸料固化之后增加韧性的效果,并且可以起降低热膨胀系数和弹性模量以减轻半导体封装的翘曲的作用。热塑性树脂的具体实例包括基于(甲基)丙烯酸酯的聚合物。
基于(甲基)丙烯酸酯的聚合物的实例没有特别限制,例如,其可以为包含源自(甲基)丙烯酸酯单体的重复单元和源自(甲基)丙烯腈的重复单元的丙烯酸酯共聚物;或包含源自丁二烯的重复单元的丙烯酸酯共聚物。例如,基于(甲基)丙烯酸酯的聚合物可以为通过分别使用1重量%至40重量%(相对于全部单体的总重量)范围内的单体例如丙烯酸丁酯、丙烯酸乙酯、丙烯腈、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯等共聚的共聚物。
基于(甲基)丙烯酸酯的聚合物的重均分子量可以为500,000至1,000,000。如果基于(甲基)丙烯酸酯的聚合物的重均分子量太小,则在固化之后,增加预浸料的韧性以及降低热膨胀系数和弹性模量的效果劣化,这是技术上是不利的。此外,如果基于(甲基)丙烯酸酯的聚合物的重均分子量太大,则预浸料的流动性可能降低。
对于热塑性树脂,使用的含量可以考虑最终产品的用途和特性来确定。例如,基于100重量份的热固性树脂,用于半导体封装的热固性树脂组合物可以包含10重量份至200重量份的热塑性树脂。
用于半导体封装的树脂组合物还可以包含烷氧基硅烷低聚物。烷氧基硅烷低聚物使得使用用于半导体封装的树脂组合物形成的预浸料表现出优异的对金属箔的粘合性。
通常,当制造金属包层层合体或预浸料时,添加单体型偶联剂以改善对金属箔的粘合性。然而,当添加大量的单体型偶联剂以实现上述目的时,由于偶联剂的低沸点,可能引起诸如金属箔和预浸料的分层、耐热性降低、以及介电常数增加的问题。
烷氧基硅烷低聚物是具有烷氧基硅烷骨架的低聚物,即使当大量添加时,也可以提供在抑制耐热性降低和介电常数增加的同时具有优异的对金属箔的粘合性的预浸料。
优选地,烷氧基硅烷低聚物可以为包含由以下化学式1表示的重复单元的低聚物。
[化学式1]
在化学式1中,
X和Y各自独立地为烯基、甲基丙烯酰基、丙烯酰基、苯基、甲基、或环氧基,
R1至R4各自独立地为甲基或乙基,以及
m和n各自独立地为大于1的整数。
具体地,烷氧基硅烷低聚物可以为选自以下的至少一种化合物:甲氧基官能化的乙烯基硅氧烷低聚物、乙氧基官能化的乙烯基硅氧烷低聚物、和甲氧基官能化的乙烯基/苯基低聚物。
基于总计100重量份的在两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、热固性树脂和弹性(共聚)聚合物,可以以5重量份至30重量份的量包含烷氧基硅烷低聚物。为了充分表现出上述效果,烷氧基硅烷低聚物的含量优选为5重量份或更大。然而,当过量添加烷氧基硅烷低聚物时,可能引起相对介电常数和介电损耗因子增加的问题,因此,优选以30重量份或更小的量包含烷氧基硅烷低聚物。
用于半导体封装的树脂组合物还可以包含醌化合物。可以添加醌化合物。
醌化合物的实例包括1,4-萘醌、1,4-苯醌等。
此外,如有必要,根据一个实施方案的用于半导体封装的热固性树脂组合物可以通过添加溶剂而作为溶液使用。溶剂的类型没有特别限制,只要其在树脂组分中表现出良好的溶解性即可。例如,可以使用醇型、醚型、酮型、酰胺型、芳族烃型、酯型、腈型等,这些溶剂可以单独使用或者以两者或更多者的组合使用。此外,溶剂的含量没有特别限制,只要其可以在预浸料的生产期间用树脂组合物浸渍玻璃纤维即可。
此外,用于半导体封装的热固性树脂组合物还可以包含各种其他聚合物化合物例如其他热固性树脂、热塑性树脂及其低聚物和弹性体,以及其他阻燃剂化合物或添加剂,只要其不损害热固性树脂组合物的固有特性即可。这些化合物没有特别限制,只要它们选自本领域通常使用的那些即可。添加剂的实例包括紫外线吸收剂、抗氧化剂、光聚合引发剂、荧光增白剂、光敏剂、颜料、染料、增稠剂、润滑剂、消泡剂、分散剂、流平剂、增白剂等,并且可以通过将这些添加剂混合来使用这些添加剂以满足目的。
同时,根据本公开内容的另一个实施方案,可以提供预浸料,其包含用于半导体封装的热固性树脂组合物和有机或无机纤维。
预浸料意指用于半导体封装的热固性树脂组合物以半固化状态浸渍到纤维基底中。
有机或无机纤维的类型没有特别限制,但可以使用玻璃纤维基底;由织造或非织造织物制成的合成纤维基底,其具有以下作为主要成分:基于聚酰胺的树脂纤维,例如聚酰胺树脂纤维、芳族聚酰胺树脂纤维等;基于聚酯的树脂纤维,例如聚酯树脂纤维、芳族聚酯树脂纤维、或全芳族聚酯树脂纤维;聚酰亚胺树脂纤维;聚苯并唑纤维;氟树脂纤维等;以及纸基底,其具有牛皮纸、棉绒纸、或者绒和牛皮纸浆的混合纸作为主要成分。优选地,使用玻璃纤维基底。
玻璃纤维基底可以改善预浸料的强度并降低预浸料的吸水性和热膨胀系数。
玻璃基底可以选自用作用于各种印刷电路板的材料的玻璃基底。其实例可以包括玻璃织物,例如E玻璃、D玻璃、S玻璃、T玻璃、NE玻璃、L玻璃和Q玻璃,但不限于此。如有必要,玻璃纤维可以根据期望的目的或性能来选择。玻璃纤维的形式通常为织造织物、非织造织物、粗纱、短切原丝毡、或表面毡。玻璃纤维基底的厚度没有特别限制,但可以使用厚度为约0.01mm至0.3mm的玻璃纤维基底等。在上述材料中,考虑到强度和吸水性特性,玻璃纤维材料可以是更优选的。
此外,预浸料的制备方法没有特别限制,并且预浸料可以通过本领域公知的方法来制备。例如,作为预浸料的制备方法,可以使用浸渍法、使用各种涂覆机的涂覆法、喷洒法等。
在浸渍法的情况下,预浸料可以通过制备清漆然后用清漆浸渍纤维基底的过程来制备。
即,预浸料的制备条件没有特别限制,但优选地,用于半导体封装的热固性树脂组合物以通过添加溶剂的清漆状态使用。用于树脂清漆的溶剂没有特别限制,只要其可与树脂组分混溶并且具有优异的溶解性即可。其具体实例可以包括:酮,例如丙酮、甲基乙基酮、甲基异丁基酮和环己酮;芳族烃,例如苯、甲苯和二甲苯;酰胺,例如二甲基甲酰胺和二甲基乙酰胺;脂族醇,例如甲基溶纤剂、丁基溶纤剂等。
此外,优选地,在制备预浸料时,使至少80重量%的使用的溶剂挥发。由于此,在制备方法或干燥条件等方面没有限制。在干燥时,温度可以为约80℃至200℃,并且时间由于与清漆的凝胶时间的平衡而没有特别限制。此外,清漆的浸渍量优选被设定成使得基于清漆和基底的树脂固体组分的总量,清漆的树脂固体含量变为约30重量%至80重量%。
根据本公开内容的又一个实施方案,可以提供金属包层层合体,其包括具有片形的上述预浸料;以及形成在预浸料的至少一侧上的金属箔。
金属箔包括铜箔;铝箔;具有三层结构的复合箔,其具有镍、镍-磷、镍-锡合金、镍-铁合金、铅或铅-锡合金作为在任一侧上的具有不同厚度的铜层之间的中间层;或者具有包括铝箔和铜箔的两层结构的复合箔。
根据一个优选的实施方案,本文使用的金属箔为厚度为约2μm至200μm,优选约2μm至35μm的铜箔或铝箔。优选地,金属箔为铜箔。此外,金属箔为具有三层结构的复合箔,其具有镍、镍-磷、镍-锡合金、镍-铁合金、铅或铅-锡合金作为在任一侧上的0.5μm至15μm铜层与10μm至300μm铜层之间的中间层;或者具有包括铝箔和铜箔的两层结构的复合箔。
将一个或更多个由此制备的包括预浸料的金属包层层合体层合,然后用于制造双面或多层印刷电路板。双面或多层印刷电路板可以通过在金属包层层合体上加工电路来制造,并且电路可以通过在一般双面或多层印刷电路板的制造过程中进行的方法来加工。
同时,根据本公开内容的另一个实施方案,可以提供金属包层层合体,其包括:第一层,所述第一层包含上述一个实施方案的用于半导体封装的热固性树脂组合物或其固化产物和厚度为15μm至90μm的有机或无机纤维;第二层,所述第二层形成在第一层的两个表面上,并且包含一个实施方案的用于半导体封装的热固性树脂组合物或其固化产物和厚度为10μm至30μm的有机或无机纤维;以及金属薄膜,所述金属薄膜形成在第二层中的每一者的外表面上。
如上所述,通过包括各自包含一个实施方案的用于半导体封装的热固性树脂组合物的第一层和第二层,金属包层层合体可以在表现出优异的可加工性和耐热性的同时同时满足低介电特性和低介电损耗。
此外,通过包含一个实施方案的用于半导体封装的热固性树脂组合物,第二层可以具有较高的对金属薄膜的粘合性。具体地,通过IPC-TM-650 2.4.8的测试方法测量的第二层与金属薄膜之间的剥离强度可以为0.50kgf/cm或更大。
第一层和第二层的厚度等可以根据金属包层层合体的最终用途和特性来确定。更具体地,第二层与第一层的厚度比可以为0.2至0.7。
有益效果
根据本公开内容,可以提供在表现出优异的可加工性和耐热性的同时同时满足低介电特性和低介电损耗的用于半导体封装的热固性树脂组合物、通过使用用于半导体封装的热固性树脂组合物提供的预浸料、和包括预浸料的金属包层层合体。
具体实施方式
在下文中,将通过实施例更详细地描述本公开内容。然而,这些实施例仅出于举例说明目的而给出,并且本公开内容的范围不旨在限于这些实施例或被这些实施例限制。
<实施例和比较例:用于半导体封装的热固性树脂组合物、预浸料和金属包层层合体>
(1)用于半导体封装的热固性树脂组合物的制备
根据下表1的组成,将各组分添加到环己酮中并与环己酮混合以符合50%的固体含量,然后以400rpm的速度在室温下搅拌1天以制备实施例和比较例的各用于半导体封装的树脂组合物(树脂清漆)。
(2)预浸料A-1的制备
将制备的用于半导体封装的树脂组合物(树脂清漆)浸渍到厚度为15μm的玻璃纤维(由Nittobo制造,NE-玻璃#1017)中,然后在130℃的温度下用热空气干燥2分钟至5分钟以生产厚度为30μm的预浸料A-1。
(3)预浸料B-1的制备
将制备的用于半导体封装的树脂组合物(树脂清漆)浸渍到厚度为30μm的玻璃纤维(由Nittobo制造,NE-玻璃#1067)中,然后在170℃的温度下用热空气干燥2分钟至5分钟以生产厚度为40μm的预浸料B-1。
(4)金属包层层合体A-2的制造(用于测量相对介电常数和介电损耗因子)
将两个生产的预浸料A层合,然后将MT18Ex铜箔(铜箔厚度2μm/载体厚度18μm,由Mitsui制造)放置并层合在其两侧上。使层合体在220℃和35kg/cm2的条件下固化120分钟以制造绝缘层厚度为60μm的铜包层层合体。
(5)金属包层层合体B-2的制造(用于测量相对介电常数和介电损耗因子)
将两个生产的预浸料B层合,然后将MT18Ex铜箔(铜箔厚度2μm/载体厚度18μm,由Mitsui制造)放置并层合在其两侧上。使层合体在220℃和35kg/cm2的条件下固化120分钟以制造绝缘层厚度为80μm的铜包层层合体。
(6)金属包层层合体B-3的制造(用于测量铜箔的剥离强度)
将两个生产的预浸料B层合,然后将3EC-M3-VLP铜箔(铜箔厚度12μm,由Mitsui制造)放置并层合在其两侧上。使层合体在220℃和35kg/cm2的条件下固化120分钟以制造绝缘层厚度为80μm的铜包层层合体。
(7)金属包层层合体A/B/A的制造(用于测量对铜箔的粘合强度)
对(5)中制造的铜包层层合体B-2的两侧上的铜箔进行蚀刻并将其除去,然后将预浸料A-1放置并层合在其两侧上。将3EC-M3-VLP铜箔(铜箔厚度12μm,由Mitsui制造)放置并层合在其两侧上,然后使层合体在220℃和35kg/cm2的条件下固化120分钟以制造铜包层层合体A/B/A。
(8)金属包层层合体A/B/A的制造(用于激光通孔可加工性实验)
对(5)中制造的铜包层层合体B-2的两侧上的铜箔进行蚀刻并将其除去,然后将预浸料A-1放置并层合在其两侧上。将MT18Ex铜箔(铜箔厚度2μm/载体厚度18μm,由Mitsui制造)放置并层合在其两侧上,然后使层合体在220℃和35kg/cm2的条件下固化120分钟以制造铜包层层合体A/B/A。
<实验例:实施例和比较例中获得的用于半导体封装的热固性树脂组合物、预浸料和铜包层层合体的物理特性的测量>
通过以下方法测量实施例和比较例中获得的用于半导体封装的热固性树脂组合物、预浸料和铜包层层合体的物理特性,结果示于表3中。
1.确认预浸料裂纹的出现
在预浸料A-1的制备期间,将用于半导体封装的树脂组合物(树脂清漆)浸渍到厚度为15μm的玻璃纤维(由Nittobo制造,NE-玻璃#1017)中,然后在130℃下用热空气干燥2分钟至5分钟,然后冷却至室温。此时,视觉观察预浸料的表面上裂纹的出现。
2.相对介电常数(Dk@1GHz)和介电损耗因子(Df@1GHz)
在对实施例和比较例中获得的铜包层层合体(A-2、B-2)的铜箔进行蚀刻并将其除去之后,使用相对介电常数测量装置(谐振腔法)在1GHz下测量相对介电常数和介电损耗因子。具体地,使用网络分析仪(E5071C,Agilent Technologies)和SPDR(Split PostDielectric Resonator,分离介质谐振器,QWED)进行测量。
3.对铜箔的粘合强度(剥离强度,P/S,kgf/cm)
根据IPC-TM-650 2.4.8的测试方法,测量实施例和比较例的(6)和(7)中获得的铜包层层合体的对铜箔的粘合强度。
4.激光通孔可加工性的评估
在仅除去分别在实施例和比较例的(8)中制造的铜包层层合体A/B/A(7)的两侧上的载体之后,通过使用CO2激光的直接激光钻孔技术(ML605GTW4-5350U,MitsubishiElectric)加工直径为90μm的通孔。
*当孔周围出现铜箔的分层时评估为X,当无异常时评估为O。
[表1]
实施例的用于半导体封装的热固性树脂组合物的组成和预浸料的物理特性的确认(单位:g)
[表2]
比较例的用于半导体封装的热固性树脂组合物的组成和预浸料的物理特性的确认(单位:g)
*(a1)OPE-2St-1200(在两端处具有乙烯基苄基的改性亚苯基醚低聚物,数均分子量1187g/mol,乙烯基当量:590g/eq.,由Mitsubishi Gas Chemical Company Inc.制造)
(a2)OPE-2St-2200(在两端处具有乙烯基苄基的改性亚苯基醚低聚物,数均分子量2250g/mol,乙烯基当量:1189g/eq.,由Mitsubishi Gas Chemical Company Inc.制造)
(a3)SA-9000(在两端处具有甲基丙烯酰基的改性亚苯基醚低聚物,数均分子量2300g/mol,乙烯基官能度:1.9,由Sabic Innovative Plastics制造)
(a4)SA-90(在两端处具有羟基的改性亚苯基醚低聚物,数均分子量1600g/mol,羟基官能度:1.9,由Sabic Innovative Plastics制造)
(b1)BMI-5100(双马来酰亚胺,由Daiwa Kasei Industry Co.Ltd.制造,CAS#105391-33-1)
(c1)Ricon181(液体SBR聚合物,由Cray Valley制造,Tg-64℃,数均分子量3200g/mol,苯乙烯含量28%)
(c2)Tuftec P1500(选择性氢化的苯乙烯-丁二烯嵌段共聚物,由Asahi KaseiCorporation制造)
(c3)ULL-950S(含聚丁二烯的氰酸酯,由Lonza制造)
(c4)NZ-375(含二环戊二烯的氰酸酯,由Nanokor制造)
(c5)B1000(具有85%或更大的1,2-乙烯基含量的聚丁二烯液体树脂,数均分子量900g/mol至1300g/mol,由Nippon Soda Ltd.制造)
(c6)TAIC(三烯丙基异氰脲酸酯,由Tokyo Chemical Industry Co.,Ltd.制造,CAS#1025-15-6)
(d1)SC2050HNJ(经乙烯基三甲氧基硅烷处理的浆料型微二氧化硅,平均颗粒尺寸0.5μm,由Admatechs制造)
(e1)Dynasylan 6490(甲氧基官能化的乙烯基硅氧烷低聚物,由Evonik DegussaGmbH制造)
如表1所示,确定在实施例中提供的预浸料或金属包层层合体的情况下,在具有3.50或更小的低相对介电常数和0.0035或更小的低介电损耗因子的同时在预浸料的生产期间未出现裂纹,并且对铜箔的粘合强度和激光通孔可加工性是相对优异的。
另一方面,确定在比较例中提供的预浸料或金属包层层合体的情况下,在预浸料的生产期间出现裂纹,或者它们中的大部分表现出低的对铜箔的粘合强度,并且在激光孔加工期间,出现铜箔的分层。
Claims (15)
1.一种用于半导体封装的热固性树脂组合物,包含:
在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚);
热固性树脂;
选自以下的一种或更多种弹性(共聚)聚合物:a)数均分子量为1500至10000的基于丁二烯的橡胶,b)数均分子量为1500至10000且苯乙烯含量为10重量%至40重量%的基于苯乙烯-丁二烯的橡胶,c)以10重量%至70重量%的量包含苯乙烯的热塑性弹性体,和d)分子中包含聚丁二烯橡胶、聚二甲基硅氧烷或氟化热塑性树脂的氰酸酯;以及
无机填料。
2.根据权利要求1所述的用于半导体封装的热固性树脂组合物,
其中所述在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)的数均分子量为1000至3000。
3.根据权利要求1所述的用于半导体封装的热固性树脂组合物,
其中在两端处的所述烯键式不饱和基团包括乙烯基、烯丙基、甲代烯丙基、丙烯基、丁烯基、己烯基、辛烯基、环戊烯基、环己烯基、丙烯酰基、甲基丙烯酰基、乙烯基苄基、或乙烯基萘基。
4.根据权利要求1所述的用于半导体封装的热固性树脂组合物,
其中所述热固性树脂包括选自双马来酰亚胺树脂、氰酸酯树脂和双马来酰亚胺-三嗪树脂中的至少一种树脂。
5.根据权利要求4所述的用于半导体封装的热固性树脂组合物,
其中所述热固性树脂还包括选自以下的至少一种环氧树脂:双酚A型环氧树脂、苯酚酚醛清漆环氧树脂、四苯基乙烷环氧树脂、基于萘的环氧树脂、基于联苯的环氧树脂、二环戊二烯环氧树脂、以及基于二环戊二烯的环氧树脂和基于萘的环氧树脂的混合物。
6.根据权利要求1所述的用于半导体封装的热固性树脂组合物,包含:
基于总计100重量份的所述在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、所述热固性树脂和所述弹性(共聚)聚合物,
5重量份至70重量份的所述在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚),
10重量份至50重量份的热固性树脂,以及
5重量份至70重量份的弹性(共聚)聚合物。
7.根据权利要求1所述的用于半导体封装的热固性树脂组合物,
其中基于总计100重量份的所述在其两端处具有烯键式不饱和基团的改性亚苯基醚低聚物或改性聚(亚苯基醚)、所述热固性树脂和所述弹性(共聚)聚合物,所述无机填料的含量为30重量份至200重量份。
8.根据权利要求1所述的用于半导体封装的热固性树脂组合物,
其中所述用于半导体封装的热固性树脂组合物还包含烷氧基硅烷低聚物。
10.根据权利要求8所述的用于半导体封装的热固性树脂组合物,
其中所述烷氧基硅烷低聚物为选自甲氧基官能化的乙烯基硅氧烷低聚物、乙氧基官能化的乙烯基硅氧烷低聚物、和甲氧基官能化的乙烯基/苯基低聚物中的至少一种化合物。
11.一种预浸料,包含根据权利要求1所述的用于半导体封装的热固性树脂组合物和有机或无机纤维。
12.一种金属包层层合体,包括具有片形的根据权利要求11所述的预浸料;和形成在所述预浸料的至少一侧上的金属箔。
13.一种金属包层层合体,包括:
第一层,所述第一层包含根据权利要求1所述的用于半导体封装的热固性树脂组合物或其固化产物和厚度为15μm至90μm的有机或无机纤维;
第二层,所述第二层形成在所述第一层的两个表面上,并且包含根据权利要求1所述的用于半导体封装的热固性树脂组合物或其固化产物和厚度为10μm至30μm的有机或无机纤维;以及
金属薄膜,所述金属薄膜形成在所述第二层中的每一者的外表面上。
14.根据权利要求13所述的金属包层层合体,
其中所述第二层与所述第一层的厚度比为0.2至0.7。
15.根据权利要求13所述的金属包层层合体,
其中通过IPC-TM-650 2.4.8的测试方法测量的所述第二层与所述金属薄膜之间的剥离强度为0.50kgf/cm或更大。
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