反应诱导相分解制备丙烯酸橡胶/环氧胶粘剂的结构与性能

Tetsuro Iwakura, T. Inada, M. Kader, Takashi Inoue
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引用次数: 9

摘要

随着电子器件小型化的发展,半导体封装需要高性能的二粘胶膜。二粘膜应具有较高的耐热性和良好的粘接性能。为了达到这样的性能和可靠性,我们选择了富含橡胶的环氧胶粘剂。本文研究了丙烯酸橡胶(ACM)的反应部位、固化剂和固化条件对二粘膜性能的影响。在固化初期,ACM/环氧树脂/固化剂(如DDM:二氨基二苯甲烷)体系为单相混合物。随着固化反应的进行,由于环氧树脂分子量的增加,通过spinodal分解发生相分离。光散射曲线随固化时间的特征变化证实了反应诱导的spinodal分解。相衬显微镜和原子力显微镜也发现了有规律的相分离结构的形成,这是spinodal分解的特征。该结构的周期距离变化范围很广,从几μm到十nm不等。ACM中活性位点(甲基丙烯酸缩水甘油酯)用量越高,固化温度越低,周期距离越短。周期距离越短,粘接强度越高。然而,10 nm的距离较短,导致粘接强度较差。亚μm结构可以获得最佳强度。10 nm结构材料热膨胀小,透明度好。
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Structure-Properties of Acrylic Rubber/Epoxy Adhesive by Reaction-Induced Phase Decomposition
The advancement in the miniaturization of electric devices requires high performance diebond adhesive films for semiconductor packages. The diebond film should have high thermal-stress resistance and good retention of adhesive properties. To achieve such performance and reliability, we choose a rubber-rich epoxy adhesive. In the present work, we investigated the influence of reactive site of acrylic rubber (ACM), cure agent and curing condition on the performance of diebond film. In the early stage of curing, ACM/epoxy/curing agent (e.g., DDM: diaminodiphenylmethane) system was a single-phase mixture. As the cure reaction proceeded, phase separation took place via the spinodal decomposition, induced by the increase in the molecular weight of epoxy. The reaction-induced spinodal decomposition was confirmed by the characteristic change in light scattering profile with curing time. Phase contrast microscopy and atomic force microscopy also revealed the formation of regularly phase-separated structure characteristic to the spinodal decomposition. The periodic distance of the structure varied in a wide range, from a few μm to ten nm. The higher amount of reactive site (glycidylmethacrylate) in ACM and the lower cure temperature rendered the shorter periodic distance. The shorter periodic distance yielded the higher adhesive strength. However, much shorter distance of 10 nm resulted in poor adhesive strength. The sub-μm structure seems to lead to optimum strength. The 10 nm structure material showed low thermal expansion and nice transparency.
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