電子用之新型環氧樹脂與新型BT樹脂共交聯材料之研究

Abstract

在這本篇論文研究中，我們發展出新型含矽氧烷及亞醯胺基環氧樹脂和氰酸酯化合物。在第Ⅰ章中我們成功合成含矽氧烷、亞醯胺四官能基環氧樹脂，這項設計主要目的是希望藉此改善傳統環氧樹脂之機械性、熱穩定性及尺寸安定性。在第II章中，我們將有機-無機混成材料-POSS導入商用環氧樹脂，藉著POSS的高度自由體積及其他特性降低介電常數。 另外，商業上BT樹脂是由氰酸脂及BMI所混成，他可以提供良好的機械強度及電氣性質，因此廣泛的被應用於封裝產業。然而，商業用BT樹脂存在著不易硬化、加工困難及介電常數較高等問題；因此，在本論文中第III，IV 和V章主要的研究目標在於利用分子結構設計將低介電常數之官能基如siloxane，imide等，設計為高分子主鏈。另外為增加與BT樹脂中BMI交聯性及反應性吾人將 allyl C=C鍵結併入合成新穎的氰酸脂樹脂。吾人利用這種新型含矽氧烷亞醯胺、乙烯基氰酸脂與等當量BMI混合形成新型的BT 樹脂。然後該新穎的BT樹脂在與不同當量的商用環氧樹脂共交聯反應，藉以改善商用環氧樹脂的物性及電氣性質。 為了更進一步了解氰酸脂/環氧樹脂最佳應用及共交聯行為過程，在第III章中我們利用FT-IR觀察交聯過程中官能基變化。而在第III, IV, and V.章中我們利用DSC、TGA、TMA、Gel fraction測試材料的各種物性，在第V章，利用新穎的BT樹脂與商業用環氧樹脂摻混，並進一步與新型的含矽氧烷亞醯胺基環氧樹脂形成新型的共交聯材料，以改善傳統環氧樹脂缺點，使得這類共交聯材料達到多數微電子製程應用上的要求。最後在第VI章中吾人利用FT-IR觀測氰酸脂、BMI、環氧樹脂三成分間交聯硬化動力學參數之研究，分別探討氰酸脂/BMI、氰酸脂/環氧樹脂、氰酸脂/BMI/環氧樹脂各成分系統間官能基的變化，發現其中氰酸脂之反應機構與文獻上發表大致相同，且其中在三個系統中反應級數n值極為相近，趨近於2。其中自催化反應常數k2大約為非催化反應常數k1大10倍；在活化能測試上，自催化活化能E2及未催化活化能E1皆可以得到，且E2、E1隨成分增加而逐漸升高，可能是因為多成分共交聯間會有較小的凝膠分率所致。

In this study novel materials based on epoxy and cyanate ester containing siloxane and imide groups were investiged.Chapter I dealed with siloxane- and imide-containing tetrafunctional epoxy, which was designed mainly to improve mechanical performance , thermal stability and dimensional stability. In chapter II, incorporating POSS moiety into epoxy resin resulted in reduction of dielectric constant with sacrifice of some other properties. BT resin, ie., blend of cyanate ester and bismaleimide (BMI), possesses good mechanical strength and is currently used in packaging material. However, lack of resin curing and dielectric constant are drawbacks of the commercial BT resin. Therefore, focus on the improvement of resin curing, dielectric constant and mechanical performance was the important goal in chapters III, IV and V, where siloxane , imide and allyl groups were incorporated into a cyanate ester. This cyanate ester was blended with equivalent amounts of modified BMI to form a novel BT resin. Materials are then prepared by co-curing this novel BT resin with different epoxies to improve the resin curing and material performances. For better understanding of optimal application, curing behavior was studied in chapter III. Properties of the co-cured materials were studied in chapters III, IV, and V. In chapter V, co-cured materials were also prepared by blending the novel BT resin with commercial epoxy to form part A resin, which then, further co-cured with different amounts of a novel epoxy containing siloxane and imide. This co-cured material possessed most of the properties required for microelectronic application. Study of curing kinetics is given in chapter VI. In kinetic studies of the three components system (cyanate ester/ BMI/epoxy), functional group changes basically were the combination of the two systems ( cyanate ester/epoxy and cyanate ester/BMI). There was no new chemical bonding found between the two net works( cyanate ester/epoxy and cyanate ester/BMI). Kinetic parameters found indicated very similar to one another among the three different systems. The rate constant of catalytic reaction (k2) was approximately 10 times higher than that of non-catalytic reaction (k1). Increased activation energies for both catalyzed (E2) and non-catalyzed (E1) reactions were observed, compared with those of the component material. This finding explained the lower gel fractions of co-cured materials.