第一部：矽氧烷與亞醯胺改質之環氧樹脂製備、交聯行為、物性及在電子領域應用;第二部：矽氧烷與亞醯胺改質之雙丙烯雙酚、矽氧烷改質雙馬來亞醯胺與氰酸酯互穿高分子交聯網之材料之研究

Abstract

摘 要

第一部分的研究是先用nadic anhydride 與tetramethyldisiloxane 進行矽氫化反應得到5,5’-（1,1,3,3-tetramethyl-1,1,3,3-disiloxanedialyl）-bis-norbornane-2,3- dicarboxylic anhydride (I)；再藉由亞醯胺反應製備矽氧烷亞醯胺改質之雙胺化合物(IIb)與雙酚化合物(II)：最後利用此雙酚化合物(II)與epichlorohydrin反應得新型主鏈含矽氧烷及亞醯胺基圑改質之環氧樹脂(Ⅲ)。分別將此環氧樹脂(Ⅲ)、商用環氧樹脂(830LVP) 與此矽氧烷雙酸酐(I)以不同當量比(1/1,1/0.8)混合配料。以FT-IR及動態DSC研究其交聯行為，可以瞭解到此新型環氧樹脂的亞醯胺基圑對環氧樹脂交聯反應具有很明顯的催化效應，使得其交聯只有12.4KJ/mole-14.40KJ/mole較商用環氧樹脂反應活化能低。硬化後材料DMA和TMA研究都顯示主鏈上同時含有柔軟的矽氧烷結構和硬質之亞醯胺基團(bis-norborane-2,3-dicarboximide)設計使得此材料具有較高Tanδ以及較大的轉移能量而達到增韌效果，同時又可以保有相當高的玻璃轉移溫度(III/I=1/1之Tg：173.2℃)。矽氧烷與亞醯胺基圑也使得此硬化材料展現良好的耐熱特性，尤其是裂解過程中材料本身會產生片狀的Silicone dioxide而阻礙了裂解反應的進行。 此新型硬固型環氧樹脂擁有這樣良好的熱機械特性、熱安定性以及較低的介電常參數都說明是十分適合應用於高性能半導體構裝產品上。所以在本研究的第四章就用此矽氧烷與亞醯胺改質之環氧樹脂(III)、雙酚化合物(II)與雙胺化合物(IIb)以當量比1/0.7/0.3製備驅動IC用內部聯通材料。構裝實驗結果顯示此三種化合物結構中的亞醯胺基團對交聯硬化反應具有催化效果使得系統180℃/10s.就可以有高且穩定的接著強度(1108.5gf)。也由於此熱固型材料本身有柔軟性的矽氧烷基團所以不需要聚摻混增韌劑(如:CTBN)就可以製成薄膜材料；而將低吸濕特性的矽氧烷基團設計在高分子主鏈上，又在其鄰近就伴隨有硬質基團的亞醯胺基團，所以用此系統製備之內部聯通材料在構裝信賴性測試上顯示電性非常的穩定, 完全符合驅動IC構裝產品特性需求。 同時在第五章研究中用此矽氧烷與亞醯胺改質之環氧樹脂(III)與雙胺化合物(IIb)以當量比1/1在不外加柔軟劑下製備適用於高密度印刷電路基板增層製程用之環氧樹脂材料。因其組成物：環氧樹脂、硬化劑，都同時存在有低吸濕性、低介電常數之矽氧烷(silynorbornane)基團及耐熱性佳、高Tg之亞醯胺基團，硬化材料之Tg為172.74℃且接著強度為1.34kg/cm，這顯示由此新型環氧化合物製成之材料可以同時保有矽氧烷、亞醯胺及環氧樹脂原有的機械特性。經過完整的熱壓合製程、雷射鑽孔、化學鍍銅以及電性信賴性評估，結果顯示此薄膜介電絕緣材料可以滿足高密度印刷電路基板增層製程特性要求，並具有大幅降低材料成本之功效。 第二部分研究是合成出含矽氧烷之雙馬來亞醯胺之化合物（Si-BMI）及矽氧烷及亞醯胺結構改質之雙丙烯雙酚化合物（Si-DABP），其結構均以經由1H NMR及FT-IR之鑑定無誤，再與低介電之氰酸酯(Cyanate ester：LECY)形成IPNs系統(Si-BMI/Si-DABP/LECY)。Si-BMI/Si-DABP/LECY系統經由詳細的FT-IR動力學研究發現： Si-DABP的OH基因IPN的網目互鎖結構使得對Cyanate ester環化交聯催化果消失，跟一般具有催化效果的預期相反。Cyanate ester環化交聯反應動力學是符合一級的未催化反應動力學且反應活化能也因IPNs的立體障礙變得較高。 硬化後的熱固型材料具有很高的玻璃轉移溫度（Tg=243℃），擁有良好的熱穩定性(T5wt%=311℃)，同時具有較低的介電常數（2.8）及良好的柔韌性，這是因為組成中含有柔軟矽氧烷的雙馬來亞醯胺（Si-BMI），因此可以成功的降低介電常數及增加韌性。更因為IPN的互穿網目結構以及norborane-2,3-dicarboximide基團，使得材料雖然加入柔軟的部分卻仍可以保有材料的機械特性。

關鍵字：矽氧烷與亞醯胺改質環氧樹脂、矽氧烷與亞醯胺改質雙丙烯雙酚、交聯活化能、熱裂解活化能、互穿透高分子交聯網、動態FT-IR、氰酸酯反應動力學、電子應用材料

ABSTRACT

Hydrosilylation of nadic anhydride with tetramethyldisiloxane yielded 5,5’-(1,1,3,3-tetramethyl-Disiloxane-1,3-diyl)-bis-norborane-2,3-dicarboxylic anhydride (I), which further reacted with 4-aminophenol to give N,N’-bis(4-hydroxyphenyl)-5,5’- bis -(1,1,3,3-tetramethyl disiloxane-1,3- diyl)- bisnorborane-2,3-dicarboximide (II). Epoxidation of II with excess epichlorohydrin formed a siloxane- and imide-modified epoxy oligomer (i.e diglycidyl ether of N,N’-bis(4-hydroxyphenyl)- 5,5’-bis- (1,1,3,3-tetramethyl disiloxane-1,3- diyl)- bisnorborane-2,3-dicarboximide) (III). Various equivalent ratios of III/ I for 1/1, 1/0.8 and Bisphenol F epoxy (830LVP DIC Co.)/I for 1/1, 1/0.8 were prepared and cured to produce four crosslinked materials. Kinetic analysis was studied with dynamic DSC, which revealed a relatively lower curing activation energy of III/I systems, because the tertiary amine on the imide group catalyzed the curing reaction. Thermal and dynamic mechanical properties were investigated with TMA and DMA. It is noted that each of these two materials show glass transition temperature (Tg ) higher than 160℃ with moderate moduli . These phenomena were interpreted by the fact that the siloxane group in III toughened the crosslinked materials. The thermal degradation kinetics was studied with dynamic TGA and the estimated apparent activation energy were 111.40 (in N2), 117.80 (in air), 149.18 (in N2) for III /I =1/ 0.8, and 147.61KJ/Mole (in air) for III/I=1/1, respectively. White flaky residue of the TGA char was confirmed to be silicone dioxide, which formed a barrier at the surface of the polymer matrix and, in part, accounts for the unique heat resistance of this material. We choose the equivalent ratio of III/II/IIb=1/0.7/0.3 to fabricate the film type interconnecting material for LCD drive IC application. The film type material could achieve the stable and good bonding adhesion within 5seconds on 180℃ since the tertiary amine on the imide group catalyzed the curing reaction. We evaluated the reliability performance and the result revealed the siloxane and imide modified epoxy possess the excellent properties for LCD package. Furthermore, the III/IIb=1/1 could be directed coated on the PET substrate without adding flexible additives. The Tg of the film type dielectric material is 172.74℃ and the PCB bonding strength is 1.34kg/cm after heating compressing process. The film type material could be competent the complete build-up PCB processing evaluations.

Keywords: Siloxane- and imide-modified epoxy oligomer; crosslinked materials; dynamic mechanical properties; thermal degradation kinetics; apparent activation energy ; SiO2 char residual. Electronic application