- 學位論文
光固化型環氧樹脂在透明封裝材上之製備與性質研究
Preparation and Characterization of the Photo-curing Epoxy Resin in the Transparent Encapsulated Material
摘要
本研究藉由有機化改質天然無機層狀材料(Clay)作為補強材，再將其添加於環氧樹脂中，製備環氧樹脂/天然黏土的奈米級複合材料，以改善環氧樹脂材料特性，包括熱性質、阻氣性…等。本研究將天然無機層狀材料以離子置換法進行改質，雙改質系統選用2-苯基咪唑(2-Phenylimidazole ,PI)及氯化苄二甲烴銨(Benzokonium chloride ,BEN)作為改質劑，單改質系統選用二苯基-(4-苯基硫)苯基硫六氟銻酸鹽及二[4-二苯基硫苯基]硫醚二六氟銻酸鹽(Diphenyl(4-phenylthio)phenylsulfonium hexafloroatimonate and (Thiodi-4,1-phenylene)bis(diphenylsulfonium) dihexafluoroatimonate,C1176)，製備成二種不同的有機官能化改質型天然無機層狀材料，透過X光粉末繞射分析儀(XRD)、傅立葉轉換紅外線光譜儀(FT-IR)、掃描式電子穿透顯微鏡(SEM)判別經改質製程改質型天然黏土層間距變化及鑑定其改質型黏土之官能基，以及實際的堆疊情形與表面型態，再利用熱重分析儀(TGA)改質型無基層材之插層量所佔之比例。改質型無基層材進而與光固型環氧樹脂單體反應生成環氧樹脂/天然黏土奈米複材，對其熱穩定性、阻氣性、吸水性、親水性及耐刮和附著度性質相互比較並探討影響之原因。 奈米複材藉由X光粉末繞射分析儀(XRD)與穿透式電子顯微鏡(TEM)驗證層狀材料在環氧樹脂中的分散型態，並利用熱重分析儀(TGA)和動態機械分析儀(DMA)測量其熱裂解溫度(T5d)及玻璃轉移溫度(Tg)的變化，添加雙改質系統CL120-PI/BEN熱裂解溫度可增加53.5 ℃，玻璃轉移溫度上升 7.39 ℃，添加單改質系統CL42-C1176及CL120-C1176於80 %環氧樹脂中熱裂解溫度可分別提升73.2 ℃及59.1 ℃，玻璃轉移溫度則分別上升39.23 ℃及55.23 ℃；阻氣性質之探討由氣體滲透分析儀(GPA)量測得雙改質系統其氧氣及氮氣BIF值分別為1.2874及1.3398，單改質性多數均無氣體滲透；吸水率實驗顯示雙改質系統吸水率上升1.04 %，而單改質系統於80 %環氧樹脂中最多分別減少0.30 %及0.23 %；親疏水性使用接觸角分析儀測得雙改質系統接觸角提升由至70.52°，而單改質系統CL42-C1176及CL120-C1176，於80 %環氧樹脂中最明顯增加之接觸角分別為84.32°與77.05°；最後利用鉛筆硬度法和百格測試檢視複材之耐刮性及附著度，顯示雙改質系統中硬度提升至4H，耐刮性到達6H； 單改質系統中CL42-C1176於80 %環氧樹脂中硬度最高上升達4H，耐刮至6H；而CL120-C1176於80 %環氧樹脂中硬度最高同樣上升至4H，但耐刮性達到7H等級；而添加無機填充物後附著度上升一階層達到4B等級。
並列摘要
In This study, photocuring Epoxy resin nanocomposites were prepared by mixing the modified clay and monomer, before photo polymerization of resin. Epoxy/Clay nanocomposites show enhanced thermal stability, gas barrier etc. when compared to pure resin. Intercalating 2-Phenylimidazole (PI) and Benzokonium chloride (BEN) or Photoinitiator (C1176) in to the layers by ion-exchange method of the double modified system, and prepare the different of modified clays.Through a X-Ray Diffraction (XRD), Fourier Transform Infrared(FT-IR), Sanning electron microscope (SEM) and Thermogravimetry Analyer (TGA) could understand the before-and-after changes of the interlayer spacing and modification of modified clay and observations form the layered material. Adding the Inorganic layered materials which were modified into the epoxy in the preparation of nanocomposites when photocuring, and discuss the reasons and influence of its thermal stability, gas barrier,hydrophobicity,mar resistance and adhesive properties. From X-Ray Diffraction (XRD), Transmission electron microscopy (TEM),nanocomposites would understand the layered material in epoxy in the dispersion,using Thermogravimetry Analyer (TGA) and Dynamic Mechanical Analyzer(DMA) to measure the thermal decomposition temperature (T5d) and glass transition temperature (Tg), added CL120-PI/BEN thermal decomposition temperature increased by 53.5 ℃, glass transition temperature increased by 7.39 ℃. Added CL42-C1176 or CL120-C1176 thermal decomposition temperature increases by 73.2 ℃ and 59.1 ℃, glass transition temperatured increased by 39.23 ℃ and 55.23 ℃ in 80 % epoxy. Composites resistance of the gas tested by Gas Permeability Analyzer (GPA), Barrier Improvement Factor (BIF) of O2 and N2 is 1.2874 and 1.3398 by adding CL120-PI/BEN, all most no gas Permeability by adding C1176 system. Composites hydrophobicity testd shown increase 1.04 % by adding CL120-PI/BEN, added CL42-C1176 or CL120-C1176 reduced by 0.30 % and 0.23 % in 80 % epoxy. Contact Angle Analyzer shown increased to 70.52° by adding CL120-PI/BEN, added CL42-C1176 or CL120-C1176 increased to 84.32° and 77.05° in 80 % epoxy. Finally, the Pencil Hardness test method, Cross-Cut method to were used testing the composites mar resistance and adhesive property, mar resistance increased to 6H by adding CL120-PI/BEN, added CL42-C1176 or CL120-C1176 increased to 6H and 7H in 80 % epoxy, added modified clay ASTM to race the original 3B to 4B.