本研究主要分為三部分：第一部分根據無色聚亞醯胺之分子結構設計概念選用兩種二酸酐和兩種二胺進行合成及性質檢測，評估其最佳之合成單體種類。實驗結果證實，選用bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA)和3,4'-oxydianiline (3,4'-ODA)所合成之聚亞醯胺為性質最佳，其光學透光度約86.7 %（約22.0μm），熱膨脹係數為57.4 ppm/℃。第二部分為增加其尺寸安定性，利用第一部分選擇之合成單體導入二官能或三官能乙烯基交聯劑，並利用自由基加成反應製備一系列交聯結構之聚亞醯胺。由變溫FTIR光譜圖可觀察到雙鍵之吸收峰隨著反應溫度增加而減少，證實聚亞醯胺上之二酸酐π鍵逐漸反應而消耗掉；光學性質分析方面，UV-vis穿透光譜圖中，PIBO-3N45之光學穿透度高達88.2 %（約27.0μm），由阿貝、螢光分析可得知聚亞醯胺因導入交聯劑而有破壞電荷轉移的現象，對於透光度有明顯的增加。另外，霧度值也相當低。而阿貝數則高達194，為相當優良之光學材料；在熱及機械性質顯示出，添加交聯劑後其熱穩定性未有太大的改變，失重最大溫度皆高於425℃，Tg點約在330~340℃之間，而熱膨脹係數皆有下降的傾向，其中PIBO-3N45熱尺寸安定性增加的幅度最大，熱膨脹係數下降為33.1 ppm/℃。綜觀第二部分具最佳光學穿透度與低熱膨脹性之聚亞醯胺為PIBO-3N45混成薄膜；第三部分為交聯結構之聚亞醯胺/Silica sol混成薄膜製備與性質分析，於光學性質方面，由UV-vis光譜圖中顯示，少量添加Silica sol透光度波長550 nm時，其透光度有些許的提升，但隨著Silica sol含量增加至30 wt%即未能明顯的提升透光度。加入Silica sol後折射率呈現下降的趨勢，而霧度值小於1，顯示出混成薄膜與Silica未有凝聚的現象。熱及機械性質方面，由DTG曲線可觀察到添加Silica sol後失重最大溫度皆有上升的現象，而Tg點從335℃小幅提升至338℃，且阻尼有大幅下降的趨勢，顯示出聚亞醯胺/二氧化矽複合薄膜具有相當優越的熱穩定性及剛性。另外，藉由塗佈抗反射層以提升聚亞醯胺之透光性，實驗結果指出塗佈抗反射層後明顯減少表面粗糙度（Ra < 0.499 nm），而光澤度亦有顯著的下降，改善光學透光性並提升至89 %（@550 nm）。

This thesis is divided into three parts: (1) monomer selection, (2) crosslinkable reagent addition and (3) silica sol incorporation. Two kinds of dianhydride and diamine were investigated to obtain colorless PI with low coefficient of thermal expansion (CTE). The results indicated that the PI film synthesized from bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and 3,4'-oxydianiline (3,4'-ODA) presented excellent properties. The transmittance and CTE of this PI film are 86.7% and 57.4 ppm/oC, respectively. With the introduction of crosslinkable reagent into the above PI, crosslinking structure was formed by free radical addition reaction and enhanced dimensional stability. With the increasing reaction temperature, a gradual decrease in the intensity of characteristic absorption band of π bond from dianhydride BCDA was observed from variable-temperature FTIR spectra. The PIBO-3N45, which was prepared from BCDA and 3,4'-ODA with the addition of 45% crosslinkable agent of triallylamine, is most transparent among other PI films. As presented in the UV-Vis spectra, the transmittance at 550 nm of PIBO-3N45 film with the thickness of 27 μm is 88.2%. The fluorescent spectra and Abbe refractive analysis confirm the charge transfer (CT) phenomenon was diminished and consequently the transparency was increased after crosslinking. Furthermore, its Abbe value is as high as 194 for optical application. The crosslinked PI films have excellent thermal and mechanical properties: The maximum weight loss temperatures from DTG curves higher than 425 oC, the glass transition temperature ranging from 330 to 340 oC, and the CTE being lower than pure PI. The CTE of PIBO-3N45 is the lowest (33.1 ppm/ oC) among crosslinkable PIs. Therefore, the PIBO-3N45 has the best properties for optical, thermal and mechanical applications.
With the incorporation of silica sol (< 30 wt%) into PIBO-3N45, the transmittance at 550 nm of this PIBO-3N45 hybrid film increases slightly with silica content. The refractive indices slightly increase with the increasing silica content. In addition, the small haze value (<1) indicates the well dispersion of silica particles in PI matrix. The hybrid film containing 30wt% silica sol shows slightly increased maximum weight loss temperature, enhanced Tg, from 335 oC to 338 oC, and reduced damping intensity indicating improved rigidity and stiffness of hybrid films.
Finally, in order to reduce the surface roughness and reflection of PI films, an anti-reflection (AR) coating procedure was applied on a series of crosslinked PI films. After AR coating, significant decreases in the surface roughness (Ra < 0.499 nm) and gloss were observed. The optical transmittance at 550 nm of PIBO-2N63 film with the AR coating thinkness (Ti/Si) of 10/10 nm is further enhanced from 87% to close 90%.

中文摘要 i
Abstract iii
誌謝 v
目錄 vii
表目錄 xi
圖目錄 xiii
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 5
第二章 文獻回顧及儀器原理 6
2-1聚亞醯胺 6
2-1-1 簡介 6
2-1-2 聚醯亞胺的製備 8
2-2 無色聚亞醯胺 11
2-2-1 簡介 11
2-2-2 結構設計原理 12
2-3 溶膠-凝膠法 15
2-4 抗反射膜 16
2-5 儀器原理 19
2-5-1 傅立葉變換紅外光譜儀 19
2-5-2 熱機械分析儀 20
2-5-3 熱重量分析儀 22
2-5-4 動態機械分析 23
2-5-5 紫外光/可見光光譜儀 25
2-5-6 螢光光譜儀 27
2-5-7 霧度計 29
2-5-8 阿貝折射計 30
2-5-9 光澤度計 31
3-1 實驗藥品 33
3-2 實驗步驟 35
3-2-1 單體評估：全芳香與半芳香族聚亞醯胺之合成 35
3-2-2 合成交聯之半芳香族聚亞醯胺 38
3-2-3 交聯結構聚亞醯胺/Silica sol混成薄膜之合成 39
3-2-4 抗反射膜之塗佈 40
3-3 實驗儀器與設備 41
第四章 結果與討論 45
4-1 單體評估 45
4-1-1 FTIR光譜分析 45
4-1-2 紫外光/可見光光譜分析 47
4-1-3 螢光放射光譜分析 49
4-1-4 熱穩定性及熱尺寸安定性分析 50
4-2交聯結構之聚亞醯胺鑑定與特性分析 53
4-2-1 傅立葉變換紅外光譜分析 53
4-2-2 紫外光/可見光光譜分析 57
4-2-3 螢光放射光譜分析 59
4-2-4 折射率與霧度分析 62
4-2-5 熱穩定性質分析 65
4-2-6 熱尺寸安定性質分析 68
4-2-7 動態機械性質分析 70
4-3 交聯結構之聚亞醯胺/Silica sol混成材料鑑定與特性分析 72
4-3-1 傅立葉變換紅外光譜分析 72
4-3-2 紫外光/可見光光譜分析 74
4-3-3 折射率與霧度分析 75
4-3-4 熱穩定性質分析 77
4-3-5 熱尺寸安定性質分析 78
4-3-6 動態機械性質分析 79
4-3-7 抗反射層塗佈之紫外光/可見光光譜分析 81
4-3-8 抗反射層塗佈之表面粗糙度分析 85
4-3-9光澤度分析 92
結論 94
單體評估 94
交聯結構之聚亞醯胺鑑定與特性分析 95
交聯結構之聚亞醯胺/Silica sol混成材料鑑定與特性分析 96
交聯結構之聚亞醯胺表面抗反射處理 96
參考文獻 98

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