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標題: | 兼具透明及耐熱特性聚醯亞胺之合成及應用 Synthesis and Applications of New Polyimides with High Thermal Stability and Transparence |
作者: | Mao-Chun Fu 傅茂鈞 |
指導教授: | 陳文章(Wen-Chang Chen) |
關鍵字: | 感光型聚醯亞胺,軟性透明基材,高透明性,色淡,光鹼起始劑, photosensitive polyimides,flexible transparent substrates,high optical transparency,colorless,photo-base generator, |
出版年 : | 2014 |
學位: | 碩士 |
摘要: | 聚醯亞胺為傳統高性能高分子,已經泛用於各個領域與產業中。近年來由於可撓式及穿戴式裝置蓬勃發展,軟性透明基材的需求也日益漸增,然而開發具有高透明性及優良熱機械性質之透明軟性基板仍具挑戰性。本論文由分子結構設計出發,合成出一系列具有高透明性,高熱機械性質且色淡的軟性光學膜。再進一步導入感光基團使其成為感光型聚醯亞胺,茲敘述如下:
由分子設計的概念導入含有脂環族(CHDA)和含六氟芳香族(TFMB)單體雙胺與剛硬芳香族雙酸酐(BPDA)合成高透明性,高熱機械性質且色淡聚醯亞胺及其共聚物, poly[t-1,4-cyclohexyldiamine-biphenylimide])(CHBPDAPI), poly[2,2'–Bis-(trifluoromethyl)-4,4'-diaminobiphenyl-biphenylimide]) (TFMBBPDAPI)和poly[t-1,4-cyclohexyldiamine/2,2'-Bis(trifluoromethyl)-4,4' -diaminobiphenyl -biphenylimide]) (CH/TFMBBPDAPI)。利用脂環族及含六氟之芳香族雙胺單體降低電子轉移能力來達到色淡及增加膜的穿透度,同時藉由導入含六氟之芳香族雙胺單體降低折射率,而脂環族雙胺單體與芳香族雙酸酐單體之剛硬結構,以進一步提升熱性質與機械性質。由研究結果顯示藉由調控脂環族與含六氟之芳香族雙胺之比例,可以調控聚醯亞胺的各項物理性質,而隨著含六氟之芳香族雙胺比例增加,聚醯亞胺的折射率能因導入氟原子由1.68降低至1.59, 且由於芳香基團的比例提高,其熱裂解溫度亦由474 oC提升至534 oC;另一方面隨著脂環族雙胺比例增加,由於規整且剛硬的結構,而使聚醯亞胺的熱膨脹係數能由28 ppm/oC下降到6 ppm/oC,且其玻璃轉移溫度同時也從275 oC上升至335 oC。此外所合成的聚醯亞胺在膜厚28到30 μm擁有良好的透明性,在CHBPDAPI中膜厚甚至可以增加至50到52 μm仍擁有良好的透明性,穿透度在波長400 nm下仍大於85 %,且維持極佳之機械性質(Tensile Strength= 200 MPa, Tensile Modulus= 5.8 GPa and Elongation= 3.2 %),且不溶解於有機溶劑,顯示其在軟性透明基板上的應用有相當大的潛力。 第二部分延續半脂環族聚醯亞胺(CHBPDAPI)良好的光學性質及熱機械性質再從中導入感光基團:肉桂酸型光鹼起始劑 (Cinnamic-type PBG) ,可成功將此系統轉變為感光性聚醯亞胺(PSPIs) 。藉由導入光鹼起始劑除了能有效的光圖案化之外,光鹼起始劑所產生的鹼更能有效的催化聚醯胺酸(PAA),使其在較低的溫度轉變為聚醯亞胺(< 250 oC) ,且在較6 μm的薄膜依然擁有良好的解析度(50 μm)。上述研究結果顯示此感光性聚醯亞胺系統除了保有良好光學性質及熱性質外,能直接進行光圖案化,使得製程上更有效率,而於電子工業所需之感光塗層具應用潛力。 Polyimides have been widely recognized as high-performance functional materials for the applications in electronic and optoelectronic industry. In recent years, the rapid growth of the wearable devices has a high demand for flexible transparent substrates. However, the development of the flexible substrates with high optical transparency as well as excellent thermal and mechanical properties remains challenges. In this thesis, we develop a series of polyimides and photosensitive polyimides to meet the above requests, as described in the following. In the first part, we prepared new polyimides consisted of diamines (alicyclic(CHDA) or hexafluorine diamine(TFMB)) and rigid aromatic dianhydride(BPDA), poly[t-1,4-cyclohexyldiamine-biphenylimide])(CHBPDAPI), poly[2,2'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl-biphenylimide] (TFMBBPDAPI) and poly[t-1,4-cyclohexyldiamine/2,2'-Bis(trifluoromethyl) -4,4'-diaminobiphenyl -biphenylimide] (CH/TFMBBPDAPI). The charge transfer in polyimide backbone was reduced by alicyclic and hexafluorine moieties for optical transparence. In addition, introducing the linear/stiff alicyclic diamine(CHDA) and aromatic dianhydride(BPDA) further improved the thermal and mechanical properties. Furthermore, the refractive index was decreased by incorporating the moiety of hexafluorine diamine(TFMB). The experimental results showed that introducing alicyclic moiety improved the heat-resistant, transparency and mechanical properties of polyimides. Also, we could control the properties by tuning the ratio between alicyclic diamine(CHDA) and hexafluorine diamine(TFMB). As the hexafluorine aromatic diamine(TFMB) increased, the refractive index of polyimide effectively reduced from 1.68 to 1.59. The thermal decomposition temperature increased from 474 oC to 534 oC with enhancing the BPDA content. Also, the thermal expansion coefficients of the prepared polyimides were effectively reduced from 28 to 6 ppm/oC due to the rigid structure, while glass transition temperatures also increased from 275 to 335 oC. The prepared polyimides also exhibited very good mechanical properties, with tensile strength of 200 MPa, tensile modulus of 5.8 GPa and elongation of 3.2 %. High optical transmittance greater than 85% at 400 nm was also observed for the prepared polyimide film with the thickness around 28 to 30 μm. In the prepared CHBPDAPI polyimide film, high optical transparence as well as good thermal and mechanical properties could be maintained even if the thickness was increase to around 50 to 52 μm. The prepared polyimides are insoluble in organic solvents. The above results indicated that the prepared polyimides could have potential applications in flexible transparent substrates. The second part of the thesis is to explore the photosensitive semi-alicyclic polyimide(CHBPDAPI) using cinnamic-type photo-base generator. Introducing the cinnamic-type photo-base generator not only effective catalyzed polyimide precursor: poly(amic acid) but also undergoes a low-temperature imidization(< 250 oC). The developed photosensitive polyimides showed good optical properties and thermal mechanical properties. Also, it could be directly photo-patterned and exhibited a very nice resolution(50 μm) in thicker film(6 μm), which could be potentially used in electronic industry. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57755 |
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顯示於系所單位: | 高分子科學與工程學研究所 |
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