本論文之目的是製備具有耐磨耗性與表面疏水性之有機-無機混成材料之光電鍍膜材料。 本研究首先使用帶有triethoxysilane group的矽氧烷交聯劑(γ-methacrylate propyl trimethoxysilane, γ- MPTS)與丙烯酸單體（methyl methacrylate, MMA）以自由基聚合反應方式，形成共聚合物。更進一步利用共聚合物鏈上的矽氧烷官能基團與加入的tetraethoxylsilane(TEOS)、fluoroalkylsilane(FAS)與colloid silica在酸性條件下進行溶膠-凝膠反應，在反應過程中有機相與無機相間會形成共價鍵結合，以製備出poly(MMA-co-MPTS)-colloid silica之光學鍍膜材料。更進一步，本論文也探討二氧化矽凝膠粒子對材料之光學性質、耐磨耗性質、表面性質及熱穩定性之影響。
本論文所提出光學鍍膜製備方法之優點與未添加凝膠粒子方法比較，本論文方法對材料之光學性質、耐磨耗性質、及熱穩定性皆有明顯提升。 本論文方法之另一優點是由於鍍膜表面具有氟素官能基團及二氧化矽凝膠粒子，使鍍膜本身具有較佳之表面粗糙度與疏水性之特性。

The aim of this thesis is to synthesize the optical thin film for hydrophobic and abrasion-resistant inorganic/organic hybrid materials. The copolymer of poly(MMA-co-MPTS)-colloid silica were synthesized by using the free radical polymerization of the methyl methacrylate (MMA) with γ-methacrylate propyltriethoxysilane(γ-MPTS). Furthermore we hydrolyzed the above copolymer with tetraethoxylsilane (TEOS), fluoroalkylsilane (FAS) and colloid silica on the weak acid condition by a sol-gel process to obtain the optical thin film of hybrid material of poly(MMA-co-MPTS)-colloid silica. On the sol-gel reaction proceeding, the covalent bond was formed between organic phase and inorganic phase. Moreover, the effects of the colloid silica content on the optical properties, abrasion-resistant, morphology and thermal stability of the hybrid thin films were discussed in this thesis.
The advantage of our purposed method is the optical thin film being the good optical property, abrasion-resistant, and thermal stability in comparison with the optical thin film without colloid silica. The other merit is the surface of our thin film having the good properties of surface roughness and hydrophobic because of fluoroalkylsilane and colloid silica coexisted in the surface of our purposed method.

目 錄
中文摘要 i
英文摘要 ii
誌謝 iii
目錄 v
表目錄 viii
圖目錄 x
第一章 緒 論 1
1.1前言 1
1.2文獻回顧 4
1.2.1耐磨耗硬鍍膜材料製備相關文獻 4
1.2.2疏水性材料製備相關文獻 7
1.3相關原理 11
1.3.1疏水原理 12
1.3.2溶膠-凝膠法 15
1.3.3矽氧烷交聯劑 16
1.3.4氟素的特性 17
1.4研究動機 18
1.5論文架構 19
第二章 實驗方法 25
2.1實驗步驟及流程 25
2.2實驗藥品及材料 27
2.3實驗用分析儀器 29
2.4混成光學薄膜結構與性質鑑定 31
第三章 實驗結果與討論 41
3.1 混成光學薄膜紅外線吸收光譜分析結果 41
3.2 共聚合物(MMA-co-MPTS)之化學結構分析 44
3.3 共聚合物(MMA-co-MPTS)之分子量分布分析 45
3.4 XPS表面元素分析 46
3.5 混成材料之熱重損失分析 45
3.6 光學薄膜特性分析 50
3.6.1穿透度與折射率之分析 50
3.6.2光學薄膜表面性質與接觸角暨表面能分析 50
3.7光學鍍膜之硬度與耐磨耗量測 53
3.7.1光學鍍膜之硬度量測 53
3.7.2光學鍍膜之耐磨耗與霧度計量測 53
3.8光學薄膜之散射率分析 55
第四章 結論與未來展望 96
4.1結論 92
4.2未來展望 98
參考文獻 100
個人簡歷 106

[1] G. Philipp, and H. Shmidt, Journal of Non-Crystalline Solids, 63,283-292, (1984).
[2] Morikawa, Y. Iyoku, M. Kakimoto, and Y. Imai, “Preparation of new polyimide–silica hybrid materials via the sol–gel process”, Journal of Material Chemistry, 2, 679-690, (1992).
[3] 黃元昌等，”超疏水自潔技術與建築塗料上之應用”，化工資訊與商情，32 期，頁52-57，2 月，(2006)。
[4] 鄭總輝，陳振鑾，陳致源，鄭欽峰，”疏水自潔塗層結構概論”，工業材料雜誌，218 期，頁80-88，2 月，(2005)。
[5] R. Roy, and J. Am, Ceram. Soc., 52, 44, (1969).
[6] H. Dislich, Glastechn. Ber., 44, 1, (1971).
[7] 徐國財，張立德，化學工業出版社，北京，(2002)。
[8] A. Hozumi, Y. Kato, and O. Takai, “Two-layer hard coatings on transparent resin substrates for improvement of abrasion resistance ”, Surface and Coatings Technology,82, 16-22, (1996).
[9] S. K. Medda, D. Kundu, and Goutam De, “Inorganic-organic hybrid coatings on polycarbonate Spectroscopic studies on the simultaneous polymerizations of methacrylate and silica networks”, Journal of Non-Crystalline Solids, 318, 149-156, (2003).
[10]Wenxiu Que, Q. Y. Zhang, Y. C. Chan, C. H. Kam,”Sol-gel derived hard optical coatings via organic/inorganic composites ”, Composites Science and Technology, 63, 347-351, (2003).
[11]E. Rubio, J. Almaral, R. R. Bon, V. Castano, and V. Rodriguez, “Organic-inorganic hybrid coating (poly (methyl methacrylate)/ monodisperse silica) ”, Optical Materials, 27, 1266-1269, (2005).
[12]Y. Akasmatsu, K. Makita, H. Inaba, and Tsutomu Miinami,
“Water-repellent coating film on glass prepared from hydrolysis and polycondensation reactions of fluoroalkyltrialkoxylsilane”, Thin Solid Films, 389, 138-145, (2001).
[13]A. V. Rao, and Ravindra R. Kalesh, “Comparative studies of the physical and hydrophobic properties of TEOS based silica aerogels using different co-precursors”, Science and Technology of Advanced Materials, 4, 509-515, (2003).
[14]Dong J. Kang, T. H. Lee, and Byeong Soo Bae, “Fabrication and Characteristics of Sol-Gel Derived Fluorinated Hybrid Material Films”,Journal of Sol-Gel and Technology, 31, 113-116, (2004).
[15]K. Teshima, H. Sugimura, Y. Inoue, O. Takai, and Atsushi Takano,“Ultra-Water-Repellent Poly(ethylene terephthalate) Substrates”,Langmuir, 19, 10624-10627,2003.
[16]A. Nakajima, K. Hashimoto, and ToshiyaWatanabe, “Transparent Superhydrophobic Thin Films with Self-Cleaning Properties”,Langmuir, 16, 7044-7047, (2000).
[17]A. Nakajima, K. Abe, K. Hashimoto, and Toshiya Watanabe,
“Preparation of hard super-hydrophobic film with visible light transmission”, Thin Solid Films, 376, 140-143,(2000).
[18]C. J. Brimker, K. D. Keefer, D. W. Schaefer, C. S. Assink, J. Non-Cryst.Solids., 63, 45, (1984).
[19]A. Hozumi, Y. Kato, and O. Takai, “Two-layer hard coatings on transparedt resin substrates for improvement of abrasion resistance”,Surface and Coatings Technology, 82, 16-22, (1996).
[20]M. A. Rodriguez, and M. J. Liso, “Study of the reaction of 3-methacryloxypropyltrimethoxysilane(MPS) with Slate Surfaces”, J. Mater. Sci., 34, 3867-3873, (1999).
[21]Frank Bauer, H. Ernst, M. Findeisen, E. Hartmann, H. Langguth, R.Mehnert, R. Schubert, “Preparation of Scratch and Abrasion Resistant Polymeric Nanocomposites by Monomer Grafting Onto Nanoparticles,1”, Macromol. Chem. Phys., 201, 2654-2659, (2000).
[22]C. A. Capozzi, R. A. Condrate, L. D. Dye, and R. P. Hapannowicz,Mater. Lett. 18, 349, (1994).
[23]S. S. Hou, and P. L. Kuo, Macromol. Chem. Phys., 200, 2501-2507,(1999).
[24]詹勳昌，2000 年，”UV 光聚合法製備壓克力-二氧化矽混成光學薄膜及其特性之研究”，台灣大學，碩士論文。
[25]G. V. Schulz, and G. Haborth, Macromol. Chem., 1, 106, (1948).
[26]詹佳樺，2001 年，”以溶膠-凝膠法製備具甲基丙烯酸甲酯-二氧化矽混成體之研究”，中央大學，碩士論文。
[27]Yang-Yen Yu, C. Y. Chen, andWen-Chang Chen, “Synthesis and characterization of organic-inorganic hybrid thin film from poly(acrylic)and monodispersed colloidal silica”, Polymer, 44, 593-601, (2003).
[28]Katsuya Teshima et al., “Ultra-Water-Repellent Poly(ethylene terephthalate) Substrates”, Langmuir, 19, 10624-10627, (2003)
[29]Wenxiu Que et al., “Sol-gel derived hard optical coatings via organic/inorganic composites”, Composites Science and Technology, 63,347-351, (2003).
[30]Guotuan Gu. Zhijun Zhan, and Hongxin Dang, “Hydrophobic
inorganic-organic thin film with a low coefficient of friction”,Materials Research Bulletin, 39, 1037-1044, (2004).
[31]Guotuan Gu, Zhijun Zhang, and Hongxin Dang, “Preparation and characterization of hydrophobic organic-inorganic composite thin film of PMMA/SiO2/TiO2 with low friction coefficient”, Applied Surface Science, 221, 129-135, (2004).
[32]Hye-Jeong Jeong et al., “Preparation ofWater-Repellent Glass by Sol-Gel Process Using Prefluoroalkylsilane and Tetraethoxysilane”,Journal of Colloid and Interface Science, 235, 130-134, (2001).
[33]Hiroyuki Sugimura et al., “Organosilane self-assembled monolayers formed at the vapour/solid interface”, Surface and Interface Analysis,34, 550-554, (2003).
[34]Y. L. Liu, C. Y. Hsu, and K. Y. Hsu, “Poly methylmethacrylate)-silica nanocomposites films from surface-functionalized silica nanoparticles”,Polymer, 46, 1851-1856, (2005).
[35]鍾順雄，2004 年，”sol-gel 法製備壓克力-奈米二氧化矽混成光學薄
膜及其特性研究”，台北科技大學，碩士論文。
[36]Cacioii P, Moad G, Rizzardo E, Serelis AK, Solomon DH. Pliym Bull,1984; 11:325.
[37]B. S. Hong, J. H. Han, S. T. Kim, Y. J. Cho, M. S.Park, T.Dolukhanyan, and C. Sung, Thin Solid Films, 351, 247,1999.