臺灣博碩士論文加值系統

本研究主要是探討奈米金屬氧化物和矽烷以溶凝膠(Sol-Gel)法合成有機-無機混成塗料。此一塗料可塗佈在各種塑膠表面而具有保護作用，同時具備抗磨、高硬度等性質，且與基材附著良好。
實驗的步驟為利用奈米氫氧化鋁(AlOOH)和具壓克力基矽烷 (MPTS)在高溫下進行水解縮和，而後以溶劑稀釋至固成分45wt%之溶膠。製備完成的溶膠可儲存30天以上而黏度維持穩定。此一溶膠加入UV起始劑及其他補助劑後配成塗料，以旋鍍或線棒方式塗佈於PC、PMMA、PVC板材和PET 膜(厚度38μm)等基材上，經UV光照射硬化後，以標準測試方法來檢測此塗佈層與塑膠基材的黏著性，抗磨性及硬度。測試結果發現此塗佈層完全不會剝落。並且經過研磨機上研磨500轉後，PC、PVC和PMMA的透光度只下降5∼10％；而PET 膜在研磨100轉後透光度僅下降2％。已達到實用規格要求。

This work describes the reaction of nanoscaled metal oxides and silane by the sol-gel process to make inorganic/organic hybrid coatings. These hybrid coatings are UV curable, hard, transparent and can improve the abrasion resistance of plastics ( eg. PC、PMMA、PVC and PET).
The nanoscaled boehmite particles and methacrylate functionalized silanes were used for the preparation of the UV curable hard coatings. After the hydrolysis and condensation of the methacryloxysilane in presence of the nanoparticles at high temperature, the sol was diluted with solvents. The solid content of this coating sol was 45wt% and it had a long pot life. The transparent coatings on plastics were produced by spin coating or wire bat and the coatings show good optical quality and excellent adhesion on plastics coated with primers.

The transparent coatings show good abrasion resistance after performing the Taber abrader test. After 500 abrasion cycles, haze values of the coating on PC、PVC、PMMA were 5~10% and for the coatings on PET film (38μm, thickness) the haze values were 2% after 100 cycles.

目錄
摘要 …………………………………………………………………Ⅰ
目錄 …………………………………………………………………Ⅱ
圖目錄……………………………………………………………… Ⅳ
表目錄……………………………………………………………… Ⅵ
第一章 緒論………………………………………………………….1
1-1 奈米粒子的特性…………………………………………………2
1-2 矽烷與金屬氧化物反應…………………………………………3
1-3 有機-無機混成材料的合成與應用……………………………...9
1-3.1 有機-無機混成材料的合成方法…………………………...11
1-3.2 有機-無機混成材料的應用 ……………………………….13
第二章 文獻回顧 …………………………………………………..15
第三章 氫氧化鋁奈米粒子與矽烷之水解縮合……………………21
3-1 實驗藥品………………………………………………………..21
3-2 反應溫度………………………………………………………..22
3-3 反應速率………………………………………………………..24
3-4 氫氧化鋁/MPTS的紅外線吸收光譜分析……………………..26
3-5 配方之再次研究………………………………………………..32
3-6 粒徑分析結果…………………………………………………..38
3-7 紫外線曝光後之紅外光譜分析………………………………..40
3-8 綜合討論………………………………………………………..42.
第四章 無機/有機抗磨塗料之性質測試…………………………..44
4-1 塑膠基材之選擇………………………………………………..45
4-2 光硬化塗料之配製及塗佈……………………………………..46
4-3 機械性質測試…………………………………………………..47
4-3.1 黏著性………………………………………………………47
4-3.2 抗磨性………………………………………………………48
4-3.3 硬度…………………………………………………………49
4-4 抗磨層之機械性質……………………………………………...50
4-4.1 PC板材及PET膜…………………………………………..51
4-4.2 PVC、PMMA板材…………………………………………56
4-5 塗佈層之抗化學性……………………………………………...63
第五章 結果與建議…………………………………………………65
參考文獻……………………………………………………………..70

1. C.J. Brinker, G.W.Scherer, ”Sol-Gel Science”, (1992)。2. H.Schmidt, E.Arpac, H.Schirra, S.Sepeur, G. Jonschker, ”Aqueous Sol-Gel Derived Nanocomposite Coating Materials”, Mat. Res. Soc. Symp. Proc., 519, 297-308, (1998)。3. K.-H.Haas, S. Amberg-Schwab, K.Rose, G.Schottner, ”Functionalized Coatings based on Inorganic-Organic Polymers (ORMOCER)and their combination with vapor deposited inorganic thin films”, Surface ang Coatings Technology , 111, 72-79 (1999)。4. A.Morikawa, Y. Iyoku, M.Kakimoto, Y.Imai, J. Mater.Chem. , 2(7), 679-690 (1992)。.5. G. Philipp, H.Shmidt, ”New Materials for Contact Lenses Prepared From Si- and Ti-Alkoxides by the Sol-Gel process” J. Non-Crystalline Solids, 63, 283-292 (1984)。6. Y. Pang, M. Samoc and P. N. Prasad, J. Chem. Phys., 94, 5282 (1991)。.7.D. Levy and D. Avnir, J. Phys. Chem., 92, 4734 (1988)。8. S. Ikoma, K. Kawakita and H. Yokoi, J. Non-Cryst. Solids, 122, 183 (1990)。9. G. E. Badini, K. T. V. Grattan, A. W. Palmer and A. C. C. Tseung, Springer Proceedings in Physices, 44, 436 (1989)。10. U. Kunzelmann and H. Bottcher, Sensors ＆ Actuators B, 38-39, 222 (1997)。11. R.Kasemann, H.Schmidt, E.Wintrich, ”A New Type of Sol-Gel- Derived Inorganic-organic Nanocomposite”, Mat.Res.Soc. Symp.Proc., 346, 915-921 (1994)。.12. J.Wen, K.Jordens, G.L.Wilkes, ”Hybrid Organic/Inorganic Coatings for Abrasion Resistance on Plastic and Metal Substrates”, Mat. Res. Soc. Symp. Proc., 435, 207-213 (1996)。13. J.Gilberts , H.A.Tinnemans, ”UV Curable Hard Transparent Hybrid Coating Materials on Polycarbonate Prepared by the Sol-Gel Method”, J. Sol-Gel Sci. Tech., 11, 153-159 (1998)。14. S.Sepeur, N.Kunze, B.Werner, H.Schmidt, ”UV Curable Hard Coatings on Plastics”, Thin Solid Films, 351, 216-219 (1999)。15. 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 2a”, Macromol.Chem.Phys., 201, 2765-2770 (2000)。16. M.A.Rodriguez, M.J.Liso, ”Study of the reaction of 3-methacryloxypropyltrimethoxysilane (MPS) with Slate Surfaces", J.Mater.Sci., 34, 3867-3873(1999)。17. 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)。18.Wen-Chang Chen, Shu-Ten Lee, ”Synthesis and Characterization of Poly(methyl methacrylate)。-Silica Hybrid Optical Thin Films”, Polymer Journal , 32, 67-72(2000)。19.S. Musić, Ð. Dragčević, S. Popović, “Hydrothermal crytallization of Boehmite from freshly precipitated aluminium hydroxide”,Materials Letters, 40, 269-274(1999)。20. H.Schmidt, H.Krug, Bernhard Zeitz, Elisabeth Geiter, ”Inorganic- Organic Nanocomposites for Optical Coatings”, SPIE, 3136, 220-227(1996)。21. Donald L. Pavia, Gary M. Lampman, George S. Kriz, Instroduction of Spectroscopy (second edition)。 22. J.H.Harreld, Bruce Dunn, Jeffrey I.Zink, ”Organic and Inorganic Network Development in ORMOSILs:Effects on Optical Properties", SPIE, 3136, 25-35(1996)。23. Ivan Sondi, Theodore H., Fedynyshyn, Roger Sinta, Egon Matijević , ”Encapsulation of Nanosized Silica by In Situ Polymerization of tert-Butyl Acrylate Monomer”, Langmuir, 16, 9031-9034(2000)。24. J.H.Harreld, Bruce Dunn, Jeffrey I.Zink, ”Effects of Organic and Inorganic Network Development on the Optical Properties of ORMOSILs”, J. Mater.Chem., 7(8), 1511-1517(1997)。25. Xiaochun Li, Therence A. King, ”Spectroscopic studies of Sol-Gel -Derived Organically Modified Silicates”, J.Non-Crystalline Solids , 204, 235-242(1996)。26. J. Mèndez-Vivar, A. Mendoza-Bandala, ”Spectriscopic study on the early stages of the polymerization of hybrid TEOS-RSI(OR’)3 sols”, J.Non-Crystalline Solids, 261, 127-136(2000)。27.Zhi Hua Huang, Kun Yuan Qiu, ”Preparation and Thermal Property of Poly(methyl methacrylate)/Silicate Hybrid Materials by the In-Situ Sol-Gel Process”, Polymer Bulletin, 35, 607-613(1995)。28. Zhi Hua Huang, Kun Yuan Qiu, ”The effects of interactions on the properties of acrylic polymers/silica hybrid materials prepared by the in-situ sol gel process”, Polymer, 38, 521-526 (1997)。29. Yoshimoto Abe, Yuki Honda, Takahiro Gunji, ”Preparation and Properties of Silicon-Containing Polymer Hybrids from 3-Methacryloxypropyltrimethoxysilane ”, Appl.Organometal. Chem., 12, 749-753 (1998)。30. Goutam De, Debtosh Kundu, ”Gold-Nanocluster-Doped Inorganic-Organic Hybrid Coatings on Polycarbonate and Isolation of Shaped Gold Microcrystals from the Coating Sol”, Chem.Mater. (2001)。31.董志偉, ”具環氧基矽烷包覆奈米粒子之研究”, 國立中央大學 化工所碩士論文(2001)。32. S.S. Hou, P.L.Kuo, Macromol. Chem. Phys., 200, 2501-250(1999)。