本論文研究有機/無機奈米複合聚胺酯材料：二氧化矽奈米顆粒表面經甲基丙烯酸環氧丙酯改質後摻合含矽氧烷紫外光硬化型PU薄膜，探討二氧化矽奈米顆粒改質後的薄膜性質差異。以聚二甲基矽氧烷(KF-6001, Polydimethyl- siloxane, PDMS, 1800 g/mol)為雙醇基，先和過量之IPDI進行反應，形成末端-NCO官能基之PU預聚合物(PDMS-NCO)，接著再與2-HEMA反應，形成末端具雙鍵之UV-PU。最後在與改質後奈米二氧化矽進行紫外光架橋反應成模。
在硬度方面(Shore-A)，未添加奈米二氧化矽聚胺酯薄膜硬度為76 ( kg/m2)，而隨著奈米二氧化矽加入，上升至86 ( kg/m2)；鉛筆硬度也從6B等級上升至5B等級。在接觸角方面，因為奈米二氧化矽表面帶有-OH基，所以接觸角從112°下降至108°。另外在透溼度方面，隨著奈米二氧化矽添加有效從275.05g/(m2．day)下降至38.2 g/(m2．day)，證實具有良好的密封性；而且密著度測試可達5B等級 。

In this article, two series organic -inorganic nano composites were invetigated and compared with each other. Hybridization of UV-curable Polysiloxane-containg PU composite with surface modified nano-silica particles via glycidyl methacrylate (GMA). A PDMS-containing PU oligomer that is obtained from NCO-terminated PU prepolymer with 2-hydroxyethyl methacrylate.
    The physical properties (such as gel content, water-uptake, enthanol-uprtake, ect.), the thermal properties (thermalgravimentric analysis and dynamic mechanical analysis), the UV/vis spectra transmittance, and scanning electron microscope (SEM) of the orangic-inorangic nanocomposites were evaluated in this article.

總     目     錄
中摘........................................................

英摘........................................................

誌謝........................................................

一、前言...................................................1
1-1 前言...................................................1
1-2 研究動機...............................................3
1-3 聚胺酯介紹.............................................4
1-3-1 聚胺酯的基本材料.....................................4
1-4 紫外光硬化型PU樹脂之介紹..............................12
1-4-1 不飽和高分子寡聚物..................................12
1-4-2 活性稀釋劑..........................................13
1-4-3 光起始劑或光敏化劑..................................14
1-4-4 光硬化型樹脂硬化的機制..............................15
1-5 聚矽氧烷簡介..........................................17
1-5-1 歷史發展............................................18
1-5-2 聚二甲基矽氧烷基本性質..............................20
1-5-3 聚二甲基矽氧烷的應用................................23
1-6 奈米材料簡介..........................................24
1-6-1 奈米材料之物理特性..................................24
1-6-2 奈米二氧化矽介紹....................................26
1-6-3 奈米二氧化矽表面改質................................26
1-6-4 奈米高分子複合材料..................................29
1-7 封裝材料的特性........................................31

二、實驗..................................................33
2-1 儀器..................................................33
2-2 藥品..................................................34
2-3 紫外光硬化型聚胺酯的製備..............................35
2-3-1 固含量測試 (Solid Content) .........................35
2-3-2 聚胺酯預聚物異氰酸酯含量(NCO%)測定..................35
2-3-3 聚二甲基矽氧烷聚胺酯之合成..........................37
2-3-4 紫外光硬化型聚二甲基矽氧烷聚胺酯合成................38
2-3-5 反應型奈米二氧化矽之製備............................39
2-4 紫外光硬化型聚胺酯薄膜之製備..........................40
2-5 聚胺酯薄膜物理性質分析測試............................41
2-5-1 光譜鑑定測試........................................41
2-5-2 薄膜物理性質測試....................................41
(a) 膠含量(Gel content)測定...............................41
(b) 去離子水浸泡吸水率與對水損失率........................42
(c) 95%乙醇溶液浸泡吸收率與對乙醇損失率...................43
(d) 薄膜接觸角(Contact Angle)測定.........................44
2-6 水氣透過率測試(WVTR)..................................45
2-7 薄膜硬度測試..........................................47
2-7-1 Shore-A硬度測試.....................................47
2-7-2 鉛筆硬度測試........................................47
2-8 附著度測試 (Cross-Cut) ...............................49
2-9 掃描式電子顯微鏡測試(SEM).............................50
2-10 薄膜熱性質測試.......................................51
2-10-1 熱重分析測試 (TGA).................................51
2-10-2 動態機械分析測試 (DMA).............................52

三、結 果 與 討 論........................................53
3-1 紅外光光譜分析(FT-IR).................................53
3-1-1 紫外光硬化型聚胺酯光譜分析..........................53
3-1-2 反應型奈米二氧化矽合成光譜分析......................56
3-2 紫外光硬化型含矽聚胺酯薄膜的物理性質分析..............59
3-2-1 薄膜膠含量分析......................................60
3-2-2 薄膜吸水率與對水損失率..............................61
3-2-3 薄膜乙醇吸收率與對乙醇損失率........................62
3-2-4 薄膜接觸角分析......................................63
3-3 紫外光硬化型含矽聚胺酯薄膜透濕度表現..................64
3-4 紫外光硬化型含矽聚胺酯薄膜機械性質分析................65
3-4-1 薄膜硬度分析 (Shore-A Hardness Test)................65
3-4-2 薄膜鉛筆硬度測試....................................66
3-5 密著度測試 (Cross-Cut test)...........................67
3-6 紫外光硬化型含矽聚胺酯薄膜之熱性質分析................68
3-6-1 薄膜熱重分析 (TGA)..................................68
3-6-2 薄膜動態機械分析 (DMA)..............................70
3-7 掃描式電子顯微鏡測試 (SEM)............................77

四、結論..................................................84

五、參考資料..............................................85


圖 表 目 錄

Scheme 2-3.a 聚二甲基矽氧烷聚胺酯之合成...................37
Scheme 2-3.b 紫外光硬化型含矽聚胺酯之合成.................38
Scheme 2-3.c 反應型奈米二氧化矽之合成.....................39

表2-4 紫外光硬化型含矽聚胺酯薄膜調配......................40
表2-8 紫外光硬化型含矽聚胺酯coating比例...................50
表3-2.a 含奈米二氧化矽之紫外光硬化行聚胺酯成分表..........59
表3-2.b 各比例UV-SiPU/SiO2膠含量..........................60
表3-2.c 各比例UV-SiPU/SiO2之吸水率與損水率................61
表3-2.d 各比例UV-SiPU/SiO2之乙醇吸收率與對乙醇損失率......62
表3-2.e 各比例UV-SiPU/SiO2之接觸角表現....................63
表3-3 各比例UV-SiPU/SiO2之透濕度表現......................64
表3-4.a 各比例UV-SiPU/SiO2硬度(Shore-A)表現...............65
表3-4.b 各比例UV-SiPU/SiO2鉛筆硬度表現....................66
表3-5 各比例UV-SiPU/SiO2之密著度表現......................67
表3-6.a 各比例UV-SiPU/SiO2之熱重分析......................68
表3-6.b 各比例UV-SiPU/SiO2之儲能模數、耗能模數與阻尼值....72

圖3-1.a PDMS PU prepolymer 之FT-IR光譜圖..................54
圖3-1.b 2-HEMA 之FT-IR光譜圖..............................54
圖3-1.c UV-SiPU resin 之FT-IR光譜圖.......................55
圖3-1.d Nano-SiO2 之FT-IR光譜圖...........................56
圖3-1.e GMA 之FT-IR光譜圖.................................57
圖3-1.f Reactive nano-SiO2之FT-IR光譜圖...................57
圖3-1.g GMA之NMR光譜圖....................................58
圖3-1.h Reactive nano-SiO2之NMR光譜圖.....................58
圖3-6.a 各比例UV-SiPU/SiO2聚胺酯之熱重分析圖..............69
圖3-6.b 各比例UV-SiPU/SiO2聚胺酯之DTGA熱重分析圖..........69
圖3-6.c 各比例UV-SiPU/SiO2聚胺酯之Tanδ...................72
圖3-6.d 各比例UV-SiPU/SiO2聚胺酯之儲能模數................73
圖3-6.e 各比例UV-SiPU/SiO2聚胺酯之耗能模數................73
圖3-6.f UV-SiPU-0之動態機械分析...........................74
圖3-6.g UV-SiPU-10之動態機械分析..........................74
圖3-6.h UV-SiPU-20之動態機械分析..........................75
圖3-6.i UV-SiPU-30之動態機械分析..........................75
圖3-6.j UV-SiPU-40之動態機械分析..........................76
圖3-6.k UV-SiPU-50之動態機械分析..........................76
圖3-7.a UV-SiPU-0之SEM圖(3萬倍) ..........................78
圖3-7.b UV-SiPU-0之SEM圖(5萬倍) ..........................78
圖3-7.c UV-SiPU-10之SEM圖(3萬倍) .........................79
圖3-7.d UV-SiPU-10之SEM圖(5萬倍) .........................79
圖3-7.e UV-SiPU-20之SEM圖(1萬倍) .........................80
圖3-7.f UV-SiPU-20之SEM圖(3萬倍) .........................80
圖3-7.g UV-SiPU-30之SEM圖(1萬倍) .........................81
圖3-7.h UV-SiPU-30之SEM圖(3萬倍) .........................81
圖3-7.i UV-SiPU-40之SEM圖(1萬倍) .........................82
圖3-7.j UV-SiPU-40之SEM圖(3萬倍) .........................82
圖3-7.k UV-SiPU-50之SEM圖(1萬倍) .........................83
圖3-7.l UV-SiPU-50之SEM圖(3萬倍) .........................83

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