臺灣博碩士論文加值系統

本研究以含丙烯酸酯基團之矽氧烷單體，經由溶膠凝膠反應合成梯狀聚倍半矽氧烷樹脂(Ladder-structured polysilsesquioxanes)，分別利用封端OH基、不同塗佈溫度、使用消泡機、消泡劑或稀釋劑後，再加入光起始劑製出具有紫外光固化型有機奈米複合膠材，藉棒形自動塗佈機塗佈，經紫外光固化後在軟性基材PET上，並進行性質檢測。
結果顯示：塗佈固化後平均膜厚0.54微米；表面鉛筆硬度介於 2H到4H；黏著性由百格測試方法檢測，結果均可達5B；平坦度經由原子力顯微鏡(AFM)，可達到：平均值粗糙度Ra=0.229奈米、均方根粗糙度Rq=0.287奈米、最大高度差粗糙度Rz=2.671奈米；透光度於可見光550奈米下介於91.1到92.8%間；水氣滲透率(WVTR)介於: 3.4至4.1 (g/m2-day)。由結果顯示：此梯狀聚倍半矽氧烷樹脂材料已達到工業化要求。
另外，濺鍍一層厚度50奈米氧化鋁(Al2O3)於梯狀聚倍半矽氧烷樹脂層上，平坦度經由原子力顯微鏡(AFM)，可達到： Ra=0.676奈米、Rq=0.844奈米、Rz=6.345奈米；水氣滲透率(WVTR)：0.407 gm/m2-day，顯示出氧化鋁無機層可以降低水氣滲透率。
上述結果可見：此有機奈米複合膠材對PET具備固化迅速、透光率優、平坦化佳、附著力高；若另外添加氧化鋁(Al2O3)，則能使水氣阻隔性提高不少。另外，單一層單一材料，且高溫度，有助於薄膜塗佈平坦化。期許能有效應用於工業軟性電子元件封裝或相關領域，提升產品效能及延長使用壽命。

In this research, ladder-structured polysilsesquioxanes were synthesized by sol-gel reaction using acrylate groups containing acrylate groups. To make different way of synthesizing blocked OH groups, or different coating temperatures, or using defoaming machine, or adding diluent or defoamer, to change organic resin coating conditions. Before UV coating, these different resins are mixed with photo-initiator, respectively. Finally, these organic nanocomposites would be coated by stick automatic coating machine and be cured in UV light on the substrate of 125μm PET.
The results show that the average film thickness after coating and curing was 0.54μm; the pencil hardness was between 2H to 4H; the adhesion by cross-cut test were all up to 5B; the flatness was achieved by AFM: arithmetical mean deviation roughness Ra=0.229 nm, root mean square deviation roughness Rq=0.287 nm, maximum height od profile roughness Rz=2.671 nm; the optical transmittances of substrates PET at visible light 550 nm are from 91.1 to 92.8%; the water vapor transmission rate (WVTR) is between 3.4 to 4.1 gm/m2-day. As stated above, they show that the ladder-like polysesquioxane resin material has reached industrial standard requirements.
In addition, one layer from 50 nanometers of alumina (Al2O3) is sputtered on the ladder layer of polysilsesquioxane resin, and the results show that value of AFM at Ra=0.676 nm, Rq=0.844 nm, Rz=6.345 nm; and WVTR is 0.407 (g/m2-day). These data exhibit that the inorganic layer of aluminum oxide can reduce WVTR obviously.
To sum up, these results show that the organic nanocomposite adhesive has fast curing, excellent light transmittance, good flatness and high adhesion to PET. If aluminum oxide (Al2O3) is additionally added on polysesquioxane layer, the water vapor barrier property can be improved a lot. In addition, coating one organic material in high temperature for one single layer, which can raise the planarization to the film. On the whole, this photo-curable organic resin is expected to apply for soft electronic components in opto-electronic industry to improve efficiency and extend service life on electronic products.

摘要 i
Abstract iii
誌謝 v
目錄 vi
圖目錄 x
附圖目錄 xii
表目錄 xiv
第一章 緒論 1
1.1 前言 1
1.2 研究背景與動機 3
第二章 文獻回顧 9
2.1 軟性有機電子薄膜封裝發展 9
2.2 液滴運動 11
2.3 無溶劑塗佈技術 12
2.3.1 旋轉塗佈 (Spin coating) 12
2.3.2 離心旋轉塗佈 (Off-centre spin coating) 13
2.3.3 滴落塗佈 (Drop casting) 13
2.3.4 棒型塗佈 (Bar coating) 14
2.3.5 溶液剪切塗佈 (Solution shearing) 15
2.4 液滴成膜產生之現象與因素 16
2.4.1 圈環現象 (Ring stain or Coffee ring effect) 16
2.4.2 多重圈環現象 (Multiple ring formation) 16
2.4.3 表面張力與接觸角 17
2.4.4 溶解度 18
2.4.5 蒸氣壓 18
2.4.6 黏滯性 19
2.5 溶膠-凝膠法 (Sol-gel process) 20
2.5.1 溶膠-凝膠技術歷史 20
2.5.2 溶膠-凝膠法反應程序 20
2.5.3 醇鹽(Alkoxides)的水解和縮合反應 22
2.5.4 梯形聚倍半矽氧烷 24
2.6 紫外光固化 28
2.6.1 紫外光反應機制和配方 28
2.6.2 紫外光觸發自由基聚合[59] 29
2.6.3 紫外光觸發陽離子聚合[59] 30
2.6.4 光起始劑之選擇(自由基) 31
第三章 實驗部分 34
3.1 實驗藥品 34
3.2 儀器設備 36
3.3 薄膜平坦化設計概念 40
3.4 配方命名與組成 41
3.5 實驗設計架構 43
3.6 合成反應步驟 45
3.6.1 酸催化合成溶膠-凝膠寡聚物 45
3.6.2 鹼催化合成溶膠-凝膠寡聚物 46
3.6.3 酸催化後的寡聚物之酯化封端反應 46
3.7 性能鑑定項目與樣品製作 48
3.7.1 薄膜樣品製作 48
3.7.2 底材附著力測試 48
3.7.3 鉛筆硬度測試 49
3.7.4 水氣滲透率測試 49
3.7.5 光學測試 50
3.7.6 薄膜厚度測試 51
3.7.7 表面形貌鑑定 51
第四章 結果與討論 53
4.1 寡聚物A與酯化封端反應之IR鑑定 53
4.2 黏度分析 55
4.3 膜厚 56
4.4 硬度與附著性 57
4.5 透光度與色度 59
4.6 表面缺陷與粒子數 62
4.6.1 OM影像 62
4.6.2 顆粒數 (Particle) 63
4.6.3 缺陷數 64
4.7 表面粗糙度 66
4.7.1 表面粗糙度數值 66
4.7.2 AFM表面影像 69
4.8 水氣滲透率 71
4.9 水接觸角 73
4.10 熱性質 74
4.11 最佳配方之選擇 77
4.12 平坦化成效確認 80
第五章 結論 83
參考文獻 84
附圖 92

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