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研究生： 劉乃慧
Nai-Hui Liu
論文名稱： 快速成型光固化水溶性材料的開發
The Development of Water- Soluble Materials for Photo-Curing Rapid Prototyping
指導教授： 何明樺
MING-HUA HO
口試委員: 鄭逸琳
Yih-Lin Cheng
陳孟專
Meng-Zhuan Chen
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 131
中文關鍵詞： 快速成型 、水溶性材料 、光固化材料 、三維列印
外文關鍵詞： rapid prototyping,, photo-curable resin, 3-dimensional printing
相關次數： 點閱：159  下載：0 
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    • 3D列印(three dimensional printing)技術透過模型材料與支撐材料完美地配合，能製造出複雜度高的產品，然而，物件完成列印後，支撐材料將去除。目前商業化的光固化支撐材料在去除過程中，容易破壞產品的外觀而留下不期望的痕跡。因此，我們的目標是開發一種理想的新型式犧牲型(novel sacrifice layer)樹脂作為光固化快速成型的支撐材料，此樹脂必須固化速率快、具有一定的機械強度，並且在不損壞產品的情況下容易地移除。
    本實驗使用乙醇酸(glycolic acid, GA) 為寡聚物(oligomer)的中心，再經由合成反應，在每個寡聚物的末端接上光反應性的官能基碳碳雙鍵，並將此寡聚物稱之為GA-GMA，同時藉由與功能性單體混合，調節光固化樹脂的機械性質、流變性和收縮率、降解、水解特性。本實驗的樹脂GA-GMA，在光固化後浸泡於水中30分鐘後，機械性質降低79%，混合聚乙二醇(poly ethylene glycol, PEG)後，機械性質可在浸泡水中10分鐘後下降84%。
    根據ISO10993的生物相容性測試，可得知光固化型樹脂具有良好的生物相容性。因其親水性佳，與天然物質蠶絲蛋白具有高達1:1的最高混合比例，溶液混合後不產生分層或相分離現象，代表本研究所開發的樹脂適於攜帶親水性生物分子及天然物質。

    In rapid prototyping, the supporting materials would be necessary to support complex and delicate structures or to be served as molds. The supporting materials must be solidified as efficiently as the other 3D printing resin, and be removed easily without damaging the products. However, the removal of commercial photo-cured scarified materials without affecting the appearance of printed surface is still difficult nowadays. Thus, we aim to develop an ideal and novel sacrificed resin as the supporting materials for photo-cured rapid prototyping.
    In this experiment, We use glycolic acid as a basic part to form a oligomer in the center of our oligomer. And then we add C=C to be a photo reactive part in the end of oligomer. So that we can get photo-reactive glycolic acid. And we name it as GA-GMA. Then, we blended the novel photo-curable oligomers with functional monomers to adjust the mechanical, rheological, shrinkage and the hydrolysis profile of the photo-curable resin. The results showed that the novel photocurable resin GA-GMA would lose its Young’s modulus by 79% after immersing in warm water for 30 minutes. After mixing with polyethylene glycol (PEG), the mechanical properties would lose 84% after soaking in a water 10 minutes.
    According to the biocompatibility tests from ISO10993, it is known that the photocurable resin shows good biocompatibility. Due to its high hydrophilicity, the photo-resin developed in this research can be mixed with natural substances, silk fibroin, with the highest ratio as 1:1. There is no deposition or phase separation in the blending of photo-resin and silk fibroin. The experimental results support that the resin is suitable for carrying hydrophilic biomolecules and natural substances.

    摘要 I Abstract II 致謝 IV 目錄 VI 圖目錄 X 表目錄 XIX 專有名詞縮寫 XX 第一章 緒論 1 第二章 文獻回顧 2 2.1 積層製造介紹 2 2.1.1 積層製造的發展現況與未來趨向 2 2.1.2 積層製造系統的種類 3 2.1.3 積層製造於生醫領域的應用 4 2.2 光固化系統 6 2.2.1 光固化系統製程 6 2.2.2 光固化樹脂主要成分 7 2.2.3 光固化系統反應成型機制 10 2.2.4 影響光固化表現的因素 14 2.3 3D列印支撐材料 16 2.4 可分解型或降解型光固化材料 23 2.5 天然物或生物分子3D列印 25 2.6 聚合物降解的機制 27 第三章 實驗材料與方法 34 3.1 實驗藥品 34 3.2 實驗儀器 36 3.3 實驗材料與流程 38 3.3.1 寡聚物的合成 38 3.3.2 樹脂配方及混合方式 38 3.4 材料鑑定與性質檢測 39 3.4.1 傅立葉轉換紅外線光譜儀(FTIR)分析 39 3.4.2 降解測試 39 3.4.3 黏度測試 42 3.4.4 多功能固體密度測試儀 42 3.4.5 表面接觸角(Contact Angle)分析 42 3.4.6 MiiCraft Plus 3D 列印機 44 3.5 體外細胞測試 44 3.5.1 光固化材料試片製作 44 3.5.2 生物相容性檢測方式與操作 44 3.5.3 細胞來源 47 3.5.4 細胞培養 47 3.5.5 細胞冷凍保存 48 3.5.6 細胞解凍及培養 49 3.5.7 細胞計數 50 第四章 結果與討論 52 4.1 光起始劑濃度選擇 52 4.2 新舊光起始劑的影響 54 4.2.1光源波長分析 54 4.2.2傅立葉轉紅外線光譜儀(FTIR)分析轉化率 56 4.2.3新舊光起劑對機械性質與水解性質影響 60 4.3 材料接觸角測量 69 4.4 材料的黏度性質分析 71 4.4.1溫度對寡聚物GA-GMA的黏度影響 71 4.4.2添加寡聚物或單體對黏度的影響 72 4.5 聚合物降解性質 77 4.5.1攪拌速率對機械性質的影響 77 4.5.2添加不同寡聚物對機械性質的影響 80 4.5.3添加不同稀釋單體對機械性質的影響 82 4.6 蠶絲蛋白性質確認、混摻與列印性評估 87 4.6.1純蠶絲蛋白溶液於室溫下乾燥時間 87 4.6.2不同溫度對純蠶絲蛋白溶液穩定性的影響 89 4.6.3不同蠶絲蛋白濃度對樹脂穩定性的影響 92 4.6.4不同溫度對純蠶絲蛋白黏度的影響 96 4.6.5不同濃度蠶絲蛋白對樹脂黏度的影響 97 4.6.6蠶絲蛋白濃度對機械性質的變化 99 4.6.7 材料收縮率 111 4.6.8材料生物相容性檢測 114 4.7 與傳統支撐材料比較 117 第五章 結論 120 參考文獻 122 附錄 131 附錄A: 轉速與測量黏度範圍對照表 131

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