臺灣博碩士論文加值系統

此研究旨在開發具低收縮率並可以用簡易的設備和快速生產的光固化樹脂，
成 功 合 成 以 溶 膠 - 凝 膠 法 (Sol-Gel) 將 含 3-Methacryloxypropyltrimethoxysilane
(MAPTMS)搭配不同比例之 Pentaerythritol triacrylate(PETA)與固定比例的異丙醇
和鹽酸水溶液在 pH~2 下合成出矽氧烷丙烯酸酯，再搭配 3 種不同雙官能基之稀
釋劑和光起始劑製出 3D 列印光固化樹脂，探討改變雙鍵密度與固化後的收縮率、
熱性質間之關係。結果顯示在沒有加任何填充物下最低可以達到 5%.，熱性質方
面，在氮氣環境下 5%及 10%熱裂解溫度(T d )為 293 o C~346 o C 及 367 o C~390 o C。
此光固化壓克力樹脂具有製備簡單、快速、透明無色、、T g 高、熱裂解溫度
高、容易移除以及固化收縮率低等優勢，可以應用於 3D 列印支撐材，在高精密
度的 3D 成型技術中有良好的表現外，在改善收縮率方面仍有很大的進步空間。

The aim of the research is to develop a low shrinkage resin which could be
produced rapidly by simple equipment. Herein, 3D-printing UV-curing resin of silicon
acrylates which were prepared by sol-gel condensation with 3-
Methacryloxypropyltrimethoxysilane (MAPTMS), different portion of pentaerythritol
triacrylate(PETA) and equal portion of isopropyl alcohol and HCl (aq ) to MAPTMS
under pH~2 atmosphere, then incorporate three different kinds of bi-functional diluent
each other and photo initiator. The effects of changing double bond density on shrinkage,
and on the influence of thermal properties were invested. The results show the lowest
shrinkage value after curing is 5.0% without adding any filler. The temperature at 5%
and 10% weight loss measured by TGA under nitrogen were in the range of 293 o C to
346 o C and 367 o C to 390 o C.
These results suggest that photo-curable acrylic resin has the advantages of easy
and rapid preparation, high pyrolysis temperature, easy removable and low cure
shrinkage, and it should have a good performance in the high-precision 3D molding
technology whether in use directly or as a support material for 3D-printing resin. There
is still room for improving shrinkage.

摘要 i
Abstract ii
致謝 iv
目錄 v
表目錄 vii
圖目錄 viii
第一章 緒論 1
第一節 前言 1
第二節 研究動機 1
第二章 文獻回顧及相關原理 2
2.1 收縮率[1-2] 2
2.1.1光固化樹脂收縮率的改善 4
2.1.1.2填充物的摻入 7
2.2 3D列印成型方法[7-9] 8
2.2.1 光固化3D列印的技術 8
2.2.2 3D列印DLP及SLA的比較[15] 11
2.3紫外光固化反應 13
2.3.1自由基聚合 14
2.3.2陽離子聚合 16
2.3.3 自由基與陽離子聚合的比較[16, 18-19, 21] 17
2.4紫外光固化之起源[17, 22-24] 18
2.4.1紫外光固化樹脂之特性[17, 22, 24-25] 19
2.4.2紫外光固化樹脂之組成[17, 24, 26-29] 20
2.5影響紫外光硬化樹脂之因素 36
2.5.1氧阻聚現象 37
2.5.2光源 37
2.5.3光起始劑及波長選擇 38
2.5.4輻射設備 40
2.5.5溫度效應 40
2.6溶膠-凝膠技術(Sol-Gel Science)[45-48] 41
2.6.1溶膠-凝膠法之pH值的依屬性值(pH-Dependence)[49] 43
2.6.2溶膠-凝膠法之水含量多寡的影響 46
2.6.3溶膠-凝膠法之溶劑比例的影響 46
2.7 分子設計概念 47
第三章 實驗藥品與設備 48
3.1實驗藥品 48
3.2儀器設備 49
第四章 實驗方法 51
4.1 AS寡聚物合成方法 51
4.2 ASP系列寡聚物合成方法 51
4.3 BS寡聚物合成方法[51] 52
4.4 BSP系列寡聚物合成方法[51] 52
4.5光固化樹脂配方命名法 53
第五章 結果與討論 54
5.1 ASP Series and BSP series 寡聚物IR鑑定 54
5.2 ASP及BSP Series 做法之比較 56
5.3成型秒數測試 57
5.4體積收縮率之測試 58
5.5熱性質分析 62
5.5.1 ASP series和BSP series熱性質分析 62
5.5.2 ASP series混入稀釋單體之熱性質比較 65
5.6黏度測試 74
第六章 結論 75
文獻資料 77

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