臺灣博碩士論文加值系統

使用三羥基單體(B3)、二異氰酸酯(A2)和含羥基丙烯酸酯(BR)的混合物，經由逐步聚合法合成超分枝聚胺基甲酸酯丙烯酸酯(HBPUAs,編號為TIH4)。接著，將合成的TIH4與三環癸二甲醇二丙烯酸酯(TCDDMDA)和光起始劑2,4,6-三甲基苯甲醯二苯基磷氧化物(TPO)混合。使用數位光處理(DLP)3D列印機在405 nm光源下列印樣品。後固化則是以溫控光固化機(Form Cure)在60°C下後固化30分鐘。樹脂以重量比9：1 (TCDDMDA：TIH4) 的比例混合所列印的樣品，在水中浸泡50小時後，測得的撓曲強度和模數分別為101.1 MPa和2.57 GPa。實驗結果機械性質皆符合ISO 20795-1假牙基底聚合物的標準。此外，合成的樹脂與商業樹脂相比表現出更低的吸水率(12.05μg/mm³)與更強的抗斷裂應力。

A hyperbranched polyurethane acrylate (HBPUAs, coded as TIH4) was synthesized via stepwise polymerization using a mixture of a tri-hydroxyl monomer (B3), diisocyanate (A2),and a hydroxyl-containing acrylate (BR). This synthesized TIH4 resin was then mixed with tricyclodecane dimethanol diacrylate (TCDDMDA) and a photoinitiator,2,4,6-trimethylbenzoyl diphenyl phosphine oxide (TPO). Samples were printed using a digital light
processing (DLP) 3D printer under a 405 nm light source. Post-curing was performed using a temperature-controllable light-curing machine (Form cure). For the sample printed using the blended resin at a weight ratio of 9:1 (TCDDMDA:TIH4), post-cured at 60°C for 30 minutes
and then soaked in water for 50 hours, the flexural strength and modulus were approximately 101.1 MPa and 2.57 GPa, respectively. These properties met the ISO 20795-1 standards for denture base polymers.Additionally, the synthesized resin exhibited a lower water absorption rate of 12.05 μg/mm³ and higher resistance to fracture stress compared to the commercial resin.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
圖目錄 vii
表目錄 x
第一章 緒論 1
1.1 前言 1
1.2 研究動機 3
第二章 文獻回顧 4
2.1 超分支高分子結構與特性 4
2.2 聚胺酯丙烯酸酯結構與特性 5
2.3 數位光源處理系統(DLP) 6
2.4 光起始劑反應原理與種類 10
2.5 光硬化樹酯 11
2.5.1 光硬化樹酯成分 11
2.5.2 光硬化牙科樹酯特性 11
2.5.3 光起始劑TPO之介紹 14
2.6 3D列印參數設定 17
2.7 後固化 17
2.8 丙烯酸酯雙鍵轉化率 21
2.9 義齒假牙基底床之ISO規範介紹 24
第三章 實驗方法 27
3.1 實驗藥品 27
3.2 實驗儀器 33
3.3 實驗流程 37
3.4 超分枝聚胺酯丙烯酸樹脂之合成 38
3.5 合成之HBPUAs性質分析與測量方法 40
3.5.1 凝膠滲透色層分析儀 (GPC) 40
3.5.2 衰減全反射式傅立葉轉換紅外線光譜儀(ATR-FTIR) 40
3.6 3D列印參數設定與樣品測試 41
3.6.1 3D列印參數與後固化參數設定 41
3.6.2 收縮率測試(Shrinkage) 43
3.6.3 吸水率與溶出率測試(Water Sorption and Solubility) 43
3.6.4 三點彎曲測試 (Three-point Bending Test) 44
3.6.5 應力鬆弛實驗 (Stress Relaxation Test) 45
3.6.6 斷裂韌性實驗 (Fracture toughness Test) 46
3.6.7 丙烯酸脂雙鍵轉化率測試 47
3.7 統計分析 47
第四章 結果與討論 48
4.1 超分枝聚胺基甲酸酯丙烯酸酯合成 48
4.1.1 HBPUA分子量測量 49
4.1.2 傅立葉轉換紅外線光譜儀(FTIR)分析 51
4.2 收縮率測試 54
4.2.1 Phrozen cure後固化 54
4.2.2 Form cure後固化 56
4.3 吸水率與溶出率測試 59
4.4 三點彎曲測試 62
4.4.1 Phrozen cure後固化 62
4.4.2 Form cure後固化 64
4.5 應力鬆弛測試 71
4.5.1 Phrozen cure後固化 71
4.5.2 Form cure後固化 71
4.5.3 Kohlrausch-Williams-Watts (KWW) 73
4.6 斷裂韌性測試 78
4.7 丙烯酸酯雙鍵轉化率 82
第五章 結論 87
未來工作 88
參考文獻 89
附錄 93

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