臺灣博碩士論文加值系統

在本論文中，我們提出一種在波長250 nm 深紫外線中反應的丙烯酸系光固化樹酯，做為以數位光處理(Digital Ligh Processing, DLP)製程技術的三維列印機(3D printer)中應用。本研究的丙烯酸系光固化樹酯是以三乙二醇二丙烯酸酯(Triethyleneglycoldiacrylate, C12H18O6, 簡稱TEGDA)為壓克力寡聚物，1,6-己二醇二丙烯酸酯(Hexamethylenediacrylate, C12H18O4, 簡稱HDDA)為反應性稀釋單體，安息香雙甲醚(2,2-Dimethoxy-2-phenylacetophenonce, C16H16O3, 簡稱DMPA)為光起始劑，以固定光功率紫外光發光二極體(UVLED)照射硬化，探討光起始劑及反應性稀釋單體的濃度對壓克力樹脂光硬化行為。由實驗數據得知光起始劑DMPA在丙烯酸系HDDA/TEGDA混和樹酯中的最大溶解度為2.0 ％，在樹酯黏度影響列印精度下，HDDA/TEGDA混和樹脂中不同配方比由黏度9 mp·s，隨著TEGDA的重量百分率增加，整個混和物的黏度也隨之增加至14 mp·s。DMPA在0.5 % 含量時即可作用並且無論HDDA/TEGDA混和樹脂的比例如何，均可達到70的硬度，在DMPA提升至2.0 %含量時，TEGDA在30 %時，UV 光照射35分鐘才量測到硬度為70，在TEGDA為70 %時，UV 光照射55分鐘後才量測到硬度為71，原因為DMPA太高的量會使大部分的反應只在表層，紫外光初期在樹酯表層被大量吸收，妨礙內層樹酯的反應，但少量的紫外光還是能進入內層反應，所以固化時間增加。

In this thesis, we propose a kind of acrylic light-cured resin which was reacted to a wavelength of 250 nm ultraviolet as the 3D printer application of the process technology of digital light processing, DLP. The acrylic light-cured resin of the study used triethylene glycol diacrylate (Tri-ethylene glycol diacrylate, C12H18O6, abbreviated TEGDA) as acrylic oligomers, 1,6- hexamethylene diacrylate (Hexamethylene diacrylate, C12H18O4, Acronym HDDA)as a reactive diluent monomer and benzoin dimethyl ether (2,2-Dimethoxy-2-phenylacetophenonce, C16H16O3, called DMPA) as the photoin-itiator to irradiate and complete the cure at a fixed optical power of ultraviolet light-emitting diode (UVLED). Then to discuss the light-cured reaction of the den-sity of photoinitiator and reactive-diluted monomer to acrylic oligomers. According to the experimental data, the maximum solubility in acrylic HDDA/TEGDA mixed resin of photoinitiator DMPA is 2.0% and the viscosity in diferent formula ratio of HDDA / TEGDA mixed resin is 9 mp•s the resin under print accuracy influenced by resin viscosity. The viscosity of the whole mixture is up to 14 mp•s along with the increase of TEGDA weight percentage. When DMPA is 0.5% of the content, it is able to react and no matter what the ratio of HDDA/TEGDA mixed resin is, it can reach the hardness of 70. When DMPA increases to 2.0% with 30% of TEGDA, the hardness can be measured by 70 while UV light irradiates 35 minutes. When TEGDA is 70%, the hardness is 71 with 55 minutes of UV irradiation. This is because too much DMPA leads reaction only happened on the surface. The ultraviolet is absorbed by the surface of resins on the initial stage and interferes with the reaction of inner resins. However, a small amount of ultraviolet can still enter the inner reaction and that’s the reason why the curing time increases.

摘 要 ………………………………………………………………………………………I
ABSTRACT …………………………………………………………………………………II
目 次……………………………………………………………………………………III
圖目次……………………………………………………………………………………IV
表目次 …………………………………………………………………………………V
第一章 緒論 ………………………………………………………………………………1
1.1 前言 ……………………………………………………………………………1
1.2 3D列印源由簡介 ………………………………………………………………1
1.3 3D列印成型技術介紹 …………………………………………………………1
1.4 3D列印成型方式分類 …………………………………………………………2
1.4.1 FDM（熔融沉積成型）………………………………………………………2
1.4.2 LOM（層狀物體製造）………………………………………………………3
1.4.3 DLP（數位光處理）…………………………………………………………4
1.4.4 SLA（立體平板印刷） ……………………………………………………6
1.4.5 3DP …………………………………………………………………………7
1.4.6 SLS（選擇性雷射燒結）……………………………………………………9
1.4.7 SLM（選擇性雷射熔化）……………………………………………………10
1-5光硬化樹脂簡介…………………………………………………………………11
1.6 光硬化樹脂的特性型 …………………………………………………………12
1.7 研究動機及目的 ………………………………………………………………15
第二章 文獻回顧…………………………………………………………………………16
2.1 光硬化型樹脂的起源 …………………………………………………………16
2.2 光硬化型樹脂的種類 …………………………………………………………16
2.2.1 乙烯基類（Vinyl base）……………………………………………………17
2.2.2 非乙烯基類（Non-vinyl base）……………………………………………17
2.2.2.1聚硫醇－多烯系統（Polythio-Polyene system）……………………17
2.2.2.2陽離子硬化系統（Cation UV. Curing system）……………………18
2.3 光硬化型樹脂組成 …………………………………………………………… 19
2.3.1光聚合性預聚物（prepolymers）或稱寡聚體（oligomer）…………………19
2.3.1.1 環氧丙烯酸酯（Epoxy acrylates）…………………………………20
2.3.1.2 胺酯丙烯酸酯（Urethane acrylates）………………………………20
2.3.1.3 聚酯丙烯酸酯（Polyester acrylates）………………………………20
2.3.2 光聚合性單體（Reactive Monomer）………………………………………21
2.3.3 光起始劑（Photoinitiatiors）………………………………………………23
2-3-3-1 自由基反應型光起始劑……………………………………………24
2-3-3-2 陽離子反應型光起始劑……………………………………………24
2.3.4 添加劑………………………………………………………………………24
2.3.5 溶劑…………………………………………………………………………25
2.3.6 助劑…………………………………………………………………………25
2.3.7 染、顏料……………………………………………………………………25
2.4 丙烯酸脂系與環氧樹脂系樹脂的比較 ………………………………………26
2.5 影響光硬化反應的因素 ………………………………………………………28
2-5-1 起始劑與UV 燈源之強度、波長…………………………………………28
2-5-2 照射劑量(dose) ……………………………………………………………29
2-5-3 光源強度 …………………………………………………………………29
2-5-4 光起始劑的吸收波長及吸收感度 ………………………………………29
2-5-5 光起始劑含量 ……………………………………………………………29
2-5-6 塗膜之厚度 ………………………………………………………………29
第三章 實驗藥品、設備及方法…………………………………………………………31
3.1 實驗簡介 ………………………………………………………………………31
3.2 實驗材料及試片裝備 …………………………………………………………31
3.3 實驗設備 ………………………………………………………………………33
3.4 結果與討論 ……………………………………………………………………36
第四章 結論與未來展望…………………………………………………………………41
4.1 結論 ……………………………………………………………………………41
4.2 未來展望 ………………………………………………………………………41
參考文獻 …………………………………………………………………………………43

[1] Jane Bird. Exploring the 3D printing opportunity. The Financial Times. [2012-08-30]
[2] Hideo Kodama, "A Scheme for Three-Dimensional Display by Automatic Fabrication of Three-Dimensional Model," IEICE TRANSACTIONS on Elec-tronics (Japanese Edition), vol.J64-C, No.4, pp.237-241, April 1981
[3] Hideo Kodama, "Automatic method for fabricating a three-dimensional plas-tic model with photo-hardening polymer," Review of Scientific Instruments, Vol. 52, No. 11, pp 1770-1773, November 1981
[4] 3D Printing: What You Need to Know. PCMag.com. [2013-10-30]
[5] Apparatus for Production of Three-Dimensional Objects by Stereolithogra-phy (8 August 1984)
[6] Freedman, David H. "Layer By Layer." Technology Review 115.1 (2012): 50–53. Academic Search Premier. Web. 26 July 2013
[7] MAKE:3D printing by Anna Kaziunas France
[8] Cura and Slic3r have some fixup tools, despite being mainly a slicer program
[9] FDM is a proprietary term owned by Stratasys. All 3-D printers that are not Stratasys machines and use a fused filament process are referred to as or fused filament fabrication (FFF)
[10] Apparatus for production of three-dimensional objects by stereolithogra-phy by Charles W. Hull
[11] NSF JTEC/WTEC Panel Report-RPA
[12] UV Curable樹脂於不同波長之反應探討，碩士論文，國立台北科技大學有機高分子研究所，陳奇毅，台北，2002