臺灣博碩士論文加值系統

　　聚甲基丙烯酸甲酯由粉劑和液劑混合而成，具有良好的生物相容性、機械強度佳、容易塑形且固化時間短，廣泛應用於牙科、骨科及外科手術。
　　市售臨時假牙產品裡，普遍添加鄰苯二甲酸酯類之化合物作為增塑劑，而此類化合物已被指出對人類健康有危害性，故本實驗中採用美國食品藥物管理局核准之檸檬酸酯類化合物以替代鄰苯二甲酸酯類的增塑劑。
　　此研究中，探討交聯劑及增塑劑對PMMA 樹脂之性質影響，包含操作性、溫度測量、色彩變化、吸水值與溶解值、表面硬度、抗彎強度及細胞毒性測試。實驗結果顯示：(1)交聯劑及增塑劑對最高聚合溫度沒有影響；(2)交聯劑及增塑劑影響樣品的顏色、影響操作性時間、抗彎強度、表面硬度；(3)交聯劑不影響吸水值，但會影響溶解值；增塑劑會影響吸水值及溶解值；(4)粉液比會影響溫度、固化時間及抗彎強度；(5)細胞毒性測試表現出增塑劑乙醯基檸檬酸三丁酯的毒性確實小於鄰苯二甲酸二丁酯；(6)樣品浸泡水份會顯著影響色彩。

　　Polymethyl methacrylate (PMMA), is a mixture of powder and liquid. It has good biocompatibility, good mechanical strength, easy shaping and short curing time. It is widely used in dentistry, orthopedics and surgery fields.
　　It is commonly used phthalate ester compound as plasticizer in the commercial temporary crown, and this compound has be proved is harmful to human health. Therefore, the FDA-approved citrate compound was used in this experiment to replace the phthalate plasticizer.
　　In this study, we investigated the effects of cross-linking agent and two plasticizers on the properties of PMMA resins, including working time, temperature measurement, color variation, water sorption, water solubility, surface hardness, flexural strength and cytotoxicity assay. The experimental results show that: (1) cross-linking agent and plasticizer have no effect on temperature; (2) both cross-linking agent and plasticizer affect sample color, operating time, flexural strength and surface hardness; (3) The cross-linking agent doesn’t affect water sorption, but affects the water solubility; the plasticizer affects the water sorption and the water solubility; (4) the liquid-to-powder ratio affects the temperature, the curing time and the flexural strength; (5) the cytotoxicity test shows that the toxicity of the acetyl tributyl citrate plasticizer is less than the dibutyl phthalate; (6)
Sample soaking water significantly affects its color.

摘 要 i

ABSTRACT iii

誌 謝 v

目 錄 vi

表目錄 x

圖目錄 xii

第一章 緒論 1

1.1 前言 1

第二章 文獻回顧 2

2.1 臨時假牙 2

2.1.1 臨時假牙材料 3

2.1.2 臨時假牙製作方式 4

2.2 聚甲基丙烯酸甲酯 6

2.2.1 歷史回顧 6

2.2.2 PMMA 臨時假牙 6

2.2.3 PMMA 聚合反應 8

2.3 增塑劑 12

2.3.1 簡介 12

2.3.2 鄰苯二甲酸酯 12

2.3.3 檸檬酸酯 13

2.3.4 抗塑化效應 14

2.4 聚合物性質 15

2.4.1 水分子對聚合物的影響 15

2.5 PMMA 臨時假牙市售產品 16

第三章 研究動機與目的 18

第四章 實驗材料與方法 19

4.1 實驗儀器與設備 19

4.2 實驗藥品 20

4.3 實驗架構 22

4.4 材料分析 23

4.4.1 掃描式電子顯微鏡(Scanning Electron Microscope，SEM) 23

4.4.2 膠體滲透層析儀(Gel Permeation Chromatography，GPC) 24

4.5 操作性 25

4.6 溫度及固化時間測試 26

4.7 維氏硬度試驗 27

4.8 三點彎曲試驗 28

4.9 色彩量測及色彩穩定度試驗 29

4.10 吸水值與溶解值試驗 31

4.11 接觸角量測 32

4.12 細胞毒性測試 33

第五章 結果與分析 34

5.1 材料分析 34

5.1.1 PMMA 粒徑大小及分佈 34

5.1.2 PMMA 分子量分析 37

5.2 調整交聯劑 38

5.2.1 操作性之影響 38

5.2.2 最高聚合溫度及固化時間之影響 40

5.2.3 顏色變化之影響 41

5.2.4 表面硬度之影響 42

5.2.5 抗彎強度及韌性之影響 43

5.2.6 接觸角之影響 44

5.2.7 吸水值與溶解值之影響 45

5.2.8 表面形貌之觀察 47

5.3 調整粉液比 50

5.3.1 最高聚合溫度及固化時間之影響 50

5.3.2 抗彎強度及韌性之影響 51

5.4 添加增塑劑 52

5.4.1 操作性之影響 52

5.4.2 最高聚合溫度及固化時間之影響 57

5.4.3 顏色變化之影響 60

5.4.4 表面硬度之影響 62

5.4.5 抗彎強度及韌性之影響 65

5.4.6 接觸角之影響 69

5.4.7 生物相容性之影響 70

5.4.8 吸水值與溶解值之影響 71

5.2.8 表面形貌之觀察 73

5.5 臨床前試驗：與市售產品相較 75

5.5.1 色彩穩定度試驗 75

第六章 結論 79

參考文獻 80

附錄 87

1. 衛生福利部國民健康署統計處: https://www.hpa.gov.tw/Home/Index.aspx

2. Misha Singla, et al. "Provisional Restorations in Fixed Prosthodontics: A Review," International Journal of Dental and Medical Research, vol. 1, no. 4, 1973, pp. 148-151.

3. Allen Godwin, "Plasticizers," Applied Polymer Science 21st Century, 2000, pp. 157-175.

4. Thuy T. Bui, et al. "Human exposure, hazard and risk of alternative plasticizers to phthalate esters," Science of the Total Environment, vol. 541, 2016, pp. 451-467.

5. Melissa Gurgel Adeodato Vieira, et al. "Natural-based plasticizers and biopolymer films: A review," European Polymer Journal, vol. 47, no. 3, 2011, pp. 254-263.

6. Mario H. Gutierrez-Villarreal, et al. "The Effect of Citrate Esters as Plasticizers on the Thermal and Mechanical Properties of Poly (Methyl Methacrylate)," Journal of Applied Polymer Science, vol. 105, no. 4, 2007, pp. 2370-2375.

7. Graciela Shimizu Oliva, Mechanical Properties of Provisional Restorative Materials, M.S.D., Indiana University School, Indiana, 2010.

8. Debra R. Haselton., et al. "Flexural strength of provisional crown and fixed partial denture resins," The Journal of Prosthetic Dentistry, vol. 87, no. 2, 2002, pp. 225-228.

9. Kenneth W. Fritts, et al. "Fabrication of temporary crowns and fixed partial dentures," Journal of Prosthetic Dentistry, vol. 30, no. 2, 1973, pp. 151-155.

10. Vahid Rakhshan, "Marginal integrity of provisional resin restoration materials: A review of the literature," The Saudi Journal for Dental Research, vol. 6, no. 1, 2015, pp. 33-40.

11. Herman B.Dumbrigue, "Composite indirect-direct method for fabricating multiple-unit provisional restorations," The Journal of Prosthetic Dentistry, vol. 89, no. 1, 2003, pp. 86-88.

12. Panagiotis C.Psichogios and Edward J.Monaco, "Expedient direct approach for esthetic and functional provisional restorations," The Journal of Prosthetic Dentistry, vol. 89, no. 3, 2003, pp. 319-322.

13. 鍾國雄，牙科材料學，臺灣：合記圖書出版社，2001，第 259-348 頁。

14. Konstantinos Michalakis, et al. "Comparison of temperature increase in the pulp chamber during the polymerization of materials used for the direct fabrication of provisional restorations," The Journal of Prosthetic Dentistry, vol. 96, no. 6, 2006, pp. 418-423.

15. Maj Ronauk Singh, et al. "Intrapulpal thermal changes during direct provisionalization using various autopolymerizing resins: Ex-vivo study," Medical Journal Armed Forces India, vol. 71, no. 2, 2015, pp. S313-S320.

16. Kim, Sung-hun and David C. Watts, "Exotherm behavior of the polymer-based provisional crown and fixed partial denture materials," Dental Materials, vol. 20, no. 4, 2004, pp. 383-387.

17. PaulSeelbach, et al. "Temperature rise on dentin caused by temporary crown and fixed partial denture materials: influencing factors," Journal of Dentistry, vol. 38, no. 12, 2010, pp. 964-973.

18. Chao Siev Kay, et al. "Effect of three repairing materials on the flexural strength of repaired heat-cured acrylic resin denture base material," Mahidol Dental Journal, vol. 37, no. 1, 1994, pp. 37-45.

19. K. M. Regish, et al. "Techniques of Fabrication of Provisional Restoration:An Overview," International Journal of Dentistry, vol. 2011, 2011, pp. 1-5.

20. Jung-Hwan Lee, et al. " Nano-graphene oxide incorporated into PMMA resin to prevent microbial adhesion," Dental Materials, vol. 34, no. 4, 2018, pp. e63-e72.

21. Robert Q. Frazer, et al. "PMMA: an essential material in medicine and dentistry," Journal of long-term effects of medical implants, vol. 15, no. 6, 2005, pp. 629-639.

22. Bana Abdulmohsen, et al. "A study to investigate and compare the physicomechanical properties of experimental and commercial temporary crown and bridge materials," Dental Materials, vol. 32, no. 2, 2016, pp. 200-210.

23. Umar Ali, et al. "A review of the properties and applications of poly (methyl methacrylate)(PMMA)," Polymer Reviews, vol. 5, no. 4, 2015, pp. 678-705.

24. Lamia Zuniga Linan, et al. "Pilot-scale synthesis and rheological assessment of poly (methyl methacrylate) polymers: Perspectives for medical application," Materials Science and Engineering: C, vol. 51, 2000, pp. 107-116.

25. Eugenia Eftimie Totu, et al. "Poly(methyl methacrylate) with TiO2 nanoparticles inclusion for stereolitographic complete denture manufacturing - the fututre in dental care for elderly edentulous patients?," Journal of Dentistry, vol. 59, 2017, pp. 68-77.

26. KEMAL ŞERBETÇİ, et al. "Mechanical and thermal properties of hydroxyapatite-impregnated bone cement," Turkish Journal of Medical Sciences, vol. 30, 2000, pp. 543-549.

27. Surya Prakash Sharma, et al. "An In Vitro Evaluation of Flexural Strength of Two Provisional Restorative Materials Light Polymerised Resin And Autopolymerised Resin," Journal of Dental and Medical Sciences, vol. 6, no. 5, 2013, pp. 5-10.

28. Michael Wiegand, A material characterization of two-solution bone cement containing ethylene glycol-dimethacrylate as a crosslinker, B.S., Clarkson University, United States of America, 2013.

29. Yoshikazu Okuyama, et al. "Influence of composition and powder/liquid ratio on setting characteristics and mechanical properties of autopolymerized hard direct denture reline resins based on methyl methacrylate and ethylene glycol dimethacrylate," Dental Materials Journal, vol. 33, no. 3, 2014, pp. 522-529.

30. Tomohiro Kawaguchi, et al. "Mechanical properties of denture base resin cross-linked with methacrylated dendrimer," Dental Materials, vol. 27, no. 8, 2011, pp. 755-761.

31. Hasinah K Albeladi, et al. "Role of cross-linking process on the performance of PMMA," International Journal of Biosensors & Bioelectronics, vol. 3, no. 3, 2017, pp. 279-284.

32. Myer Kutz, "Applied Plastics Engineering Handbook," New York:William Andrew, 2011, pp. 487-501

33. Mounira Maiza, et al. "Biobased additive plasticizing Polylactic acid (PLA)," Polimeros, vol. 25, no. 6, 2015, pp. 581-590.

34. Giuseppe Latini, et al. "Plasticizers, infant nutrition and reproductive health," Reproductive Toxicology, vol. 19, no. 1, 2004, pp. 27-33.

35. Sachin B. Somwanshi, et al. "Pharmaceutically used plasticizers: A review," European Journal of Biomedical and Pharmaceutical Sciences, vol. 3, no. 2, 2016, pp. 277-285.

36. SailasBenjamin, et al. "Phthalates impact human health: Epidemiological evidences and plausible mechanism of action," Journal of Hazardous Materials, vol. 340, 2017, pp. 360-383.

37. Mustafizur Rahman, et al. "The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges," Progress in Polymer Science, vol. 29, no. 12, 2004, pp. 1223-1248.

38. Mohammad Luqman, "Recent Advances in Plasticizers," Saudi Arabia: InTech, 2012, pp. 46-55.

39. Federica Chiellini, et al. "Perspectives on alternatives to phthalate plasticized poly(vinyl chloride) in medical devices applications," Progress in Polymer Science, vol. 38, no. 7, 2013, pp. 1067-1088.

40. The Joint FAO/WHO Expert Committee on Food Additives: www.fao.org/home/en/

41. Richard J. Lewis, Sax's Dangerous Properties of Industrial Materials. 11th Edition, New York: John Wiley & Sons, 2004, pp.3546.

42. TOXNET: https://toxnet.nlm.nih.gov/

43. United States Environmental Protection Agency: https://www.epa.gov/

44. Johnson W Jr, "Final report on the safety assessment of acetyl triethyl citrate, acetyl tributyl citrate, acetyl trihexyl citrate, and acetyl trioctyl citrate," International journal of toxicology, vol. 21, 2002, pp. 1-17.

45. J. S. Vrentas, "Antiplasticization and Volumetric Behavior in Glassy Polymers," Macromolecules, vol. 21, no. 5, 1988, pp. 1470-1475.

46. Jun Liang, et al. "Effects of glycerol on the molecular mobility and hydrogen bond network in starch matrix,” Carbohydrate Polymers, vol. 115, 2015, pp. 401-407.

47. Job Ubbink, "Structural and thermodynamic aspects of plasticization and antiplasticization in glassy encapsulation and biostabilization matrices," Advanced Drug Delivery Reviews, vol. 100, 2016, pp. 10-26.

48. Jack L. Ferracane, "Hygroscopic and hydrolytic effects in dental polymer networks," Dental Materials, vol. 22, no. 3, 2006, pp. 211-222.

49. S.Kalachandra and D.T.Turner, "Water sorption of poly(methyl methacrylate): 3. Effects of plasticizers," Polymer, vol. 28, no. 10, 1987, pp. 1749-1752.

50. Rungsinee Sothornvit and John M. Krochta, "Plasticizers in edible films and coatings," Innovations in Food Packaging, 2005, pp. 403-433.

51. S.Mali, et al. "Water sorption and mechanical properties of cassava starch films and their relation to plasticizing effect," Carbohydrate Polymers, vol. 60, no. 3, 2005, pp. 283-289.

52. Mohammad Ali Hemmati, et al. "Water Sorption and Flexural Strength of Thermoplastic and Conventional Heat-Polymerized Acrylic Resins," Journal of Dentistry of Tehran University of Medical Sciences, vol. 12, no. 7, 2015, pp. 478–484.

53. Rajesh Saini, et al. "Comparative study of sorption and solubility of heat cure and self-cure acrylic resins in different solutions," Indian Journal of Dental Research, vol. 27, no. 3, 2016, pp. 288-294.

54. MSDSonline: https://www.msdsonline.com/

55. ISO 4049-2009. Dentistry — Polymer-based restorative materials.

56. ISO 10477-2004. Dentistry — Polymer-based crown and bridge materials.

57. ISO 6507-1-2018. Metallic materials — Vickers hardness test — Part 1: Test method.

58. ISO10993-5-2009. Biological evaluation of medical devices — Part 5: Tests for in vitro cytotoxicity.

59. ISO 10993-12:2009 - Biological evaluation of medical devices - Part 12: Sample preparation and reference materials.

60. Victor Kuete, "Medicinal Spices and Vegetables from Africa," American: Academic Press, 2017, pp. 271-297.