臺灣博碩士論文加值系統

本論文是以BPA型環氧樹脂與雙酚型氰酸酯樹脂 (商品名B-10) 做摻合硬化反應，利用FTIR來探討兩者之間的硬化反應機構，並且推導其新穎反應機構，而DMA、DSC、介電阻抗分析及吸濕性質探討硬化後摻合物結構與物性之變化，再藉由環境老化測試探討材料的可靠性。
由IR光譜結果可看出，BPA型環氧樹脂/氰酸酯摻合物於低溫 (150℃、160 ℃及170 ℃) 下硬化反應，可得其新穎硬化反應機構。由DMA與DSC可知，摻合物隨著硬化條件不同 (A∼E) 下之Tα值皆往高溫上升，其添加促進劑的量以2 phr為最佳。由介電性質結果顯示，隨著前端硬化時間不同 (40 min、120 min及200 min) 所測得介電值 (Dk) 最低為3.20，其消耗值 (Df) 為0.051。而改變中端硬化溫度 (250 ℃降低至220 ℃) 及後端硬化時間 (40 min增加至60 min)所測Dk最低值為3.15。由吸水率結果可知，以硬化條件E下硬化之材料 (LCE05-E) 吸水率為0.44％ 最低。添加促進劑 (DICY) 硬化後樹脂較不易吸水。由老化測試結果可知，老化後材料Tα值明顯降低 (189 ℃降至174 ℃)，而添加促進劑 (DICY) 之硬化材料在長期老化後Tα降低最多，故Tα值由165 ℃降至144 ℃。由老化之IR結果可看出有產生氫鍵作用，故老化後對材料結構是有所影響。

The aim of this research is to study the reaction mechanism of cyanate ester and its blends with bisphenol A type epoxy resins. Fourier transform infrared (FTIR) spectroscopy investigation of these systems through curing allowed us to analyze the reaction mechanism of these reactive systems. Structural and physical properties of the resin blends are studied by dynamic mechanism analyzer (DMA), differential scanning calorimeter (DSC), impedance analyze (IEA) and moisture absorption measurements. The environmental reliability of the materials are tested by aging measurements.
For IR spectra, The novel curing reaction mechanism can be obtained from bisphenol A type epoxy resins/cyanate ester blends curing reaction on low temperature (150 ℃、160 ℃ and 170 ℃). For DMA and DSC results, the value of Tα is varied with the different curing condition (A∼E) for polymer blends. The added optimal advance agents for these blends are at low contents (2 phr). The dielectric constant can be lowered to 3.2 with the forward curing time (40 min、120 min and 200 min). Change the curing temperature from 250 ℃ to 220 ℃ and the post curing time from 40 min up to 60 min, the dielectric constant can be lowered to 3.15. From the moisture absorption, the water uptake of the cured materials (LCE05-E) is 0.44％. The cured resins display markedly lower values of moisture uptake than those without the addition of advance agents (DICY). After aging, values of Tα of curing materials descend markedly from 189 ℃ to 174 ℃. However, values of Tα dropped from 165 ℃ to 144 ℃ for the cured materials with the addition of advance agents (DICY) after aging. From IR analysis, it shows the presence of hydrogen-bond interactions, which is caused by aging.

誌謝---------------------------------------------------------------------------------iv
目錄---------------------------------------------------------------------------------v
摘要-------------------------------------------------------------------------------viii
Abstrac-----------------------------------------------------------------------------ix
圖表目錄--------------------------------------------------------------------------xi
第一章 緒論-----------------------------------------------------------------------1
1-1 前言----------------------------------------------------------------------------1
1-2 印刷電路板之發展簡介----------------------------------------------------4
1-3 研究動機與方向-------------------------------------------------------------7
第二章 文獻回顧-----------------------------------------------------------------8
2-1 環氧樹脂脂之簡介----------------------------------------------------------8
2-1-1 環氧樹脂之發展及性質--------------------------------------------8
2-1-2 環氧樹脂之種類-----------------------------------------------------9
2-2 氰酸酯之簡介---------------------------------------------------------------14
2-2-1 氰酸酯之發展及性質----------------------------------------------14
2-2-2 氰酸酯之硬化反應-------------------------------------------------18
2-3 環氧樹脂/氰酸酯之硬化反應--------------------------------------------23
第三章 實驗----------------------------------------------------------------------26
3-1 實驗藥品---------------------------------------------------------------------26
3-2 儀器設備---------------------------------------------------------------------28
3-3 實驗步驟---------------------------------------------------------------------29
3-3-1 實驗流程------------------------------------------------------------29
3-3-2 樣品製備------------------------------------------------------------30
3-3-2-1 BPA型環氧樹脂與DCBA氰酸酯樹脂的混合製備------30
3-3-2-2 環氧樹脂/DCBA氰酸酯/促進劑三者混合製備-----------30
3-3-2-3 硬化程序----------------------------------------------------------30
3-4 物性分析--------------------------------------------------------------------32
第四章 結果與討論------------------------------------------------------------35
4-1 紅外線光譜 (FTIR) 分析------------------------------------------------35
4-1-1 BPA型環氧樹脂/DCBA氰酸酯摻合物硬化反應機構之探
討-------------------------------------------------------------------35
4-1-2 針對150 ℃下恆溫比較BPA型環氧樹脂/DCBA氰酸酯摻合物(當量比為1/0.5與1/1) 對反應機構之影響-----------------------------------------------------------------------38
4-1-3 探討BPA型環氧樹脂/DCBA氰酸酯摻合物於高溫 (250 ℃與275 ℃) 下，溫度對反應機構的影響-----------------------------------------------------------------------39
4-2 微差掃描熱卡 (DSC) 與動態機械分析 (DMA)--------------------53
4-3 介電性質與吸水性--------------------------------------------------------64
4-4 老化試驗--------------------------------------------------------------------70
4-4-1老化之紅外線光譜 (FTIR)分析---------------------------------70
4-4-2老化之動態機械分析-----------------------------------------------75
第五章 結論----------------------------------------------------------------------81
第六章 參考文獻----------------------------------------------------------------84

1. D. A. Shimp, F. A. Hudock, S. J. Ising, Proc. SAMPE symp., 33, 754 (1988).
2. B. S. Kim, J. Appl. Polym. Sci., 65, 85 (1997).
3. 林建中，"高分子材料性質與應用"，高立書局，1998.
4. D. Mathew, C. P. R. Nair, K. N. Ninan, J. Appl. Polym. Sci., 74, 1675 (1999).
5. M. Grenier-Loustalot, C. Lartigau, J. Polym. Sci., Polym. Chem. Ed., 35, 3101 (1997).
6. C. P. R. Nair, T. Francis, T. M. Vijayan, K. Krishnan, J. Appl. Polym. Sci., 74, 2737 (1999).
7. 徐鏡堯，國立台灣大學材料科學與工程學研究所碩士論文，1998.
8. 工研院化工所產資組IT IS計畫，2000.
9. "產業經濟"，合作金庫銀行調查編印，p.245，2002.
10. P. Castan , U. S. Pat., 2,324,483 (1943).
11. S. O. Greenlee , U. S. Pat., 2,456,408 (1948).
12. 馬振基, "高分子複合材料" 上冊，正中書局，p.255，1995.
13. C. S. Wang, T. H. Ho, Chinese J. Mater. Sci., 24, 123 (1992).
14. C. S. Wang, H. J. Hwang, T. H. Ho, Proc. Natl. Counc. ROC., A7, 347 (1993).
15. C. S. Wang, J. R. Berman, A. Mendoza, J. Appl. Polym. Sci., 43, 1315 (1991).
16. D. Derouet, F. Morvan, J. C. Bross, J. Appl. Polym Sci., 62, 1885 (1996).
17. G. Camino, C. L. Osta, G. Martinasso, Polym. Deg. Stab., 23, 359 (1989).
18. A. S. V. Cadiz, P. A. Martinez, A. Mantecon, Angew. Makromol. Chem., 140, 113 (1996).
19. P. A. Martinez, A. S. V. Cadiz, A. Mantecon, A. Serra, Angew. Makromol. Chem., 133, 97 (1985).
20. U. S. Pat., 3,796,731 (1974).
21. D. W. van Krevelen, Polymer, 16, 615 (1975).
22. C. S. Cho, L. W. Chen, S. C. Fu, T. R. Wu, J. Polym. Res., 5, 59 (1998).
23. C. S. Cho, L. W. Chen, Y. S. Chiu, Polymer Bulletin, 41, 45 (1998).
24. 邱國展，工業材料雜誌，170，二月，2001.
25. G. H. Hsiue, W. J. Wang, F. C. Chang, J. Appl. Polym. Sci., 73, 1231 (1999).
26. I. Hamerton, "Chemistry and Technology of Cyanate Ester Resins", chapter 2 (1994).
27. R. Stroh, H. Gerber, Angew. Chem., 72, 1000 (1960).
28. R. Kubens, H. Schulthesis, W. Wolf, E. Grigat, Kunststoffe, 58, 827 (1968).
29. 王文洋，"電路板資訊"，42, 42 (1991).
30. M. Guku, K. Nakamichi , U. S. Pat., 4,110,364 (1978).
31. I. Hamerton, J. N. Hay, Polym. Int., 47, 465 (1998).
32. M. Bauer, J. Bauer, G. Kuhn, Acta. Polymerica, 37, 715 (1986).
33. A. Osei-Owusu, G. C. Martin, J. T. Gotro, Polym. Mater. Sci. Eng., 65, 304 (1991).
34. A. Osei-Owusu, G. C. Martin, Polym. Eng. Sci., 32, 535 (1992).
35. S. L. Simon, J. K. Gillham, J. Appl. Polym. Sci., 47, 461 (1993).
36. S. L. Simon, J. K. Gillham, D. A. Shimp, Polym. Mater. Sci. Eng., 62, 96 (1990).
37. S. L. Simon, J. K. Gillham, Polym. Prepr., 32, 182 (1991).
38. R. H. Lin, J. L. Hong, A. C. Su, Polymer, 36, 3349 (1995).
39. J. Y. Chang, J. L. Hong, Macromol. Chem. Phys., 196, 3753 (1995).
40. A. Osei-Owusu, G. C. Martin, Polym. Eng. Sci., 31, 1604 (1991).
41. V. Mirco, F. Mechin, J. P. Pascault, ACS Div. Polym. Mater. Sci. Eng., 71, 688 (1994).
42. D. A. Shimp, S. J. Ising, ACS Div. Polym. Mater. Sci. Eng., 66, 504 (1991).
43. J. L. Hong, C. K. Wang, R. H. Lin, J. Appl. Polym. Sci., 53, 105 (1994).
44. P. Bartolomeo, J. F. Chailan, J. L. Vernet, Eur. Polym. J., 37, 659 (2001).
45. J. M. Charesworth, Polym. Eng. Sci., 28, 221 (1988).
46. A. C. Grillet, J. Galy, J. F. Gerard, J. P. Pascault, Polymer, 32, 1885 (1991).
47. H. Stutz, J. J. Mertes, J. Polym. Sci., Polym. Chem. Ed., 31, 2031 (1993).
48. F. de Nogravo, P. Guerrevo, M. A. Corcuera, I. Mondragon, J. Appl. Polym. Sci., 56, 177 (1995).
49. R. H. Lin, J. Polym. Sci. Polym. Chem. Ed., 38, 2934 (2000).
50. J. Bauer, M. Bauer, J. Macromol. Sci. Chem., A27, 97 (1990).
51. J. Bauer, M. Bauer, Makromol. Chem., Macromol. Symposium, 30, 1 (1989).
52. M. D. Martin, M. Ormaetxea, I. Harismendy, P. M. Remiro, I. Mondragon, Eur. Polym. J., 35, 57 (1999).
53. Japan. Pat., 80-43130.
54. I. Hamerton, "Chemistry and Technology of Cyanate Ester Resins", chapter 5 (1994).
55. K. Biemann, "Tables of Spectral Data for Structure Determination of Organic Compounds", 1981.