臺灣博碩士論文加值系統

本論文主要分為兩個部分，第一部分在探討硬桿鏈狀環氧樹脂和氰酸脂固化後材料的熱性質、介電性質、固化動力學及固化程序之流變行為，並且與商業用非硬桿鏈狀環氧樹脂做比較。
硬桿型並呈液晶態的環氧樹脂: 4,4-bis(2,3-epoxy propoxy) biphenyl epoxy(BP) 及商業用環氧樹脂: diglycidyl ether of bisphenol A (DGEBA)分別與氰酸脂類硬化劑: 2,2’-bis(4- cyanatophenyl) propane (AroCy B10)依當量比1 : 0.5及1:1 固化。利用微差熱掃描計(DSC)研究硬化反應的活化能，藉由熱機械分析儀(TMA)、動態機械分析儀(DMA)及熱重分析儀(TGA)來分析玻璃轉移溫度(Tg)、熱膨脹係數、裂解溫度等熱性質。介電分析儀(DEA)分析其介電性質，以及流變儀(Rheometer)探討其固化程序之流變行為。
固化後呈現anisotropic之BP/B10(1:0.5)有較高的Tg、5%重量損失之裂解溫度，且熱膨脹係數(CTE)最低。BP因具有分子不易移動之硬桿鏈狀結構，故需較高的反應溫度與較長的反應時間，並且與氰酸脂在固化後形成的網狀結構，展現了較佳的熱性質及介電性質。
由於液晶環氧樹脂熔融黏度低可用於覆晶液態封裝材料(underfill)，而液態封裝材料其中填料(filler)SiO2的粒徑大小也影響其黏度，所以本論文第二部分探討合成粒徑和形狀可掌握的SiO2，以降低液態封裝材料的黏度與增加流動性。SiO2粒徑已達到650nm，其顆粒形狀大小均勻且排列整齊之立體結構可用於photonic crystal材料。

This thesis comprises two parts. In the first part, we investigate the differences of thermal properties, dielectric properties , curing kinetics, curing chemorheologies between cyanate ester cured rigid rod epoxy and cyanate ester cured flexible commercial epoxy.
Rigid rod resin with liquid crystalline properties: biphenol epoxy resin (BP) and conventional epoxy resin of diglycidyl ether of bisphenol A (DGEBA), were cured by 2,2’-bis(4-cyanatophenyl) propane (B10) with the ratio of 1: 0.5 and 1:1. The curing activation energy were obtained by using differential scanning calorimetry (DSC). Thermomechanical analyzer (TMA), dynamic mechanical analyzer (DMA) and thermogravimetric analyzer (TGA) were used to determine the thermal properties, including the glass transition temperatures, thermal expansion coefficients and decomposition temperatures. Dielectric analyzer (DEA) was used to determine the dielectric properties. The curing chemorheologies were investigated by rheometer.
Anisotropic BP/B10(1: 0.5) with higher Tg , decomposition temperature and lowest thermal expansion coefficients. The rigid rod structures of epoxy affect the molecular motion and result in higher curing temperature and longer cure time than flexible epoxies. Cyanate cured rigid rod epoxy resins exhibit good thermal properties and dielectric properties due to the rigid structure of cured networks .
Liquid crystalline epoxy resin with low melting viscosity can be used in underfill materials. SiO2 (filler) particle size also affect the viscosity of underfill materials. In the second part, we discuss how to control the underfill filler's(silica) particle size , shape and to reduce underfill viscosity. The silica particle in the size of 650nm with close packed ordered structure can be used in photonic crystal materials.

中文摘要………………….i
英文摘要…………………ii
目錄……………….…….iii
圖目錄……………..vi
表目錄………………...x
導言……………………...1
第一章 緒論……………...2
1.1前言…………………………………….....2
1.2環氧樹脂…………………………….3
1.3液晶簡介…………………………………...5
1.4液晶與液晶相排列………………………...5
第二章 原理與文獻回顧…………….....8
2.1 Biphenyl 系統…………………………...........9
2.2 Azomethine (Schiff base)系統…………………....11
2.3 其他系統……………………………...........11
2.4 氰酸脂………………………………............13
2.5環氧樹脂之硬化反應動力學………………………...16
2.5.1文獻回顧………………………….......19
2.6環氧樹脂之化學流變分析…………………...........20
2.7儀器原理………………………………............24
2.7.1微差掃描卡計………………………….........24
2.7.2熱重分析儀…………………………..........25
2.7.3介電分析儀…………………………….....26
2.7.4動態機械分析儀…………….......31
2.7.5熱機械分析儀……………………..32
2.7.6流變儀…………………….......33
第三章 實驗…………………………….........37
3.1實驗藥品………………….........37
3.2實驗儀器……………......................39
3.3實驗步驟………………………………..........42
3.3.1實驗流程……………..........42
3.3.2液晶環氧樹脂的合成….......43
3.3.3環氧當量滴定…..............43
3.3.4環氧樹脂的硬化........44
3.3.5 環氧樹脂之硬化動力………….................45
3.3.6 形態學觀察……………………..........45
3.3.7環氧樹脂之化學流變分析…………….......45
3.3.8測試項目......47
3.3.8.1微差掃描卡計(DSC)測試………….....47
3.3.8.2熱重分析儀(TGA)測試………….......47
3.3.8.3動態機械分析(DMA)測試……………….......48
3.3.8.4熱機械分析儀(TMA)測試……………….........48
3.3.8.5介電分析儀(DEA)測試……...............49
3.3.8.6流變儀(Rheometer)測試…..........49
3.3.8.7偏光顯微鏡(Polarized Optical Micrograph) ………….49
第四章 結果與討論………………………....50
4.1 液晶環氧樹脂:biphenol環氧樹脂的合成....................50
4.2 環氧樹脂之硬化反應動力學...........................53
4.2.1硬化反應之活化能.....................................53
4.2.2硬化反應之模式.................................55
4.3 環氧樹脂之化學流變分析................................58
4.3.1硬化反應黏度變化模式.....................................58
4.4形態學觀察..................................65
4.5 TGA分析...........................................67
4.6 DMA分析................................................73
4.7 TMA分析......................................78
4.8 DEA分析.........................................81
第五章 結論與建議......................................88
第六章 參考文獻...........................90

1. D. Demus in “Liquid Crystals :Applications and Users”, Vol. 1,Ed. B. Bahadur, World Scientific, Singapore. P.20-22 (1992)
2. 桓內弘著，賴耿陽譯，環氧樹脂應用實務，復漢出版社
3. B. Ellis, “Chemistry and Technology of Epoxy Resin”, Blackie Academic &Professional, England (1993)
4. F. Reinitzer, Monast. Chem., 9, 421 (1888)
5. O. Lehmann, Z. Physik. Chem., 4, 462 (1889)
6. G. Friedel, Annals of Physics, 18, 19, Paris (1942)
7. A. M. Donald, A. H. Windle, “Liquid Crystal Polymer”, Cambridge University, Cambridge, England (1992)
8. G. W. Gray, J. W. Goodby, “Semectic Liquid Crystal, Textures and Structures”, Leonard Hill, Glasgow (1984)
9. D. Demus, S. Chemie, “Liquid Crystal, Applications and Uses” ed. B. Bahadur, 1, 1 (1990)
10. L. Strzelecki, L. Liebert, Bull. Soc. Chem., 597 (1973)
11. S. B. Clough, A. Blumstein, E. C. Hsu, Marcomolecules, 9, 123 (1976)
12. Jpn, Kokai Tokyo, Jp 58, 206, 579
13. H. P. Muller, R. Gipp, H. Heine; U. S. Patent: 4,764,58, (1988)
14. J. D. Earls, R. E. Hefner; Eur. Pat. Appl. :EP379,057, (1990)
15. R. Dhein, H. P. Huller, H. M. Meier, R. Gipp; U. S. Patent:4,762,901, (1988)
16. W-F. A. Su, “Thermoplastic and thermoset main chain liquid crystal polymers prepared from biphenyl mesogen”, J. Polym. Sci., Part A：Polym. Chem., 31, 3251, (1993)
17. C. Carfagna, E. Amendola, M. Giamberini, Composite Structure, 27, 37, (1993)
18. M. Ochi, N. Tsuyuno, K. Sakaga, Y. Nakanishi, Y. Murata, “Effects of network structure on thermal and mechanical properties of mesogenic epoxy resin cured with aromatic amine”, J. Appl. Polym. Sci., 56, 1161, (1995)
19. M. Ochi, Y. Shimizu, Y. Nakanishi, Y. Murata, “Effect of the network structure on thermal and mechanical properties of mesogenic epoxy resin cured with aromatic amine”, J. Polym. Sci., Part B：Polym. Phys., 35, 397, (1997)
20. W. Mormann, M. Brocher, “Liquid crystalline thermosets from 4,4’-bis(2,3-epoxy propoxy)biphenyl and aromatic diamines”, Macromol. Chem. Phys., 197, 1841, (1996)
21. W-F A. Su, K. C. Chen, S. Y. Tseng, 國立台灣大學工程學刊, 77, 73, 1999
22. W-F. A. Su, K. C. Chen, S. Y. Tseng, Effects of chemical structure changes on thermal, mechanical and crystalline properties of rigid rod epoxy resins , J. Appl. Polym. Sci. (2000)
23. J. Y. Lee , Synthesis and curing liquid crystalline epoxy resins based on 4,4’-biphenol , Polymer , 39 , 24 , 6121-6126 , (1998)
24. J. A. Mikroyannidis, “Synthesis, characterization and polymerization of new epoxy compounds containing Azomethine linkages”, Makromol. Chem., 190, 1867, (1989)
25. J. A. Mikroyannidis, “Self-curing epoxy compounds”, J. Appl. Polym. Sci., 41, 2613, (1990)
26. J. A. Mikroyannidis, “Epoxides bearing azomethine linkages”, Polym. Inter., 25, 91, (1991)
27. C.S.Wang, H.J.Hwang, Investigation of Bismaleimide Containing Naphthalene Unit.II Thermal Behavior and Properties of Polymer , J.Polym.Sci.Part A.Polym. Chem, 34,1493,(1996)
28. J. Y. Lee , Synthesis and curing liquid crystalline epoxy resins based on Napthalene Mesogen , J. of Polym. Sci. Part A Polym. Chem., 37, 419-425, (1999)
29. J. Y. Lee , Effect of Substituent on the Curing of Liquid Crystalline Epoxy Resin, J. of Polym. Sci. Part A Polym. Chem., 36, 911-917, (1998)
30. J. Y. Lee , Relationship between the structure of bridging group and curing of liquid crystalline epoxy resins , Polymer , 40 , 3197-3202 , (1999)
31. G. G. Barclay, C. K. Ober, K. I. Papathomas, D.W. Wang, Rigid-Rod Thermoset Based on 1,3,5-Triazine-Linked Aromatic Ester Seqments, Macromolecules, 25, 2947, (1992)
32. W. Mormann, J.G. Zimmermann, Liquid Crystalline Thermosets through Cyclotrimerization of Diaromatic Dicyanates, Macromolecules, 29, 1105, (1996)
33. Shiow-Ching Lin, Eii M. Pearce, High-Performance Thermosets : Chemistry, Properties, Applications, Hanser Publishers, New York, (1994)
34. R.B.Prime, Differential Scanning Calorimeter of the Epoxy Cure Reaction, Polym. Eng. Sci.,13,365(1973)
35. K. Dusek and M. Bleha , Curing of Epoxide Resins :Model Reaction of Curing with Amine, J. Polym. Sci. , Polym. Chem. Ed. , 15,2393(1977)
36. Y. S. Pusatciolu, A. L. Fricke and J. C. Hassler, Heats of Reaction and Kinetics of a Thermoset Polyester , J. Appl. Polym. Sci. ,24,937(1979)
37. Horie , Calorimetric Investigation of Polymerization Reactions. III. Curing Reaction of Epoxides with Amines , J. Polym. Sci. ,A-1 , 8 , 1357(1970)
38. A. Moroni , J. Mijovic , E. M. Pearce and C. C. Foun , Cure Kinetics of Epoxy Resins and Aromatic Diamines , J. Appl.Polym.Sci.,32,3761(1986)
39. K. W. Lem and C. D. Han , Thermokinetics of Unsaturated Polyester and Vinyl Ester Resins , Polym. Eng. Sci. , 24 , 175(1984)
40. M. , E. Ryan and A. Dutta , Kinetics of Epoxy Cure: A rapid Technique for Kinetic Parameter Estimation , Polym. , 20 , 203(1979)
41. J. Mijovic , Cure Kinetics of Neat Versus Reinforced Epoxies, J. Appl. , Polym., Sci. , 31 , 1177(1986)
42. P. Punchaipetch , Epoxy + liquid crystalline epoxy coreacted networks: I. Synthesis and curing kinetics , Polymer , 42 , 2067-2075(2001)
43. Yi He , DSC and DEA studies of underfill curing kinetics , Thermochimica Acta 367-368 , 101-106(2001)
44. M. A. Golub and N. R. Lerner , Kinetic Study of Polymerization/Curing of Filament-Wound Composite Epoxy Resin Systems with Aromatic Diamines , J. of Appl. Polym. Sci., 32 , 5215(1986)
45. F. G. Mussati and C. W. Macosko , Rheology of Network Forming Systems , Polym. Eng. Sci., 13,236(1973)
46. Y. A.Tajima and D. Crozier , Themokinetic Modeling of an Epoxy Resin I , Chemoviscosity , Polym. Eng. Sci., 23 , 186(1983)
47. J. M. Castro , C. W. Macosko and S. J. Perry , Viscosity Changes during Urethane Polymerization with Phase Separation , Polym. Comm. , 25 , 82(1984)
48. R. P. White , Jr., Time-Temperature Superpositoning of Viscosity-Time Profiles of Three High Temperature Epoxy Resins , Polym. Eng. Sci. , 14 , 50(1974)
49. M. B. Roller , Characterization of the Time-Temperature-Viscosity Behavior of Curing B-Staged Epoxy Resin , Polym. Eng. Sci. , 15 , 406(1975)
50. J. Mjiovic and C. H. Lee , A Comparison of ChemorheoIogical Models for Themoset Cure , J. Appl. Polym. Sci. 38,2155(1989)
51. C. W. Macosko , Rheological Changes During Crosslinking ,Brit. .Polym. J., 17 , 239(1985)
52. I. M. Ward,in Mechanical Properties of Solid Polymers, 2nd Ed. , John WiIey & Sons ,Chichester (1983)
53. L. H., Sperling, in Introduction to Physical Polymer Science, John Wiley & Sons , New York(1986)
54. G. W. Scherer , in Relaxation in Glass and Composites , John Wiley & Sons , New York , (1986)
55. 黃國書, Flip Chip Underfill封裝用環氧樹脂之組成，流動行為及物性之研究, 國立台灣科技大學碩士論文, (1998)
56. 黃宏文, 液晶環氧樹脂與氰胍及磺醯二苯胺固化後之物性研究, 國立台灣大學碩士論文, (2001)
57. 莊智閔, 液晶環氧樹脂與氰酸酯固化之物性研究, 國立台灣大學碩士論文, (1999)
58. 張榮語, 旋轉式流變儀, 儀器總覽, 94, (1998)
59. T. Ozawa , A New Method of Analyzing Thermogravimetric Data, Bull., Chem., Soc., Jpn., 38 , 1881 , (1965)
60. H. E. Kissinger , Anal. Chem., 29, 1072 , (1957)
61. K. C. Cheng , Chemorheology of epoxy resin Part I Epoxy resin cured with tertiary amine , J. of Material Science , 29 , 721-727, (1994)