臺灣博碩士論文加值系統

環氧樹脂具有很多的特性，如加工容易、黏著性佳、耐化學溶劑和耐酸鹼腐蝕，以及優異的電氣和機械特性，因而廣用於電子工業。但環氧樹脂高介電常數和高吸濕性，且高溫下性能會變差，加上半導體構裝型式已由插孔式(PTH)轉成表面黏著式(SMT)，使其無法滿足目前技術上的需求。取而代之的是由双馬來醯亞胺和和氰酸酯調製成的BT樹脂，此樹脂能提供耐銲錫溫度及較環氧樹脂更佳的物性。然而此樹脂中双馬來醯亞胺和氰酸酯間的共聚合反應較不完全，因而影響硬化物之物性。
本研究之目的在於合成一低黏度共硬化劑，其特色為芳香環結構上同時含有不飽和乙烯基和環氧基，利用此共硬化劑(APGE)中的不飽和雙键與雙馬來醯亞胺反應，而環氧基則和氰酸酯反應，以改善傳統BT樹脂之間的反應性，且低黏度的共硬化劑將可降低原來BT樹脂的黏度，以增加加工性及減少溶劑的使用。利用DSC、DEA、TGA及DMA等儀器來探討共硬化劑對BT樹脂的物性影響。實驗結果顯示，加入共硬化劑後BT樹脂混掺物之硬化反應熱明顯地增加，使BT樹脂混掺硬化物之Tg提升，證實共硬化劑確能增加BT樹脂間的反應性，並提升BT樹脂混掺硬化物之熱穩定性。進一步為降低使用成本而添加環氧樹脂，由物性測試結果顯示，氰酸酯/雙馬來醯亞胺/環氧樹脂混掺硬化物的Tg、熱穩定性都隨著環氧樹脂添加量的增加而有明顯地降低，但對於加工性、使用的黏度上及成本上得到良好的改善。
而為了改善BT樹脂的反應性及降低使用上的成本，直接將商用液態環氧樹脂改質導入乙烯基作為BT樹脂之共硬化劑，利用共硬化劑中的不飽和雙键與雙馬來醯亞胺反應，而環氧基和氰酸酯反應。並利用DSC、TGA、DMA、TMA及介電儀等儀器來探討環氧樹脂改質與否對BT樹脂組成物的物性影響。由結果顯示，無論環氧樹脂改質與否氰酸酯/雙馬來醯亞胺/環氧樹脂混掺硬化物的Tg、熱穩定性都隨著環氧樹脂添加量的增加而逐漸降低；環氧樹脂本身的熱穩定性及Tg皆比純BT樹脂較低，但因改質的環氧樹脂帶有不飽和雙鍵，改善了BT樹脂之間的反應性，才使得氰酸酯/雙馬來醯亞胺/環氧樹脂混掺硬化物的物性並不因環氧樹脂的添加而大幅下降。因此，在氰酸酯/雙馬來醯亞胺/環氧樹脂中添加適量改質過含乙烯基環氧樹脂可有效降低成本、黏度及提高加工性，並保有其優異的熱穩定性及Tg。

Epoxy resins, which represent some of the most widely used resins in electronics applications, are characterized by easy processability, good adhesion to various substrates, high chemical and corrosion resistance, and excellent electric and mechanical properties. However, epoxy resins have relatively poor performance at high temperatures, have high dielectric constants, and exhibit significant water absorption. Generally, bismaleimide is combined with cyanate ester to create a resin class generally known as BT resins using in the fabrication of flip chips, ball grid arrays (BGAs) and chip-scale packages. These resins provide improved glass transition temperature performance and other improved properties as compared to epoxy resins. They are also less expensive than cyanate ester resins. However, the mixture of cyanate esters and bismaleimides exhibits little co-polymerization, therefore, the combination has inferior properties compared to pure cyanate ester or bismaleimide resins.
The goal of this research is focused on the syntheses of co-curing agent and the incorporation of ally group into epoxy resin as a co-curing agent. These co-curing agents comprise two different reactive groups: 1) a moiety having unsaturated aliphatic group capable of reacting with bismaleimides and 2) a glycidyl ether group that is reactive to cyanate ester. These co-curing agents may work as a bride who improves the copolymerization between cyanate ester resins and bismaleimides. A thermosetting resin system including an epoxy resin, a bismaleimide, a cyanate ester and a low viscosity co-curing agent will be providing. Additional, the co-curing agent reduces the viscosity of the resin system because of its low viscosity. The curing behaviors of curable resin system blends were studied using differential scanning calorimetry (DSC) in the dynamic mode. The heat of curing reaction is increasing up to 579.7 J/g for the resin system with co-curing agent. The thermal mechanical and dynamic viscoelastic properties of cured resin systems were also investigated. The cyanate ester/bismaleimide/co-curing agent blends have excellent physical properties than the BT resins and have a low cost. The resin system can be employed as an encapsulant for electronic components and as dielectric layers with microvias on printed circuits.

中文摘要......................................................I
英文摘要.....................................................II
致謝........................................................III
目錄.........................................................IV
Scheme.......................................................VI
表目錄......................................................VII
圖目錄.....................................................VIII
第一章、緒論..................................................1
1.1半導體的發展趨勢……………………………………………………….1
1.2半導體構裝技術的發展趨勢…………………………………………….1
1.3印刷電路板材料的發展………………………………………………….2
1.4高性能基板的材料…………………………………………….…………3
1.5研究之目的及主要內容……………………………………….…………4
第二章、論文回顧………………....……………………….….……...11
2.1氰酸酯(Cyanate ester)的介紹…………………......…….......11
2.2雙馬來醯亞胺的介紹…….......………………………………...…16
2.3環氧樹脂…………….……….......................……………18
第三章、實驗部份……......…………………………..……………...21
3.1材料與藥品………………..................................…21
3.2實驗流程圖………………….........……………………….......22
3.2.1環氧化2-Allylphenol作為BT樹脂之共硬化劑之實驗流程圖...........................................................22
3.2.2改質環氧樹脂作為BT樹脂之共硬化劑之實驗流程圖............23
3.3實驗裝置圖……………….……………….......................24
3.4共硬化劑之合成…………………….………………...............25
3.4.1 2-Allylphenol glycidyl ether (APGE)的製備..............25
3.4.2環氧樹脂的乙烯化反應(Vinylization)......................26
3.5試片之製備................................................27
3.5.1環氧化2-Allylphenol作為BT樹脂之共硬化劑.................27
3.5.2改質環氧樹脂作為BT樹脂之共硬化劑........................27
3.6 環氧樹脂環氧當量重（EEW）之測定…......................…28
3.7物性測試……………............………………………..........29
第四章、環氧化2-Allylphenol作為BT樹脂之共硬化劑..............33
4.1前言…....................................................33
4.2合成與鑑定…………………………............................33
4.3 APGE對BT樹脂的物性影響……....………………….……........34
4.4環氧樹脂對BT樹脂物性之影響……………………………………....36
4.5結論……………….....…...................................37
第五章、改質環氧樹脂作為BT樹脂之共硬化劑.....................51
5.1前言……….......………...................................51
5.2合成與鑑定…………………….......….......................51
5.3示差掃描熱分析(DSC)………........…………….……....…....51
5.4熱重分析(TGA)……….......………………….…...............52
5.5動態黏彈性質的分析…….........……………….…..…........52
5.6介電性質………………...…………...........................52
5.7熱機械性質…………………….....…….......................53
5.8結論………….……………...................................53
第六章、結論.................................................61
參考文獻....................................................62
Scheme
Scheme 3.1 The preparation of 2-allylphenol glycidyl ether (APGE).......................................................25
Scheme 3.2 The Preparation of Vinylization of an Epoxy Resin form a Macromonomer..........................................26
Scheme 4.1 Reaction scheme proposed between bismaleimide and APGE.........................................................39
表目錄
Table 1.1半導體構裝的分類、高度、腳數的比較...................5
Table 1.2 印刷電路板產品種類..................................6
Table 1.3 BGA構裝的發展趨勢...................................7
Table 1.4常用BGA基板材料的種類及特性..........................7
Table 3.1 Sample Formulations……............................31
Table 3.2 Sample Formulations................................32
Table 3.3 Sample Formulations................................32
Table 4.1 Results of Thermal Analysis of CE/BMI/APGE Blends
Measured Via DSC at a Heating Rate of 5℃/min................40
Table 4.2 FTIR Spectra Assignments for the Compounds Involved in the Reaction Between Cyanate and epoxy........................................................40
Table 4.3 Thermal Stabilities of CE/BMI/APGE Blends..........41
Table 4.4 Dynamic Viscoelastic Properties of CE/BMI/APGE Blends.......................................................41
Table 4.5 Dielectric Constants and Moisture Absorption of CE/BMI/APGE Blends….........................................42
Table 4.6 Results of Thermal Analysis of EP/CE/BMI/APGE Blends
Measured Via DSC at a Heating Rate of 5℃/min................42
Table 4.7 Thermal Stability and Dielectric Constants of
EP/CE/BMI/APGE Blends........................................43
Table 4.8 Dynamic Viscoelastic Properties of EP/CE/BMI/APGE Blends.......................................................43
Table 5.1 Results of Thermal Analysis of CE/BMI/EP blends Measured Via
DSC at a Heating Rate of 5℃/min.............................54
Table 5.2 Thermal Stability and Dielectric Constants of CE/BMI/ EP Blends............................................55
Table 5.3 Dynamic Viscoelastic Properties of CE/BMI/ EP Blends.......................................................55
Table 5.4 Thermal Mechanical Properties of CE/BMI/ EP Blends….....................................................56
圖目錄
Figure 1.1半導體構裝技術趨勢..................................8
Figure 1.2 IC構裝的演化與趨勢.................................8
Figure 1.3 台灣印刷電路板產業圖...............................9
Figure 1.4 BGA封裝示意圖.....................................10
Figure 1.5 常用基板樹脂的Dk和Tg值............................10
Figure 2.1 General Structure of Commercial Cyanate Easter.......................................................11
Figure 2.2 Proposed reaction paths of bismaleimide/cyanate ester systems................................................12
Figure 2.3 Reaction scheme proposed between cyanate esters and epoxy........................................................15
Figure 2.4 The synthesis of bismaleimide.................................................16
Figure2.5 Polymerization of BMI with o,o’-diallylbisphenol A via complex ENE and Diels-Alder reactions....................18
Figure 2.6 環氧預聚物之構造與性能的關係......................19
Figure 3.1 環氧化2-Allylphenol作為BT樹脂之共硬化劑之實驗流程圖...........................................................22
Figure 3.2 改質環氧樹脂作為BT樹脂之共硬化劑之實驗流程圖...........................................................23
Figure 3.3 Apparatus for synthesis of the co-curing agent and vinylization of epoxy resin..................................24
Figure 4.1 IR spectra of the (A) 2-Allylphenol, (B) APGE.....44
Figure 4.2 測定EEW的電位滴定圖...............................45
Figure 4.3 DSC thermograms of various molar ratio of CE/BMI/APGE blends:(－) 4/0.5/0, (--)4 / 0.5 / 0.5. Heating rate is 5℃/min......................................46
Figure 4.4 The IR Spectra of C4B0.5A0.5 measured at the various temperatures.........................................47
Figure 4.5 TGA thermograms of various molar ratio of CE/BMI/APGE blends: (－) 4/0.5/0, (--)4 / 0.5 / 0.5. Heating rate is 20℃/min.............................................48
Figure 4.6 Dynamic mechanical analyses of various molar ratio of CE/BMI/APGE blends: (－) 4/0.5/0, (--) 4 / 0.5 / 0.5. Heating rate is 5℃/min......................................48
Figure 4.7 DSC Thermograms of various molar ratio of EP/CE/BMI/APGE blends: (--) 0/4/0.5/0.5, (-▪-) 1/4/0.5/0.5, (-•-) 2/4/0.5/0.5, (--) 4/4/0.5/0.5. Heating rate is 5℃/min......................................................49
Figure 4.8 TGA thermograms of various molar ratio of EP/CE/BMI/APGE blends: blends:(-▪-) 1/4/0.5/0.5, (-•-) 2/4/0.5/0.5, (--) 4/4/0.5/0.5. Heating rate: 20℃/min.....................................................49
Figure 4.9 Dynamic mechanical analysis various molar ratio of EP/CE/BMI/APGE blends:(-▪-) 1/4/0.5/0.5, (-•-) 2/4/0.5/0.5, (--) 4/4/0.5/0.5.Heating rate: 5℃/min.......................50
Figure 5.1 IR spectra of the (A) EP185 (B) EPAP..............56
Figure 5.2 DSC Thermograms of CE/BMI/EP blend at various contents of unmodified epoxy resin: (-▪-) BT, (--) BT-N5, (--) BT-N10, (--) BT-N25, Heating rate: 5℃/min…….......57
Figure 5.3 DSC Thermograms of CE/BMI/EP blend at various contents of modified epoxy resin: (-▪-) BT, (--) BT-M5, (--)BT-M10,(--) BT-M25. Heating rate: 5℃/min.................57
Figure 5.4 TGA traces of CE/BMI/EP blend at various contents of unmodified epoxy resin: (-▪-) BT, (--) BT-N5, (--) BT-N10, (--) BT-N25,Heating rate: 20℃/min.................58
Figure 5.5 TGA traces of CE/BMI/EP blend at various contents of modified epoxy resin: (-▪-) BT, (--) BT-M5, (--) BT-M10, (--) BT-M25. Heating rate:20℃/min..................58
Figure 5.6 Dynamic mechanical analysis of CE/BMI/EP blend at various contents of unmodified epoxy resin: (-▪-) BT, (--) BT-N5,(--) BT-N10, (--) BT-N25, Heating rate: 5℃/min....59
Figure 5.7 Dynamic mechanical analysis of CE/BMI/EP blend at various contents of modified epoxy resin: (-▪-) BT, (--) BT-M5, (--) BT-M10, (--) BT-M25. Heating rate: 5℃/min…..…...........................................................59
Figure 5.8 Effect of epoxy resin contents on Tg of cured CE/BMI/ EP blends: (--) Modified Epoxy, (-•-) Unmodified Epoxy.....….................................................60

1.E. M. Davis, et al., 2000,”Solid logic technology: versatile, high performance microelectronics”, IBM J. Res. Develop., 44(1/2), pp.56-68.
2.L. F. Miller, 1969,”Controlled collapse reflow chip joining”, IBM J. Res. Develop., 13(3), pp.239-250.
3.P. A. Totta and R. P Sopher, 1969, ”SLT device metallurgy and its monolithic extensions”, IBM J.Res.Develop., 13 (3) , pp.226-238.
4.J. H. Lau, 1995,”Flip Chip Technologies”, McGraw-Hill, New York,
5.K. Puttlitz and P. Totta, 2001,”Area Array Technology Handbook for Microelectronic Packaging”, Kluwer Academic Publishers. Norwell, MA.
6.T. O. Steiner and D. Suhl, 1987, IEEE Trans. Comp. Hybrids Manuf. Technol., 10, p.209.
7.D. Suhl, M. Kirloskar, and T. O. Steiner, 1988, Proc. IEEE IEMJ Symp., p.125.
8.R. R. Tummala, E. J. Rymaszewki, 1989, “Microelectronics Packaging Handbook”, Van Nostrand Reinhold, New York, Chap. 1, p.25.
9.A.Fukuda, 1994, Nikki Electronic Asia, P40 May
10.G. Murakami, 1996,”Next Generation High Density Packaging Technology”, Lecture Note Presented at ITRI-ERSO.
11.G. Houglam, G. Tesoro, and Shaw., 1994, Macrmolecules, 27, p.3642.
12.A. E. Feiring, B. C. Auman, and E. R. Wonchoba, 1993, Macrmolecules, 26, p.2779.
13.Matsuura, T., Ando, S., Sasaki, S., and Yamamoto, 1994, F., Macromolecules, 27, p.6665.
14.C. S. Wang and H. J. Hwang, 1996, Polymer, 37(3), p.499.
15.C. S. Wang and H. J.Hwang, 1994, J. Appl. Polym. Sci., 60, p.875.
16.C. S. Wang and H. J. Hwang, 1994, J. Polym. Sci. part A: Polym. Chem., 34, p.1493.
17.Stenzenberger and P. Hergenrother, 1991, in Polyimides. Ed. D. Wilson et al., Blackie, Glasgow, U. K.
18.K. K. Weirauch, P. G. Gemeinhardt and A. L. Baron, Soc., 1976, Plast. Eng. Technical, 22, p.317.
19.R. B. Graver, 1990, in International Encyclopaedia of Composites, Vol. 1, ed. Lee, S. M., VCH, New York, p.548
20.M. Guku, K. Suzuki, and K. Nakamichi, 1978, US Patent 4,110,364.
21.Sunil K. Karad, David Attwood, Frank R. Jones, 2002, Composites: Part A, 33, p1665.
22.Baochun Guo et al, 2003, Polymer Degradation and Stability, 79, p521.
23.R. H. Lin, 2000, J. Polym. Sci. Part A: Polymer Chemistry, 38, p2934.
24.M. Suguna Lakshmi, B.S.R. Reddy, 2001, European Polym. J, 38, p795.
25.I. Hamerton, 1994, in Chemistry and Technology of Cyanate Ester Resin, Blackie Academic and Professional, New York, Chap.1.
26.D. A.Shimp, J.R. Christenson and S.J. Ising , 1989, Int. SAMPE Symp. Exhibit., 34, p.222.
27.K. K. Weirauch, P.G. Gemeinhardt, and A.L. Baron, 1976, Soc. Plast Eng., Technical, 22, p.317.
28.M. GuKu, K. Suzuki, and K. Nakamichi, 1978, US Patent 4,110,364.
29.J. Kiefer and Hiborn, 1996, Macromolecules, 30, p.6837.
30..McConnell, V.P., 1992, Advanced Composites May/June issue, p28.
31.D. Martin, 1964, Angew. Chem.,76, p.303
32.D.A. Shimp, 1992, 37th Int. SAMPE Symp. and Exhibit., March 9-12, p.293
33.M Bauer, et al. 1989, Acta Polymerica, 40(5), p.335.
34.J.Bauer, M. Bauer, R. Ruhmann, and G. Kuhn, 1989, Acta Polymerica, 40(6), p.397.
35.R. H. Lin, J. H. Hong, A. C. Su., 1995, Polymer, 36, p.3349.
36.J. H. Hong, C. K. Wang, R. H. Lin., 1994, J Appl. Polym. Sci., 53, p.105.
37.R. H. Lin, J. H. Hong, A. C. Su., 1997, J Polym. Res., 4, p.191.
38.R. H. Lin, J. H. Hong, A. C. Su., 1999, J Appl. Polym. Sci., 73, p.1927.
39.R. H. Lin, J. H. Hong, A. C. Su., 1997, Comput. Theore. Polym. Sci.,7, p.95.
40.R. H. Lin, J. H. Hong, A. C Su., 2000, J Polym. Sci. Part B: Polym. Phys., 38, p.726.
41.R. H. Lin, J. H. Hong, A. C. Su. 2000, Polym. Int., 49. p.345..
42.R. H. Lin, 2001, Polym. Int., 50, p.1073.
43.P. Bartolomeo, J. F. Chailan, J. L. Vernet, 2001, European Polym. J, 37, p.659.
44.M. D. Martin et al., 1999, “Cure chemo-rheology of mixtures based on epoxy resins and ester cyanates”, European Polym. J, 35, p.57.
45.H. D. Stenzenberger, 1990, in Polyimides, D. Wilson et al. Eds. Blackie, Glasgow/London, p79.
46.I. K. Varma, R. Tiwari, Angew. 1988, Makromol. Chem., 157. p.59
47.K. Iwata, J. K. Stille, 1976, J Polym. Sci. Polym. Chem. Ed., 14, p.2841.
48.H. D. Stenzenberger, M. Herzog, W. Romer, R. Scheiblich, S. Pierce, M. Canning, 1985, 30th Int. SAMPE Symp., 30, p.1568.
49.R. J. Morgan, E. E. Shin, 1997, Polymer, 38 (3), P.639.
50.J. C. Phelan, C. S. Paik Sung, 1997, Macromolecules, 30, p.6845.
51.M. Gaku, et al., 1977, Japanese Patent. 75 129700, 1975; JP 77 31279.
52.F. Iguchi, et al., 1979, Proc. Electr./Electron. Insul. Conf. 14, p.344.
53.S. Motoori, et al., 1981, Proc. Electr./Electron. Insul. Conf. 15, p.168.
54.M. D. Soucek, R. H. Pater, S. L. Ritenour, 1993, Polym. Prep., 27, p.408.
55.A. Chaplin, 2000, Polymer, 41, p.3945
56.F. Hickman, B. Forcier, 1996, Printed Circuit Fabrication, 19 (8), p.22
57.Rictard G. Pitler, et al., 1998, ”Engineering Plastics”, ASM International, P.240