臺灣博碩士論文加值系統

隨著近年來 5G 無線網路系統的發展，更高傳輸速度及越來越小的電子元件尺寸在無線通訊領域引起許多關注。另一方面，軟性電路板由於其可撓性、高空間利用性及輕量化可被用來發展未來可穿戴式裝置。然而，對於軟性電路板應用於高頻傳輸仍有許多挑戰需要被克服，其中最嚴重的問題在於高頻傳輸時的訊號損失及能量損耗。解決此問題的最好辦法為開發並取代軟性電路板中的黏著材料，其需同時符合低介電常數、低消散因子及高剝離強度的要求。而其中最受關注的材料為聚苯醚高分子，其具有優異的熱性質、高尺寸安定性及低介電常數的特性。然而，最常見的聚苯醚對於銅箔的接著力不佳及高玻璃轉化溫度致使其難加工。在本研究中合成具丙烯側鏈的聚苯醚 (Allyl-PPE)，其具有可交聯、易容解於工業溶劑及較低玻璃轉移溫度等特性使其易於加工。我們更進一步結合 Allyl-PPE 與環氧樹脂、具有羧酸基的橡膠、聚四氟乙烯及其他低介電常數添加劑以開發具有高剝離強度(> 1 N/mm) 及低介電性質(Dk < 2.5, Df ~ 0.010 to 0.025)的高頻軟性電路板黏著劑。
本研究第二章，成功透過氧化耦合開發具有丙烯基側鏈的 Poly(2-allyl-6-methylphenol-co-2,6-dimethylphenol) (Allyl-PPE)聚苯醚系列高分子。進一步透過混摻方式與環氧樹脂、羧酸改質丁腈橡膠及聚四氟乙烯開發出具有低介電常數、低消散因子、高剝離強度及可撓性的軟板黏著劑材料。其中含有丙烯側鏈的聚苯醚(Allyl-PPE) 含有可交聯的特性，其提供高機械性質及疏水性，而環氧樹脂結合縮酸改質的丁腈橡膠作為黏著促進劑且展現優異的可撓性使其適用於軟板黏著劑。聚四氟乙烯則作為低介電常數添加劑且分散在黏著劑中。在本章所開發的系統其剝離強度能夠大於 1 N/mm、10GHz 下介電常數低於 2.5 且消散因子介於 0.012 到0.025間。其中最適化配方為剝離強度1.22 N/mm、介電常數2.17及消散因子0.012。
本研究第三章，我們引入有機及無機的低介電常數材料於第二章所開發的系統降低其消散因子，其中包含 1,2-雙(乙烯基苯基)乙烷、中空玻璃球及多面體矽氧烷寡聚物 (POSS)。其中 BVPE 由於在氯仿中的溶解度不佳導致剝離強度下降及介電性質上升，而中空玻璃球具有過大的粒子尺寸，雖其成功將介電性質最小化，卻也造成剝離強度降低過多。在本章的添加物中多面體矽氧烷寡聚物為一優異的添加物，其能使剝離強度維持高於 1 N/mm 及介電常數低於 2.5。同時透過其高自由體基及奈米尺寸的性質使消散因子降低，在本章所開發的系統最適化配方為剝離強度 1.23 N/mm、介電常數 2.24 及消散因子 0.010。
在本論文，我們透過混摻 Allyl-PPE、環氧樹脂、羧酸改質丁腈橡膠、聚四氟乙烯及添加劑開發具有高剝離強度及低介電常數、低消散因子的黏著劑性統，其能應用於高頻應用，在結果上顯示以可交聯及易加工的 Allyl-PPE 開發低介電常數黏著材料，其能夠達到高剝離強度及優異的介電性質，本研究中所開發系統具有潛力應用於軟性電路板黏著材料。

As the development of next generation internet in recent years, 5G wireless systems, higher proceeding speed and smaller size of devices have attracted extensive research attention in wireless communication. On the other hand, flexible printed circuit (FPC) is applied in future wearable devices based on its flexibility, high space utilization, and lightness. For the future flexible printed circuit applications with a higher transmission frequency, there are some challenges must be overcome. One of the most serious problems is the signal transmission loss at a high frequency, and the best way to solve this problem is to develop adhesive materials with a low dielectric constant, a low dissipation factor, and a high peel strength. Among the potential materials for applying in flexible printed circuit, poly (phenylene ether) is one of the best candidates because of its excellent thermal properties, high dimensional stability, and low dielectric constant. However, the most common poly (phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether), shows a poor adhesion to copper foil and a high Tg making it difficult to process. In this study, we synthesized poly (2-allyl-6-methylphenol-co-2,6-dimethylphenol) (Allyl-PPE), with a good solubility and a lower Tg, to be processed for commercial applications. We further combined Allyl-PPE with epoxy resin, rubber, PTFE, and other fillers to develop an adhesive system having a high peel strength (> 1 N/mm), a low dielectric constant (Dk < 2.5), and a low dissipation factor (Df ~ 0.010 to 0.025).
In chapter 2, we successfully synthesized poly (2-allyl-6-methylphenol-co-2,6-dimethylphenol) (Allyl-PPE) with different ratios of the allyl groups by the oxidative coupling polymerization. We further developed an easy-processing adhesives by blending with Allyl-PPE, epoxy resin, carboxyl-modified nitrile-butadiene rubber, and PTFE filler, which showed low dielectric constant, low dissipation factor, high peel strength, and highly flexibility. The crosslinkable Allyl-PPE provided high mechanical properties and low moisture adsorption. Meanwhile, the epoxy resin combined with a carboxyl-modified rubber providing a high peel strength and an excellent flexibility. PTFE exhibited the low dielectric property and it could be well-dispersed in the adhesive matrix. The adhesive system we developed shows that the peel strength could be higher than 1 N/mm. Besides, the dielectric constant was lower than 2.5 at 10 GHz, and dissipation factor was between 0.012 to 0.025. The optimum Allyl-PPE based adhesive possessed the peel strength of 1.22 N/mm, Dk= 2.17, and Df = 0.012.
In chapter 3, we would like to reduce the dissipation factor in the developed laminate system. Therefore, we introduced organic or inorganic low dielectric constant filler, including 1,2-bis (vinylphenyl) ethane (BVPE), hallow glass bubble, and POSS into the adhesion based on chapter 2. The BVPE could help the dielectric properties if it was in lower concentration. The hallow glass bubble with large particle size (~45μm) successfully minified the dielectric property, however; the aggregation let peel strength decrease. Among them, POSS was a superior candidate as the filler, and it could maintain the peel strength higher than 1 N/mm and the dielectric constant was lower than 2.5. Meanwhile, it lowered the dissipation factor by the introduce the large free volume and nano-sized particles. The optimum system we developed in this chapter had the peel strength with 1.23 N/mm, Dk= 2.24, and Df = 0.010.
In conclusion, we developed a system by blending with Allyl-PPE, epoxy resin, carboxyl-modified rubber, PTFE, and filler to enhance peel strength, while it showed a low dielectric constant and a low dissipation factor for high frequency applications. The result showed that the laminates based on Allyl-PPE system successfully provided an excellent peel strength and splendid dielectric properties, for applying in the flexible printed circuit adhesive.

Abstract I
摘要 IV
Content VI
Table captions IX
Scheme captions XI
Figure captions XII
Chapter 1 1
1.1 General Introduction 1
1.2 Requirement of low dielectric constant materials 4
1.2.1 Dielectric Requirement 4
1.2.2 Adhesion Requirement 6
1.3 Potential candidates for Low-k polymers 9
1.3.1 Polyimide (PI) 10
1.3.2 Epoxy resin 12
1.3.3 Poly(arylether) 13
1.3.4 Poly(phenylene ether) 14
1.4 Research Objectives 17
Chapter 2 34
2.1 Introduction 34
2.2 Experimental Section 36
2.2.1 Materials 36
2.2.2 Synthesis of Allyl-PPE 38
2.2.3 Laminates Manufacturing Process 39
2.2.3.1 Peel Strength Sample 40
2.2.3.2 Dielectric Properties Sample 41
2.2.4 Characterization 42
2.3 Results and Discussion 43
2.3.1 Chemical Structure Characterization 43
2.3.2 Thermal Properties 46
2.3.3 Effect of Component on Peel Strength and Dielectric Properties 47
2.3.3.1 Allyl-PPE 48
2.3.3.2 Epoxy Resin 49
2.3.3.3 Carboxyl-modified Nitrile-Butadiene Rubber 52
2.3.3.4 SiO2-modified Polytetrafluoroethylene Particles 53
2.3.4 Reaction between DGEBA and NBR 54
2.4 Conclusion 56
Chapter 3 76
3.1 Introduction 76
3.2 Experimental Section 78
3.2.1 Materials 78
3.2.2 Laminates Manufacturing Process 80
3.2.2.1 Peel Strength Sample 81
3.2.2.2 Dielectric Properties Sample 81
3.2.3 Characterization 82
3.3 Results and Discussion 83
3.3.1 1,2-Bis(vinylphenyl)ethane 83
3.3.2 Hallow Glass Bubble 84
3.3.3 MonovinylIsobutyl-POSS 86
3.3.4 Glycidyl-POSS 87
3.4 Conclusion 89
Chapter 4 102
Conclusion 102
Prospective 104
Reference 108

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