臺灣博碩士論文加值系統

近年來全世界對環保意識日益加深，許多新產品開發以環保為前提，
就現今電路基板所採用的難燃劑是溴含量甚高的溴化環氧樹脂，雖然對阻
燃有相當的效果，但因燃燒發生時會產生腐蝕性和具毒性的鹵化氫氣體以
及燃燒時可能會產生戴奧辛的疑慮，因此非鹵難燃基板已成為必然的發展
趨勢，所以研發具阻燃的新型奈米複合材料勢在必行。
本研究以二種不同的無機層狀材料 (1)天然黏土CL88 (2)人工層狀材
料Mg-Al-LDH，經過膨潤、改質等步驟，並藉由廣角X 光繞射儀（WAXRD）
來檢測改質劑與無機層狀材料層間離子進行離子交換後層間距變化的情
形，再將此改質型無機層材加入酚醛環氧樹脂製成奈米級複合材料，藉由
廣角X 光繞射儀(WAXRD) 、穿透式電子顯微鏡(TEM)來觀察無機層狀材料
在酚醛環氧樹脂中的分散情形，了解無機層狀材料分散型態與性能提升的
相依性。此外，經由熱重分析儀(TGA)、動態機械分析儀(DMA)的檢測來了
解複合材料的玻璃轉移溫度(Tg)、熱穩定性及熱裂解溫度(Td)。在耐燃的部
份，期望利用黏土的層狀結構來阻隔傳播熱源，並將可燃性氣體或助燃物
隔離，以減緩可燃物受熱分解，利用Mg-Al-LDH 其層間受熱脫出的水及羥
基分解產生的水均能稀釋空氣中的氧氣和高分子分解生成的可燃性氣體，
並藉由極限氧指數儀(LOI)、圓錐量熱儀 (Cone calorimeter)來測試其難燃
性。最後將添加入改質型層狀材料的酚醛環氧樹脂實際應用到銅箔基板的
製程上，期望可以達到耐熱及耐燃效果。

The fire-resistance is one of the most important properties that need to pay
much attention to improve the general electronic product. The halogenatedepoxy
compounds are used in printed circuit board (PCB) to improve the
thermal and fire resistant properties for mamy years. However, this kind of
material produces large amount of smoke and toxic material like dioxin during
combustion. It is necessary to replace the halogenated-epoxy to the novel
organic-inorganic hybrid nanocomposites as far as the environmental pollution
are concerned. Polymer/layered silicate nanocomposites (PLSNs) have been
studied extensively since past two decades due to their outstanding improvement
in the physical, mechanical, and chemical properties. Epoxy resin is
commonly used to make the printed circuit board. If small amount of inorganic
fillers such as clay or layer double hydroxide could be dispersed into the
novolac cured epoxy resin, the properties might have been improved. This idea
has encouraged me to prepare and study the novolac cured epoxy resin/layered
material hybrid nanocomposites.
The synthesis, characterization and properties of novolac epoxy
resin/layered silicate nanocomposites have been discussed in this report.
Montmorillonite clay (MMT) and Mg-Al-layered double hydroxide (Mg-Al
LDH) are used as layered materials. At beginning, clays or LDHs are modified
by long chain organic compound with cycloalkene backbone to increase the
compatibility between the polymer and layered materials. The novolac epoxy
resin/layered silicate nanocomposites are successfully prepared using these
organically modified clay/LDH with novolac cured epoxy resin by in situ
cross-linking polymerization method. The morphology of these nanocomposites
was investigated by using wide angle X-rays diffraction (WAXD) and
transmission electron microscopy (TEM) techniques. Thermo-gravimetric
analysis (TGA) and dynamic mechanical analysis (DMA) were used to study the
thermal and mechanical properties. Their combustion behavior has been
evaluated using limiting oxygen index (LOI) and Cone calorimeter test.
According to the measurement, these novolac cured epoxy-clay nanocomposites
have been shown the significant improvement in the thermal, mechanical and
barrier properties that may be applied to make printed circuit board.

中文摘要 ................................................................................................. I
英文摘要 ................................................................................................. II
謝誌 ......................................................................................................... IV
目錄 ......................................................................................................... V
圖目錄 ..................................................................................................... VIII
表目錄 ..................................................................................................... XII
第一章 緒論
1-1 研究動機 .......................................................................................... 1
1-2 層狀材料簡介 .................................................................................. 2
1-3 環氧樹脂 .......................................................................................... 10
1-3-1 環氧樹脂簡介 .......................................................................... 10
1-3-2 環氧樹脂的種類及特性 .......................................................... 11
1-3-3 環氧樹脂硬化反應 .................................................................. 13
1-3-4 環氧樹脂的特性與應用 .......................................................... 14
1-4 無機層狀材料之改質 ..................................................................... 15
1-5 奈米複合材料 .................................................................................. 18
1-5-1 奈米複合材料的製備 .............................................................. 18
1-5-2 無機層狀材料於高分子中之分散型態 ................................. 19
1-6 銅箔基板簡介 ................................................................................ 23
1-6-1 銅箔基板的組成 .................................................................... 26
1-6-2 銅箔基板的製作過程 ............................................................ 28
1-7 高分子材料燃燒的因素 ............................................................... 31
1-7-1 高分子燃燒機構 .................................................................... 32
1-7-2 難燃劑阻燃原理 .................................................................... 35
第二章 藥品與儀器
2-1 實驗藥品 ........................................................................................ 40
2-2 實驗設備 ........................................................................................ 44
2-3 檢測儀器 ........................................................................................ 45
第三章 實驗部份
3-1 C60 有機官能化 ............................................................................... 49
3-2 黏土改質有機化 ............................................................................ 51
3-3 人工層狀雙氫氧化物有機化 ....................................................... 54
3-4 酚醛環氧樹脂奈米複合材料之製備 ........................................... 56
第四章 結果與討論
4-1 碳60 有機化(C60-O)之結構與性質探討 ...................................... 58
4-1-1 結構探討 ................................................................................. 58
4-1-2 對水溶解度的探討 ................................................................. 60
4-1-3 產率分析 ................................................................................ 61
4-2 無機層狀材料之官能化研究 ....................................................... 61
4-2-1 天然黏土 ................................................................................. 61
4-2-2 人工層狀雙氫氧化物 ............................................................. 69
4-3 酚醛環氧樹脂奈米複合材料性質之檢測 ................................... 74
4-3-1 膠化時間( Gel test ) ................................................................ 74
4-3-2 無機層狀材料在酚醛環氧樹脂奈米複材的分散型態 ......... 78
4-3-3 酚醛環氧樹脂奈米複材熱性質分析 ..................................... 88
4-3-4 耐燃測試 ................................................................................ 103
4-3-4-1 極限氧指數儀 (LOI)燃燒測試 ...................................... 103
4-3-4-2 圓錐量熱儀 (Cone calorimeter)測試 ............................. 105
4-4 銅箔基板抗爆板研究 .................................................................. 108
4-4-1 物性分析 ................................................................................ 110
4-4-2 耐燃測試 (UL94) ................................................................. 115
第五章 結論與未來展望 .................................................................... 118
第六章 參考文獻 ................................................................................ 119




圖目錄
圖1-1 蒙脫土結構 ................................................................................ 4
圖1-2 LDH 結構示意圖 ....................................................................... 7
圖1-3 不同系列LDH 相對於AEC 值關係圖 ................................... 7
圖1-4 環氧樹脂硬化反應機制 .......................................................... 15
圖1-5 界面活性劑形成微胞示意圖 .................................................. 16
圖1-6 兩性界面活性劑改質Clay 之示意圖 ..................................... 17
圖1-7 Driving force concept 示意圖 ................................................... 17
圖1-8 傳統型複合材料分散型態示意圖 .......................................... 20
圖1-9 (a)海型插層；(b)島型插層分散型態示意圖 .......................... 21
圖1-10 (a)海型脫層；(b)島型脫層分散型態示意圖 ........................ 22
圖1-11 銅箔基板的製作過程 ............................................................. 30
圖3-1 C60 官能化流程圖 ...................................................................... 49
圖3-2 C60 官能化機制圖 ...................................................................... 50
圖3-3 C60 -O 反應機構 ........................................................................ 50
圖 3-4 黏土改質流程圖 ..................................................................... 53
圖3-5 人工層狀材料(Mg-Al-LDH)改質流程圖 ............................... 55
圖3-6 酚醛環氧樹脂奈米複合材料之流程圖 .................................. 56
圖4-1 C60-O 結構圖 ............................................................................. 58
圖4-2 (a) C60 (b) C60-O IR 圖譜 ........................................................ 59
圖4-3 C60-O NMR 圖 ........................................................................... 59
圖4-4 (a) C60 溶於水 (b) C60-O 溶於水 .............................................. 60
圖4-5 MI/BEN PI/BEN 改質型黏土XRD 繞射圖 ............................ 65
圖4-6 C60-O C60-O/BEN 改質型黏土XRD 繞射圖 .......................... 65
圖4-7 C60-O 插層入黏土示意圖 ......................................................... 66
圖4-8 PI/BEN MI/BEN 改質型黏土之FT-IR 圖譜 ........................... 66
圖4-9 C60-O 改質型黏土之FT-IR 圖譜 ............................................. 67
圖4-10 C60-O/BEN 改質型黏土之FT-IR 圖譜 .................................. 67
圖4-11 C60-O/PI/BEN 改質型黏土之FT-IR 圖譜 .............................. 68
圖4-12 PI-BEN MI-BEN 改質型黏土之TGA 圖譜 .......................... 68
圖4-13 C60-O C60-O/BEN C60-O/PI/BEN
改質型黏土之TGA 圖譜 ................................................................. 69
圖4-14 Mg-Al-LDH/6A-改質XRD 繞射圖 ....................................... 71
圖4-15 Mg-Al-LDH Mg-Al-LDO/6A-FT-IR 圖譜 .......................... 71
圖4-16 Mg-Al-LDH Mg-Al-LDO/6A 之TGA 圖譜 ....................... 72
圖4-17 純黏土酚醛環氧樹脂XRD 繞射圖譜 .................................. 80
圖4-18 PI/BEN 改質型黏土酚醛環氧樹脂XRD 繞射圖譜 ............. 81
圖4-19 MI/EN 改質型黏土酚醛環氧樹脂XRD 繞射圖譜 .............. 81
圖4-20 CL88-PI/BEN-3wt% TEM (50k 100nm) ................................ 82
圖4-21 CL88-MI/BEN-3wt% TEM (a)40K 200nm (b)100K 50nm .... 82
圖4-22 C60-O 改質型黏土酚醛環氧樹脂XRD 繞射圖譜 ................ 83
圖4-23 C60-O/BEN 改質型黏土酚醛環氧樹脂XRD 繞射圖譜 ....... 83
圖4-24 C60-O/PI/BEN 改質型黏土酚醛環氧樹脂XRD 繞射圖譜 .. 84
圖4-25 CL88-C60-O-3wt% TEM (a)40K 200nm (b)100K 50nm ........ 84
圖4-26 CL88-C60-O/BEN-3wt% TEM(a)40K 100nm (b)100K 50nm 85
圖4-27 CL88-C60-O/PI/BEN-3wt% TEM
(a)50K 100nm(b)100K 50nm ............................................................ 85
圖4-28 Mg-Al-LDH 酚醛環氧樹脂XRD 繞射圖譜 ......................... 86
圖4-29 Mg-Al-LDO/6A 酚醛環氧樹脂XRD 繞射圖譜 ................... 86
圖4-30 Mg-Al-LDH-3wt% TEM (a)40K 200nm (b)200K 50nm ........ 87
圖4-31 Mg-Al-LDO-6A-3wt% TEM (a)50K 100nm (b)100K 50nm . 87
圖4-32 CL88 酚醛環氧樹脂TGA 圖譜 ............................................. 93
圖4-33 CL88-PI/BEN 酚醛環氧樹脂TGA 圖譜 ............................... 93
圖4-34 CL88-MI/BEN 酚醛環氧樹脂TGA 圖譜 .............................. 94
圖4-35 CL88-C60-O 酚醛環氧樹脂TGA 圖譜 .................................. 94
圖4-36 CL88-C60-O/BEN 酚醛環氧樹脂TGA 圖譜 ......................... 95
圖4-37 CL88-C60-O/PI/BEN 酚醛環氧樹脂TGA 圖譜 .................... 95
圖4-38 Mg-Al-LDH 酚醛環氧樹脂TGA 圖譜 .................................. 96
圖4-39 Mg-Al-LDO-6A 酚醛環氧樹脂TGA 圖譜 ........................... 96
圖4-40 CL88 酚醛環氧樹脂DMA 圖譜 ............................................ 98
圖4-41 CL88-PI/BEN 酚醛環氧樹脂DMA 圖譜 .............................. 99
圖4-42 CL88-MI/BEN 酚醛環氧樹脂DMA 圖譜 ............................ 99
圖4-43 CL88-C60-O 酚醛環氧樹脂DMA 圖譜 ................................ 100
圖4-44 CL88-C60-O/BEN 酚醛環氧樹脂DMA 圖譜 ....................... 100
圖4-45 CL88-C60-O/PI/BEN 酚醛環氧樹脂DMA 圖譜 .................. 101
圖4-46 Mg-Al-LDH 酚醛環氧樹脂DMA 圖譜................................ 101
圖4-47 Mg-Al-LDO-6A 酚醛環氧樹脂DMA 圖譜 ......................... 102
圖4-48 CL88-MI/BEN-1wt% 酚醛環氧樹脂 IR 圖譜 ..................... 102
圖4-49 CL88-C60-O/BEN PI/BEN 酚醛環氧樹脂
Cone calorimeter 圖譜 ................................................................... 106
圖4-50 Mg-Al-LDH Mg-Al 酚醛環氧樹脂Cone calorimeter 圖 ..... 106
圖4-51 Mg-Al-LDO-6A-3wt%-CCL-XRD 繞射圖譜 ....................... 112
圖4-52 CL88-C60-O/BEN-3wt%-CCL-XRD 繞射圖譜 ..................... 112
圖4-53 Mg-Al-LDO-6A-3wt%-CCL- TEM
(a)50K 100nm (b)100K 50nm ........................................................ 113
圖4-54 CL88-C60-O/BEN-3wt%-CCL-TEM ...................................... 113
圖4-55 Pure novolac epoxy-CCL-UL94 燃燒條 ................................ 117
圖4-56 CL88-C60-O/BEN-3wt%-CCL-UL94 燃燒條 ........................ 117


表目錄
表1-1 黏土的種類分類 ....................................................................... 5
表1-2 印刷電路板分類表 .................................................................. 24
表1-3 銅箔基板一覽表 ...................................................................... 25
表4-1 元素分析C60-O ........................................................................ 60
表4-2 改質型無機層狀材料整理表 ................................................... 73
表4-3 膠化時間整理表 (天然黏土) .................................................. 76
表4-4 膠化時間整理表 (人工層狀材料) .......................................... 77
表4-5 奈米複材熱性質數據整理表(天然黏土) ................................ 91
表4-6 奈米複材熱性質數據整理表(人工層狀材料) ........................ 92
表4-7 奈米複材玻璃轉移溫度整理表 (天然黏土) .......................... 97
表4-8 奈米複材玻璃轉移溫度整理表 (人工層狀材料) .................. 98
表4-9 極限氧指數測試結果 ............................................................. 104
表4-10 Cone calorimeter 數據整理表 ............................................... 107
表4-11 基板性質整理 ......................................................................... 114
表4-12 銅箔基板UL94 測試結果 ..................................................... 116

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