臺灣博碩士論文加值系統

Type II光起始劑系統因具有較佳的光敏感性等特性，常被用於光固化製程，如負型光阻乾膜 (Photoresist dry film) 及影像成像(Imaging) 系統之中。本研究透過傅立葉轉換紅外光譜 (Fourier Transform Infrared Spectrometer; FT-IR)、Gel fraction、螢光光譜 (Fluorescence Spectrometry ; PL)、電子順磁共振波譜儀 (Electron Spin Resonance ; ESR) 等檢測方式，對不同重量下之鄰氯代六芳雙基咪唑 (o-Cl-HABI)/N-苯基甘氨酸 (NPG) 光起始劑系統於三官能基單體三羥甲基丙烷三甲基丙烯酸酯 (TMPTMA)下進行光聚合動力學之探討。其中隨著NPG的含量增加 (0.05、0.1、0.25 wt%)，其固化速率越快；然而o-Cl-HABI從0.5 wt%、1 wt%到2 wt%時，其雙鍵反應趨勢是呈現曲線變化。此外，於本研究中亦針對於照光環境不同情況下如空氣與氮氣其固化速率之探討，並了解其電子傳遞之路徑。
由於NPG為最後提供自由基進行固化反應之重要角色，因此本研究中亦針對NPG進行結構上之修飾，合成了對位含有-OCH3、-Cl、-NO2等取代基團之p-substituted NPG衍生物，其結構以氫譜核磁共振 (1H-NMR) 和質譜法 (Mass) 鑑定分析其衍生物之結構與分子量，並透過上述光固化檢測之方法，對於o-Cl-HABI與NPG衍生物所組成之光起始劑體系進行光聚合動力學以及物性之探討。
於光聚合動力學方面，以相同重量下 (2:0.05 wt%) 下之o-Cl-HABI/NPG衍生物光起始劑系統，透過Gel fraction方法得到其轉化率之表現為NPG > OMe-NPG > Cl-NPG > NO2-NPG。
於物性方面，以示差熱掃描分析儀 (DSC) 分析鑑定熔點介於127-238 oC之間。紫外/可見光光譜 (UV/Visible spectra) 分析量測其莫耳消光係數其大小分別為NPG > OMe-NPG > Cl-NPG > NO2-NPG。同時也對於光起始劑進行溶解度之探討，發現到在溶劑二氯甲烷 (DCM) 下，光起始劑溶解度表現最差。
另外，也對一系列之不同光起始劑進行物性之分析以及循環伏安法量測其氧化還原電位得知其HOMO值與LUMO值。進一步以Rehm-Weller equation計算得到OMe-NPG之ΔGET為-1.49 eV，NPG之ΔGET為-1.54 eV，Cl-NPG之ΔGET為-1.22 eV，NO2-NPG之ΔGET為-0.05 eV。ΔGET之值以NPG之值最小，可利於電子之轉移。此外，NPG之莫耳消光係數較大，因而得到最佳之轉化率。

Type II photoinitiator systems are widely used in photocuring processes due to their low cost, faster photospeed which applied in many industrial applications such as photoresist dry film and imaging. One of the typical Type II photo-initiator package based on o-Cl-HABI (hydrogen acceptor) and NPG (hydrogen donor) systems (where o-Cl-HABI is a 2-chlorohexaaryl biimidazole, NPG is an N-phenyl glycine) was investigated in this study. The photocuring behavior for different weight ratios of o-Cl-HABI and NPG was studied through FT-IR, gel-fraction, electron spin resonance (ESR) and photoluminescence (PL) methodologies. As the amount of NPG increased from 0.05 wt% to 0.1and 0.25 wt%, the faster curing speed was achieved. However, the curvature photo-reactivity phenomenon was observed as the amount of o-Cl-HABI at 0.5, 1 and 2 wt%, respectively. In this study, the air and nitrogen atmospheres effect are conducted.
Since NPG is an important factor on the photocuring reactivity, the structural modification of NPG is also performed for comparison. The p-OCH3, -Cl, -NO2 NPG derivatives were synthesized accordingly. These structures were identified by 1H-NMR and mass spectrometry. The NPG derivatives exhibited melting temperatures of 146-238 oC that was higher than the reference NPG (127 oC). The NPGs also displayed good solubility in Acetone, THF and DMF. In addition, the molar extinction coefficients of NPG, OCH3-NPG, Cl-NPG and NO2-NPG were 4.34×104 M-1cm-1, 2.36×104 M-1cm-1, 2.08×104 M-1cm-1, 1.13×103 M-1cm-1, respectively.
In addition, the HOMO, LUMO levels and their corresponding ΔGET values were calculated to correlate with the photoreactivity. The double bond conversion was final tested through the gel fraction method under the same weight ratios (o-Cl-HABI/NPG = 2:0.05 wt%). The order of conversion rate is NPG > OCH3 -NPG > Cl-NPG > NO2-NPG that is consisted with ΔGET values mentioned above.

目錄
摘要 I
Abstract III
致謝 V
目錄 VI
表目錄 IX
圖目錄 X
第一章 緒論 1
1.1 前言 1
1.2 光固化體系與機制之簡介 2
第二章 文獻回顧與研究動機 3
2.1 光源之簡介 3
2.2 不飽和單體/寡聚體之簡介 3
2.3 光固化反應機制之介紹 7
2.3.1 陽離子型光固化 7
2.3.2 自由基型光固化 8
2.4 光起始劑 (Photo-initiators) 之簡介 10
2.4.1 陽離子型光起始劑之簡介 10
2.4.2 自由基型光起始劑之簡介 10
2.5 研究動機及策略 20
第三章 實驗方法 22
3.1 實驗架構 22
3.2 儀器設備 23
3.2.1 分析儀器 23
3.2.2 實驗設備 26
3.3 實驗藥品 27
3.4 有機溶劑 30
3.5 實驗部分 (I) 32
3.5.1 光固化反應動力學 - Gel fraction分析方法之建立 32
3.5.2 光固化反應動力學 - 傅立葉轉換紅外光譜分析方法之建立 33
3.5.3 光化學性分析 - 紫外/可見光光譜方法之建立 34
3.5.4 光化學性分析 - 螢光光譜分析方法之建立 36
3.5.5 光化學性分析 - 電子順磁共振波譜儀分析方法之建立 37
3.5.6 電化學分析 - 循環伏安法分析方法建立 40
3.5.7 不同環境下 (氮氣/空氣) 對於反應速率之比較 40
3.6 實驗部分 (II) 41
3.6.1 NPG衍生物之合成 42
3.6.2 o-Cl-HABI、NPG及其衍生物之DSC分析 45
3.6.3 o-Cl-HABI、NPG及其衍生物之溶解度 (Solubility) 分析 45
第四章 結果與討論 47
4.1 不同重量比下o-Cl-HABI/NPG在TMPTMA下之光固化性質分析 47
4.1.1 Gel fraction轉化率分析 47
4.1.2 FT-IR之轉化率分析 50
4.2 以不同重量比下o-Cl-HABI/NPG之光化學性質分析 51
4.2.1 紫外光/可見光光譜 (UV/Visible spectra) 之分析結果 51
4.2.2 螢光光譜 (PL spectra) 之分析結果 54
4.2.3 電子順磁共振波譜儀 (ESR) 之分析 56
4.3 在不同環境下反應固化之轉化率比較 57
4.4 含NPG衍生物之光起始劑體系 59
4.4.1 NPG衍生物之合成鑑定 60
4.4.2 DSC分析 65
4.4.3 溶解度分析 66
4.4.4 UV/Visible分析 67
4.5 光起始劑 (o-Cl-HABI、NPG及其衍生物) 之氧化還原電位比較 68
4.5.1 循環伏安法 (CV) 電流-電壓圖的比較 69
4.5.2 含NPG衍生物之光起始劑體系在TMPTMA下之光固化反應動力學分析 73
第五章 結論與建議 75
第六章 參考文獻 77
附錄 A 84

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