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研究生:張文鐘
研究生(外文):Wen-Chung Chang
論文名稱:感光型水性PU色素樹脂之合成與應用
論文名稱(外文):On the Study of Synthesis and Application of Photosensitive Colored Polyurethane Ionomers
指導教授:趙鼎揚
指導教授(外文):D. Y. Chao
學位類別:碩士
校院名稱:中國文化大學
系所名稱:應用化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:84
中文關鍵詞:感光型水性PU色素樹脂水性PU感光型PU色素PU樹脂PU色素樹脂PU
外文關鍵詞:PUIonomersPolyurethanePhotosensitive
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甲苯二異氰酸鹽(TDI)與螢光染料Fluorescein、聚醚系之多元醇(PPG2000、PPG700)、二甲醇丙基酸(DMPA)、Hydroxypropyl acrylate及其它添加劑反應合成之感光型水性PU色素樹脂,由FT-IR光譜圖證實。
由實驗數據得知,感光型水性PU色素樹脂照光成膜之時間,會隨著Hydroxypropyl acrylate濃度的增高而有縮短的現象,這是因為Hydroxypropyl acrylate濃度的增高會提供較多的自由基因而促進反應加速進行。同時,Benzoin及Benzophenone的添加也有促進其反應之加快。
根據實驗數據顯示,感光型水性PU色素樹脂溶液之平均粒徑和黏度會隨著螢光染料Fluorescein濃度、Hydroxypropyl acrylate濃度增加而上昇,這是因為感光型水性PU色素樹脂分子間之極性基與水分子間彼此的相互作用(Intermolecular interaction),而使
得樹脂分子的自由體積變大所導致。至於此樹脂薄膜之拉應力分別會隨著螢光染料Fluorescein濃度和Hydroxypropyl acrylate濃度的增加而上昇,這是因為螢光染料Fluorescein和Hydroxypropyl acrylate的官能基會增強樹脂分子之架橋能力的原故。

The reaction of toluene diisocyanate with fluorescent dye, polypropylene glycol (PPG2000, PPG700), dimethyl propionic acid, hydroxypropyl acrylate and other additives to form photosensitive colored polyurethane ionomer has been proven by FT-IR spectra.
Experimental data show that the time of curing under UV absorbance is found to become short, as the concentration of hydroxypropyl acrylate increases. This is the result of increased interaction between free radicals. Meanwhile, for the addition of benzoin and benzophenone, respectively, the time of curing under UV absorbance could be also found to become short.
The experiment results indicate that for photosensitive colored polyurethane ionomers the average particle size and the viscosity are seen to increase with increasing the concentration
of fluorescent dye and hydroxypropyl acrylate, respectively. This is because the intermolecular interaction of the polar groups of photosensitive colored polyurethane ionomer molecule with water molecule makes the free volume of the ionomer molecule become large. The tensile strengths of self-cured film of photosensitive polyurethane ionomers are found to increase with increasing the concentration of fluorescent dye and hydroxypropyl acrylate, respectively. This is due to increase the capability of cross-linking.

中文摘要 Ⅰ
英文摘要 Ⅱ
壹、 前言 1
貳、理論部份 5
2.1水性聚胺基甲酸乙酯 5
2.1-1水性聚胺基甲酸乙酯之簡介與特徵 5
2.1-2 感光型水性PU色素樹脂之簡介與優點 5
2.2 原料 6
2.2-1異氰酸酯(Isocyanate) 6
2.2-2多元醇(Polyol) 11
2.2-3 鏈延長劑 12
2.2-4 離子基單體 12
2.2-5 催化劑 13
2.2-6 架橋劑(Cross-linking Agent) 15
2.2-7 溶劑的選擇 17
2.2-8 染料 17
2.3螢光染料之簡介、原理以及分類 19
2.3-1螢光染料的簡介、原理 19
2.3-2螢光染料分子構造分類 22
2.4 感光型水性PU色素樹脂 30
2.5感光型水性PU色素樹脂之合成 38
參、實驗部份 41
3.1 實驗所使用的儀器 41
3.2實驗藥品 43
3.3感光型水性PU色素樹脂之合成 43
3.3-1 實驗步驟 43
3.3-2 感光型水性PU色素樹脂之皮膜及薄膜的製備 44
3.4 物性之測試 45
3.4-1 紅外線光譜儀測試 45
3.4-2 粒徑及擴散係數之測定 45
3.4-3 紫外線照射成膜測試 47
3.4-4 表面張力之測試(Wilhelmy 法) 47
3.4-5 黏度之測試 48
3.4-6 機械性質之測定 50
3.4-7 紫外線光譜儀測試 52
肆、結果與討論 53
4.1 IR光譜之探討 53
4.2 分別改變螢光染料Fluorescein和Hydroxypropyl acrylate
之濃度對感光型水性PU色素樹脂溶液黏度的影響情形 58
4.3 分別螢光染料Fluorescein和Hydroxypropyl acrylate之
濃度對感光型水性PU色素樹脂溶液表面張力的影響情形61
4.4 UV光譜圖之探討 64
4.4-1 改變UV照光時間對感光型水性PU色素樹脂溶液黏度影
響之情形 64
4.4-2 改變螢光染料Fluorescein之濃度對感光型水性PU色素
樹脂UV吸收強度影響之情形 64
4.5 分別改變Hydroxypropyl acrylate、Benzoin及Benzophenone
之濃度對感光型水性PU色素樹脂溶液UV照光成膜時間影響
之情形 71
4.6 分別改變螢光染料Fluorescein及Hydroxypropyl acrylate
之濃度對感光型水性PU色素樹脂溶液拉應力影響之情形 74
4.7 分別改變Fluorescein 及Hydroxypropyl acrylate之濃度
對感光型水性PU色素樹脂溶液平均粒徑大小影響之情形 77
伍、結論 80
陸、參考文獻 82
圖目錄
圖1 一般常見的芳香族及脂肪族異氰酸酯結構 8
圖2 離子基單體的種類 13
圖3 螢光劑吸收、放射能量圖 22
圖4 單或多光反應型稀釋單體 31
圖5 各種光起始劑的化學結構 36
圖6 各種光敏感劑的化學結構 37
圖7 感光型水性PU色素樹脂分散液之製程 39
圖8 實驗裝置圖 41
Fig.9 Spectra of toluene diisocyanate at 25±0.05℃ 54
Fig.10 Spectra of hydroxypropyl acrylate at 25±0.05℃ 55
Fig.11 Spectra of fluorescein at 25±0.05℃ 56
Fig.12 Spectra of photosensitive colored NCO-terminated
polyurethane formed after 2 hour reaction at 25±0.05℃ 57
Fig.13 Plot of the viscosity versus fluorescein for use in
preparing photosensitive colored polyurethane ionomer, at
25±0.05℃ 59
Fig.14 Plot of the viscosity versus the hydroxypropyl acrylate
for use in preparing photosensitive colored polyurethane
ionomer, at 25±0.05℃ 60
Fig.15 Plot of the surface tension versus the fluorescein for use
in preparing photosensitive colored polyurethane ionomer,
at 25±0.05℃ 62
Fig.16 Plot of the surface tension versus the hydroxypropyl
acrylate for use in preparing photosensitive colored
polyurethane ionomer, at 25±0.05℃ 63
Fig.17 Plot of the viscosity versus the time of UV absorbance for
a fixes concentration of hydroxypropyl acrylate (0.02
equivalent) used to prepare photosensitive colored
polyurethane ionomer, at 25±0.05℃ 66
Fig.18 Plot of the viscosity versus the time of UV absorbance for
a fixes concentration of hydroxypropyl acrylate (0.03
equivalent) used to prepare photosensitive colored
polyurethane ionomer, at 25±0.05℃ 67
Fig.19 Plot of the viscosity versus the time of UV absorbance for
a fixes concentration of hydroxypropyl acrylate (0.01
equivalent) and benzion (1.0%) used to prepare photo-
sensitive colored polyurethane ionomer, at 25±0.05℃ 68
Fig.20 Plot of the absorbance(λ=460.0NM) versus the fluorescein
for use in preparing photosensitive colored polyurethane
ionomer, at 25±0.05℃ 69
Fig.21 Plot of the absorbance(λ=484.0NM) versus the fluorescein
for use in preparing photosensitive colored polyurethane
ionomer, at 25±0.05℃ 70
Fig.22 Plot of the time of UV absorbance (time/15 sec) versus the
hydroxypropyl acrylate for use in preparing photosensitive
colored polyurethane ionomer, at 25±0.05℃ 72
Fig.23 Plot of the tensile strength versus the fluorescein for
use in preparing photosensitive colored polyurethane
ionomer, at 25±0.05℃ 75
Fig.24 Plot of the tensile strength versus the hydroxypropyl
acrylate for use in preparing photosensitive colored
polyurethane ionomer, at 25±0.05℃ 76
Fig.25 Plot of the number average partical size versus the
fluorescein for use in preparing photosensitive colored
polyurethane ionomer, at 25±0.05℃ 78
Fig.26 Plot of the number average partical size versus the
hydroxypropyl acrylate for use in preparing photosensitive
colored polyurethane ionomer, at 25±0.05℃ 79
表目錄
表1 二異氰酸鹽與CH3OCH2CH2OH的反應性 7
表2 TDI的物理性質 9
表3催化劑對於Diisocyanate反應的催化效果 14
表4 DMAC的物性表 17
表5 紅外線光譜特性吸收峰頻率 45
Tab.6 Plot of the time of curing under UV absorbance versus the
benzoin and benzophenone for a fixes concentration of
hydroxypropyl acrylate(0.01 equivalent)used to prepare
photosensitive colored polyurethane ionomer,
at 25±0.05℃ 73

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