非氟疏水劑開發及其在製備水性奈米溶膠凝膠疏水塗料之探討

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研究生：	湯偉鉦 Tang, Wei-Cheng
論文名稱：	非氟疏水劑開發及其在製備水性奈米溶膠凝膠疏水塗料之探討 Development of perfluorocarbon-free water-repellent agents and their use in the water-based nano sol-gel water-repellent coating materials
指導教授：	朱一民 Chu, I-Ming 陳信龍 Chen, Hsin-Lung
口試委員:	劉大佼 Liu, Ta-Jo 葉瑞銘 Yeh, Jui-Ming 陳俊太 Chen, Jiun-Tai
學位類別：	博士 Doctor
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	中文
論文頁數：	107
中文關鍵詞：	非氟、疏水、溶膠凝膠、塗料、奈米疏狀、自分層
外文關鍵詞：	non-fluoro, water-repelling, sol-gel, coating, nano-brush, self-stratifying
相關次數：	點閱：3 下載：0
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全氟烷基化合物(PFCs)廣泛用於疏水塗料中，但是由於它們的致癌性和對環境的有害影響而引起ZDHC綠色組織關注並禁用；本研究主要使用fumed silica和n-Octyltriethoxysilane作為原料，透過溶膠-凝膠(sol-gel)化學合成方法，製備了新潁的水性非氟nano-brush疏水劑，搭配線性黏彈區域(LVR)分析和不對稱流場場流分析(AF4)，證明了nano-brush非氟疏水劑和市售的水性樹脂之間的交互作用力可最小化，達到水性塗料中自分層的特性，並且利用SEM、TEM分析證明了塗膜自分層微結構；此外，本研究利用封閉型異氰酸酯(blocked-isocyanate)交聯設計，提升了nano-brush非氟疏水塗料的耐磨耗性能，並利用拉曼光譜(Raman)、近緣X光吸收細微結構光譜(NEXAFS)等分析了交聯化學反應。具體研究結果發現nano-brush非氟疏水劑與外乳化的丙烯酸基樹脂，較能表現出優異的相容性和自分層能力，當nano-brush非氟疏水劑以7%含量摻入時，可達到104.3°的水接觸角，在熱塑性聚氨酯(TPU)上其他性能測試顯示，最終配方具有優異的附著性(5B, 100%)，並且在TPU塗佈後水接觸角從80.1°顯著增加至103.8°，表面污泥污染附著面積從48%降至1%，此外，在經過1000次耐刷洗與500次耐磨耗測試後，性能維持不變。本研究的發現證明了所合成的nano-brush非氟奈米疏水劑，不但具有水性、非氟環保特性，也能滿足未來商業需求的水性疏水防污塗料需求。

While perfluoroalkyl chemicals (PFCs), also known as C8s, are used extensively in textile repellent coatings, concerns have arisen for their carcinogenicity and hazardous effects on the environment. In this study, a novel water-based, non-fluoro, and nano-brush textile repelling agent was prepared by conventional sol-gel chemistry using amorphous fumed silica and n-Octyltriethoxysilane as starting materials. Minimal interaction between the designed repelling agent and marketed water-based resins was confirmed using linear viscosity region (LVR) analysis and asymmetric-flow field-flow fractionation (AF4), suggesting the self-stratification potential of the repelling agent. The SEM and TEM were used to observe the morphology and chemical composition of coatings prepared from nano-brush repelling agents. More specifically, the repelling agent exhibited excellent compatibility and self-stratifying ability with a force-emulsified acrylic-based resin, affording a water contact angle of 104.3° when incorporated at 7% solid content. Furthermore, this study introduced the blocked-isocyanate functional group to nano-brush repelling agents to enhance the wear resistance of nano-brush non-fluoro coating. Also, we utilized the Raman spectroscopy (Raman) and near edge X-ray absorption fine structure (NEXAFS) to analyze the crosslinking chemistry. The performance tests carried out on thermoplastic polyurethane (TPU) revealed excellent adhesion (100/100) of a final formulation, and significant increase in water contact angle from 80.1° to 103.8° after treatment. In addition, the fouling area after removal of a submerged sample from a mixture of slurry, polymer, and oil decreased from 48% to 1% when the repelling agent was added. Moreover, the sludge-fouling property remained unchanged after 1000 cycles of wet abrasion and after 500 cycles of Taber abrasion tests. These findings demonstrate the potential of the described non-fluoro, nano-brush repelling agent as an environmentally-safe alternative for use with commercial resins, in turn realizing a fully water-based hydrophobic coating.

摘要
誌謝
目錄
第一章 研究動機與目的...............................................1
第二章 基礎研究與文獻回顧............................................3
2-1水性、非氟塗料的技術發展需求......................................3
2-1-1水性塗料技術佔比將逐漸擴大......................................3
2-1-2水性疏水防污塗料技術具有瓶頸....................................4
2-1-3非氟疏水防污塗料將逐漸成為趨勢..................................5
2-1-4現有疏水劑只能用在多孔基材但平坦基材需求大    ........................7
2-2史托伯法(Stöber Process)與溶膠-凝膠法(Sol-gel)無機材料合成技術.....9
2-2-1 Stöber Process............................................9
2-2-2 Sol-gel無機材料化學合成機制..................................12
2-2-3 Sol-gel原料篩選與塗料製備....................................13
2-2-4塗料應用之特殊sol-gel單體.....................................17
2-3 非氟疏水防污原理..............................................22
2-3-1蓮花效應(Lotus effect)......................................22
2-3-2接觸角與滑落角...............................................23
2-3-3非氟低表面能分子設計理論.......................................26
2-4自分層疏水塗料設計與分析技術......................................28
2-4-1控制分子交互作用達到自分層機制..................................28
2-4-2封閉型異氰酸酯(blocked-isocyanate)分子設計.....................30
2-4-3拉曼(Raman)及近緣X光吸收細微結構光譜術(NEXAFS)..................31
2-4-4以X-ray reflectivity分析自分層後奈米粒子分布...................33
2-4-5水相中分子交互作用量化分析理論..................................35
第三章 研究構想與實驗用品...........................................36
3-1水性非氟疏水自分層塗料研究構想....................................36
3-1-1 Nano-brush結構非氟水性疏水劑.................................36
3-1-2 Blocked-isocyanate (Blocked-NCO)改質nano-brush非氟水性疏水劑.37
3-2 實驗部份.....................................................39
3-2-1藥品與原物料.................................................39
3-2-2實驗設備、儀器設備............................................39
第四章 實驗方法與步驟..............................................41
4-1疏水劑合成與塗料配方實驗步驟......................................41
4-1-1 NF-C8水性非氟、F-C8水性含氟nano-brush奈米疏水劑合成.............41
4-1-2 NF-C8-tbnco Blocked-NCO改質水性非氟疏水劑....................42
4-1-3 水性疏水防污自分層塗料配方....................................44
4-2分析方法與實驗步驟..............................................45
4-2-1水接觸角測試方法(參考JIS R3257靜滴法)..........................45
4-2-2不對稱流場場流分析水性自分層塗料中疏水劑與樹脂分子間作用力..........46
4-2-3耐刷洗測試方法(參考CNS 10757).................................48
4-2-4防污測試方法.................................................49
4-2-5百格測試(參考ASTM D3359-17)：................................50
4-2-6氟含量測試方法...............................................50
4-2-7耐磨耗測試...................................................50
第五章 結果與討論..................................................51
5-1 Nano-brush水性非氟疏水劑結構分析................................51
5-2 不同界面活性劑分散之水性非氟nano-brush奈米疏水劑評估...............57
5-3 Nano-brush水性非氟疏水劑有機光譜分析............................58
5-4本研究合成nano-brush含氟疏水劑有機光譜分析........................61
5-5 市售疏水劑及本研究合成nano-brush疏水劑性能比較....................63
5-6 自乳化與外乳化樹脂對於水性疏水塗料自分層影響.......................65
5-7 以流變儀分析自乳化系統與外乳化系統分子交互作用差異..................67
5-8 以3D-DLS分析自乳化系統與外乳化系統分子交互作用差異.................69
5-9疏水劑含量對於水性自分層防污塗料特性影響...........................71
5-10 LVR分析水性自分層塗料中疏水劑與樹脂分子間作用力...................73
5-11 不對稱流場場流分析水性疏水塗料中疏水劑與樹脂分子交互作用............76
5-12以電子顯微鏡進行自分層塗膜微結構分析..............................83
5-13水性非氟防污塗料防污性與耐久性測試...............................88
5-14 Blocked-NCO改質Nano-brush水性非氟疏水劑.......................89
5-15 利用拉曼光譜分析Blocked-NCO silane溫度效應.....................92
5-16 NEXAFS光譜分析Blocked-NCO高溫開環再交聯.......................94
5-17 AFM奈米刮痕測試Blocked-NCO改質後塗膜耐刮性.....................95
5-18 Blocked-NCO 疏水劑對於耐刷洗與耐磨耗性之影響....................96
第六章 結論與展望.................................................101
參考文獻........................................................103
附錄.......................   .................................106
                                

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