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

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。

關鍵字

非氟；疏水；溶膠凝膠；塗料；奈米疏狀；自分層

並列摘要

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.