可聚合界面活性劑：膠囊化有機色料於水相溶液中展現膠體穩定性及於纖維素上的防水性能

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陳怡吟(Yi-Yin Chen) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

可聚合界面活性劑：膠囊化有機色料於水相溶液中展現膠體穩定性及於纖維素上的防水性能
(Polymerizable Fatty Acid Surfactant: Encapsulation of Organic Pigments for Colloidal Stability in Aqueous Solution and Water-repellent Property on Cellulose)

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至系統瀏覽論文 (2029-7-31以後開放)

摘要(中)

有機色料具備鮮豔且明亮的色澤，對於光、熱、酸及鹼的環境具有優異的耐受性，廣泛應用於印刷、染色及塑膠等工業。然而，有機色料表面極性非常低導致於水相介質中的分散性差，過去多以有機溶劑作為分散相，而且色料與纖維素的作用力較低，幾乎無親和力，使其發展受限。為了解決這些限制，我們針對界面活性劑及膠囊化技術進行探討。在本研究中，我們合成一種可聚合界面活性劑11-甲基丙烯醯胺基十一酸鈉 (Sodium 11-methacrylamidoundecanoic acid, NaMAAUA)，因其含有脂肪酸的長碳鏈及羧酸基團頭部，該兩親性結構可作為分散劑或乳化劑用以分散聚集的色料，NaMAAUA中的非極性尾部提供與顏料的疏水作用，而極性羧基頭部則暴露在水相中提供靜電斥力以達懸浮，該結構還具備雙鍵可與疏水性單體苯乙烯 (Styrene, ST) 或甲基丙烯酸丁酯 (Butyl methacrylate, BMA) 進行聚合，疏水性單體可以增強色料與分散劑間的疏水作用力，進而降低顆粒粒徑並提高均勻性。透過微乳化聚合形成共聚物殼層於色料外圍，達到奈米級之膠囊化色料。除此之外，羧酸基團能夠與以羥基 (-OH) 為主的纖維素形成氫鍵，增加色料與纖維素基材間之作用力，因此，膠囊化後的色料在應用於紙張和棉質織物時，能夠展現出優異抗潑水性、耐洗性及抗紫外線之能力。
本研究中，我們使用動態光散射 (Dynamic Light Scattering, DLS)、熱重分析 (Thermogravimetric analysis, TGA) 及水接觸角等分析，探討了製程中可聚合界面活性劑NaMAAUA及兩不同疏水性單體的用量對於膠囊化色料粒徑的影響。最後，我們利用微乳化聚合合成出奈米級之膠囊化色料，不僅展現出優越的膠體穩定性及增強的耐候性，還具備抗潑水性能及抗紫外線能力。我們成功修飾有機色料使其成為水溶性色料，並於印刷、噴墨影印及手寫塗佈等方面有良好的應用，拓展有機色料在環保方面的實用價值，開闢了新途徑。

摘要(英)

Organic pigment has been widely used in many printing industries due to its excellent fastness to light, heat, acid, and alkalis environments. However, the organic pigment exhibited minimal affinity to the fibers and had poor dispersion stability in any aqueous medium. To address these limitations, dispersants and encapsulation techniques have been explored. In this study, nanoscale encapsulated pigments were synthesized using a novel polymerizable surfactant, sodium 11-methacrylamidoundecanoic acid (NaMAAUA), along with hydrophobic monomer of styrene or butyl methacrylate. NaMAAUA contains a pendant group of amphiphilic fatty acid, and acts as a dispersant and emulsifier, forming a copolymer shell around the pigments. The NaMAAUA has small critical micelle concentration (CMC) which can enhance the encapsulation and water dispersion. Besides, the apolar tail in NaMAAUA provides hydrophobic interaction with pigments, and the polar carboxyl headgroup exposes in the water phase and enables the formation of strong hydrogen bonds with cellulose which consisting of β-anhydroglucose units with dominant hydroxyl groups. Therefore, the resulting encapsulated pigment exhibits excellent dispersion stability, water-repellent property, washing fastness and UV resistance when applied to paper and cotton fabric, expanding the practical utility of organic pigments in an environmentally conscious manner. Characterization via various analytical techniques validates the efficacy of this approach, paving the way for enhanced pigment applications. Besides, the hydrophobic monomer can increase the hydrophobic interaction between pigments and polymeric dispersants resulting smaller particle diameter and better uniformity.
In this study, the effect of weight ratios of hydrophobic monomer in the formulation on encapsulation efficiency has been investigated by using Dynamic Light Scattering (DLS), Thermogravimetric analysis (TGA) and contact angle analysis. Ultimately, the encapsulated pigment featuring nano-sized particles shows superior dispersion stability, enhanced weather resistance, waterproof performance, and anti-ultraviolet intrusion ability. Moreover, the versatility of the water-soluble pigment extends its applications to printing, inkjet printing, handwriting, and various other uses, thereby significantly increased the practical value of pigments in an environmentally friendly way.

關鍵字(中)

★ 色料
★ 膠囊化色料
★ 可聚合界面活性劑
★ 膠體穩定性
★ 油墨印刷

關鍵字(英)

★ Pigment
★ polymeric encapsulation
★ polymerizable surfactant
★ colloidal stability
★ ink printing

論文目次

中文摘要 i
Abstract ii
致謝 iv
目錄 v
圖目錄 viii
表目錄 x
化學品及產物名詞代稱 xi
一、文獻回顧 1
1-1 顏料的發展 1
1-1-1 色料與染料之區別 2
1-1-2 酞菁藍 (Phthalocyanine Blue, PB) 3
1-1-3 C.I Pigment 15:3 之困境 4
1-2膠囊化色料製程 5
1-2-1 微乳化聚合 5
1-3界面活性劑之應用 8
1-3-1界面活性劑之分散機制 9
1-3-2 膠體穩定性 10
1-4可聚合界面活性劑 11
1-4-1 可聚合界面活性劑開發 14
1-4-2 氫鍵作用力 15
二、研究目的 17
三、實驗藥品清單與實驗方法 18
3-1實驗藥品清單 18
3-2實驗設備清單 19
3-3材料合成及樣品製備 20
3-3-1合成 NaMAAUA 可聚合界面活性劑 20
3-3-2微乳化聚合成膠囊化色料 21
3-3-3樣品製備 22
3-4實驗方法 23
3-4-1液態核磁共振光譜儀鑑定 (1H NMR) 23
3-4-2臨界微胞濃度之量測 (CMC) 23
3-4-3吸附行為之量測 (QCM-D) 24
3-4-4動態光散射儀分析 (DLS) 25
3-4-5傅立葉轉換紅外光譜儀分析 (FTIR) 25
3-4-6 X射線光電子能譜儀分析 (XPS) 25
3-4-7水接觸角測量儀分析 (Water contact angle) 26
3-4-8熱重分析儀 (TGA) 26
3-4-9穿透式電子顯微鏡分析 (TEM) 26
3-4-10膠體穩定性測試 27
3-4-11防水塗佈測試 (Water-repellent test) 28
3-4-12耐洗度測試 (Washing fastness test) 28
3-4-13抗紫外線測試 (UV resistance test) 28
3-4-14統計分析 28
四、結果與討論 29
4-1可聚合界面活性劑NaMAAUA之結構鑑定與分析 29
4-1-1 1H NMR圖譜 29
4-1-2 FTIR圖譜 30
4-1-3 臨界微胞濃度 (CMC) 31
4-1-4 計算界面活性劑吸附量 32
4-1-5 PD 比 33
4-2 膠囊化色料之結構鑑定與分析 34
4-2-1 FTIR圖譜 34
4-2-2 XPS圖譜 35
4-2-3 TGA分析 36
4-2-4 水接觸角分析 38
4-2-5 DLS分析 39
4-2-6 TEM分析 41
4-2-7膠體穩定性分析 42
(1) 熱處理之膠體穩定性 42
(2) 離心處理之膠體穩定性 43
4-3競品分析與應用 44
4-3-1 KH-10之CMC分析 44
4-3-2 KH-10之QCM-D分析 45
4-3-3 防水塗佈之應用 46
4-3-4 耐洗度測試 49
4-3-5 抗紫外線之測試 51
五、結論 52
六、未來展望 53
參考文獻 54

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指導教授

黃俊仁(Chun-Jen Huang)

審核日期

2024-7-18

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