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研究生:鄭妃婷
研究生(外文):Fei-Ting Cheng
論文名稱:水性壓克力感壓膠添加不同增稠劑之流變探討
論文名稱(外文):Rheology effect of various thickeners on the adhesion property of water-based acrylic PSA
指導教授:芮祥鵬芮祥鵬引用關係
口試委員:魏騰芳張淑美
口試日期:2013-07-27
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:有機高分子研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:68
中文關鍵詞:乳化聚合感壓膠增稠劑流變剪切稀化牛頓流體
外文關鍵詞:Emulsion PolymerizationPressure Sensitive AdhesiveThickenerRheologyShear ThinningNon Newtonian Flow
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本研究分別利用陰離子型乳化劑、非離子型乳化劑於78℃下,以起始劑過硫酸鉀 (KPS)進行丙烯酸-2-乙基己酯 (2-EHA)、甲基丙烯酸甲酯 (MMA)、醋酸乙烯酯 (VAc)、丙烯酸 (AA)、 甲基丙烯酸 (MAA)之乳化聚合反應製備水性感壓膠。反應透過配方中的丙烯酸 (AA) 及甲基丙烯酸 (MAA) 來控制羧酸含量。探討羧酸含量對粒徑、黏度、初期黏著力、黏著力、內聚力及動態黏彈性質之影響。
為了調整的水性感壓膠的流變性質,分別加入不同量的鹼溶脹型丙烯酸增稠劑 (HASE)和疏水改性乙氧基化的聚氨基甲酸酯增稠劑 (HEUR)。增稠後的黏膠水溶液,定性分析其流變性質、黏度及pH值變化之影響。
乳化聚合反應後的水性感壓膠,我們發現隨羧酸含量增加,粒徑逐漸降低,黏度則些微升高。由於AA與MAA的增加,經由動態機械分析儀 (DMA)的分析,我們發現感壓膠的Tg逐步上升,內聚力亦升高,導致初期力和黏著力遞減,保持力提升。
HASE增稠劑的添加,由於增稠劑與感壓膠的相互作用,會使水性感壓膠的黏度增加,呈現剪切稀化行為。從實驗中觀察到,黏膠的羧酸含量增加,HASE增稠效果受到影響,黏度上升幅度明顯變小。同時也發現到,黏膠pH值的改變,對於HASE增稠後的黏度產生劇烈影響,顯著地降低。相對地,HEUR增稠劑的添加,同樣會使水性感壓膠的黏度增加,但隨黏膠中羧酸含量的增加,流變性質會從接近牛頓行為逐漸趨向於剪切稀化行為。而黏膠pH值的降低,對於HEUR增稠溶液的影響不大。


Acrylic copolymer latexes were prepared by emulsion polymerization process using anionic surfactant and nonionic surfactant as the emulsifier, respectively, and potassium persulfate (KPS) as the initiator at 78℃. The co-monomers used were 2-ethylhexyl acrylate (2-EHA), methyl methacrylate (MMA), vinyl acetate (VAc), acrylic acid (AA) and methacrylic acid (MAA). The latex was converted to pressure-sensitive adhesive (PSAs) then. Acrylic acid (AA) and methacrylic acid (MAA) to control the carboxylic acid content in the formula. Explore the carboxylic acid content on the particle size, viscosity, initial adhesion, adhesion, cohesion and the impact of the dynamic viscoelastic properties.
To adjust the rheology of waterborne pressure-sensitive adhesives, different amounts of a alkali swellable acrylic emulsions (HASE) and hydrophobically modified ethoxylated polyurethane thickener (HEUR) were added. The thickened adhesive solutions were characterized by flow rheology, viscosity and the effect of changes in pH.
After polymerization of the waterborne pressure-sensitive adhesives, we found that along with the increase of carboxylic acid content, the particle size decreases, the viscosity is slightly increased. By dynamic mechanical analyzer (DMA) analysis, we found that AA and MAA increases, the Tg of the Pressure Sensitive Adhesive gradually increased, cohesion has also increased, leading to the initial adhesion and peel strength decreasing.
For HASE thickener, the viscosity of the waterborne pressure-sensitive adhesives increased, showing shear thinning behavior, which can be ascribed to the existence of interactions between the water-based pressure-sensitive adhesives and the thickener. From the experiments it was observed that the adhesive of carboxylic acid content increased, HASE thickening effect is affected, the viscosity rise significantly slower. Also found that the pH value of the adhesive change, HASE thickened viscosity have a dramatic impact, significantly reduced. Furthermore, water-based adhesives add HEUR thickeners to increase the viscosity. However, the carboxylic acid content of the adhesive increases, the rheological properties from Newtonian behavior gradually became the shear thinning behavior. The decrease in pH of viscose, the solution of the HEUR thickener is not.

摘 要 i
ABSTRACT ii
致謝 iv
目錄 v
圖索引 viii
表索引 x

第一章 緒論 1
1.1 前言 1
1.2 研究動機 2

第二章 實驗原理與文獻回顧 3
2.1 乳化聚合(Emulsion Polymerization) 3
2.1.1 乳化聚合過程 3
2.1.2 粒子成核理論 6
2.2 黏著理論 7
2.3 感壓型黏著劑的物性 10
2.3.1 初期黏著力 (Tack) 11
2.3.2黏著力 (Adhesion) 12
2.3.3內聚力 (Cohesion) 12
2.4 增稠作用 (Thickening Effect) 13
2.4.1 疏水改性鹼溶性乳液型增稠劑(HASE)增稠機制 14
2.4.2 締合型聚氨酯增稠劑(HEUR)增稠機制 15
2.5 流變學 (Rheology) 17
2.5.1 牛頓流體 (Newtonian Fluid) 18
2.5.2 賓漢塑性流體 (Binham-Plastic Fluid) 18
2.5.3 剪切稀化 (Shear Thinning) 19
2.5.4 剪切增稠 (Shear Thickening) 20
2.5.5 Power Law model 21
2.5.6 觸變性 (Thixotropy)和反觸變性 (Rheopexy) 21
2.5.7 屈服應力 (Yield Stress) 22
2.6 塗佈技術 22
2.6.1 凹版輪塗佈 (Gravure coating) 23
2.6.2 逗號輪塗佈 (Comma coating) 25

第三章 實驗方法 26
3.1 藥品及儀器 26
3.2 實驗方法 29
3.2.1感壓膠乳化聚合的製備 29
3.2.3黏度之測定 (Brookfield Viscometer) 30
3.2.4酸價之測定 31
3.2.5 HASE水溶液的製備 32
3.2.6 HEUR水溶液的製備 32
3.2.7 HASE增稠乳液的製備 32
3.2.8 HEUR增稠乳液的製備 32
3.3 樣品特性分析 33
3.3.1粒徑、介面電位分析儀 33
3.3.2凝膠透析層析儀 34
3.3.3動態黏彈機械分析儀 35
3.3.1流變儀 (Rheometer) 36
3.4 感壓膠物性試驗方法 37
3.4.1 塗佈方法 37
3.4.2 初期黏著力之測試方法 (Tack) 37
3.4.3 剝離強度之測試方法 (Peel strength) 38

第四章 結果與討論 40
4.1 乳化聚合(Emulsion Polymerization) 40
4.1.1 乳液性質分析 40
4.1.2 酸價測定 40
4.1.3 粒徑分析 41
4.2 增稠劑水溶液之性質分析 47
4.3 HASE、HEUR增稠劑之流變探討 47
4.3.1 乳液鹼增稠之流變 47
4.3.2 HASE、HEUR增稠劑含量之黏度變化 48
4.3.3 羧酸對HASE增稠乳液之流變探討 50
4.3.4 羧酸對HEUR增稠乳液之流變探討 51
4.3.5 HASE、HEUR增稠乳液之Power law index 54
4.3.6 pH值對HASE增稠乳液之流變探討 55
4.3.7 pH值對HEUR增稠乳液之流變探討 56
4.3.8 HASE、HEUR增稠乳液之觸變性 58
4.3.9 HASE、HEUR增稠乳液之回復性 59
4.3.10 HASE、HEUR增稠乳液之物性 63
第五章 結論 66
參考文獻 68


[1] D. Satas, Ch. 1 in “Handbook of Pressure-sensitive Adhesive Technology”, ed. by D. Satas, 2nd ed.,Van Nostrand Reinhold Company, NY, 1989.
[2] 薛敬和,黏著劑全書-材料與技術, Ch. 32, 高立圖書有限公司, 1985.
[3] W.D. Harkins, J. Am. Chem. Soc.,69,1428 (1947).
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[6] W.J.Priest, J . Phys . Chem., 56,1077 (1952).
[7] B.Jacobi, Angew.,Chem.,64,539 (1952).
[8] J. Ugelstad, F. K. Hansen and S. Lange, Markromol. Chem., 175,507 (1974).
[9] F. K. Hansen, E. B. Ofstad and J. Ugelstad, Smith (ed.), Academic Press, New York ,13 (1976).
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[11] R. M. Fitch and C. H. Tsai, Polymer Colloids, R. M. Fitch (ed.), 73 (1984).
[12] P. J. Feeney, D. H. Napper and R. G. Gilbert, Macromol., 17, 25 (1984).
[13] Miss M. Gainsly and J. Dow, Adhesion and Adhesives Fundament-als and Practice, John Wiley & Sons, Inc. .
[14] 李松泰, 化工技術, 第9卷, 第五期, 53-58, 1985.
[15] N. A. De Bruyne, J. App1 . Chem., 303 (1956).
[16] S. S. Voyutskiĭ (1961) Elastomeric Adhesion and Adhesives. Rubber Chemistry and Technology: September 1961, Vol. 34, No. 4, pp. 1188-1189.
[17] D. Satas, ”Handbook of Pressure-Sensitive Adhesive Technolo-gy”, 2nd ed., Van Nostrand Reinhold Company, NY, 1989.
[18] Jung Soo Lim, Jin Hee Kim, Chongyoup Kim and Seung Wook Kim , Korea-Australia Rheology Journal ,Vol. 14, No. 1, March 2002 pp. 1-9.
[19] e.g. G. W. Scott Blair et al., J. Phys. Chem., (1939) 43 (7) 853–864. Also the de Waele-Ostwald law, e.g Markus Reiner et al., Kolloid Zeitschrift (1933) 65 (1) 44-62
[20] 陳聖偉,透明質酸與牛血清蛋白之流變性質與磨耗探討,國立臺北科技大學有機高分子研究所,2006.


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