新穎聚矽氧烷水膠材料之開發及其在隱形眼鏡之應用｜國立臺灣科技大學博碩士論文系統

簡易檢索 / 詳目顯示

回結果列表

研究生：	葉怡杏 Yi-hsing Yeh
論文名稱：	新穎聚矽氧烷水膠材料之開發及其在隱形眼鏡之應用 Novel silicon hydrogel based on PDMS-polyurethane-HEMA for contact lens application
指導教授：	楊銘乾 Ming-chienYan
口試委員:	邱顯堂 none 王大銘 Da-ming Wang
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	88
中文關鍵詞：	PDMS-PU預聚物、HEMA 、親水性、矽水膠、隱形眼鏡
外文關鍵詞：	PDMS-PU macromer, hydrophilicity silicone hydrogel, ophthalmic application
相關次數：	點閱：359 下載：14
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

上一筆

本研究利用PDMS-diol為軟鏈段，IPDI為硬鏈段與PEGMA為鏈延長劑來合成聚矽氧烷水膠 (PDMS-PU-PEGMA)，最後加入HEMA，利用光聚合(copolymerizaed)的方式合成水膠(PDMS-PU-HEMA)，以提高水膠之親水性。由實驗結果可知，其含水率隨著HEMA的增加而上升，而接觸角也因HEMA的加入而降低，因而提高水膠的親水性，然而透氧率(oxygen permeability，Dk )則相對地降低，但降低的量並不大，而透光率也有些微地降低。在機械強力(mechanical strength)及楊氏係數(Young’s modulus)方面會隨著HEMA的增加而有增加的趨勢。而在蛋白質吸附試驗中，我們利用BCA 蛋白質測定方法來探討，結果顯示HEMA上由於親水性的影響吸附些微的lysozyme。在細胞毒性方面，以ISO10993-5的判定上屬於0-1 級，所以其細胞毒性是通過標準的。針對這些特性，未來可以利用此水膠來作為長戴型的隱形眼鏡及眼科材料之運用

A novel hydrogel based on the block copolymer of polydimethylsiloxane-polyurethane (PDMS-PU) and 2-hydroxyethyl methacrylate (HEMA) was synthesized. This novel hydrogel was consisting of soft segment of poly(dimethylsiloxane) dialkanol with hydroxyethyl propoxy end groups and hard segment of isophorone diisocyanate (IPDI). Poly(ethylene glycol) methacrylate (PEGMA) was added as the chain-extender. Finally, by reacting silicone macromer (PDMS-PU) with HEMA under UV-photopolymerization, the copolymer was resulted (PDMS-PU-HEMA). The results showed that the water content of the hydrogel increased with the HEMA content. The Young’s modulus and tensile strength of the dry hydrogel also increased with HEMA content. At a HEMA content of 40%, the oxygen permeability (Dk) would remain 77% of that of the PDMS-PU. The optical transmittance of the PDMS-PU-HEMA hydrogel remained 94% of that of PDMS-PU. Furthermore, these hydrogels were non-cytotoxic through in vitro L929 fibroblasts assay. Overall results demonstrated that the PDMS-PU-HEMA hydrogel exhibited relatively high oxygen permeability, hydrophilicity, and optical transparency, therefore would be applicable as an ophthalmic material.

目錄
中文摘要	I
英文摘要	II
誌謝	III
目錄	IV
圖索引	VI
表索引	VII
第一章	緒論	1
1-1	研究背景	1
1-2	研究目的	2
第二章	文獻回顧	4
2-1	水膠的定義	4
2-2	水膠之分類	5
2-3	功能性水膠	7
2-4	隱形眼鏡的介紹	11
2-5	隱形眼鏡的分類	15
2-6	隱形眼鏡材料的特殊性質	20
2-7	隱形眼鏡之蛋白質吸附	25
2-8	反應型矽酮寡聚物
(Hydroxyl-terminated polydimethylsiloxane，PDMS-diol)	28
2-9	異佛爾酮二異氰酸酯(Isophorone diisocyanate，IPDI)	29
2-10	紫外光硬化交聯原理	30
第三章	實驗材料與方法	32
3-1	實驗項目流程圖	32
3-2	實驗原理	33
3-3	實驗材料	34
3-4	實驗設備	36
3-5	實驗步驟	37
3-6	平衡含水量(Equilibrium water content)的測試	39
3-7	UV可見光的測定	39
3-8	熱重分析(Thermogravimetric Analysis)	39
3-9	FTIR之光譜鑑定	40
3-10	透氧係數測定	40
3-11	接觸角測試(Contact angle measurement)	41
3-12	強力試驗	42
3-13	原子力顯微鏡(AFM)	43
   3-14	蛋白質吸附實驗	44
3-15	細胞毒性	45
3-16	細胞增生	48
第四章	結果與討論	50
4-1	PDMS-PU-HEMA水膠之合成	50
4-2	FTIR官能基分析	52
4-3	TGA熱重量分析	55
4-4 	機械強度	57
4-5	透光率測試	60
4-6	含水率測試	62
4-7	透氧率測試	64
4-8	AFM表面粗糙度	69
4-9	接觸角測試	72
4-10	蛋白質吸附	74
4-11	細胞毒性	76
4-12	細胞增生性	78
第五章	結論	80
第六章	參考文獻	83
作者簡介	88

圖索引
Figure 2-1	水膠交鏈方式	5
Figure 2-2	pH敏感性水膠於不同pH 下之變化	8
Figure 2-3	溫度敏感型高分子poly( NIPAAM )於高低溫下之結構變化	9
Figure 2-4	光敏感性高分子之結構	10
Figure 2-5	典型隱形眼鏡結構和名稱	14
Figure 2-6	聚甲基丙烯酸甲酯結構	16
Figure 2-7	矽氧烷甲基丙烯酸酯共聚物	16
Figure 2-8	PHEMA之結構	17
Figure 2-9	水膠之水合作用	20
Figure 2-10	淚液沉澱物與鏡片之作用	21
Figure 2-11	淚液膜之位置	25
Figure 2-12	IPDI結構式	30
Figure 2-13	PDMS-diol結構式	30
Figure 2-14	光起始劑衍生物	31
Figure 3-1	接觸角之原理圖	41
Figure 3-2	BCA 測試方法之步驟	44
Figure 4-1	PDMS-PU-HEMA水膠合成之FTIR分析圖	53
Figure 4-2	不同HEMA比例之水膠之FTIR分析圖	54
Figure 4-3	PDMS-PU-HEMA水膠之TGA熱分析圖	56
Figure 4-4	PDMS-PU-HEMA水膠之應力應變圖	58
Figure 4-5	PDMS-PU-HEMA水膠之最大應力及楊氏係數	59
Figure 4-6	PDMS-PU-HEMA水膠之透光度	61
Figure 4-7	PDMS-PU-HEMA水膠之含水率	63
Figure 4-8	PDMS-PU-HEMA之透氧率(Dk)	65
Figure 4-9	AFM表面結構圖(A)P12H1(B)P12H2(C)P12H6(D)P12H8	70
Figure 4-10	PDMS-PU-HEMA水膠之表面粗糙度值	71
Figure 4-11	PDMS-PU-HEMA之接觸角測試	73
Figure 4-12	PDMS-PU-HEMA水膠之蛋白質吸附	75
Figure 4-13	細胞毒性測試：(A)試劑對照組(Blank)、(B) P12H1、(C) P12H4、(D) P12H8	77
Figure 4-14	PDMS-PU-HEMA水膠之細胞增生性	79

表索引
Table 2-1	隱形眼鏡常用的材料單體與其特徵	14
Table 2-2	淚液膜(tear film)之組成與濃度	27
Table 3-1	主要的官能基吸收峰位置表	40
Table 4-1	PDMS-PU-HEMA水膠之組成比例與產率	51
Table 4-2	PDMS-PU-HEMA水膠與市面上隱形眼鏡之比較	68

                                

[1] 許瓊文，”嬌生攻下五成眼鏡族市場的秘密”，今周刊，期518，pp.112-113，2006。
[2] 吳志凌，”隱形眼鏡自動光學檢測系統之設計與開發”，碩士論文(2007)。
[3] Mei-Hui Yang, Lain-Jong Li, Tsang-Feng Ho, Synthesis and Characterization of polymethylsiloxane／poly(ethylene glycol) monomethyl ether copolymers. ,J. Ch. Colloid & Interface Soc, 1994 ,vol17,(3),p19-28.
[4] Yu-Chin Lai, A Novel Crosslinker for UV Copolymerization of N-vinyl Pyrrolidone and Methacrylates To Give Hydrogels, J. Polym. Sci., A, Polym. Chem., 1997, vol 35, p1039-1046.
[5] Ratner B. D. and Hoffman.A. S., “Synthetic hydrogel for biomedical application”, ACS Symposium Ser., 31, 1 (1976).
[6] Barenberg S. A., “Abridgel Report of the Committee to Survey the Needs and Opportunities for the Biomaterials Industry”, J. Biomed. Mater. Res., 22, 1267 (1988).
[7] Hoffman A. S., “Hydrogels for biomedical applications”, Advanced Drug Reviews 43, 3-12 (2002).
[8] Wichterle O. and Lim. D., “Hydrophilic gels for biological use”, Nature, 185, 117 (1960).
[9] Peppas.N. A. (Ed.), “Hydrogels in medicine and pharmacy”, Vol. 1 CRC Press, (1988).
[10] 陳進富，淺談水膠在生醫之應用，化工科技與商情，2002， V38
[11] http://www.chemnet.com.tw/magazin/200211/index9.htm
[12] O. Wichterle, D. Lim, Hydrophilic gels in biologic use, Nature 1960,185, 117.
[13] R. Bettini, P. Colombo, N. A. Peppas, Solubility effects on drug transport through pH-sensitive, swelling-controlled release system :Transport of theophylline and metoclopramide monohydrochloride, J. Controlled Release 1995, 37, 105-111.
[14] H. Cicek, A. Tuncel, Immobilization of á-chymotypsin in thermally reversible iso-propylacrylamide-hydroxy-ethylmethacrylate copolymergel, J. Polym. Sci., Part A Polym. Chem. 1998, 36, 543-552.
[15] H. Brondsted, L. Hovgaard, L. Simonsen, Dextran hydrogels forcolon-specific drug delivery. Comparative release study of hydrocortisone and prednisolone sodium phosphate, Stp. Pharma. Sci.1995, 5, 65-69
[16] T. Coviello, M. Grassi, G. Rambone, E. Santucci, M. Carafa, E. Murtas,F. M. Riccieri, F. Alhaique, Novel hydrogel system from sceroglycan :synthesis and characterization, J. Controlled Release 1999, 60, 367-378.
[17] A. J. Kuijpers, G. H. M. Engbers, T. K. L. Meyvis, S. C. de Smedt, J.Demeester, J. Krijgsveld, S. A. J. Zaat, J. Dankert, J. Feijen, Combined gleatin-condroitin sulfate hydrogels for controlled release of cationic antibacterial proteins, Macromolecules 2000, 33, 3705-3713.
[18] N. A. Peppas, R. E. Benner, Proposed method of intracordal injectionand gelation of poly(vinyl alcohol) solution in vocal cords: polymer consideration, Biomaterials1980, 1, 158-162
[19] W.R. Gombotz, S.F. Wee, Protein release from alginate matrices, Adv. Drug Deliv. Rev. 1991, 31, 267-285.
[20] F. Yokoyama, I. Masada, K. Shimamura, T. Ikawa, K. Monobe, Morphology and structure of highly elastic poly(vinyl alcohol) hydrogel prepared by repeated freezing-and-melting, Colloid Polym. Sci. 1986,264, 595-601.
[21] D. W. Lim, T.G. park, Stereo complex formation between enantiomeric PLA-PEG-PLA triblock copolymers: characterization and use as protein delivery microparticulate carriers, J. Appl. Polym. Sci. 2000, 75,1615-1623.
[22] N. A. Peppas. (Ed.), Hydrogels in medicine and pharmacy, Vol. 1 CRC Press, 1988.
[23] 李書豪，具環境應答型之網狀互穿型生醫水膠之合成及其藥物制放之應用，國立清華大學化學工程研究所碩士論文(2002)
[24] Yong Qiu and Kinam Park, Environment-sensitive hydrogels for drug delivery, Adv. Drug Deliv. Rev. 53 (2001) p321
[25] H.Katono, A.Maruyama, K.Sanui, T.Okano, Y.Sakurai, Thermoresponsive swelling and drug release switching of interpenetrating polymer networks composed of poly(acrylamide-co-butylamide) and poly(acrylic acid),J.Contr.Release 16(1991) p215
[26] 佘勝雄，利用二階段式自由基共聚合製備酸鹼應答型水膠及性質探討，國立中興大學化學工程研究所碩士論文(2002)
[27] J. Anzai, A. Ueno, H. Sasaki, K. Shimokawa and T. Osa. Photo controlledPermeation of alkali cation through poly (vinyl chloride)crown ether membrane. Makromol. Chem. Rapid Commun,4, 731 (1983)
[28] K. Ishihara and I. Shionhara. Photo induced permeation control of proteins using amphiphilic azoaromatic polymer membrane. J. Polym. Sci. Polym. Let. Ed., 22, 515 (1984)
[29] A. Mamada, T.Tanaka, D.Kungwachakum, M.Irie, Photo induced phase transition of gels ,Macromolecules 23(1990),p1517-1519
[30] I. C. Kwon, Y. H. Bae, and S. W. Kim. Electrically erodible polymer gel for controlled release of drugs. Nature, 354, 291 (1991)
[31] Vasilevskaya, V. V., Starodubtzev, S. G. and Khokhlov, A. R. “Conformational transitions in polymer gels: theory and experiment,” Adv. Polym. Sci, 109, 123-171（1993）
[32] Chung, D. J., Ito, Y. and Imanishi, Y. “An insulin-releasing membrane system on the basis of oxidation reaction of glucose,” J. Control. Release, 18, 45-54 （1992）
[33] T. A. Horbeet, B. D. Ratner, J. Kost and M. Singh. A bioresponsive membrane for insulin delivery, Recent Advances in Drug Delivery System, Penum Press, 1984.
[34] 陳翊中，”台系隱形眼鏡廠打進世界前五大”，今周刊，期518，pp.114，2006。
[35] 原著 Richard P. Franz, R. Erich Bauman，主譯瞿佳，隱形眼鏡基礎，上海科學技術出版社，1994
[36] 齊備，隱形眼鏡手冊，上海科學技術出版社，1997
[37] 瞿佳、呂帆，隱形眼鏡學，上海科學技術出版社，1997
[38] Robert Edwards, ”CONTACT LENSES A-Z”, Caroline Makepeace
[39] Speckhard T. A.; Cooper, S. L. Rubber Chem. Technol. 1986, 59,405
[40] Cooper, S. L. et. al, J. Macromol. Sci. Phys. 23,175(1984)
[41] Cooper, S. L. et. al, J. Macromol. Chem.. 184, 651 (1983)
[42] Knutson, K. J. Polym. Sci. Polym. Chem. Ed. 15, 1655(1977)
[43] Matton, W. and Schneider, N. S., Pplom. Eng. Sci. 19, 1122(1979)
[44] Yves Camberlin and Jean Pierre PAscault , J. Polym. Sci.：Polymer Chemisty Edition,1983, 21, 415-423
[45] Mitsui Nisso Corp.Japan Kokai,Tokkyo，Koho，Jpn.Pat.58,217,515
[46] V. Y. Kotomkin, V. A. Baburina, E. P. Lebedov, V. A. Bylev, T. E.Yasmikova, and V. O. Reikhsfeld, Khimyai Parki Primonennie,Kremnii I Fosforogan, Soedin L, 23(1980); Chem. Abstr., 95:43841d.
[47] V. Y. Kotomkin, V. A. Baburna, V. P. Lebdev, and Y. Y. Kercha, Plastic Massy, 27(1981); Chem, Abstr., 95: 43841d.
[48] Sava, m. Bruma, B. Schulz, F. Mercer, V. N. Reddy, and N. Belomoina, J. Appl. Polym. Sci. 65, 1553~1538 (1997).
[49] Ming-Fung Lin,Yao-Chi Shu, Wen-Chi Tsen, Fu-Sheng Chuang, J. Appl. Sci. 81, 3489(2001)
[50] Yao-Chi Shu, Ming-Fung Lin, Wen-Chi Tsen, Fu-Sheng Chuang, J. Appl. Polym. Sci., 81, 3502 (2001)
[51] Ming-Fung Lin, Wen-Chi Tsen, Yao-Chi Shu and Fu-Sheng Chuang , J. Appl. Polym. Sci.,79, 881 (2001)
[52] Tai Ho and K. J. Wynne, Prepr. ACS Polym. Mat. Sci. Eng. Div.,67,445(1992)
[53] V. P. Kuznetsova, K. Zapunnaya, USSR 422,246; Chem. Abstr., 90;7759.
[54] B. Masiulanis and R. Zielinski, J. Appl. Polym. Sci., Vol. 30,2731(1985).
[55] Z. S. Petrovic et. al. ,J. Appl. Polym. Sci., Vol51, 1087 (1994).
[56] H.H.WANG and M. F. LIN，J. Appl. Polym. Sci.，Vol.43，263(1991)
[57] Ming-Fung Lin, Fu-Sheng Chuang ，Yao-Chi Shu and Wen-Chi Tsen, Polymer-Plastics Technology and Engineering , 37(1),71~102(1998)
[58] Huei-Hsiung Wang , Ming-Fung Lin, Journal of Applied Polymer Science, Vol.68, 1031~1043(1998).
[59] C. J. Hilado, C j. Casey, D. F. Chistenson, and J. Lipowitz, J. Combust. Toxicol. 5, 130(1978).
[60] Y. L. Liu G. H. Hsiue, C. W. Lan, J. K. Kuo, R. J. Jeng, and Y. S. Chiu, J. Appl. Polym. Sci., 63, 875~882(1997).
[61] Beek MV, Jones L, Sheardown H. Hyaluronic acid containing hydrogels for the reduction of protein adsorption. Biomaterials 2008;29:780-9.
[62] Mueller K, Hieber S, Plankl W. Strong, silicone containing polymers with high oxygen permeability. US Patent 4,486,577, 1984.
[63] W. L. Chang, Decomposition behavior of polyurethanes via mathematical simulation. J Appl Polym Sci 1994;53:1759-69.
[64] M. F. Lin, Y. C Shu, W. C. Tsen, F. S. Chuang. Synthesis of polyurethane-imide (PU-imide) copolymers with different dianhydrides and their properties. Polym Int 1999;48:433-45.
[65] M. B. Huglin and M. B. Zakaria, Observation on the Homogeneity of Crosslinked Copolymers Prepared by λ-irradiation , Polymer ,25,797(1997).
[66] L. Florkey, B.A. Fink, L. Mitchell, R.M. Hill, Tear exchange and oxygen reservoir effects in silicone hydrogel systems, Eye & Contact Lens: Science and Clinical Practice 29 (1) (2003) 90–92.
[67] Tighe B. Silicone hydrogels: structure, properties and behaviour. In: Sweeney DF, ed. Silicone Hydrogels. Continuous Wear Contact Lenses. Edinburgh: Butterworth-Heinemann; 2004:1-27.
[68] N. Efron, P. B. Morgan, I. D. Cameron, N. A. Brennan, M. Goodwin. Oxygen Permeability and Water Content of Silicone Hydrogel. Contact Lens Materials Optom Vis Sci. 2007;84:e328-337.
[69] Nicolson PC, Vogt J. Soft contact lens polymers: an evolution. Biomaterials 2001;22:3273-83.
[70] Abbasi F, Mirzadeh H, Katab AA. Modification of polysiloxane polymers for biomedical applications: a review. Polym. Int 2001;50;1279-87.
[71] N. Efron, P. B. Morgan, I. D. Cameron, N. A. Brennan, M. Goodwin. Oxygen Permeability and Water Content of Silicone Hydrogel. Contact Lens Materials Optom Vis Sci. 2007;84:e328-337.
[72] Walker, D.; Garrison, M.; Reichert, W. , Protein Adsorption to HEMA/EMA Copolymers Studied by Integrated Optical Techniques : Journal of Colloid and Interface Science 157, no. 1 (1993): 41-49.

全文公開日期 2014/07/16 (校內網路)
全文公開日期本全文未授權公開 (校外網路)
全文公開日期本全文未授權公開 (國家圖書館：臺灣博碩士論文系統)

簡易檢索 / 詳目顯示

相關論文