光固化粉末涂料的研制
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摘要
近年来随着环境保护意识的提高，大大促进了对低污染、环保型涂料的研究开发。粉末涂料出现正是这些涂料品种的典型代表。但普通的粉末涂料存在固化温度偏高，不能用于热敏性底材，限制了其应用范围。如何降低粉末涂料的固化温度引起了研究者的很大兴趣。引入光固化技术，开发光固化粉末涂料被认为是解决这一难题的最好方法。
本文以研究光固化粉末涂料基体树脂目的，开发了适合于此类涂料用的不饱和聚酯树脂、环氧丙烯酸酯树脂。研究了不饱和聚酯的合成工艺、单体选择、物料配比与分子量、玻璃化温度之间的关系：研究了环氧丙烯酸酯合成过程中反应温度、催化剂、物料配比的不同对树脂性能的影响。确定了这两种光敏树脂的合成工艺。
本文还系统的考察了树脂在光固化时，两种基体树脂配比的不同、光引发剂用量的变化、光照时间的不同对于涂料固化交联度的影响。研究了交联度变化对于涂膜性能的影响。并研究了三缩水甘油异氰酸酯(TGIC)改性体系与端基改性不饱和聚酯体系的固化情况。研究表明在合适固化条件下，自制的光敏树脂具有较快的光固化速度，可以制得固化交联度合适，具有良好物化性能的涂料；并得到了基体树脂的配比、光引发剂用量与光照强度之间的关系。
Increasingly stringent health, safety and environmental regulations promote formulators to focus on the development of technologies that meet these regulations. Powder coating, a strict environmentally friendly technology, is gaining double-digit growth. For traditional thermal curing powder coatings, there has a big limit of high curing temperature. They can't coat on heat sensitive substrates such as plastic and wood. How to reduce the powder coatings' curing temperature attracts great interest among researchers. In this aspect, UV curing technology is considered to be the very alternative.
In this study, we aimed at developing resins for UV curing powder coatings. To this end, Unsaturated Polyester (UP) and Epoxid Acrylate oligomer (EA) resins was synthesized. For UP resin, the influence of synthesizing process and conditions on molecular weight and glass transform temperature was studied. For EA resin, we studied the relationship between reaction temperature, catalysts, and material proportion and resin property. Two resins which have suitable properties has been developed.
The influence of the ratio of two resins, concentration of photoinitiator, and LTV' irradiation time on the properties of cured film was investigated also. The relationship between the coatings corsslinking and performances of coatings film was explored then. The curing process of TGIC modified resin and acrylate end-capped UP resin was tried. It was found that under comfortable curing conditions, the synthesized photosensitive resins have fast enough photo-curing rate. The resulted coating film has high crosslinking degree and acceptable properties.
本文以研究光固化粉末涂料基体树脂目的，开发了适合于此类涂料用的不饱和聚酯树脂、环氧丙烯酸酯树脂。研究了不饱和聚酯的合成工艺、单体选择、物料配比与分子量、玻璃化温度之间的关系：研究了环氧丙烯酸酯合成过程中反应温度、催化剂、物料配比的不同对树脂性能的影响。确定了这两种光敏树脂的合成工艺。
本文还系统的考察了树脂在光固化时，两种基体树脂配比的不同、光引发剂用量的变化、光照时间的不同对于涂料固化交联度的影响。研究了交联度变化对于涂膜性能的影响。并研究了三缩水甘油异氰酸酯(TGIC)改性体系与端基改性不饱和聚酯体系的固化情况。研究表明在合适固化条件下，自制的光敏树脂具有较快的光固化速度，可以制得固化交联度合适，具有良好物化性能的涂料；并得到了基体树脂的配比、光引发剂用量与光照强度之间的关系。
Increasingly stringent health, safety and environmental regulations promote formulators to focus on the development of technologies that meet these regulations. Powder coating, a strict environmentally friendly technology, is gaining double-digit growth. For traditional thermal curing powder coatings, there has a big limit of high curing temperature. They can't coat on heat sensitive substrates such as plastic and wood. How to reduce the powder coatings' curing temperature attracts great interest among researchers. In this aspect, UV curing technology is considered to be the very alternative.
In this study, we aimed at developing resins for UV curing powder coatings. To this end, Unsaturated Polyester (UP) and Epoxid Acrylate oligomer (EA) resins was synthesized. For UP resin, the influence of synthesizing process and conditions on molecular weight and glass transform temperature was studied. For EA resin, we studied the relationship between reaction temperature, catalysts, and material proportion and resin property. Two resins which have suitable properties has been developed.
The influence of the ratio of two resins, concentration of photoinitiator, and LTV' irradiation time on the properties of cured film was investigated also. The relationship between the coatings corsslinking and performances of coatings film was explored then. The curing process of TGIC modified resin and acrylate end-capped UP resin was tried. It was found that under comfortable curing conditions, the synthesized photosensitive resins have fast enough photo-curing rate. The resulted coating film has high crosslinking degree and acceptable properties.
引文
[1] J.Howard., Chemisty & Industry, 1996,799.
[2] Webster G., Accelerated UV drying system, Surface Coatings International, 1996,79(5): 215～220.
[3] Witter F.M., Radiation-Curable Powder Coatings. Europe Coatings J., 1996,(3):1157.
[4] 洪啸吟，涂料化学，北京化工出版社，1998。
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[8] 徐伟良，新型光固化涂料制备及应用，涂料与应用，1996，26(3)：13～16。
[9] Larry Dill. Moden Paint and Coatings, 1996, (4):22.
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[11] S .T.Harris, "Developments in powder coatings", Paintindia 1999(1):41-48.
[12] J.M. Loutz, M. Baudour, "New developments in powder coating",PowderCoatings 1993(12):584-594.
[13] C. Decker, Khalil Moussa, "Recent Advances in UV-Curing Chemistry", Journal of Coating Technology Vol.65,No.819,1993.
[14] 居学成，电子束固化机理，涂料工业，1999，1。
[15] 冯邵炜，涂料与应用，1996，1。
[16] 洪啸吟，冯汉保。涂料化学，科学出版社，1997。
[17] Sander, M,R.,Osbon, C.L.,J.polymer sci., A- 1,10.3173 (1972).
[18] Ledwith,A.,J.O.C.C.A.,59,157-165 (1976).
[19] Xu Yan,DeLiang He,"Development of UV curing coating & its application",Electroplaing & Finishing Vol. 19,No. 1,2000(4).
[20] Nickerson,R.,Sr.,Industrial Finishing,p. 10, (Feb. 1974).
[21] Calvert,J.G. and Pitts,J.N; Photochemistry J. Wiley, New York. (1966).
[22] Li Shanjun, Polymer photochemistry Principle and Apply. Shanghai Fudan University Press, 1993.
[23]陈明、洪啸吟等，涂料工业，1999，12。
[24] DaridsonR. S. Eur, Polym. J. 18. 589(1982).
[25]陈明、洪啸吟等，涂料工业，1999，12。
[26] Visconyti M, Cattaneo M, Esacure TZT- an effective method of Surface Curing [J]., 1997, 187: 25-36.
[27] Crivello,J.V.,UV Curing: Science & Technology, (Ed.S.Peter Pappas),PP. 24-77,Technology Marketing Corporation, (1978).
[28] Fouassier J P, Rabak J F. Radiation Curing in Polymer Science & Technology. Vol 2 London & New York: Elsevier Applied Science 1993.
[29] Lu Jiuzu, JOURNAL OF PETROCHEMICAL UNIVERSITIES, 2001,6.
[30] United States Patent 5,824,373.
[31]俞郭义、史铁京，涂料工业，1996，6。
[32] United States Patent 5,935,661.
[33] D.R.Holman et al., UV & EB Curing Formulation for Printing inks Coatings & Paints London, U.K. (1988).
[34] J.Kirland, J. Polmer Sci. Chem. 18(1980)P1139.
[35]冯素兰，辐射固化用丙烯酸涂料，化工部涂料工业科技情报中心编，1984。
[36]金养智，UV固化油墨与功能性丙烯酸单体、树脂，辐射固化通讯，1997(1)：4-13。
[37] Bo Yong, Weathering Resistant Oligomers, Rad. Tech. Asia’95 Conference Proceedings, Gulling China, 1995:43.
[38] K.H. Lee, B.K. Kim, Structure property Relationships of Polyurethane Anionomer Acrylates, Polymer 1996(11):2251.
[39]荣家成，屈秀宁，高分子学报，1996(5)：526。
[40]朱庆红，辐射固化涂料的发展，中国涂料，2001(1)：36-39。
[41] Frank M. Witte, ECJ, 1996, 3.
[42][英]霍尔曼．奥尔镕林著，徐茂均等译，印刷油墨、涂料、色漆紫外光和电子束固化配方，原子能出版社，1994。
[43] 洪啸吟，冯汉保编著，涂料化学，科学出版社，1997。
[44] U.S. Patent 57,03,198.
[45] U.S. Patent 3,364,308.
[46] Roffey, C.G.; Photopolymerization of surface Coatings; (1982).
[47] UK Patent 2,056,885.
[48] U.S. Patent 3,364,387 (1986).
[49] 风翔、曹健等，涂料工业，1998(6)。
[50] United States Patent 5,824,373.
[51] United States Patent 5763099.
[52] United States Patent 4,070,262.
[53] 张士茜、尹华兵等，涂料工业，1998(5)。
[54] 钱逢麟、竺玉书，涂料助剂，化学工业出版社，1990。
[55] Borong Wei, Haiyan Zhang, Thermosetting Resin, Vol. 16 No.2 Mar. 2001.
[56] 胡和丰，涂料工业，1990(4)。
[57] Zhu hen,Yanwu Wang, "Development of UV curable epoxy acrylate coating", J. WuHan Institute Chemical Technology, Vol.21 No.3 1999.
[58] 张志贤、张瑞镐，有机官能团定量分析，化学工业出版社，1985。
[2] Webster G., Accelerated UV drying system, Surface Coatings International, 1996,79(5): 215～220.
[3] Witter F.M., Radiation-Curable Powder Coatings. Europe Coatings J., 1996,(3):1157.
[4] 洪啸吟，涂料化学，北京化工出版社，1998。
[5] 陈山南，光固化有机聚硅复烷．涂料工业，1996(2)：42。
[6] 陈山南，食品包装用紫外光固化涂料．涂料工业。1996(2)：43。
[7] 冯昭炜，紫外光固化涂料及其发展．涂料与应用，1996，26。
[8] 徐伟良，新型光固化涂料制备及应用，涂料与应用，1996，26(3)：13～16。
[9] Larry Dill. Moden Paint and Coatings, 1996, (4):22.
[10] Chros Brandl, "UV Curing applications for the automotive market", Modern Paint & Coatings 2000(2): 10-28.
[11] S .T.Harris, "Developments in powder coatings", Paintindia 1999(1):41-48.
[12] J.M. Loutz, M. Baudour, "New developments in powder coating",PowderCoatings 1993(12):584-594.
[13] C. Decker, Khalil Moussa, "Recent Advances in UV-Curing Chemistry", Journal of Coating Technology Vol.65,No.819,1993.
[14] 居学成，电子束固化机理，涂料工业，1999，1。
[15] 冯邵炜，涂料与应用，1996，1。
[16] 洪啸吟，冯汉保。涂料化学，科学出版社，1997。
[17] Sander, M,R.,Osbon, C.L.,J.polymer sci., A- 1,10.3173 (1972).
[18] Ledwith,A.,J.O.C.C.A.,59,157-165 (1976).
[19] Xu Yan,DeLiang He,"Development of UV curing coating & its application",Electroplaing & Finishing Vol. 19,No. 1,2000(4).
[20] Nickerson,R.,Sr.,Industrial Finishing,p. 10, (Feb. 1974).
[21] Calvert,J.G. and Pitts,J.N; Photochemistry J. Wiley, New York. (1966).
[22] Li Shanjun, Polymer photochemistry Principle and Apply. Shanghai Fudan University Press, 1993.
[23]陈明、洪啸吟等，涂料工业，1999，12。
[24] DaridsonR. S. Eur, Polym. J. 18. 589(1982).
[25]陈明、洪啸吟等，涂料工业，1999，12。
[26] Visconyti M, Cattaneo M, Esacure TZT- an effective method of Surface Curing [J]., 1997, 187: 25-36.
[27] Crivello,J.V.,UV Curing: Science & Technology, (Ed.S.Peter Pappas),PP. 24-77,Technology Marketing Corporation, (1978).
[28] Fouassier J P, Rabak J F. Radiation Curing in Polymer Science & Technology. Vol 2 London & New York: Elsevier Applied Science 1993.
[29] Lu Jiuzu, JOURNAL OF PETROCHEMICAL UNIVERSITIES, 2001,6.
[30] United States Patent 5,824,373.
[31]俞郭义、史铁京，涂料工业，1996，6。
[32] United States Patent 5,935,661.
[33] D.R.Holman et al., UV & EB Curing Formulation for Printing inks Coatings & Paints London, U.K. (1988).
[34] J.Kirland, J. Polmer Sci. Chem. 18(1980)P1139.
[35]冯素兰，辐射固化用丙烯酸涂料，化工部涂料工业科技情报中心编，1984。
[36]金养智，UV固化油墨与功能性丙烯酸单体、树脂，辐射固化通讯，1997(1)：4-13。
[37] Bo Yong, Weathering Resistant Oligomers, Rad. Tech. Asia’95 Conference Proceedings, Gulling China, 1995:43.
[38] K.H. Lee, B.K. Kim, Structure property Relationships of Polyurethane Anionomer Acrylates, Polymer 1996(11):2251.
[39]荣家成，屈秀宁，高分子学报，1996(5)：526。
[40]朱庆红，辐射固化涂料的发展，中国涂料，2001(1)：36-39。
[41] Frank M. Witte, ECJ, 1996, 3.
[42][英]霍尔曼．奥尔镕林著，徐茂均等译，印刷油墨、涂料、色漆紫外光和电子束固化配方，原子能出版社，1994。
[43] 洪啸吟，冯汉保编著，涂料化学，科学出版社，1997。
[44] U.S. Patent 57,03,198.
[45] U.S. Patent 3,364,308.
[46] Roffey, C.G.; Photopolymerization of surface Coatings; (1982).
[47] UK Patent 2,056,885.
[48] U.S. Patent 3,364,387 (1986).
[49] 风翔、曹健等，涂料工业，1998(6)。
[50] United States Patent 5,824,373.
[51] United States Patent 5763099.
[52] United States Patent 4,070,262.
[53] 张士茜、尹华兵等，涂料工业，1998(5)。
[54] 钱逢麟、竺玉书，涂料助剂，化学工业出版社，1990。
[55] Borong Wei, Haiyan Zhang, Thermosetting Resin, Vol. 16 No.2 Mar. 2001.
[56] 胡和丰，涂料工业，1990(4)。
[57] Zhu hen,Yanwu Wang, "Development of UV curable epoxy acrylate coating", J. WuHan Institute Chemical Technology, Vol.21 No.3 1999.
[58] 张志贤、张瑞镐，有机官能团定量分析，化学工业出版社，1985。