摘要
紫外荧光聚合物材料是指材料本身在自然光条件下不显荧光性,在紫外光的照射下发出可见光的一类高分子材料。热致变色聚合物材料是指在温度变化时发生颜色变化的一种功能高分子材料。在印刷防伪技术和化学材料防伪技术中,紫外荧光油墨和热致变色聚合物材料分别可以作为一种防伪材料,但是单独的防伪技术已经很难满足人们的需要,而将这两者结合起来所制备的光致∕热致复合变色材料更是吸取了这两种技术的优点,实现多重防伪。
本文是以聚合物作为电子授受反应介质来制备光致∕热致复合变色材料,并将其与激光全息防伪烫印膜结合起来,制备出一种检测方法简单,集多重防伪技术于一体的新型防伪标识材料。主要包括以下内容:
(1)以发色剂结晶紫内酯为电子给体,显色剂双酚A为电子受体,分别以聚苯乙烯和丙烯酸树脂为电子授受反应介质,稀土金属Eu的配合物作为紫外荧光物质,制备光致∕热致复合变色材料。用紫外灯检测其紫外荧光性,用简单的热水喷淋的方式检测其温变性,并讨论光致∕热致复合变色材料的配方中各组分对该膜的荧光性和温变性的影响。得到在紫外灯照射下发出红色荧光,用70℃以上的热水喷淋可以从蓝色变为几乎无色的光致∕热致复合变色材料。
(2)将光致∕热致复合变色材料与激光全息防伪商标结合起来,用PET转移法制备具有紫外荧光性和热致变色性的激光全息防伪烫印膜。针对激光全息防伪烫印膜的结构及PET转移法的工艺流程,制备光致∕热致复合变色烫印膜。用紫外灯检测其紫外荧光性,用简单的热水喷淋的方法检测其温变性。讨论涂布和烫印工艺参数对光致∕热致复合变色烫印膜的影响。结合成本考虑优化工艺及配方,制备光致∕热致复合变色烫印膜。得到在紫外灯(或带有紫外灯的验钞机)下,发出明显的红色荧光,而且当用温度达到70℃以上的热水喷淋可以从蓝色变为几乎无色的光致∕热致复合变色烫印膜。优化后的烫印膜在达到相同的荧光性和温变性的同时,紫外荧光红粉的含量为之前的1/30,大大降低了生产成本。
Ultraviolet fluorescent polymeric material is a kind of polymer that can’t show its fluorescent characteristic under visible light but can emit visible light when exposing to ultraviolet light. Thermochromism polymer is a kind of polymer whose color changed with the temperature. Both of these can be used as anti-counterfeit materials separately. But how to make full use of the merits of these two polymers and prepare photo-and thermo-chromic composite materials is a more promising way in Modern Anti-counterfeit Printing Technology.
In this thesis we use polymers as reaction medium. Combine with laser holographic anti -counterfeit hot-pressure printing film Technology to prepare a new anti-counterfeit material that easy to detect. This thesis is consisted of two sections as follows:
(1) Crystal violet lactone and bisphenol A are used as electron acceptor and donator respectively, polystyrene and acrylic resin are used as reaction medium, rare earth metal organic complex is used as fluorescent material to prepare photo-and thermo-chromic composite material. Its photochromism and thermochromism performance are detected by UV lamp and hot water respectively. When exposing under ultraviolet lamp, the composite material emit red fluorescent light, when douse by hot water(>70℃), the color of the composite material changed from blue to colorless. The influences of each component are also be discussed in this chapter.
(2) Combing photo-and thermo-chromic composite material with laser holography Anti–counterfeit trademarks, PET Transfer Method is used to prepare photo-and thermo-chromic laser holography anti -counterfeit hot-pressure printing film. Its photochromism and thermochromism performance are also detected by UV lamp and hot water respectively. When exposing under ultraviolet lamp, the composite material emit red fluorescent light, when douse by hot water(>70℃), the colour of the composite material changed from blue to colorless. The influences of each technological parameters to the film and the cost are also discussed in this paper. To the same level of thermochromism and photochromism, our optimized hot-pressure printing film need only 1/30 ultraviolet fluorescent powder compared to former hot-pressure printing film, which greatly reducing the cost.
引文
[1]王旭东,徐伟箭.可逆热致变色材料的应用新进展.化工进展,2000,(3):42~45
[2]张玉喜,李子成.热色性材料的应用及变色机理.河北化工,1992,(2):23~26
[3]朱传方,徐汉红.可逆热色性化合物的研究进展.化学进展,2001,13(4):261~267
[4] Corval A., Kuldova K., Eichen Y. et al. Photochromism and Thermochromism Driven by Intramolecular Proton Transfer in Dinitrobenzylpyridine Compounds. J. Phys. Chem., 1996, 100:19315~19320
[5] Trefonas P., Damewood J.R., West R. Organosllane High Polymers: Thermochromic Behavior In Solutlon. Organometallics, 1985, 4:1318~1319
[6]余坚,苑俊章,郝志峰.新型AgmCunHgI4可逆热致变色颜料的研究.精细化工,2002,19(11):651~653
[7] Wang C.C., GaoY., Shreve A.P. et al. Thermochromism of a Poly(phenylene vinylene): Untangling the Roles of Polymer Aggregate and Chain Conformation. J. Phys. Chem. B, 2009, 113:16110~16117
[8] Leger J. M., Holt A.L., Cartera S.A. Reversible Thermochromic Effects in Poly(phenylene vinylene)-based Polymers. Appl. Phys. Lett. 2006, 88(11901):1~3
[9] Seeboth A., Kriwanek J., Vetter R. The First Example of Thermochromism of Dyes Embedded in Transparent Polymer Gel Networks. J. Matter. Chem., 1999, 9:2277~2278
[10] Kuroiwa K., Shibata T., Takada A. et al. Heat-Set Gel-like Networks of Lipophilic Co(II) Triazole Complexes in Organic Media and Their Thermochromic Structural Transitions. J. Am. Chem. Soc. 2004, 126: 2016~2021
[11] Bamfield P., Hutchings M.G. Chromic Phenomena—Technological Applicatio-ns of Colour Chemistry. Sec ed. England: Cambridge, 2001
[12] Seeboth A., Lotzsch D. Encyclopedia of Polymer Science and Technology. 3rd ed. New York: Wiley, 2003
[13] Leclerc M. Optical and Electrochemical Transducers Based on Functionalized Conjugated Polymers. Adv. Mater., 1999, 11(18): 1491~1497
[14] Beildeck C., Lucht B.L., Euler W.B. Comparison of Analytical Methods for Characterization of the Thermochromic Transition of Poly(3-alkylthiophene)s. J. Am. Chem. Soc., 2001, 42(2): 211
[15] Seeboth A., Yin C., Kriwanek J. Thermochromic Polyolefin Foils. J. Appl. Polym., 2005, 96: 1789~1792
[16]余坚,苑俊章,郝志峰.低温可逆示温涂料及性能的研究.湖北化工,2002,(6):30~31
[17]马一平,朱蓓蓉,吴科如.常温可逆温致变色建筑涂料的研究.建筑材料学报,2001,4(3):211~216
[18]刘华.热敏印刷技术及应用.丝网印刷,2008,5:33~36
[19]马一平.常温可逆温致变色功能水泥基复合材料.复合材料学报,2006, 23(4):106~111
[20]马一平.常温可逆温致变色水泥的制备及其智能调温效果研究.功能材料,2006,37(7):1076~1077
[21]武振羽,王瑞芝.带有可变色染料的胶黏剂在服装上的应用.河北化工,,1999,(1):24~26
[22]李景伟.热敏防伪在烟标印刷中的应用.今日印刷,2006,(8):84~86
[23]邓宗武,汪莲艳.一种热敏变色材料及其制法和用途.中国,发明专利,200910034527.5,2010.8~9
[24]安粒,李仲晓.一种不可逆变色喷墨墨水体系的研究.中国印刷与包装研究,2009, 6(1):40~46
[25]刘正堂.示温涂料的应用与发展.精细与专用化学品,2004,12(21):1~6
[26]张澍声.可逆热致变色材料.染料工业,2002,39(6):16~18
[27] Jaw H.C., Mooney M.A., Novinson T. et al. Optical Properties of theThermochromic Compounds Ag2HgI4 and Cu2HgI4. Inorg. Chem., 1987, 26(9): 1387~1392
[28]张引莉.Schiff碱及其配合物应用研究及进展.化工时刊,2008,22(5):56~60
[29] Bloomquist D.R., Willett R.D. Thermochromic Phase Transition in Transition Metal Salts. Coord. Chem. Rev., 1982, 47(2): 125~154
[30]唐紫蓉,张燮.可逆有机热变色材料.华东地质学院学报,2002,25(1):50~54
[31]庞冬梅,志伟,王雷.热致变色液晶材料在防伪包装领域的应用.包装工程,2006,27(6):124~125
[32] Seredyuk M., B. Gaspar A., Ksenofontov V. et al. Room Temperature Operational Thermochromic Liquid Crystals. Chem. Mat., 2006, 10(18): 2513~2519
[33]李天文,刘鸿生.变色材料的研究与应用.现代化工,2004,24(2):62~64
[34] Dufresne G., Bouchard J., Belletete M. Thermochromic and Solvatochromic Conjugated Polymers by Design. Macromolecules, 2000, 33: 8252~8257
[35] Seeboth A., Kriwanek J., Patzak A. et al. Chromogenic Polymers Gels for Reversible Transparency and Color Control with Temperature at a Constant Volume. Polym. Adv. Technol., 2002, 13: 507~512
[36] Goncalves V.C., Balogh D.T. Synthesis and Characterization of a Dye-functionalized Polythiophene with Diverent Chromic Properties. Eur. Polym. J., 2006, 42: 3303~3310
[37] Seeboth A., L?tzsch D., Potechius E. et al. Thermochromic Effects of Leuco dyes Studied in Polypropylene. Chin. J. Polym. Sci., 2006, 24(4): 363~368
[38] Baron M.G., Elie M. Temperature Sensing Using Reversible Thermochromic Polymeric Films. Sens. Actuator B-Chem., 2003, (90): 271~275
[39] Srivastava J., Alam S., Mathur G.N. Synthesis of Polyacrylic Acid Based Thermochromic Polymers. Smart Mater. Struct., 2003, 5062: 111~115
[40] Giovana G.N., Geraldo R.F., Jose Luiz B.S. et al. The First Thermochromic Vanadium (IV) alkoxide System. Inorg. Chem., 2005, (8): 83~88
[41] Carmona.N., Herrero-Hernandez.E., Llopis.J. et al. Novel Sol–Gel ReversibleThermochromic Materials for Environmental Sensors. J. Sol-Gel Sci. Technol., 2008(47): 31~37
[42] Nakagawa N., Yamada T., Murata M. et al. Thermochromic Triangular [MCo2] (M=Rh, Ir, Ru) Clusters Containing a Planar Metalladithiolene Ring inη3 Coordination. Inorg. Chem., 2006, 45(1): 14~16
[43] Day J.H. Thermochromism of Inorganic Compounds. Chem. Rev., 1968, 68(6): 649~658
[44] Donia A.M., EI-Boraey H.A. Reversible and Irreversible Thermochromism of some Schiff Base Metal Complexes. Transit. Met. Chem., 1993, 18: 315~31
[45]吴宝龙,吴赞敏,冯文昭.有机热敏变色材料及应用.济南纺织化纤科技,2008,(1):22~27
[46]刘瑞蓝,王答琪,赵富中.光(热)致变色剂一单和双吲哚啉螺苯并叱喃.有机化学,1987,2:123~127
[47]钱鹰,林保平,孙岳明等.有机敏感变色功能材料的研究.功能材料,2002,33(6):573~577
[48]徐汉红,朱传方.席夫碱及其络合物的可逆热致变色材料.化学通报,2000,(8):15~20
[49]梁小蕊,张勇,江炎兰.几种席夫碱衍生物的室温固相合成及可逆热致变色研究.热加工工艺技术与材料研究,2010,(2):69~72
[50] Patel R.G., Patel M.P., Patel R.G. 3,6-Disubtituted Fluorans Containing 4(3H)-quinazolinon-3-yl, Diethyl amino Groups and Their Application in Reversible Thermochromic Materials. Dyes Pigment., 2005, 66: 7~13
[51]于永,高艳阳.三芳甲烷苯酞类可逆热致变色材料.化工技术与开发,2006,35(10):26~29
[52]郝志峰,杨阳,余坚.甲酚红-硼酸体系可逆热致变色颜料的研究.精细化工,2004,21(4):241~248
[53]褚衡,黄光斗,李纯清.以荧烷为变色剂的示温材料研究.湖北工学院学报,1999,14(1):71~74
[54] Tang H., White M.A. Combinatorial Approaches to Investigations of Thermochromic Materials. Symp.Proc., 2009, 1159: 6~10
[55]白木,周洁.防伪技术及材料简介.信息记录材料,2003,4(2):60~63
[56]梅约,江增.可逆型示温涂料的研制.涂料工业,2000,(3):13~16
[57]孙文秀,张琳,葛飞等.热致可逆变色涂料的发展.现代涂料与涂装,2009,12(3):24~27
[58]李文戈,朱昌中,王文芬等.可逆热致变色材料.功能材料,1997,28(4):337~341
[59]李杨,陈洪敏,熊庆荣.不可逆示温涂料的发展及应用.技术进展,2010,25(5):16~19
[60]陈立军,沈慧芳,黄洪等.示温涂料的研究现状和发展趋势.热固性树脂,2004,19(4):36~40
[61]梅约,方珑文,徐利昆.单变色不可逆示温涂料的研制.涂料工业,2002,(5):15~19
[62]刘正堂,郭家振,张新岐.高温多变色不可逆示温涂料的研制.现代涂料与涂装,2000,(1):9~12
[63] Rougeau L., Picq D., Rastello M. et al . New Irreversible Thermochromic Polydiacetylenes. Tetrahedron, 2008, 64:9430~9436
[64]黄翠华,徐伟箭.荧光高分子的应用研究进展.应用化工,2001,30 (1) :9~12.
[65]周弟,朱秀林,胡丽华等.荧光高分子材料研究进展.化学工程师,2007,(7):39~41
[66]马居良,倪惠琼,章小兵.稀土/高分子光致发光材料的研究现状和展望.安徽化工,2007,33(1):8~11
[67]杨海峰,曹锦荣,王则民等.铕、铽的苯甲酸类配合物的荧光性质.上海师范大学学报(自然科学版),1997,26(3):33~39
[68]苏文斌,谷学新,邹洪.稀土元素发光特性及其应用.化学研究,2001,12 (4):55~59
[69]赵曙辉,李文刚,刘军等.稀土配合物Eu(TTA)3Phen掺杂的PMMA树脂的制备及其发光性能研究.化工新型材料,2003,31(4):16~18
[70] Hu X.X., Li P.H., Wu S.L. et al. Synthesis and Characterization of Fluorescent Copolymer Containing Rare Earth Metal Complex and Its Interaction with DNA. J. Polym. Sci. Pol. Chem., 2010, 48: 5961~5967
[71]王振华,王佩璋.聚苯乙烯/稀土复合发光材料的制备及其性能研究.中国塑料,2009,23(1):47~50
[72] Liu D, Yu H, Wang Z.G. et al. Synthesis and Fluorescence Properties of Novel 1, 10-phenanthroline-functionalized Polyaryletherketone and Its Rare Earth Complexes. Polym. Int., 2010, 59: 937~944
[73]田君,尹敬群.稀土紫外荧光防伪油墨的制备.精细化工,1999,16(2):31~32
[74] Maclaren D.C., White M.A. Design Rules for Reversible Thermochromic Mixtures. J. Mater. Sci., 2005, 40: 669~676
[75] Zhu C.F., Wu A.B. Studies on the Synthesis and Thermochromic Properties of Crystal Violet Lactone and Its Reversible Thermochromic Complexes. Thermochim. Acta, 2005, 425: 7~12
[76]刘军,赵曙辉,李文刚等.结晶紫内酯可逆的DSC热变色复配物研究.印染助剂,2003,20(6):39~41
[77]张乐显.可逆热致变色材料的制备及其在防伪领域的应用研究:[硕士学位论文]。武汉市:华中科技大学图书馆,2009.
[78]曹华,王殿华,曹园.改变涂布工艺的五个主要趋势.印后加工,2002,(196):56~58
[79]修澄.电化铝烫印原理及工艺条件.中国包装工业,2003,(113):56~57
[80]王敏.烫印的原理与工艺.网印工业,2008,(3):38~39
[81]魏风军.纸盒的烫印工艺及其影响因素分析.专题报道,2009,(2):48~50