可逆温变转色UV油墨及其变色特性
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摘要
目的制备环保、适用范围广的温变转色防伪油墨。方法利用隐色染料(热敏黑)、显色剂(双酚A)及溶剂(十四醇)组成可逆温变转色复配物,然后用原位聚合法对复配物进行微胶囊包覆,最后将微胶囊加入UV连接料体系中制成可逆温变转色UV油墨,分析油墨的色度学特性。结果当乳化转速为16 000 r/min、p H值为2~3、乳化温度为45℃、乳化时间为30~40 min时,微胶囊粒径较小,显色效果较好。对该可逆温变转色UV油墨样品进行CIE-Lab色度学特性分析,在整个加热/冷却循环后,温变转色油墨又回到初始明度值,油墨样品明度发生滞后现象,整个过程中样品的明度值形成一个闭环的回路。结论该法制备的可逆温变转色油墨具有检测方便、变色效果明显等优点,在包装防伪印刷中具有广阔的应用前景。
The work aims to prepare the environmentally-friendly thermo-chromic anti-counterfeit ink with extensive application scope. The reversible thermo-chromatic compound was prepared with leuco dye(thermosensitive black), developer(Bisphenol A) and solvent(tetradecyl alcohol), and then the microcapsule was covered through in-situ polymerization. Finally, the microcapsules were added to UV system of binders to prepare the reversible thermo-chromic UV inks and analyze the colorimetric properties of ink. The microcapsule grain size was smaller and the color developing effect was better when the emulsification speed was 16 000 r/min, p H value of 2~3, emulsification temperature of 45 ℃ and emulsification time of 30~40 min. The CIE-Lab colorimetric properties of the reversible thermo-chromatic UV ink samples were analyzed. After the whole heating/cooling circle, the lightness(L*) of the ink was changed back to the original value and the lightness change of the ink was delayed. In the whole process, the lightness values of samples were formed as a closed loop. The reversible thermo-chromic ink prepared in such method characterized by convenient detection and significant color change effect, etc. has broad application prospects.
The work aims to prepare the environmentally-friendly thermo-chromic anti-counterfeit ink with extensive application scope. The reversible thermo-chromatic compound was prepared with leuco dye(thermosensitive black), developer(Bisphenol A) and solvent(tetradecyl alcohol), and then the microcapsule was covered through in-situ polymerization. Finally, the microcapsules were added to UV system of binders to prepare the reversible thermo-chromic UV inks and analyze the colorimetric properties of ink. The microcapsule grain size was smaller and the color developing effect was better when the emulsification speed was 16 000 r/min, p H value of 2~3, emulsification temperature of 45 ℃ and emulsification time of 30~40 min. The CIE-Lab colorimetric properties of the reversible thermo-chromatic UV ink samples were analyzed. After the whole heating/cooling circle, the lightness(L*) of the ink was changed back to the original value and the lightness change of the ink was delayed. In the whole process, the lightness values of samples were formed as a closed loop. The reversible thermo-chromic ink prepared in such method characterized by convenient detection and significant color change effect, etc. has broad application prospects.
引文
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[19]刘浩学.CIE均匀颜色空间与色差公式的应用[J].北京印刷学院学报,2003(3):3—8.
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[2]魏娜,孙诚,郝晓秀,等.可逆温致变色胶印油墨的制备及其印刷性能[J].包装工程,2010,31(17):145—147.
[3]WEI Na,SUN Cheng,HAO Xiao-xiu,et al.Preparation and Printing Performance of Reversible Thermochromism Offset Printing Ink[J].Packaging Engineering,2010,31(17):145—147.
[4]GU Y,CAO W,ZHU L,et al.Polymer Mortar Assisted Self-assembly of Nanocrystalline Polydiacetylene Bricks Showing Reversible Thermochromism[J].Macromolecules,2008,41(7):2299—2303.
[5]LEE C H,KIM J S,PARK S Y,et al.A Polydiacetylene Supramolecular System that Displays Reversible Thermochromism[J].Chemistry Letters,2007,36(5):682—683.
[6]GUO H,ZHANG J,PORTER D,et al.Ultrafast and Reversible Thermochromism of a Conjugated Polymer Material Based on the Assembly of Peptide Amphiphiles[J].Chemical Science,2014,5(11):4189—4195.
[7]TANIOKU C,MATSUKAWA K,MATSUMOTO A.Thermochromism and Structural Change in Polydiacetylenes Including Carboxy and 4-carboxyphenyl Groups as the Intermolecular Hydrogen Bond Linkages in the Side Chain[J].ACS Applied Materials&Interfaces,2013,5(3):940—948.
[8]BAO S,FEI B,LI J,et al.Reversible Thermochromic Switching of Fluorescent Poly(Vinylidene Fluoride)Composite Containing Bis(Benzoxazolyl)Stilbene Dye[J].Dyes and Pigments,2013,99(1):99—104.
[9]BAEK J,JOUNG J F,LEE S,et al.Origin of the Reversible Thermochromic Properties of Polydiacetylenes Revealed by Ultrafast Spectroscopy[J].The Journal of Physical Chemistry Letters,2016,7(2):259—265.
[10]韩玄武.UV油墨光引发剂与颜料匹配的研究[J].包装工程,2009,30(4):48—50.
[11]HAN Xuan-wu.Research on Matching between Photoinitiator and Pigment of UV Ink[J].Packaging Engineering,2009,30(4):48—50.
[12]MENDOZA K L,ORTEGA A,KIM N S.Optimization of UV LED-curable Ink for Reverse-offset Rollto-Plate(RO-R2P)Printing[J].Journal of Electronic Materials,2015,44(3):784—791.
[13]陈文,杨双明,彭学军,等.UV自由基固化油墨的研究[J].包装工程,2005,26(2):26—28.
[14]CHEN Wen,YANG Shuang-ming,PENG Xue-jun,et al.Study on UV Free Radical Curable Ink[J].Packaging Engineering,2005,26(2):26—28.
[15]杨耀,杨成克,吕彩虹,等.水性UV油墨的制备及表征[J].包装工程,2014,35(1):55—60.
[16]YANG Yao,YANG Cheng-ke,LYU Cai-hong,et al.Preparation and Characterization of Water-Borne UV-Curable Ink[J].Packaging Engineering,2014,35(1):55—60.
[17]张鹏飞,王建清,王玉峰,等.UV油墨光引发剂在食品包装材料中的残留分析[J].包装工程,2016,37(15):89—94.
[18]ZHANG Peng-fei,WANG Jian-qing,WANG Yu-feng,et al.Residues of UV Ink Photoinitiators in Food Packaging Materials[J].Packaging Engineering,2016,37(15):89—94.
[19]刘浩学.CIE均匀颜色空间与色差公式的应用[J].北京印刷学院学报,2003(3):3—8.
[20]LIU Hao-xue.The Main Parameter Effecting UV Curing Coatings Dryness Properties:the Lowest Effective Curing Energy[J].Journal of Beijing Institute of Graphic Communication,2003(3):3—8.
[21]MACLAREN D C,WHITE M A.Competition between Dye-Developer and Solvent-Developer Interactions in a Reversible Thermochromic System[J].Journal of Materials Chemistry,2003,13(7):1701—1704.