CN101417564A - 具有双变色图文的防伪薄膜及其制备方法 - Google Patents

具有双变色图文的防伪薄膜及其制备方法 Download PDF

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CN101417564A
CN101417564A CNA2008102016634A CN200810201663A CN101417564A CN 101417564 A CN101417564 A CN 101417564A CN A2008102016634 A CNA2008102016634 A CN A2008102016634A CN 200810201663 A CN200810201663 A CN 200810201663A CN 101417564 A CN101417564 A CN 101417564A
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徐良衡
董兰新
高芸
张智喜
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Shanghai Tianchen micro nano technology Co., Ltd
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Abstract

本发明提供了一种具有双变色图文的防伪薄膜及其制备方法,制备方法,包括如下步骤:(1)将含有手性结构的可聚合液晶材料与光敏引发剂混合,刮涂于基材膜上,然后烘干;(2)将步骤(1)的产物,采用紫外灯定位局部曝光,然后烘干,再通过紫外曝光,得到具有双变色图文的防伪薄膜。采用本发明的方法制备方法得到的薄膜,具有双变色图文,比较典型的图文是垂直观察时呈现红绿图像,而倾斜一定的角度后,原来的红色变色绿色,绿色变为蓝色,变色明显,容易识别,实用方便,便于推广应用。

Description

具有双变色图文的防伪薄膜及其制备方法
技术领域
本专利涉及一种防伪薄膜及其制备方法,具体涉及一种具有双变色图文的防伪薄膜及其制备方法。
背景技术
随着商品经济的日趋发展,出现了众多针对各种领域内名优企业品牌产品的假冒、仿制,经济损失严重,社会危害极大,使得防伪技术引起了人们的普遍重视。能够产生光角变色效果的材料由于易于大众的识别而得到了迅速发展,在防伪和装饰材料领域得到了广泛应用。
材料的光角变色效果可以通过形成材料的间歇层状结构而获得,将交替的金属和陶瓷片共挤压得到的薄层就具有这种效果(Dobrowolski,J.A.;Ho,F.C.and Waldorf.A.,Applied Optics,1989,28,P14),但这种材料造价较高,实用不便。
此外,具有光的选择反射性的胆甾型液晶在以前被考虑用作光学保密设施,如GB 1387398所披露的技术,但是小分子的胆甾型液晶在应用上却有一定的局限性。由于小分子胆甾型液晶易于流动,在应用上必须将它们封装起来,夹在玻璃盒中,或者制成微胶囊或别的结构。而US6410130中提到的将可聚合胆甾型液晶溶液通过转移辊涂布于基材膜上,经烘道除去溶剂后UV固化形成具有光角变色的薄膜,或将其粉碎制成颜料。但是,该技术存在的一个缺陷是光角变色图案的实现是将由该专利得到的变色颜料添加到连接料(或树脂)中制成油墨印刷得到的,由于连接料的存在降低了变色颜料的浓度,使得变色效果不够明显,颜色不够艳丽。
发明内容
本发明的目的是提供一种具有双变色图文的防伪薄膜及其制备方法,以克服现有技术存在的上述缺陷。
本发明的具有双变色图文的防伪薄膜的制备方法,包括如下步骤:
(1)将含有手性结构的可聚合液晶材料与光敏引发剂混合,加热至80~120℃,刮涂于基材膜上,控制涂膜厚度为2~15μm,然后烘干,可置于80~120℃温度下0.5~2.5分钟,此时,垂直观察时呈现一特定的颜色,如红色,倾斜一定的角度变为绿色;
(2)然后,将步骤(1)的产物,采用紫外灯定位局部曝光,曝光时间为5~30秒钟,曝光能量为1.5~15mw/cm2,使得经过紫外曝光部位的液晶材料聚合,结构固定下来,然后烘干,可置于80~120温度下0.5~2.5分钟,使得未经过紫外曝光的液晶材料呈现与原来不同的颜色,如绿色,倾斜一定的角度变为蓝色,再通过紫外曝光,曝光时间为5~30秒钟,曝光能量为1.5~15mw/cm2,将该颜色固定下来,得到具有双变色图文的防伪薄膜;
所说的含有手性结构的可聚合液晶材料的为胆甾相硅氧烷液晶,其化学结构通式如下:[RY1 pY2 qSiO]m
其中,R是C1—C10的烷基;
Y1是含有介晶基元的烷基或链烯基;
Y2是含有至少一个可聚合基团和至少一个二价环基的有机基团;
P和q为大于0小于1的正数,p+q=1;m为3~10的整数。
含有手性结构的可聚合液晶材料可采用市售的产品,如采用瓦克化学公司牌号为CC3767或CC3939的产品,CC3767和CC393均为胆甾相硅氧烷液晶,其区别在于:两者介晶基元在材料中所占的比例不同,即两者的p值不同。
所说的光敏引发剂选自二苯甲酮、过氧化苯甲酰、偶氮二异丁腈、2-羟基-甲基苯基丙烷-1-酮、1-羟基环己基苯基甲酮或2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮中的一种以上,重量用量为含有手性结构的可聚合液晶材料的2~10%;
所说的基材膜选自聚碳酸酯、聚酯或聚丙烯,优选聚酯膜,或者是涂布了聚酰亚胺类液晶取向剂或聚乙烯醇等处理了的基材膜;
紫外光源优选采用300~2000W汞氙灯,280nm~350nm处的强度为1.5~15mw/cm2
含有手性结构的可聚合液晶材料经过排列取向后,含有一种独特的超级螺旋结构,可体现出类似圆偏振光的选择反射性,可选择性反射特定波长的光,宏观表现为光角变色效果,即当改变观察角度时,会从一个色相转变为另一个色相。
采用本发明的方法制备方法得到的薄膜,具有双变色图文,比较典型的图文是垂直观察时呈现红绿图像,而倾斜一定的角度后,原来的红色变色绿色,绿色变为蓝色,变色明显,容易识别,实用方便,便于推广应用。
附图说明
图1为石英玻璃罩结构。
具体实施方式
图1为石英玻璃罩结构示意图,所说的紫外灯定位局部曝光,是指在紫外灯的外面有一个石英玻璃罩,该石英玻璃罩的一部分设有镀铝层,为不透光区域1,而另一部分则为不镀铝透光区域2,透光区域2可以设计成特定的图文,基材膜在涂布可聚合液晶材料后经过此石英玻璃罩实现定位局部曝光,如图1所示。亦或将印刷有遮盖层图案的复合膜与涂布液晶材料的基材膜覆合,由复合膜的一侧进行UV曝光,则透光部位被UV固化,而有遮盖层图案的部位未经曝光,从而实现定位局部曝光。
实施例1
含有手性结构的可聚合液晶材料为胆甾相硅氧烷液晶,可采用的瓦克化学公司的CC3939和CC3767。
将7.0克CC3767和3.0克CC3939及0.4克2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮混合均匀,加热至85℃用刮刀涂布于PET聚酯膜上,涂膜厚度为5μm,通过红外烘道,烘道温度设定为85℃,在烘道内停留60秒钟,用800W的汞氙灯,外套如图1所示的局部透光的石英玻璃罩,透光部位设定为文字“TECHSUN”)定位局部曝光10秒钟,曝光能量为3mw/cm2,再进入设定温度为105℃的烘道停留60秒钟,再用800W的汞氙灯整体曝光10秒钟,由此得到了双变色效果的图文(文字“TECHSUN”垂直观察为红色,倾斜45°观察为绿色,而其余部分垂直观察为绿色,倾斜45°观察为蓝色)。
采用透射光谱法进行检测,结果如下:
Figure A200810201663D00071
实施例2
将7.0克CC3767和3.0克CC3939及1.0克2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮混合均匀,加热至85℃用刮刀涂布于PET聚酯膜上,涂膜厚度为12μm,通过红外烘道,烘道温度设定为85℃,在烘道内停留60秒钟,与印刷有黑色“TECHSUN”的PET复合膜覆合,从PET复合膜一侧用800W的汞氙灯曝光10秒钟,曝光能量为3mw/cm2,揭去PET复合膜,再进入设定温度为105℃的烘道停留60秒钟,再用800W的汞氙灯整体曝光10秒钟,由此得到了双变色效果的图文(文字“TECHSUN”垂直观察为绿色,倾斜45°观察为蓝色,而其余部分垂直观察为红色,倾斜45°观察为绿色)。
Figure A200810201663D00081
实施例3
将10.0克CC3767及0.2克2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮混合均匀,加热至85℃用刮刀涂布于PET聚酯膜上,涂膜厚度为8μm,通过红外烘道,烘道温度设定为105℃,在烘道内停留60秒钟,与印刷有黑色“TECHSUN”的PET复合膜覆合,从PET复合膜一侧用800W的汞氙灯曝光10秒钟,曝光能量为3mw/cm2,揭去PET复合膜,再进入设定温度为120℃的烘道停留60秒钟,再用800W的汞氙灯整体曝光10秒钟,由此得到了双变色效果的图文(文字“TECHSUN”垂直观察为绿色,倾斜45°观察为蓝色,而其余部分垂直观察为红色,倾斜45°观察为绿色)。
Figure A200810201663D00082

Claims (9)

1.具有双变色图文的防伪薄膜的制备方法,其特征在于,包括如下步骤:
(1)将含有手性结构的可聚合液晶材料与光敏引发剂混合,刮涂于基材膜上,然后烘干;
(2)然后,将步骤(1)的产物,采用紫外灯定位局部曝光,然后烘干,再通过紫外曝光,得到具有双变色图文的防伪薄膜;
所说的含有手性结构的可聚合液晶材料为胆甾相硅氧烷液晶。
2.根据权利要求1所述的方法,其特征在于,所说的光敏引发剂选自二苯甲酮、过氧化苯甲酰、偶氮二异丁腈、2-羟基-甲基苯基丙烷-1-酮、1-羟基环己基苯基甲酮或2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮中的一种以上。
3.根据权利要求2所述的方法,其特征在于,光敏引发剂重量用量为含有手性结构的可聚合液晶材料的2~10%。
4.根据权利要求1所述的方法,其特征在于,所说的基材膜选自聚碳酸酯、聚酯或聚丙烯。
5.根据权利要求1所述的方法,其特征在于,所说的基材膜是涂布了聚酰亚胺类液晶取向剂或聚乙烯醇处理了的基材膜。
6.根据权利要求1所述的方法,其特征在于,将含有手性结构的可聚合液晶材料与光敏引发剂混合,加热至80~120℃,刮涂于基材膜上。
7.根据权利要求6所述的方法,其特征在于,控制涂膜厚度为2~15μm。
8.根据权利要求1所述的方法,其特征在于,将步骤(1)的产物,采用紫外灯定位局部曝光,曝光时间为5~30秒钟,曝光能量为1.5~15mw/cm2,然后置于80~120温度下0.5~2.5分钟,再通过紫外曝光,曝光时间为5~30秒钟,曝光能量为1.5~15mw/cm2,得到具有双变色图文的防伪薄膜。
9.根据权利要求1~8任一项所述的方法制备的具有双变色图文的防伪薄膜。
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CN103249810A (zh) * 2010-12-07 2013-08-14 锡克拜控股有限公司 基于手性液晶前体的复合标记物
US8951438B2 (en) 2010-12-07 2015-02-10 Sicpa Hòlding SA Simplified control of color shifting properties of a chiral liquid crystal polymer
CN112339464A (zh) * 2020-10-30 2021-02-09 河北师范大学 一种利用光照在铜箔表面产生图文的方法

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TWI506126B (zh) * 2010-12-07 2015-11-01 Sicpa Holding Sa 對於手性液晶聚合物的顏色偏移特性之簡化控制
CN103249810B (zh) * 2010-12-07 2016-06-15 锡克拜控股有限公司 基于手性液晶前体的复合标记物
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