CN100586740C - 一种防伪薄膜及其制备方法 - Google Patents

一种防伪薄膜及其制备方法 Download PDF

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CN100586740C
CN100586740C CN200810040893A CN200810040893A CN100586740C CN 100586740 C CN100586740 C CN 100586740C CN 200810040893 A CN200810040893 A CN 200810040893A CN 200810040893 A CN200810040893 A CN 200810040893A CN 100586740 C CN100586740 C CN 100586740C
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徐良衡
杨凯
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Shanghai Tianchen micro nano technology Co., Ltd
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Shanghai Techsun Anti Counterfeiting Technology Holding Co Ltd
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Abstract

本发明提供了一种防伪薄膜及其制备方法，所述防伪薄膜包括依次复合的定向回归反射层、光角变色信息层、反射层和支撑层，支撑层为高分子树脂材料，反射层为纳米级厚度的反射率材料，光角变色信息层为具有螺旋结构的手性高分子光角变色材料或纤维素光角变色材料，具有螺旋结构的手性高分子光角变色材料是将手性化合物与具有官能团的化合物的缩合产物，纤维素光角变色材料由纤维素衍生物和可聚单体组成，定向回归反射层为光学材制成的球状物，并嵌入支撑层中，定向回归反射层材料的折射率为1.9～1.93。本发明的防伪薄膜，防伪特征独特、透明、技术壁垒高、防伪力度大，可被广泛应用于各类高档商品、有价证券、证件证卡等领域。

Description

一种防伪薄膜及其制备方法
技术领域
本发明涉及一种应用于防伪领域的薄膜及其制备方法，其具有在定向回归反射条件下的视角变色特性。
技术背景
九十年代初，国外出现一种光角变色防伪产品，即随着观察角度的变化，图案会发生显著的色彩变化。此类产品具有技术领先、易于辨别、安全性高、鉴别方便等特点，逐渐成为被全球各国公共安全防伪的权威机构广泛采用的技术之一。目前已成功地应用于各国货币、证件等众多领域(如人民币、美元、欧元、国外护照、驾驶执照)。但传统光角变色防伪产品，如光变油墨OVI、光变全息膜等，其材料的光变效果均通过颜料干涉、光学镀膜或激光蚀刻技术实现，因而产品存在材料不可透视、工艺路线长、多技术复合难度大以及产品价格昂贵等许多缺陷，大大局限了光角变色防伪产品的应用范围。
新型光角变色材料利用其材料内部具有的螺旋结构能够选择性地反射特定波长的光，宏观表现为光角变色效果，这类光角变色材料为透明性材料。目前该类光角变色材料有手性高分子光角变色材料(如中国专利03114913.8)、纤维素光角变色材料(如中国专利02136974.7)等；
定向回归反射技术属一种物理光学技术，最初由二十世纪五十年代年美国华裔科学家董祺芳博士研发成功。主要技术原理为：当一束平行光线从一定的角度照射在具有特殊结构的表面上时，相当大的一部分光线呈平行光束向光源的入射方向反射。光线通过入射-折射-反射过程，形成回归定向反射特性，产生独特的反光效果。随着汽车工业与道路交通的发展，基于该技术原理的系列反光材料得以广泛应用，有关反光材料的结构设计、生产方法等方面的专利技术也不断推陈出新，如美国专利US4721649。
但是，上述几种光角变色防伪技术效果比较类同、缺少技术隐蔽性，而定向回归反射技术的应用目前也仅局限于道路交通等领域，因此，本发明研究将定向回归反射技术与光角变色技术相结合，开发具有独特视觉效果的新型防伪薄膜，以满足高端防伪领域的要求。
发明内容
本发明的目的是提供一种防伪薄膜及其制备方法，以克服现有技术所存在的效果类同、缺少技术隐蔽性等缺陷，满足有关领域发展的需要。
本发明所述的防伪薄膜，包括依次复合的定向回归反射层、光角变色信息层、反射层和支撑层；
所述支撑层为高分子树脂材料，并具有透光率高、耐候性好和韧性高的特点，优选的高分子树脂材料为聚氨酯、酚醛树脂或聚丙烯酸树脂等；
所述反射层为纳米级厚度(20～100纳米)的具有高反射率材料，优选的为ZnO、SnO、ZnS或TiO2等；
所述光角变色信息层为具有螺旋结构的手性高分子光角变色材料或纤维素光角变色材料，所述具有螺旋结构的手性高分子光角变色材料是将手性化合物与具有官能团的化合物通过缩合聚合法聚合而成，所述的官能团如羟基、羧基或氨基；
所述手性化合物为异山梨醇、D-樟脑酸、2，3-二羟基丁烷或3-甲基己二酸等中的一种以上；
所述具有官能团的化合物为对苯二酚、三甘醇、对羟基苯甲酸、乙二醇、乙二酸、对苯二甲酸等中的一种或几种，或为苯酚、脂肪酸、甲醛等中的一种或几种；
所述具有螺旋结构的手性高分子光角变色材料的组成及其制备方法，在中国专利申请号03114913.8中有详细的描述；
所述纤维素光角变色材料由纤维素衍生物和可聚单体组成；
所述纤维素衍生物的结构通式为：
Cell-O-R或
Figure C20081004089300051
式中Cell为纤维素，R为C1～C20的烷基或苯基的衍生物；
所述可聚单体包括丙烯酸酯、甲基丙烯酸酯、乙烯基醚、环氧树脂或顺丁基二酸酯中的一种或几种；
所述纤维素光角变色材料及其制备方法在中国专利申请号02136974.7中有详细的描述；
所述定向回归反射层为具有高折射率光学材制成的球状物，优选玻璃或聚碳酸酯等，同时所述定向回归反射层呈球状嵌入支撑层中；
发明人经过大量的试验发现，所述的定向回归反射层材料的折射率，对定向回归反射特性具有重要的影响，因此，本发明的定向回归反射层材料的折射率为1.9～1.93，使其只有在一定光学条件下才显现定向回归反射特性，并通过与所述的光角变色材料相结合，使得在肉眼观察下所述防伪薄膜中的光角变色信息被隐藏，只有通过特定的光学条件下观察才显现其中隐藏的光角变色信息。在专用识别器下观察，防伪薄膜表面图文消失，显现隐藏其中的光角变色图文，转动观察角度，该图文的颜色将发生转变，如由绿变红。
所述专用识别器提供定向回归反射光学条件，该专用识别器的结构为现有技术，如美国专利US6019287中所述。
本发明所述防伪薄膜的制备方法包括如下步骤：
(1)在基膜上涂布具有粘结力的离型材料，然后在离型层上植入定向回归反射层的材料，100～130℃烘干，烘干时间为2～3分钟；
所述的基膜选自透明高分子聚酯薄膜材料，优选的为聚对苯二甲酸己二醇酯、聚碳酸酯、聚苯乙烯或聚氯乙烯等；
所述的离型材料优选液态石蜡；
(2)然后在定向回归反射层上涂布或印刷光角变色信息层，然后高真空气相沉积反射层材料，再在反射层上涂布支撑层材料，100～120℃烘干，烘干时间为3～5分钟，然后去除基膜和离型层，获得所说的防伪薄膜；
所说的涂布可选用网纹涂布、热熔涂布、刮刀涂布等涂布方式或通过凹版、柔版、丝网等印刷方式印刷/涂布光角变色信息层。
采用上述方法获得的防伪薄膜，由于所述防伪薄膜的特殊的定向回归反射光学结构，如采用满版涂布光角变色材料的工艺，将所述防伪薄膜弯曲形成弧度(30～360度)时，在定向回归反射光学条件下观察，薄膜表面图文消失可显现独特的彩虹效果。
所述的满版涂布的光角变色材料可选用中国专利申请号03114913.8中具有螺旋结构的手性高分子光角变色材料或中国专利申请号02136974.7纤维素光角变色材料。
本发明利用定向回归反射的基本原理，以及特殊的光学结构结合新型光角变色材料，获得一种透明的具有独特视觉效果的防伪薄膜。其防伪特征独特、透明、技术壁垒高、防伪力度大，可被广泛应用于各类高档商品、有价证券、证件证卡等领域。
附图说明
图1为防伪薄膜结构示意图。
图2为防伪薄膜效果图。
图3为将所述防伪薄膜弯曲形成弧度时的彩虹效果。
具体实施方式
参见图1，本发明所述的防伪薄膜，包括依次复合的定向回归反射层1、光角变色信息层2、反射层3和支撑层4；
所述定向回归反射层1为具有高折射率光学材制成的球状物，优选玻璃或聚碳酸酯等，同时所述定向回归反射层1呈球状嵌入支撑层4中，球状物直径为10～100微米。
实施例1
以PET(聚对苯二甲酸己二醇酯)为基膜，涂布液态石蜡作为离型层，然后在其上植入直径为70微米的折射率为1.9的球形玻璃材料，形成定向回归反射层，110℃烘干3分钟，再在定向回归反射层上通过丝网印刷纤维素光角变色材料，其组成及制备方法如中国专利02136974.7中实施例1所述，以形成光角变色信息层，然后高真空气相沉积反射层材料ZnO，厚度为60纳米，在再反射层上涂布聚氨酯支撑层材料，120℃烘干3分钟，拨去表面的PET(聚对苯二甲酸己二醇酯)基膜和离型层，将定向回归反射层露出，即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
通过美国专利US6019287中报道的专用识别器观察，可见如图2所示效果。
由图2可见，表面印刷有图文的防伪薄膜5，在美国专利US6019287提供的专用识别器6提供定的向回归反射光学条件观察，防伪薄膜表面图文消失，显现隐藏其中的光角变色图文，采用转动观察角度的步骤7，该图文的颜色将发生转变，如由绿变红。
所述中国专利02136974.7中实施例1中具体描述如下：
将10g纤维素(由醋酸纤维素水解得到)溶于210ml吡啶中，升温至回流，加入50ml异氰酸苯酯，回流48hr，减压蒸馏除去大部分吡啶，加入0.8L甲醇，析出固体，过滤，将滤饼溶于600ml丙酮中，再加入0.8L甲醇使产品沉淀析出，过滤，洗涤，真空干燥。得20g产品。经IR证实，纤维素微晶中的羟基基本上已经完全被酯化。
实施例2
以PET(聚对苯二甲酸己二醇酯)为基膜，涂布液态石蜡作为离型层，然后在其上植入直径为100微米的折射率为1.93的球形玻璃材料，形成定向回归反射层，100℃烘干3分钟，再在定向回归反射层上通过柔版印刷手性高分子光角变色材料，其组成及制备方法如中国专利03114913.8中实施例1所述，以形成光角变色信息层，然后高真空气相沉积反射层材料ZnS，厚度为50纳米，在再反射层上涂布聚氨酯支撑层材料，100℃烘干5分钟，，拨去表面的PET(聚对苯二甲酸己二醇酯)基膜和离型层将定向回归反射层露出，即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
通过美国专利US6019287中报道的专用识别器观察，可见如图2所示效果。
由图2可见，表面印刷有图文的防伪薄膜5，在美国专利US6019287提供的专用识别器6提供定的向回归反射光学条件观察，防伪薄膜表面图文消失，显现隐藏其中的光角变色图文，采用转动观察角度的步骤7，该图文的颜色将发生转变，如由绿变红。
所述中国专利03114913.8中实施例1中具体描述如下：
13g对羟基苯甲酸，4g对苯二甲酸，1g对苯二酚，2.5g异山梨醇，4.0g3-甲基己酸，加入反应器中，加入40ml乙酸酐，机械搅拌，氮气保护，加热至回流，体系温度为150℃，保持30min；开始蒸出水和乙酸，反应温度逐渐升高至300℃，保持30min。没有液体蒸出后，开始减压蒸馏，真空度不断升高至10mbar，保持30min。体系粘度开始加大，颜色变深，加大搅拌，保持高真空、高温30min后，反应物变为蓝色，缓慢降温，恢复常压，材料的蓝色慢慢固定下来，取出，获得产物。
实施例3
以PET(聚对苯二甲酸己二醇酯)为基膜，涂布液态石蜡作为离型层，然后在其上植入直径为60微米的折射率为1.9的球形玻璃材料，形成定向回归反射层，烘干处理后再在定向回归反射层上通过网纹涂布方式，涂布纤维素光角变色材料(如中国专利02136974.7中实施例1所述的光角变色材料)，以形成满版的光角变色层，然后高真空气相沉积反射层材料ZnS，厚度为20纳米，在再反射层上涂布聚氨酯支撑层材料，经烘干处理后拨去表面的PET(聚对苯二甲酸己二醇酯)基膜和离型层将定向回归反射层露出，即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
将上述的防伪薄膜5弯曲形成60度弧度时，在美国专利US6019287中报道的专用识别器6下观察可显现独特的彩虹效果，如图3所示。
所述中国专利02136974.7中实施例1具体描述如下：
将10g纤维素(由醋酸纤维素水解得到)溶于210ml吡啶中，升温至回流，加入50ml异氰酸苯酯，回流48hr，减压蒸馏除去大部分吡啶，加入0.8L甲醇，析出固体，过滤，将滤饼溶于600ml丙酮中，再加入0.8L甲醇使产品沉淀析出，过滤，洗涤，真空干燥。得20g产品。经IR证实，纤维素微晶中的羟基基本上已经完全被酯化。

Claims (5)

1.制备防伪薄膜的方法，其特征在于，包括如下步骤：
(1)在基膜上涂布具有粘结力的离型层材料，然后在离型层材料上植入定向回归反射层的材料，烘干；所述定向回归反射层为光学材料制成的球状物，定向回归反射层材料的折射率为1.9～1.93；
(2)然后在定向回归反射层上涂布或印刷光角变色信息层，然后高真空气相沉积反射层材料，再在反射层上涂布支撑层材料，烘干，然后去除基膜和离型层，获得所说的防伪薄膜；
所述光角变色信息层为具有螺旋结构的手性高分子光角变色材料或纤维素光角变色材料，所述具有螺旋结构的手性高分子光角变色材料是手性化合物与具有官能团的化合物的缩合产物；
所述纤维素光角变色材料由纤维素衍生物和可聚单体组成；
所述反射层为纳米级厚度的反射率材料；
所述支撑层为高分子树脂材料。
2.根据权利要求1所述的方法，其特征在于，所说的涂布选用网纹涂布、热熔涂布或刮刀涂布，或者通过凹版、柔版或丝网印刷方式。
3.根据权利要求1所述的方法，其特征在于，所述的基膜选自透明高分子聚酯薄膜材料。
4.根据权利要求3所述的方法，其特征在于，所述的基膜选自聚对苯二甲酸己二醇酯、聚碳酸酯、聚苯乙烯或聚氯乙烯。
5.根据权利要求1所述的方法，其特征在于，所述的离型层材料为液态石蜡。
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