CN101318444A - 防伪薄膜及其制备方法 - Google Patents

防伪薄膜及其制备方法 Download PDF

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CN101318444A
CN101318444A CNA2008100398085A CN200810039808A CN101318444A CN 101318444 A CN101318444 A CN 101318444A CN A2008100398085 A CNA2008100398085 A CN A2008100398085A CN 200810039808 A CN200810039808 A CN 200810039808A CN 101318444 A CN101318444 A CN 101318444A
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retroreflecting
photopolymerization
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CN100589995C (zh
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徐良衡
杨凯
葛爱敏
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Shanghai Tianchen micro nano technology Co., Ltd
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Tianchen New Technology Co Ltd Fudan Univ Shanghai
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Priority to EP08783782.9A priority patent/EP2295241B1/en
Priority to PCT/CN2008/071789 priority patent/WO2010000113A1/zh
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Abstract

本发明公开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保护层(1)、粘结层(2)、回归反射层(3)、可光聚合信息层(4)和反射层(5)，所述回归反射层(3)呈球状嵌入粘结层(2)中，可光聚合信息层(4)中刻录有随观察角度变化的图文信息。本发明的防伪薄膜，具有可视图文信息随视角转变而改变的效果，防伪效果独特，易于识别，其独特的视觉效果显著区别于激光全息、视角变色、精密印刷等防伪技术，同时该技术无需借助任何工具通过肉眼即可进行鉴别，易于广大消费者进行识别。本发明将定向回归反射技术引入防伪领域，使其具有独特的防伪特征，提高技术壁垒、加大防伪力度。

Description

防伪薄膜及其制备方法
技术领域
本发明涉及一种具有可视图文信息随视角转变而改变效果的防伪薄膜及其制备方法。
背景技术
二十世纪八、九十年代以来，假冒伪造犯罪日益成为继吸贩毒、走私、环境污染之外的又一全球公害。据权威部门统计，全世界每年因假冒伪造活动产生的经济总值达到2500亿美元。不仅名优企业产品特别受到制假分子的青睐，而且假冒犯罪活动愈渐渗透到国家经济与政治安全等特殊领域(如货币、有价证券、身份证件等)，社会危害力极大，因而各国政府都将打击假冒犯罪列为一项长期艰巨的任务。
目前被广泛使用的防伪产品主要分为两大类，一种为通过肉眼或简单的方法即可识别的如激光全息、视角变色、水印、各类印刷防伪等，这种防伪技术直观易于被消费者接受和便于推广，是一种大众化的，消费者可能独自识别真伪的防伪技术。其最大的优点是现场的快速性和直观性；但目前这类防伪技术已被广泛应用造成其仿制难度较低、技术壁垒不高、易于仿制，因此其防伪力度和防伪性能不足。另一种为需要借助工具才能识别的如紫外荧光、红外荧光、电话电码、条码、二维码等，其相对于第一类防伪技术仿制难度更高，防伪性能更好；但其需要借助专用的识别工具，还更多的依赖于消费者本身技能之外的因素作出判断，如厂家、专家、技术监督部门等。
发明内容
本发明的目的在于提供一种防伪薄膜及其制备方法，以克服现有技术存在的上述缺陷。
本发明所述的防伪薄膜包括依次复合的保护层、粘结层、回归反射层、可光聚合信息层和反射层，所述回归反射层呈球状嵌入粘结层中，可光聚合信息层中刻录有随观察角度变化的图文信息；
所述保护层1的材料为透明高分子聚酯，优选PET(聚对苯二甲酸已二醇酯)、PC(聚碳酸酯)、PP(聚苯乙烯)或PVC(聚氯乙烯)等；
所述粘结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，优选聚氨酯、酚醛树脂或聚丙烯酸树脂等；
所述回归反射层为具有高折射率光学材，优选玻璃或PC(聚碳酸酯)等；
所述可光聚合信息层的材料包括如下重量百分比的组分：
光聚单体：20％～60％
光引发剂：1％～10％
粘结剂：30％～79％
上述各个组分的百分比之和为100％。
优选的，所述可光聚合信息层的材料包括如下重量百分比的组分：
光聚单体：25％～50％
光引发剂：2％～8％
粘结剂：42％～73％
所述光聚单体选自EM210(2-苯氧基乙基丙烯酸酯)、EM2211(乙氧化1，6-已二醇二丙烯酸酯)、EM224(聚乙二醇(200)二丙烯酸酯)、APG-400(烷基多苷)或BPE-500(乙氧基化双酚A二甲基丙烯酸酯)中的一种或几种；
所述粘结剂选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲脂或丙烯酸2-乙基已基脂中的一种或几种；
所述光引发剂选自二苯甲酮、二乙基氨基二苯酮、无色结晶紫或甲苯磺酸-水合物中的一种或几种；
所述反射层为具有高反射率材料，优选AL(铝)、Ag(银)或Cr(铬)；
所述防伪薄膜的制备方法包括如下步骤：
(1)在保护层上涂布粘结层材料，然后将回归反射层材料植入粘结层，100～130℃烘干2～3分钟，再在回归反射层上涂布可光聚合信息层的材料100～150℃烘干3～5分钟，获得回归反射膜；
(2)再将上述回归反射膜的保护层1的上表面置于设有模板图文的曝光模板下，对回归反射膜进行线性偏振紫外光进行第一次曝光处理，曝光时间为0.1～0.9秒，曝光能量为30～50mJ/cm2，曝光角度为60～90°；
通过紫外光辐射，光聚单体分子沿紫外光的偏振方向发生聚合反应，借助定向回归反射膜的特殊光学结构，使得光聚单体只在与紫外光偏振方向一致方向发生聚合，从而改变其光学性能，形成与曝光模板一致的图文信息；
改变曝光模板图文和曝光角度，再对回归反射膜进行线性偏振紫外光进行第二次曝光处理，曝光时间为0.1～0.9秒，曝光能量为30～50mJ/cm2，曝光角度为15～60°，在另一角度形成不同的图文信息；然后在可光聚合信息层上高真空蒸镀反射层材料，获得本发明的防伪薄膜；
术语“曝光角度”指的是曝光光源与防伪薄膜之间的角度；
优选的，第一次曝光处理和第二次曝光处理的角度差为30～50°；
进一步，上述防伪薄膜的制备方法中，所述的曝光模板为不透光聚酯材料、金属材料或不透光玻璃等；
所述曝光模板还可采用各类透射式显示器件如TN-LCD(扭曲向列液晶显示器件)、ECB-LCD(电控双折射液晶显示器件)、PC-LCD(相变液晶显示器件)、STN-LCD(超扭曲向列液晶显示器件)或TFT-LCD(低温多晶硅液晶显示器件)等；通过改变其上的显示信息可在上述回归反射膜上制备各种类型的图文信息如：随机变换的数码等；所述随机变换的数码被大量用于各种物流管理和信息防伪中。
本发明的防伪薄膜，具有可视图文信息随视角转变而改变的效果，本发明所述的可视图文信息随视角转变而改变效果是指在某一特定角度a观察时可见图文A，转变观察角度至b后，图文A消失或可见图文B，根据工艺的不同还可实现多种角度间多种图文信息的变换。
本发明的防伪薄膜，防伪效果独特，易于识别，其独特的视觉效果显著区别于激光全息、视角变色、精密印刷等防伪技术，同时该技术无需借助任何工具通过肉眼即可进行鉴别，易于广大消费者进行识别。本发明将定向回归反射技术引入防伪领域，使其具有独特的防伪特征，提高技术壁垒、加大防伪力度。
附图说明
图1为防伪薄膜结构示意图。
图2为实施例1的第一次曝光的曝光模板。
图3为实施例1的第二次曝光的曝光模板。
图4为实施例1的产品的效果图。
图5为实施例2的产品的效果图。
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保护层1、粘结层2、回归反射层3、可光聚合信息层4和反射层5，所述回归反射层3呈球状嵌入粘结层2中，球状直径为10～100微米，可光聚合信息层4中刻录有随观察角度变化的图文信息6；
优选的，保护层1的厚度为25～50微米，粘结层2的厚度为50～70微米，可光聚合信息层4的厚度为15～30微米，反射层5厚度为60～200纳米。
实施例中，如无特别说明，组分的成分均为重量百分比。
实施例1
以PET(聚对苯二甲酸已二醇酯)薄膜为保护层1的材料，在其上涂布粘结层2材料聚氨酯，然后植入直径为70微米的折射率为2.2的球形玻璃材料，形成回归反射层3，120℃烘干2分钟，再在回归反射层3上涂布可光聚合信息层4材料，其组成成分如下：
光聚单体：EM210         25％
光引发剂：二苯甲酮      2％
粘结剂：甲基丙烯酸甲酯  45％  甲基丙烯酸   28％。
140℃烘干3分钟，成为回归反射膜；
再将上述回归反射膜的保护层面置于图2所示的不锈钢材料制成的金属曝光模板下对回归反射膜进行线性偏振紫外光进行第一曝光处理，曝光时间为0.3秒，曝光能量为50mJ/cm2，曝光角度为90°；
采用如图3所示曝光模板图文和曝光角度，再对回归反射膜进行线性偏振紫外光进行第二次曝光处理，曝光时间为0.3秒，曝光能量为50mJ/cm2，曝光角度为45°，在另一角度形成不同的图文信息；
最后在可光聚合信息层上高真空蒸镀反射层5材料AL，即形成具有可视图文信息随视角转变而改变效果的防伪薄膜，如图4所示。a图为直视时的图像，b图为转变观察角度时的图像。
保护层1的厚度为36微米，粘结层2的厚度为50微米，可光聚合信息层4的厚度为20微米，反射层5厚度为100nm，回归反射层3的球状直径为70微米。
实施例2
以PET(聚对苯二甲酸已二醇酯)薄膜为保护层材料，在其上涂布聚氨酯粘结层材料，然后植入直径为50微米的折射率为2.2的球形玻璃材料，形成回归反射层，110℃烘干3分钟，再在回归反射层上涂布可光聚合信息层材料，其组成成分如下：
光聚单体：EM210  15％   EM224  10％
光引发剂：二乙基氨基二苯酮     5％
粘结剂：甲基丙烯酸甲酯         25％
丙烯酸2-乙基已基脂             45％
140℃烘干3分钟，成为回归反射膜；
再将上述回归反射膜的保护层面置于一TFT-LCD(低温多晶硅液晶显示器件，SHARP公司牌号为LQ035Q3DH01的产品)曝光模板下对回归反射膜进行线性偏振紫外光进行第一次曝光处理，曝光时间为0.6秒，曝光能量为50mJ/cm2，曝光角度为80°；
改变LCD曝光模板的显示图文为随机数码，以及改变曝光角度，进行第二次曝光处理，曝光时间为0.6秒，曝光能量为50mJ/cm2，曝光角度为30°，在另一角度形成不同的图文信息；
最后在可光聚合信息层上高真空蒸镀反射层材料AL，即形成具有可视图文信息随视角转变而改变效果的防伪薄膜，如图5所示。
保护层1的厚度为36微米，粘结层2的厚度为40微米，可光聚合信息层4的厚度为25微米，反射层5厚度为100nm，回归反射层3的球状直径为50微米。c图和d图分别为不同变观察角度时的图像。
实施例3
以PET(聚对苯二甲酸已二醇酯)薄膜为保护层材料，在其上涂布聚氨酯粘结层材料，然后植入直径为50微米的折射率为2.2的球形玻璃材料，形成回归反射层，120℃烘干3分钟，再在回归反射层上涂布可光聚合信息层材料，其组成成分如下：
光聚单体：BPE-500  15％  EM2211  25％
光引发剂：二乙基氨基二苯酮  5％  二苯甲酮  2％
粘结剂：甲基丙烯酸甲酯  15％  甲基丙烯酸  33％  丙烯酸  5％
150℃烘干3分钟，成为回归反射膜；
再将上述回归反射膜的保护层面置于不锈钢材料的金属曝光模板下对回归反射膜进行线性偏振紫外光进行第一次曝光处理，曝光时间为0.4秒，曝光能量为40mJ/cm2，曝光角度为90°；
改变曝光模板图文和曝光角度进行第二次曝光处理；曝光时间为0.4秒，曝光能量为40mJ/cm2，曝光角度为40°，在另一角度形成不同的图文信息；
最后在可光聚合信息层上高真空蒸镀反射层5材料AL，即形成具有可视图文信息随视角转变而改变效果的防伪薄膜。
保护层1的厚度为50微米，粘结层2的厚度为40微米，可光聚合信息层4的厚度为25微米，反射层5厚度为150nm，回归反射层3的球状直径为50微米。
实施例4
以PET(聚对苯二甲酸已二醇酯)薄膜为保护层材料，在其上涂布聚氨酯粘结层材料，然后植入直径为70微米的折射率为2.2的球形玻璃材料，形成回归反射层，120℃烘干3分钟，再在回归反射层上涂布可光聚合信息层材料，其组成成分如下：
光聚单体：BPE-500   25％  EM224  15％  EM2211  10％
光引发剂：二苯甲酮  3％   甲苯磺酸-水合物   5％
粘结剂：甲基丙烯酸甲酯  15％  甲基丙烯酸  17％n  丙烯酸2-乙基已基脂  10％
130℃烘干5分钟，成为回归反射膜；
再将上述回归反射膜的保护层面置于不锈钢材料的金属曝光模板下对回归反射膜进行线性偏振紫外光进行第一次曝光处理，曝光时间为0.6秒，曝光能量为50mJ/cm2；曝光角度为90°；
改变曝光模板图文和曝光角度进行第二次曝光处理；曝光时间为0.6秒，曝光能量为50mJ/cm2；曝光角度为40°；
最后在可光聚合信息层上高真空蒸镀反射层材料AL，即形成具有可视图文信息随视角转变而改变效果的防伪薄膜。
保护层1的厚度为25微米，粘结层2的厚度为70微米，可光聚合信息层4的厚度为30微米，反射层5厚度为120nm，回归反射层3的球状直径为70微米。
实施例5
以PET(聚对苯二甲酸已二醇酯)薄膜为保护层材料，在其上涂布聚氨酯粘结层材料，然后植入直径为60微米的折射率为2.2的球形PC(聚碳酸酯)材料，形成回归反射层，120℃烘干3分钟，再在回归反射层上涂布可光聚合信息层材料，其组成成分如下：
光聚单体：EM224  15％  APG-400(烷基多苷)  15％
光引发剂：二苯甲酮  3％  无色结晶紫  5％
粘结剂：甲基丙烯酸甲酯  25％  丙烯酸  22％  丙烯酸2-乙基已基脂  15％
140℃烘干4分钟，成为回归反射膜；
再将上述回归反射膜的保护层面置于不锈钢材料的金属曝光模板下对回归反射膜进行线性偏振紫外光进行第一次曝光处理，曝光时间为0.3秒，曝光能量为50mJ/cm2，曝光角度为90°；
改变曝光模板图文和曝光角度进行第二次曝光处理；曝光时间为0.3秒，曝光能量为50mJ/cm2；曝光角度为35°；
最后在可光聚合信息层上高真空蒸镀反射层材料AL，即形成具有可视图文信息随视角转变而改变效果的防伪薄膜。
保护层1的厚度为40微米，粘结层2的厚度为70微米，可光聚合信息层4的厚度为30微米，反射层5厚度为120nm，回归反射层3的球状直径为60微米。

Claims (8)

1.防伪薄膜，其特征在于，包括依次复合的保护层(1)、粘结层(2)、回归反射层(3)、可光聚合信息层(4)和反射层(5)，所述回归反射层(3)呈球状嵌入粘结层(2)中，可光聚合信息层(4)中刻录有随观察角度变化的图文信息。
2.根据权利要求1所述的防伪薄膜，其特征在于，所述回归反射层(3)的球状直径为10～100微米，保护层(1)的厚度为25～50微米，粘结层(2)的厚度为50～70微米，可光聚合信息层(4)的厚度为15～30微米，反射层(5)厚度为60～200纳米。
3.根据权利要求1所述的防伪薄膜，其特征在于，所述保护层(1)的材料为透明高分子聚酯；
所述粘结层(2)为高分子树脂材料；
所述回归反射层(3)为玻璃或聚碳酸酯；
所述可光聚合信息层(4)的材料包括如下重量百分比的组分：
光聚单体：20％～60％
光引发剂：1％～10％
粘结剂：30％～79％
上述各个组分的百分比之和为100％；
所述光聚单体选自2-苯氧基乙基丙烯酸酯、乙氧化1，6-己二醇二丙烯酸酯、聚乙二醇(200)二丙烯酸酯、烷基多苷或乙氧基化双酚A二甲基丙烯酸酯中的一种或几种；
所述粘结剂选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲脂或丙烯酸2-乙基己基脂中的一种或几种；
所述光引发剂选自二苯甲酮、二乙基氨基二苯酮、无色结晶紫或甲苯磺酸-水合物中的一种或几种；
所述反射层(5)为铝、银或铬。
4.根据权利要求1所述的防伪薄膜，其特征在于，所述保护层(1)的材料为聚对苯二甲酸己二醇酯、聚碳酸酯、聚苯乙烯或聚氯乙烯；
所述粘结层(2)为聚氨酯、酚醛树脂或聚丙烯酸树脂。
5.根据权利要求1～4任一项所述防伪薄膜的制备方法，其特征在于，包括如下步骤：
(1)在保护层(1)上涂布粘结层(2)材料，然后将回归反射层(3)材料植入粘结层(2)，烘干，再在回归反射层(3)上涂布可光聚合信息层(4)的材料，烘干，获得回归反射膜；
(2)再将上述回归反射膜的保护层(1)的上表面置于设有模板图文的曝光模板下，对回归反射膜进行线性偏振紫外光进行第一次曝光处理；
改变曝光模板图文和曝光角度，再对回归反射膜进行线性偏振紫外光进行第二次曝光处理，在另一角度形成不同的图文信息，然后在可光聚合信息层上高真空蒸镀反射层材料，获得防伪薄膜。
6.根据权利要求5所述的方法，其特征在于，第一次曝光处理时间为0.1～0.9秒，曝光能量为30～50mJ/cm2，曝光角度为60～90°，第二次曝光处理时间为0.1～0.9秒，曝光能量为30～50mJ/cm2，曝光角度为15～60°。
7.根据权利要求6所述的方法，其特征在于，第一次曝光处理和第二次曝光处理的角度差为30～50°。
8.根据权利要求5所述的方法，其特征在于，所述的曝光模板为不透光聚酯材料、金属材料或不透光玻璃，或者是透射式显示器件、电控双折射液晶显示器件、相变液晶显示器件、超扭曲向列液晶显示器件或低温多晶硅液晶显示器件。
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EP2295241A4 (en) 2014-01-22
US8444279B2 (en) 2013-05-21
EP2295241A1 (en) 2011-03-16
CN100589995C (zh) 2010-02-17
EP2295241B1 (en) 2015-02-25
WO2010000113A1 (zh) 2010-01-07

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