CN116731560B - 一种刺激响应性隐形防伪油墨的制备方法及用途 - Google Patents
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Abstract
本发明属于防伪技术领域，具体涉及一种刺激响应性隐形防伪油墨的制备方法及用途。本防伪油墨采用光学性能稳定、水溶性好、毒性低的香豆素并吡啶类衍生物构建隐形荧光防伪染料，聚乙烯醇作为连接料，过氧化氢作为刺激因子，旨在解决现有防伪油墨响应信号单一、含有有机助剂、防伪能力弱等问题。
Description
技术领域
本发明属于防伪技术领域，具体涉及一种刺激响应性隐形防伪油墨的制备方法及用途。
背景技术
“防伪”主要体现预防性，能从源头为治理伪造现象提供解决办法；“防伪”具有普适性，能为人们在日常生活中提供一种可利用的鉴别真伪的方式。随着社会经济的快速发展，各种造假技术不断升级迭代，各类制造业的造假现象愈演愈烈，这不仅会损害商家的利益，更会损害国家的利益。在此背景下，需要有效的防伪技术手段的为机密文件防伪、商品防伪、货币防伪提供保障，如数码信息防伪、生物特征防伪、印刷技术防伪等，其中印刷技术防伪中的防伪油墨在印刷技术防伪中占据重要地位。从油墨制备上来说，目前市面上存在的普通防伪油墨存在防伪特征过于单一，易被仿造的缺点，高端的防伪油墨又存在只能用研究室设备检验或只被应用于特定领域而不能普及的缺点。在此情况下，就需要更具创新性、更智能的物理和化学材料被开发应用于防伪油墨的研制之中。
刺激响应防伪油墨亦称化学加密防伪印刷油墨，是指在墨迹在外界的化学、温度、光照等因素刺激下，墨迹随之发生变化的防伪油墨。化学响应材料因其自身对刺激响应特异性强，响应前后反差较大，不易被伪造等优点，成为研制防伪油墨材料的首选。从目前染料型的防伪油墨制备工艺来看，大多防伪油墨需要采用有机溶剂进行溶解，变色信号单一，稳定性差等缺点。例如：专利CN103666457 B中提到的一种有机香豆素基光致发光防伪油墨的制备方法，仅仅采用单一波长下的颜色变化进行防伪，响应信号单一，而且在制备过程中使用了有毒的有机试剂，对人体造成了危害。综合所述，开发出一种防伪能力强、光信号稳定、环境友好、适用于多领域中精确防伪是研发的重点。
发明内容
基于上述现有技术的问题，本发明提供一种刺激响应性隐形防伪油墨的制备方法及用途，采用光学性能稳定、水溶性好、毒性低的香豆素并吡啶类衍生物构建隐形荧光防伪染料，聚乙烯醇作为连接料，过氧化氢作为刺激因子，旨在解决现有防伪油墨响应信号单一、含有有机助剂、防伪能力弱等问题。
本发明的目的通过下述技术方案实现。
一种刺激响应性隐形防伪油墨的制备方法，具体包括如下步骤：
步骤1、荧光防伪染料1的制备：
7-（二乙基氨基）-3-甲酰基香豆素和碘化1,2-二甲基吡啶鎓溶于无水乙醇中，加入哌啶作催化剂，N2保护下回流反应，冷却至室温，出现大量红色粉末，抽滤，采用无水甲醇重结晶，获得红色固体2；在红色固体2的水溶液中加入亚硫酸钠，制备荧光防伪染料1水溶液；
步骤2、刺激响应性隐形防伪油墨的制备：
在圆底烧瓶中依次加入步骤1的荧光防伪染料1水溶液、乙醇、乙二醇和聚乙烯醇（PVA），回流，充分混匀冷却至室温后得到刺激响应性隐形防伪油墨。
进一步地，步骤1中7-（二乙基氨基）-3-甲酰基香豆素质量份数2-3份，碘化1,2-二甲基吡啶鎓质量份数2.5-3.5份，哌啶份数0.1-0.2份，乙醇质量份数93.3-97.4份。
进一步地，步骤1中回流反应3-5小时。
进一步地，步骤1中红色固体2质量占比1.5-2.5份，亚硫酸钠质量份数0.5-1.0份，水质量份数96.5-98.0份。
进一步地，步骤2中荧光防伪染料1水溶液质量份数35.0-40.0份，乙醇质量份数3-8份，乙二醇质量份数10.0-15.0份，聚乙烯醇（PVA）质量份数37-52份。
进一步地，步骤2中回流1-2小时，温度100-110℃。
制备的刺激响应性隐形防伪油墨可应用于文件防伪、产品包装防伪、加密传输等领域。
与现有技术相比，本发明的有益效果在于。
1. 将聚乙烯醇（PVA）、香豆素类荧光染料、乙二醇和去离子水通过一锅法加热制备成为刺激响应性隐形防伪油墨，其中，水充当溶剂，乙二醇为保湿剂，聚乙烯醇将具有光活性的染料分子表面包覆，转化成玻璃态。
2. 刺激响应性隐形防伪油墨具有良好的耐酸性、耐碱性和光稳定性。
3. 将刺激响应性隐形防伪油墨通过丝网印刷印于纸张上，形成的墨迹能呈现隐形的印迹（可见光下为无色，荧光灯下为蓝色），经过过氧化氢处理后产生刺激响应，印迹发生明显的颜色变化（可见光下变为橙色，荧光灯下变为亮黄色）。
4. 刺激响应性隐形防伪油墨可应用于文件防伪、产品包装防伪、加密传输等方面。
附图说明
图1为实例1刺激响应性隐形防伪油墨的隐形能力的效果图。
图2为实例2刺激响应性隐形防伪油墨的刺激响应能力的效果图。
图3为实例3刺激响应性隐形防伪油墨特异性响应的效果图。
图4为实例4刺激响应性隐形防伪油墨在可见光老化下的变化关系图。
具体实施方式
以下是针对本发明的优选实例进行说明，此处所描述的优选实例仅用于说明和解释本发明，并不用于限定本发明。
一种刺激响应性隐形防伪油墨的制备方法，具体包括如下步骤：
步骤1、荧光防伪染料1的制备：
7-（二乙基氨基）-3-甲酰基香豆素（3）和碘化1,2-二甲基吡啶鎓溶于无水乙醇中，加入哌啶作催化剂，N2保护下回流反应3-5小时，冷却至室温，出现大量红色粉末，抽滤，采用无水甲醇重结晶，获得红色固体2；在红色固体2的水溶液中加入亚硫酸钠，制备荧光防伪染料1水溶液；
步骤2、刺激响应性隐形防伪油墨的制备：
在圆底烧瓶中依次加入步骤1的荧光防伪染料1水溶液、乙醇、乙二醇和聚乙烯醇（PVA），回流1-2小时，温度100-110℃，充分混匀冷却至室温后得到刺激响应性隐形防伪油墨。
进一步地，步骤1中7-（二乙基氨基）-3-甲酰基香豆素质量份数2-3份，碘化1,2-二甲基吡啶鎓质量份数2.5-3.5份，哌啶份数0.1-0.2份，乙醇质量份数93.3-97.4份。
进一步地，步骤1中红色固体2质量占比1.5-2.5份，亚硫酸钠质量份数0.5-1.0份，水质量份数96.5-98.0份。
进一步地，步骤2中荧光防伪染料1水溶液质量份数35.0-40.0份，乙醇质量份数3-8份，乙二醇质量份数10.0-15.0份，聚乙烯醇（PVA）质量份数37-52份。
制备的刺激响应性隐形防伪油墨可应用于文件防伪、产品包装防伪、加密传输等领域。
实施例1。
本发明提供的刺激响应性隐形防伪油墨的制备方法，具体实施步骤如下：
步骤1：7-（二乙基氨基）-3-甲酰基香豆素2份和碘化1,2-二甲基吡啶鎓2.5份溶于无水乙醇95.3份中，加入催化剂哌啶0.2份，在N2保护下回流反应3 h，终止反应，冷却至室温，出现大量红色粉末，抽滤，用冷的无水乙醇洗涤，粗产品采用无水甲醇进行重结晶，获得红色固体（2）；
步骤2：取红色固体1.5份，亚硫酸钠0.5份，溶于98份去离子水中，制备荧光防伪染料1水溶液；
步骤3：取步骤2制备的荧光防伪染料1水溶液40份，加入乙醇3份，乙二醇10份，PVA37份于圆底烧瓶中，油浴105℃加热，回流反应1 h，冷却至室温得到刺激响应性隐形防伪油墨。
以下是本发明制备的刺激响应性隐形防伪油墨的用途，本发明在实施例1的基础上，将刺激响应性隐形防伪油墨采用丝网印刷手绘等方式印在纸上进行刺激与隐形双重防伪的使用实例。
实例1：刺激响应性隐形防伪油墨应用于密级文件的隐形传输。
采用丝网印刷将刺激响应性隐形防伪油墨印于滤纸上，图文墨迹呈无色，实现内容的加密，如图1a所示。
在365nm紫外灯照射下，图文显示出明亮的蓝色荧光，实现内容的解密，如图1a’所示。
实例2：刺激响应性隐形防伪油墨的刺激与隐形防伪响应。
首先，采用丝网印刷将刺激响应性隐形防伪油墨印于滤纸上，在可见光下观察，印文（CIPUC）呈无色隐形状态（图2a），在365 nm的紫外光照射下，印文（CIPUC）颜色明显的蓝色（图2c），表现出隐形防伪的特性。
然后，在印文（CIPUC）上喷涂过氧化氢溶液后，防伪油墨受到刺激，在可见光下呈现橙色（图2b），在365 nm的紫外光照射下，印文（CIPUC）呈现明亮的橙黄色（图2d），可以实现刺激响应防伪。
实例3：刺激响应性隐形防伪油墨中特异性响应。
首先，花朵部分使用实施例1制备的刺激响应性隐形防伪油墨进行绘制，枝叶部分使用市售的蓝色隐形荧光防伪油墨进行绘制（图3c）。
在可见光下，均未见到任何信息，花朵与枝叶均隐藏；在365nm的紫外灯照射下，花朵与枝叶均呈现蓝色荧光信号（图3d），实现隐形防伪。
然后，采用过氧化氢对花朵与枝叶进行处理，在可见光下，只见花朵而不见枝叶（图3a）；在365nm的紫外灯照射下，花朵与枝叶呈现不同的荧光颜色（图3b），表现出刺激与隐形的双重防伪功能。
实例4：刺激响应性隐形防伪油墨的耐酸性、耐碱性和光稳定性。
首先，根据GB/T18724-2002测试油墨的耐酸、碱性，制作油墨样本，放置常温下干燥24 h。耐酸性测试，在室温条件下，取两张测试用滤纸，完全浸没在测试用的5%的乙酸溶液中，然后取出并滴至没有液滴下，把其中一张滤纸平放于玻璃板上，将被测样本置于这张滤纸上，用第二张滤纸盖在被测样本上，再放一块玻璃板在上面。将做好的测试玻璃板装入密封包装袋中，并在上方玻璃板上压上1 kg的砝码。静置30 min后取下玻璃和砝码，用蒸馏水漂洗至漂洗液呈中性，待干燥后检验滤纸变色情况。最后，按GB250-1995标准的规定评定变色等级。
对于耐碱性测试，依据GB/T18724-2008，即将耐酸性测试操作过程中的5%的乙酸溶液替换成1%的氢氧化钠溶液，将静置时间改为10 min即可。其他操作同耐酸性测试。油墨耐酸碱性测试结果如下表1所示。从表中可以看出，刺激响应性隐形防伪油墨的耐酸碱性均符合国家标准要求。
表1 刺激响应性隐形防伪油墨的耐酸、碱性测试结果。
其次，为研究刺激响应性隐形防伪油墨书写于纸张上后荧光强度随时间的变化规律，进行了刺激响应性隐形防伪油墨字迹的日光老化实验。检测在激发波长为400 nm，发射波长为475 nm处的荧光强度，如图4所示，随着时间的延长，荧光强度几乎没有变化，这意味着在可见光的作用下，刺激响应性隐形防伪油墨具有较强的光稳定性。
Claims (7)
1.一种刺激响应性隐形防伪油墨的制备方法，其特征在于，具体包括如下步骤：
步骤1、荧光防伪染料1的制备：
7-（二乙基氨基）-3-甲酰基香豆素和碘化1,2-二甲基吡啶鎓溶于无水乙醇中，加入哌啶作催化剂，N2保护下回流反应，冷却至室温，出现大量红色粉末，抽滤，采用无水甲醇重结晶，获得红色固体2；在红色固体2的水溶液中加入亚硫酸钠，制备荧光防伪染料1水溶液；
步骤2、刺激响应性隐形防伪油墨的制备：
在圆底烧瓶中依次加入步骤1的荧光防伪染料1水溶液、乙醇、乙二醇和聚乙烯醇，回流，充分混匀冷却至室温后得到刺激与隐形双重响应荧光防伪油墨。
2.根据权利要求1所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，所述步骤1中7-（二乙基氨基）-3-甲酰基香豆素质量份数2-3份，碘化1,2-二甲基吡啶鎓质量份数2.5-3.5份，哌啶份数0.1-0.2份，乙醇质量份数93.3-97.4份。
3.根据权利要求1所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，所述步骤1中回流反应3-5小时。
4.根据权利要求1所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，所述步骤1中红色固体2质量占比1.5-2.5份，亚硫酸钠质量份数0.5-1.0份，水质量份数96.5-98.0份。
5.根据权利要求1所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，所述步骤2中荧光防伪染料1水溶液质量份数35.0-40.0份，乙醇质量份数3-8份，乙二醇质量份数10.0-15.0份，聚乙烯醇（PVA）质量份数37-52份。
6.根据权利要求1所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，所述步骤2中回流1-2小时，温度100-110℃。
7.根据权利要求1-6任一项所述的刺激响应性隐形防伪油墨的制备方法，其特征在于，制备的刺激响应性隐形防伪油墨应用于文件防伪、产品包装防伪、加密传输领域。
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