CN111519469B - 一种防拍纸张材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种防拍纸张材料及其制备方法,所述防拍纸张材料,包括基纸和涂布在基纸表面的防伪涂料,所述防伪涂料由基层、曝光变色层和可见层组成。本发明提供的防拍纸张材料通过纸张表面印制多层的结构,实现在紫外区、可见光区和红外光区的多波段防拍照、防复印效果。
Description
技术领域
本发明涉及防伪技术领域,具体涉及一种防拍纸张材料及其制备方法。
背景技术
近年来,随着科学技术的迅猛发展,人们对于技术的保护越来越重视,对于记载技术内容的纸张的防复印、防拍照等防伪技术的要求也越来越高。以油墨为基础的防伪技术主要是在油墨连接料中加入具有特殊性能的防伪材料,经过特殊工艺加工而制成特种印刷油墨。其具有制备简单、成本低、隐蔽性好等特点。现有的防伪油墨主要体现为温变防伪油墨,对于纸张复印、拍照等泄密技术无法进行防伪,具有局限性。
基于此,有必要开发出一种防拍纸张材料,满足人们的要求。
在申请号为CN201510316019.1的中国专利公开了一种防伪纸,包括纸张本体和负载在纸张本体上的防伪材料,所述防伪材料包括纤维,在所述纤维上,沿纤维的长度方向呈间隔分布有至少两个光敏变色颗粒,该防伪纸中的防伪材料具有与普通防伪纤维材料不同的结构,容易分辨、难以仿制,且只需要单一的防伪油墨就能具有很好的易识别性。但上述现有技术对于如何实现防复印、防偷拍等泄密手段,没有效果,具有一定的局限性。
因此,有必要提供一种防拍纸张材料及其制备方法,以解决现有的防伪纸张在防复印、防偷拍等泄密手段管控不严的问题。
发明内容
本发明的目的在于提供一种防拍纸张材料及其制备方法,防拍纸张材料通过纸张表面印制多层的结构,实现在紫外区、可见光区和红外光区的多波段防拍照、防复印效果。
为了解决上述技术问题,本发明采用如下技术方案:
一种防拍纸张材料,包括基纸和涂布在基纸表面的防伪涂料,
所述防伪涂料由基层、曝光变色层和可见层组成;
其中,所述基层由以下重量份原料组成:碳酸钙10~20份、聚氨脂树脂10~20份、二氧化硅1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份;
所述变色层由以下重量份原料组成:光致可逆变色物质1~10份、镉双硫腙1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份;
所述可见层由以下重量份原料组成:二氧化钛1~10份、对苯二胺1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、氨乙基哌嗪1~5份、聚二甲基硅氧烷0.5~2份。
进一步地,所述光致可逆变色物质为螺(二氢吲哚) 萘并吡喃和螺呋喃按质量比1:3的混合物,二者结合可避免螺呋喃对热不稳定而显色失效的问题,显色更灵敏。镉双硫腙制备如下:将双硫腙溶于四氢呋喃中,将含镉无机盐溶于水中,将双硫腙溶液和含镉无机盐溶液混合后回流,加水沉淀,过滤,固体在坩埚中加热干燥,得到镉双硫腙。
另一方面,本发明提供一种防拍纸张材料的制备方法,具体步骤如下:
步骤1)基层的制备:取碳酸钙10~20份、聚氨脂树脂10~20份、二氧化硅1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份分散于溶剂中球磨得到分散液,加热至100~200℃进一步分散1~10min后,除去溶剂,得到基层涂料;将所得基层涂料涂覆在基纸表面,烘干后获得具有基层的纸张材料;基层可吸收近红外光谱,光谱在500~1000nm范围内,基层厚度为250~600nm;
步骤2)变色层的制备:在避光环境下,将光致可逆变色物质1~10份、镉双硫腙1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份在溶剂中在60~100℃下在震荡机上振荡剪切分散30~60min,使得固体物料被液体物料充分润湿分散,得到变色层涂料;将所得变色层涂料印刷于步骤1)所得具有基层的纸张材料表面,经真空70~90℃烘干得到具有两层结构的纸张材料;印刷压力为0.3~0.4Pa,印刷速度为60~80m/min;所述光致可逆变色物质在紫外光(220~400nm)照射下环体与氧原子距离更近,导致电子云的相互作用发生变化使得其颜色变得更深(例如橙红或紫红),在无紫外光照射下恢复为无色,变色后遮挡原文件的图文信息;镉双硫腙能够吸收波长为400~700nm的可见光,在强光照射下,吸收可见光变为暗色,遮挡原文件的图文信息,以防止被复印或拍照;曝光层厚度为2~8μm;
步骤3)曝光层的制备:将二氧化钛1~10份、对苯二胺1~10份、葵二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、氨乙基哌嗪1~5份、聚二甲基硅氧烷0.5~2份在8000~15000r/min转速下高速混合均匀,得到可见层涂料;用不干胶涂布机在步骤2)所得纸张材料表面进行涂布可见层涂料后,经过90~100℃烘干获得防拍纸张材料。可见层厚度为0.3~1.5微米,对苯二胺在紫外(220~400nm)或红外光(715~1100nm)激发下,能够发射出可见光,通过曝光进行显影,防止拍照和复印;二氧化钛为具有高折射率的材料,可将部分拍照或复印的光线进行反射,造成曝光的现象。
进一步地,所述溶剂选自水、甘油或乙二醇。
进一步地,所述胶印涂布的湿涂量为1~5g/m2,厚度为2~4μm;涂布过程中的温度为25~45℃,复合压力0.3~0.6Pa,流平时间控制在15s内,速度为15~60m/min。
紫外光、红外光或强光利用扫描器或若干光源来进行,若干光源可以是光电二极管阵列、闪光灯等;
本申请的材料在紫外、红外等特殊条件下发光物质的反应作为验证凭据,所披露的组分和配比,使材料具备变色等性能,当组分与配比发生变化后就失去了效果。发光物质经复印机或手机的强力光线激发后通过电子俘获将吸收光能量储存起来,当用一定的紫外光或红外光激励后,电子将储存的能量释放出来,形成黑影。
本申请的材料在强光等特殊条件下发光物质的反应作为验证凭据,所披露的组分和配比,使材料具备反光等性能,当组分与配比发生变化后就失去了效果。发光物质经复印机或手机的强力光线激发后光能量被反射出来,给人产生强烈的视觉差异,形成强白光,防伪效果显著。
与现有技术相比,本发明具有如下的有益效果:
(1)本发明制备的防拍纸张材料通过纸张表面多层的结构,实现在紫外区、可见光区和红外光区的多波段防拍照、防复印效果。在曝光层和显色层的双重作用下,使得防拍纸张材料上记载的文字变得模糊,实现防拍和防复印的效果。
(2)本发明提供的制备方法工艺流程简单,运行成本低,并且制备出的防拍纸张材料具有多波段防拍照、防复印效果,能够实现防拍照、防复印的目的;
(3)本发明的防拍纸张材料中的涂层直接覆盖在纸张表面,具有极高的隐秘性,肉眼和手感触摸都无法分辨,在鉴别真伪时,通过强光、紫外或红外线照射即可发现。该技术隐形不易被发现,同时在对记载在纸张上的文字进行拍照或复印时,根据使用者选择的光线不同,纸张变暗或白亮,使得文字被黑影覆盖或被白光包围,进而使得偷拍或复印的文字不清楚,达到防偷拍或盗复印的效果。
具体实施方式
下面结合具体实施例,进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1
一种防拍纸张材料,包括基纸和涂布在基纸表面的防伪涂料,
所述防伪涂料由基层、曝光变色层和可见层组成;
其中,所述基层由以下重量份原料组成:碳酸钙10份、聚氨脂树脂20份、二氧化硅1份、葵二酸异辛酯10份、十二烷基硫酸钠0.5份、聚二甲基硅氧烷2份;
所述变色层由以下重量份原料组成:光致可逆变色物质10份、镉双硫腙1份、葵二酸异辛酯10份、十二烷基硫酸钠0.5份、聚二甲基硅氧烷2份;所述光致可逆变色物质为螺(二氢吲哚) 萘并吡喃和螺呋喃按质量比1:3的混合物,
所述可见层由以下重量份原料组成:二氧化钛5份、对苯二胺5份、葵二酸异辛酯8份、十二烷基硫酸钠1份、氨乙基哌嗪3份、聚二甲基硅氧烷1份。
一种防拍纸张材料的制备方法,具体步骤如下:
步骤1)基层的制备:取碳酸钙、聚氨脂树脂、二氧化硅、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷分散于甘油中球磨得到分散液,加热至100℃进一步分散10min后,除去溶剂,得到基层涂料;将所得基层涂料涂覆在基纸表面,烘干后获得具有基层的纸张材料;基层厚度为600nm;
步骤2)变色层的制备:在避光环境下,将光致可逆变色物质、镉双硫腙、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷在乙二醇中在100℃下在震荡机上振荡剪切分散30min,使得固体物料被液体物料充分润湿分散,得到变色层涂料;将所得变色层涂料印刷于步骤1)所得具有基层的纸张材料表面,经真空70℃烘干得到具有两层结构的纸张材料;印刷压力为0.3~0.4Pa,印刷速度为60~80m/min;曝光层厚度为2~8μm;
步骤3)曝光层的制备:将二氧化钛、对苯二胺、葵二酸异辛酯、十二烷基硫酸钠、氨乙基哌嗪、聚二甲基硅氧烷在15000r/min转速下高速混合均匀,得到可见层涂料;用不干胶涂布机在步骤2)所得纸张材料表面进行涂布可见层涂料后,经过90~100℃烘干获得防拍纸张材料。可见层厚度为1.0~1.5微米。所述胶印涂布的湿涂量为5g/m2,厚度为3μm;涂布过程中的温度为40~45℃,复合压力0.5~0.6Pa,流平时间控制在15s内,速度为60m/min。
实施例2
一种防拍纸张材料,包括基纸和涂布在基纸表面的防伪涂料,
所述防伪涂料由基层、曝光变色层和可见层组成;
其中,所述基层由以下重量份原料组成:碳酸钙20份、聚氨脂树脂10份、二氧化硅10份、葵二酸异辛酯5份、十二烷基硫酸钠2份、聚二甲基硅氧烷0.5份;
所述变色层由以下重量份原料组成:光致可逆变色物质1份、镉双硫腙10份、葵二酸异辛酯5份、十二烷基硫酸钠2份、聚二甲基硅氧烷0.5份;所述光致可逆变色物质为螺(二氢吲哚) 萘并吡喃和螺呋喃按质量比1:3的混合物,
所述可见层由以下重量份原料组成:二氧化钛10份、对苯二胺1份、葵二酸异辛酯10份、十二烷基硫酸钠0.5份、氨乙基哌嗪5份、聚二甲基硅氧烷0.5份。
一种防拍纸张材料的制备方法,具体步骤如下:
步骤1)基层的制备:取碳酸钙、聚氨脂树脂、二氧化硅、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷分散于溶剂中球磨得到分散液,加热至200℃进一步分散1min后,除去溶剂,得到基层涂料;将所得基层涂料涂覆在基纸表面,烘干后获得具有基层的纸张材料;基层可吸收近红外光谱,光谱在500~1000nm范围内,基层厚度为300nm;所述溶剂选自乙二醇。
步骤2)变色层的制备:在避光环境下,将光致可逆变色物质、镉双硫腙、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷在溶剂中在60℃下在震荡机上振荡剪切分散60min,使得固体物料被液体物料充分润湿分散,得到变色层涂料;将所得变色层涂料印刷于步骤1)所得具有基层的纸张材料表面,经真空90℃烘干得到具有两层结构的纸张材料;印刷压力为0.3~0.4Pa,印刷速度为60~80m/min;曝光层厚度为2~8μm;所述溶剂选自甘油;
步骤3)曝光层的制备:将二氧化钛、对苯二胺、葵二酸异辛酯、十二烷基硫酸钠、氨乙基哌嗪、聚二甲基硅氧烷在15000r/min转速下高速混合均匀,得到可见层涂料;用不干胶涂布机在步骤2)所得纸张材料表面进行涂布可见层涂料后,经过100℃烘干获得防拍纸张材料。可见层厚度为0.5~1.0微米;所述胶印涂布的湿涂量为3g/m2,厚度为3μm;涂布过程中的温度为35~40℃,复合压力0.3~0.6Pa,流平时间控制在15s内,速度为30m/min。
实施例3
一种防拍纸张材料,包括基纸和涂布在基纸表面的防伪涂料,
所述防伪涂料由基层、曝光变色层和可见层组成;
其中,所述基层由以下重量份原料组成:碳酸钙15份、聚氨脂树脂15份、二氧化硅5份、葵二酸异辛酯8份、十二烷基硫酸钠1份、聚二甲基硅氧烷1份;
所述变色层由以下重量份原料组成:光致可逆变色物质5份、镉双硫腙5份、葵二酸异辛酯6份、十二烷基硫酸钠1份、聚二甲基硅氧烷1份;所述光致可逆变色物质为螺(二氢吲哚) 萘并吡喃和螺呋喃按质量比1:3的混合物,
所述可见层由以下重量份原料组成:二氧化钛10份、对苯二胺1份、葵二酸异辛酯10份、十二烷基硫酸钠0.5份、氨乙基哌嗪5份、聚二甲基硅氧烷0.5份。
一种防拍纸张材料的制备方法,具体步骤如下:
步骤1)基层的制备:取碳酸钙、聚氨脂树脂、二氧化硅、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷分散于溶剂中球磨得到分散液,加热至150℃进一步分散5min后,除去溶剂,得到基层涂料;将所得基层涂料涂覆在基纸表面,烘干后获得具有基层的纸张材料;基层可吸收近红外光谱,光谱在500~1000nm范围内,基层厚度为500nm;所述溶剂选自乙二醇;
步骤2)变色层的制备:在避光环境下,将光致可逆变色物质、镉双硫腙、葵二酸异辛酯、十二烷基硫酸钠、聚二甲基硅氧烷在溶剂中在70℃下在震荡机上振荡剪切分散40min,使得固体物料被液体物料充分润湿分散,得到变色层涂料;将所得变色层涂料印刷于步骤1)所得具有基层的纸张材料表面,经真空75℃烘干得到具有两层结构的纸张材料;印刷压力为0.3~0.4Pa,印刷速度为60~80m/min;曝光层厚度为2~8μm;所述溶剂选自甘油;
步骤3)曝光层的制备:将二氧化钛、对苯二胺、葵二酸异辛酯、十二烷基硫酸钠、氨乙基哌嗪、聚二甲基硅氧烷在10000r/min转速下高速混合均匀,得到可见层涂料;用不干胶涂布机在步骤2)所得纸张材料表面进行涂布可见层涂料后,经过90℃烘干获得防拍纸张材料。可见层厚度为0.5~1.0微米。所述胶印涂布的湿涂量为3g/m2,厚度为3μm;涂布过程中的温度为25~30℃,复合压力0.3~0.6Pa,流平时间控制在15s内,速度为15~60m/min。
对比例1
除了将变色层制备步骤省去外,其它组分及步骤同实施例1一致。
对比例2
除了将曝光层制备步骤省去外,其它组分及步骤同实施例1一致。
试验例1
将纸张材料进行复印,实施例1~3不能清楚复印纸张材料上的图案,而且图案周边呈现黑色,图案的墨迹消失,体现不清楚;对比例1复印的纸张材料上的图案出现隐变的黑色,而且不清楚,对比例2复印的纸张材料上的图案出现墨迹消失的样式。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种防拍纸张材料,其特征在于,包括基纸和涂布在基纸表面的防伪涂料,
所述防伪涂料由基层、曝光变色层和可见层组成;
其中,所述基层由以下重量份原料组成:碳酸钙10~20份、聚氨酯树脂10~20份、二氧化硅1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份;
所述曝光变色层由以下重量份原料组成:光致可逆变色物质1~10份、镉双硫腙1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份;
所述可见层由以下重量份原料组成:二氧化钛1~10份、对苯二胺1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、氨乙基哌嗪1~5份、聚二甲基硅氧烷0.5~2份。
2.根据权利要求1所述的防拍纸张材料,其特征在于,所述光致可逆变色物质为螺(二氢吲哚) 萘并吡喃和螺呋喃按质量比1:3的混合物。
3.一种防拍纸张材料的制备方法,其特征在于,具体步骤如下:
步骤1)基层的制备:取碳酸钙10~20份、聚氨酯 树脂10~20份、二氧化硅1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份分散于溶剂中球磨得到分散液,加热至100~200℃进一步分散1~10min后,除去溶剂,得到基层涂料;将所得基层涂料涂覆在基纸表面,烘干后获得具有基层的纸张材料;
步骤2)曝光变色层的制备:在避光环境下,将光致可逆变色物质1~10份、镉双硫腙1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、聚二甲基硅氧烷0.5~2份在溶剂中在60~100℃下在震荡机上振荡剪切分散30~60min,使得固体物料被液体物料充分润湿分散,得到曝光变色层涂料;将所得曝光变色层涂料印刷于步骤1)所得具有基层的纸张材料表面,经真空70~90℃烘干得到具有两层结构的纸张材料;印刷压力为0.3~0.4Pa,印刷速度为60~80m/min;
步骤3)可见层的制备:将二氧化钛1~10份、对苯二胺1~10份、癸二酸异辛酯5~10份、十二烷基硫酸钠0.5~2份、氨乙基哌嗪1~5份、聚二甲基硅氧烷0.5~2份在8000~15000r/min转速下高速混合均匀,得到可见层涂料;用不干胶涂布机在步骤2)所得纸张材料表面进行涂布可见层涂料后,经过90~100℃烘干获得防拍纸张材料。
4.根据权利要求3所述的防拍纸张材料的制备方法,其特征在于,所述溶剂选自水、甘油或乙二醇。
5.根据权利要求4所述的防拍纸张材料的制备方法,其特征在于,所述基层的厚度为250~600nm;所述曝光变色层厚度为2~8μm;所述可见层厚度为0.3~1.5微米。
6.根据权利要求4所述的防拍纸张材料的制备方法,其特征在于,步骤3)中所述不干胶涂布机进行胶印涂布的湿涂量为1~5g/m2,厚度为2~4μm;涂布过程中的温度为25~45℃,复合压力0.3~0.6Pa,流平时间控制在15s内,速度为15~60m/min。
7.权利要求1~6任一项所述的防拍纸张材料在制备用于防拍照和防复印材料中的用途。
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