CN111253933A - A kind of room temperature phosphorescence anti-counterfeiting material with aging and its preparation method and application - Google Patents
A kind of room temperature phosphorescence anti-counterfeiting material with aging and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种具有时效性的室温磷光防伪材料及其制备方法和应用。本发明将室温磷光物质复合到吸水性聚合物之中，即可得到具有时效性的长寿命室温磷光发光特性的聚合物材料；室温磷光物质选自吖啶及其衍生物、苯二甲酸及其衍生物、或三聚氰胺及其衍生物中的一种或几种；水性聚合物选自聚丙烯酸树酯、纤维素及其衍生物、聚乙烯吡咯烷酮、聚乙烯醇、聚马来酸酐、聚季胺盐或聚乙二醇中的一种或几种。该防伪标签的构筑简单有效，快速实现具有时效性的室温磷光防伪，可以对包装是否被开封过、以及对商品的真实出厂时间进行有效甄别。而且，本发明可以通过水性印刷工艺获得，从成本和环境友好性来说具有巨大的优势。
The invention discloses a time-effective room temperature phosphorescence anti-counterfeiting material and a preparation method and application thereof. In the invention, the room temperature phosphorescent substance is compounded into the water-absorbing polymer, so as to obtain a polymer material with time-sensitive long-life room temperature phosphorescent light-emitting properties; the room temperature phosphorescent substance is selected from acridine and its derivatives, phthalic acid and its derivatives. Derivatives, or one or more of melamine and its derivatives; the water-based polymer is selected from polyacrylic resin, cellulose and its derivatives, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary amine One or more of salt or polyethylene glycol. The construction of the anti-counterfeiting label is simple and effective, and the time-effective room temperature phosphorescence anti-counterfeiting can be quickly realized, and whether the package has been opened and the real delivery time of the product can be effectively screened. Moreover, the present invention can be obtained by an aqueous printing process, which has great advantages in terms of cost and environmental friendliness.
Description
技术领域technical field
本发明属于光学防伪材料技术领域。更具体地，涉及一种具有时效性的室温磷光防伪材料及其制备方法和应用。The invention belongs to the technical field of optical anti-counterfeiting materials. More specifically, it relates to an aging room temperature phosphorescence anti-counterfeiting material and its preparation method and application.
背景技术Background technique
光学防伪是最重要的防伪手段之一，市场上大量的商品使用了防伪商标，尤其是在烟酒、化妆品行业中使用的极为普遍。然而，常规的防伪商标无法做到具有时效性，也就是对商品包装是否被开封过，以及对商品真实的出厂时间进行标识的功能。Optical anti-counterfeiting is one of the most important anti-counterfeiting methods. A large number of products on the market use anti-counterfeiting trademarks, especially in the tobacco, alcohol and cosmetics industries. However, conventional anti-counterfeiting trademarks cannot be time-sensitive, that is, the function of marking whether the packaging of the goods has been opened and the real time of the goods leaving the factory.
磷光与荧光相比具有更大的Stokes位移，可避免激发光的干扰。同时磷光具有更长的寿命，可避免短寿命的荧光和散射光的干扰，从而获得更低的检出限。荧光由于发光条件简单以及使用方便，已经在防伪领域获得了较大的应用，如人民币防伪就用到了荧光技术。而磷光为了控制磷光分子的非辐射跃迁需要低温条件，使磷光的应用受到了极大的限制。后来发展的室温磷光由于控制了磷光分子的非辐射跃迁，而且发光条件温和，因而广泛应用于生命科学、环境科学、医学临床、工业能源和防伪等领域。室温磷光已经实现了温度响应、机械刺激响应等控制方法来调控室温磷光的开启及强度，但这些方法往往带来破坏性，而且操作过程复杂。Compared with fluorescence, phosphorescence has a larger Stokes shift, which can avoid the interference of excitation light. At the same time, phosphorescence has a longer lifetime, which can avoid the interference of short-lived fluorescence and scattered light, so as to obtain a lower detection limit. Fluorescence has been widely used in the field of anti-counterfeiting due to its simple lighting conditions and convenient use. For example, fluorescence technology is used in anti-counterfeiting of RMB. In order to control the non-radiative transition of phosphorescent molecules, phosphorescence requires low temperature conditions, which greatly limits the application of phosphorescence. The room temperature phosphorescence developed later has been widely used in life science, environmental science, medical clinic, industrial energy and anti-counterfeiting due to its controlled non-radiative transition of phosphorescent molecules and mild luminescence conditions. Room temperature phosphorescence has achieved control methods such as temperature response and mechanical stimulus response to regulate the turn-on and intensity of room temperature phosphorescence, but these methods are often destructive and the operation process is complicated.
光响应是一种无破坏、非接触的简便控制方法，可以方便实现室温磷光的开启及磷光强度的调控。华东理工大学的田禾、马骧教授课题组报道了一种制备纯有机高效室温磷光发射的固体无定形聚合物材料的简便方法及其应用：首先通过简单的几步反应合成了含有磷光体染料的单体化合物，然后与丙烯酰胺共聚，基于聚合物体系中的氢键相互作用，便得到具有高效室温磷光发射性能的无定形聚合物材料。由于聚合物体系中的氢键作用对水比较敏感，此类固体无定形材料的室温磷光发射对空气湿度有所响应，其有机溶液体系对其中的水分含量亦有所响应。但所报道的单体化合物合成复杂，成本较高，且磷光强度和时效性无法调控，使用很不方便。尤其在防伪领域，更是降低了防伪等级。Photoresponse is a non-destructive, non-contact and simple control method, which can easily realize the turn-on of room temperature phosphorescence and the regulation of phosphorescence intensity. The research group of Professor Tian He and Ma Xiang from East China University of Science and Technology reported a facile method for the preparation of pure organic high-efficiency room-temperature phosphorescence-emitting solid amorphous polymer materials and its application: First, a phosphor-containing dye was synthesized by a few simple steps. The monomer compound is then copolymerized with acrylamide, and based on the hydrogen bond interaction in the polymer system, amorphous polymer materials with efficient room temperature phosphorescence emission properties are obtained. Since the hydrogen bonding in the polymer system is sensitive to water, the room temperature phosphorescence emission of such solid amorphous materials responds to the air humidity, and the organic solution system also responds to the moisture content. However, the reported monomeric compounds are complex to synthesize, have high cost, and the phosphorescence intensity and timeliness cannot be regulated, which is very inconvenient to use. Especially in the field of anti-counterfeiting, the level of anti-counterfeiting has been reduced.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是克服上述现有技术的缺陷和不足，提供一种具有时效性的室温磷光防伪材料及其制备方法和应用。The technical problem to be solved by the present invention is to overcome the above-mentioned defects and deficiencies of the prior art, and to provide a time-effective room temperature phosphorescence anti-counterfeiting material and a preparation method and application thereof.
本发明上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种具有时效性的室温磷光防伪材料的制备方法，将室温磷光物质复合到吸水性聚合物之中，即可得到具有时效性的长寿命室温磷光发光特性的聚合物材料；A method for preparing a time-effective room temperature phosphorescence anti-counterfeiting material, which comprises compounding a room temperature phosphorescent substance into a water-absorbing polymer to obtain a time-effective long-life room temperature phosphorescence luminescent polymer material;
其中，所述室温磷光物质选自吖啶及其衍生物、苯二甲酸及其衍生物、或三聚氰胺及其衍生物中的一种或几种；Wherein, the room temperature phosphorescent substance is selected from one or more of acridine and its derivatives, phthalic acid and its derivatives, or melamine and its derivatives;
所述吸水性聚合物选自聚丙烯酸树酯、纤维素及其衍生物、聚乙烯吡咯烷酮、聚乙烯醇、聚马来酸酐、聚季胺盐或聚乙二醇中的一种或几种。The water-absorbing polymer is selected from one or more of polyacrylic resin, cellulose and its derivatives, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol.
为了克服常规常规光学防伪材料的问题，本发明通过使用室温磷光物质与吸水性聚合物复合，可简单、快速且有效地进行防伪标签的构筑，快速实现具有时效性的室温磷光防伪，可以对包装是否被开封过、以及对商品的真实出厂时间进行有效甄别。而且，本发明采用的反应体系可以完全通过水性印刷工艺获得，从成本和环境友好性来说具有巨大的优势。In order to overcome the problems of conventional optical anti-counterfeiting materials, the present invention can construct anti-counterfeiting labels simply, quickly and effectively by using room temperature phosphorescent substances and water-absorbing polymers, and can quickly realize time-effective room temperature phosphorescence anti-counterfeiting, which can be used for packaging packaging. Whether it has been opened, and the real time of delivery of the product is effectively screened. Moreover, the reaction system adopted in the present invention can be completely obtained by an aqueous printing process, which has great advantages in terms of cost and environmental friendliness.
本发明将室温磷光物质复合到吸水性聚合物之中，通过聚合物的吸水性，使得防伪材料在密封包装打开后，吸收空气中的水份从而失去磷光，达到对商品包装是否被开封过进行甄别性防伪，以及对商品出厂真实时间进行指示性防伪的功能，在贵重的烟酒、药品、食品等具有时效性防伪需求的行业中，具有重要的应用价值和广阔的应用前景。In the invention, the room temperature phosphorescent substance is compounded into the water-absorbing polymer, and through the water absorption of the polymer, the anti-counterfeiting material absorbs the moisture in the air after the sealed package is opened, thereby losing the phosphorescence, so as to determine whether the product package has been opened. The function of discriminating anti-counterfeiting and indicating the real time of the goods leaving the factory has important application value and broad application prospects in industries with time-sensitive anti-counterfeiting requirements such as valuable tobacco, alcohol, medicine, and food.
在本发明较佳的实施例中，所述室温磷光物质与吸水性聚合物的质量比为1：1000～7000。In a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent substance to the water-absorbing polymer is 1:1000-7000.
进一步地，在本发明较佳的实施例中，所述室温磷光物质与吸水性聚合物的质量比为1：3000～5000。Further, in a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent substance to the water-absorbing polymer is 1:3000-5000.
更进一步地，在本发明较佳的实施例中，所述室温磷光物质与吸水性聚合物的质量比为1：4000。Further, in a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent substance to the water-absorbing polymer is 1:4000.
室温磷光物质比例过高，会引起因聚集引起的发光效率下降；室温磷光物质比例过低，也会引起发光强度不足从而无法用肉眼观察到磷光的结果。本申请人经过创造性劳动发现，室温磷光物质与吸水性聚合物的质量比为1：1000～7000，优选1：3000～5000，更优选1：4000时，复合物的发光效率、发光强度、发光寿命较好，同时肉眼可见颜色的可控调节范围较宽。If the ratio of room temperature phosphorescent substance is too high, the luminous efficiency will decrease due to aggregation; if the ratio of room temperature phosphorescent substance is too low, it will also cause insufficient luminous intensity, so that the result of phosphorescence cannot be observed with the naked eye. The applicant found through creative work that when the mass ratio of the room temperature phosphorescent substance to the water-absorbing polymer is 1:1000-7000, preferably 1:3000-5000, more preferably 1:4000, the luminous efficiency, luminous intensity, luminescence of the composite The lifespan is good, and the controllable adjustment range of the color visible to the naked eye is wide.
在本发明较佳的实施例中，所述的复合方法为溶液溶胀法、离子交换法、共聚法、溶液成型法或共混法中的任一种；In a preferred embodiment of the present invention, the compounding method is any one of a solution swelling method, an ion exchange method, a copolymerization method, a solution molding method or a blending method;
其中所述溶液溶胀法为：使用室温磷光物质的溶液对吸水性聚合物进行溶胀后，蒸发去除溶剂，即得；The solution swelling method is as follows: after the water-absorbing polymer is swelled with a solution of a room temperature phosphorescent substance, the solvent is evaporated to remove;
所述离子交换法为：利用聚电解质交换抗衡离子的方法，将离子型室温磷光物质与吸水性聚合物进行离子交换，再蒸发去除溶剂，即得；The ion exchange method is as follows: using a method of exchanging counter ions with a polyelectrolyte, ion-exchanging the ionic room temperature phosphorescent substance with a water-absorbing polymer, and then evaporating the solvent to remove the solvent;
所述共聚法为：将室温磷光物质与吸水性聚合物单体进行共聚反应，或与吸水性聚合物进行接枝反应，即得；The copolymerization method is as follows: the room temperature phosphorescent substance is subjected to a copolymerization reaction with a water-absorbing polymer monomer, or a graft reaction is performed with the water-absorbing polymer to obtain;
所述溶液成型法为：将室温磷光物质与吸水性聚合物共同溶解于溶剂，再蒸发去除溶剂，即得；The solution molding method is as follows: the room temperature phosphorescent substance and the water-absorbing polymer are jointly dissolved in a solvent, and then the solvent is evaporated to remove the solvent;
所述共混法为：将室温磷光物质与吸水性聚合物进行熔融加工共混，即得。The blending method is as follows: the room temperature phosphorescent substance and the water-absorbing polymer are melt-processed and blended to obtain the obtained product.
在本发明较佳的实施例中，所述室温磷光物质选自吖啶酮、吖啶橙盐酸盐、吖啶黄盐酸盐或其组合。In a preferred embodiment of the present invention, the room temperature phosphorescent substance is selected from acridine, acridine orange hydrochloride, acriflavine hydrochloride or a combination thereof.
在本发明较佳的实施例中，所述吸水性聚合物选自聚丙烯酰胺。In a preferred embodiment of the present invention, the water-absorbing polymer is selected from polyacrylamide.
在本发明较佳的实施例中，所述复合方法为溶液溶胀法。In a preferred embodiment of the present invention, the compounding method is a solution swelling method.
在本发明较佳的实施例中，所述溶剂为水。In a preferred embodiment of the present invention, the solvent is water.
在本发明较佳的实施例中，所述所述室温磷光物质溶液的质量分数为0.01％～1％，优选0.01％～0.1％。室温磷光物质溶液的质量分数会直接决定室温磷光物质与吸水性聚合物的质量比，室温磷光物质比例过高，会引起因聚集引起的发光效率下降；室温磷光物质比例过低，也会引起发光强度不足从而无法用肉眼观察到磷光的结果。本申请人经过创造性劳动发现，室温磷光物质溶液的质量分数为0.01％～1％，优选0.01％～0.1％时，复合物的发光效率、发光强度、发光寿命均较佳，而且还具有肉眼可见的广泛的颜色可调范围，可从蓝色到红色的全可见光谱颜色。In a preferred embodiment of the present invention, the mass fraction of the room temperature phosphorescent substance solution is 0.01%-1%, preferably 0.01%-0.1%. The mass fraction of the room temperature phosphorescent substance solution will directly determine the mass ratio of the room temperature phosphorescent substance to the water-absorbing polymer. If the ratio of the room temperature phosphorescent substance is too high, the luminous efficiency will decrease due to aggregation; if the ratio of the room temperature phosphorescent substance is too low, it will also cause luminescence. Insufficient intensity to visually observe the result of phosphorescence. The applicant has found through creative work that when the mass fraction of the room temperature phosphorescent substance solution is 0.01% to 1%, preferably 0.01% to 0.1%, the luminous efficiency, luminous intensity and luminous lifetime of the composite are all better, and it also has the properties visible to the naked eye. A wide range of color tunability, available in full visible spectrum colors from blue to red.
本发明还涉及了采用上述制备方法制得的具有时效性的室温磷光防伪材料。The invention also relates to the time-effective room temperature phosphorescence anti-counterfeiting material prepared by the above preparation method.
本发明还涉及了采用上述制备方法制得的具有时效性的室温磷光防伪材料在作为包装密封条式的防伪材料或出厂时间的指示剂中的应用。The invention also relates to the application of the time-effective room temperature phosphorescence anti-counterfeiting material prepared by the above preparation method as a packaging sealing strip type anti-counterfeiting material or an indicator of the time of delivery.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明的室温磷光材料具有时效性，在完全干燥时体现出最强的磷光性质，而在接触空气后逐渐吸收水分而失去磷光，从而实现一般防伪标签所不具有的时效性。(1) The room temperature phosphorescent material of the present invention is time-sensitive, showing the strongest phosphorescent property when completely dry, and gradually absorbs moisture and loses phosphorescence after contacting the air, thereby realizing the time-effectiveness that general anti-counterfeiting labels do not have.
(2)本发明的室温磷光材料具有水性印刷性，可以通过简单的水溶液印刷获得图案，因此具有低成本、易加工的优点。(2) The room temperature phosphorescent material of the present invention has water-based printability, and a pattern can be obtained by simple aqueous printing, so it has the advantages of low cost and easy processing.
附图说明Description of drawings
图1为实施例1制备的具有时效性的室温磷光材料的效果展示。FIG. 1 shows the effect of the aging room temperature phosphorescent material prepared in Example 1. FIG.
图2为具有时效性的室温磷光材料的印刷品效果展示图，其中左图为印刷图案在紫外灯下的状态，右图为印刷图案在紫外灯关闭后的状态。Figure 2 is a picture showing the effect of a printed product of the aging room temperature phosphorescent material. The left picture is the state of the printed pattern under the UV lamp, and the right picture is the state of the printed pattern after the UV lamp is turned off.
具体实施方式Detailed ways
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The present invention is further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
除非特别说明，以下实施例所用试剂和材料均为市购。Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
实施例1Example 1
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液成型法制备，将吖啶酮与吸水性聚合物聚丙烯酰胺共同溶解于溶剂水中，控制吖啶酮与聚丙烯酰胺的质量比为1：4000，吖啶酮溶液的质量分数为0.1％，再于100℃加热蒸发去除溶剂水，得到具有时效性的室温磷光防伪材料。如图1所示，该室温磷光防伪材料在紫外灯下呈现蓝色荧光，关灯后出现长寿命的绿色磷光，而且该室温磷光防伪材料在暴露在相对湿度50％的空气中会逐渐失去磷光，达到对商品的真实出厂时间进行有效甄别的目的。Prepared by solution molding method, acridone and water-absorbing polymer polyacrylamide are co-dissolved in solvent water, the mass ratio of acridone and polyacrylamide is controlled to be 1:4000, and the mass fraction of acridone solution is 0.1% , and then heated and evaporated at 100° C. to remove the solvent water to obtain a time-effective room temperature phosphorescence anti-counterfeiting material. As shown in Figure 1, the room temperature phosphorescent anti-counterfeiting material exhibits blue fluorescence under ultraviolet light, and long-life green phosphorescence appears after the light is turned off, and the room temperature phosphorescent anti-counterfeiting material will gradually lose phosphorescence when exposed to air with a relative humidity of 50% , to achieve the purpose of effectively screening the real delivery time of the product.
实施例2Example 2
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液溶胀法制备，将吖啶黄素盐酸盐溶于水形成质量分数0.03％的吖啶黄素盐酸盐水溶液，使用吸水性聚合物聚丙烯酰胺薄膜作为基材，将吖啶黄素盐酸盐水溶液作为墨水进行喷墨打印；打印出图案后，将图案置于90℃条件下烘干1h，过塑密封，即可形成如图2所示的绿色荧光-绿色磷光图案。当密封袋被打开后，磷光特性会在2小时内逐渐消失，荧光特性则不会明显变化，达到对商品包装是否被开封过的甄别性防伪目标。Prepared by solution swelling method, acriflavin hydrochloride is dissolved in water to form an aqueous solution of acriflavin hydrochloride with a mass fraction of 0.03%. The aqueous hydrochloride solution was used as the ink for inkjet printing; after printing the pattern, the pattern was dried at 90°C for 1 hour, and then over-plasticized and sealed to form the green fluorescence-green phosphorescence pattern shown in Figure 2. When the sealed bag is opened, the phosphorescence characteristics will gradually disappear within 2 hours, and the fluorescence characteristics will not change significantly, achieving the goal of identifying whether the product packaging has been opened or not.
实施例3Example 3
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液溶胀法制备，将吖啶黄素盐酸盐溶于水形成质量分数0.01％的吖啶黄素盐酸盐水溶液，使用吸水性聚合物聚丙烯酰胺薄膜作为基材，将吖啶黄素盐酸盐水溶液作为墨水进行喷墨打印；打印出图案后，将图案置于90℃条件下烘干1h，过塑密封，也形成了如图2所示的绿色荧光-绿色磷光图案。当密封袋被打开后，磷光特性会在2至3小时内逐渐消失，荧光特性则不会明显变。Prepared by the solution swelling method, acriflavin hydrochloride is dissolved in water to form an aqueous solution of acriflavin hydrochloride with a mass fraction of 0.01%. Aqueous hydrochloride solution was used as ink for inkjet printing; after the pattern was printed, the pattern was dried at 90°C for 1 h, over-plastic sealed, and the green fluorescence-green phosphorescence pattern as shown in Figure 2 was also formed. When the sealed bag was opened, the phosphorescent properties gradually disappeared within 2 to 3 hours, while the fluorescent properties did not change significantly.
实施例4Example 4
采用溶液溶胀法，以吖啶酮溶于乙醇形成质量分数0.02％的吖啶酮溶液，使用交联的聚丙烯酸薄膜作为基材，以吖啶酮乙醇溶液作为印章的墨水，用木质印章吸收墨水后盖到聚丙烯酸薄膜上停留1min，随后置于100℃条件下烘干薄膜,过塑密封，得到蓝色荧光-绿色荧光的防伪图案。当密封袋被打开后，磷光特性会在0.5小时内逐渐消失，荧光特性则不会明显变化，实现一次性开封后的时效性室温磷光防伪。Using the solution swelling method, acridone was dissolved in ethanol to form an acridone solution with a mass fraction of 0.02%, a cross-linked polyacrylic acid film was used as the substrate, acridone ethanol solution was used as the ink of the seal, and a wooden seal was used to absorb the ink The back cover was placed on the polyacrylic acid film for 1 min, and then the film was dried at 100° C. and sealed with plastic to obtain a blue fluorescence-green fluorescence anti-counterfeiting pattern. When the sealed bag is opened, the phosphorescence characteristics will gradually disappear within 0.5 hours, and the fluorescence characteristics will not change significantly, achieving time-sensitive room temperature phosphorescence anti-counterfeiting after one-time opening.
实施例5Example 5
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液溶胀法，以吖啶橙盐酸盐溶于水形成质量分数0.01％的水溶液，使用聚乙烯醇作为基材，以吖啶橙盐酸盐溶液作为印刷油墨进行标签印刷，于90℃烘干薄膜，然后使用厚度为0.1mm的聚乙烯薄膜进行密封，得到橙色荧光-黄色荧光的防伪图案。所获得的防伪标签，会在12个月的过程中逐渐失去磷光特性，实现长效的时效性室温磷光防伪。Using the solution swelling method, acridine orange hydrochloride was dissolved in water to form an aqueous solution with a mass fraction of 0.01%, polyvinyl alcohol was used as the base material, and acridine orange hydrochloride solution was used as the printing ink for label printing, and dried at 90 °C. The dry film was then sealed with a polyethylene film with a thickness of 0.1 mm to obtain an orange fluorescent-yellow fluorescent anti-counterfeiting pattern. The obtained anti-counterfeiting label will gradually lose its phosphorescence characteristics in the course of 12 months, and realize long-term aging room temperature phosphorescence anti-counterfeiting.
实施例6Example 6
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液成型法制备，将吖啶酮与吸水性聚合物聚乙烯吡咯烷酮共同溶解于溶剂乙醇中，控制吖啶酮与聚乙烯吡咯烷酮的质量比为1：3000，吖啶酮溶液的质量分数为0.05％，再于100℃加热蒸发去除溶剂，得到具有时效性的室温磷光防伪材料。该室温磷光防伪材料在紫外灯下呈现荧光，关灯后出现长寿命的磷光，而且该室温磷光防伪材料在暴露在相对湿度50％的空气中会逐渐失去磷光，实现对商品的真实出厂时间进行有效甄别的目的。Prepared by solution molding method, acridone and water-absorbing polymer polyvinylpyrrolidone are co-dissolved in solvent ethanol, the mass ratio of acridone and polyvinylpyrrolidone is controlled to be 1:3000, and the mass fraction of acridone solution is 0.05 %, and then heated and evaporated at 100°C to remove the solvent to obtain an aging room temperature phosphorescence anti-counterfeiting material. The room temperature phosphorescence anti-counterfeiting material exhibits fluorescence under the ultraviolet lamp, and long-life phosphorescence appears after the light is turned off, and the room temperature phosphorescence anti-counterfeiting material will gradually lose its phosphorescence when exposed to the air with a relative humidity of 50%, so as to realize the real factory time of the product. The purpose of effective screening.
实施例7Example 7
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用离子交换法制备，将吖啶橙盐酸盐与吸水性聚合物聚季胺盐共同溶解于溶剂水中进行离子交换，控制吖啶橙盐酸盐与聚季胺盐的质量比为1：5000，吖啶橙盐酸盐溶液的质量分数为0.5％，再于100℃加热蒸发去除溶剂水，得到具有时效性的室温磷光防伪材料。该室温磷光防伪材料在紫外灯下呈现荧光，关灯后出现长寿命的磷光，而且该室温磷光防伪材料在暴露在相对湿度55％的空气中会逐渐失去磷光，实现对商品的真实出厂时间进行有效甄别的目的。Prepared by ion exchange method, acridine orange hydrochloride and water-absorbing polymer polyquaternary ammonium salt are co-dissolved in solvent water for ion exchange, and the mass ratio of acridine orange hydrochloride and polyquaternary ammonium salt is controlled to be 1:5000 , the mass fraction of the acridine orange hydrochloride solution is 0.5%, and then the solvent water is removed by heating and evaporation at 100 °C to obtain an aging room temperature phosphorescence anti-counterfeiting material. The room temperature phosphorescent anti-counterfeiting material exhibits fluorescence under the ultraviolet lamp, and has long-life phosphorescence after the light is turned off, and the room temperature phosphorescent anti-counterfeiting material will gradually lose its phosphorescence when exposed to the air with a relative humidity of 55%, so as to realize the real production time of the product. The purpose of effective screening.
实施例8Example 8
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用共聚法制备，将吖啶黄盐酸盐与吸水性聚合物聚马来酸酐共同溶解于溶剂水中进行接枝，控制吖啶黄盐酸盐与聚马来酸酐的质量比为1：1000，吖啶橙盐酸盐溶液的质量分数为1％，去除溶剂水，得到具有时效性的室温磷光防伪材料。该室温磷光防伪材料在紫外灯下呈现荧光，关灯后出现长寿命的磷光，而且该室温磷光防伪材料在暴露在相对湿度40％的空气中会逐渐失去磷光，实现对商品的真实出厂时间进行有效甄别的目的。Prepared by copolymerization method, acriflavine hydrochloride and water-absorbing polymer polymaleic anhydride are jointly dissolved in solvent water for grafting, and the mass ratio of acriflavine hydrochloride and polymaleic anhydride is controlled to be 1:1000, The mass fraction of the acridine orange hydrochloride solution is 1%, and the solvent water is removed to obtain a time-effective room temperature phosphorescence anti-counterfeiting material. The room temperature phosphorescence anti-counterfeiting material exhibits fluorescence under the ultraviolet lamp, and long-life phosphorescence appears after the light is turned off, and the room temperature phosphorescence anti-counterfeiting material will gradually lose its phosphorescence when exposed to the air with a relative humidity of 40%, so as to realize the real production time of the product. The purpose of effective screening.
实施例9Example 9
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用共聚法制备，将吖啶黄盐酸盐与吸水性聚合物聚乙烯醇共同溶解于溶剂水中进行接枝，控制吖啶黄盐酸盐与聚乙烯醇的质量比为1：7000，吖啶橙盐酸盐溶液的质量分数为0.8％，去除溶剂水，得到具有时效性的室温磷光防伪材料。该室温磷光防伪材料在紫外灯下呈现荧光，关灯后出现长寿命的磷光，而且该室温磷光防伪材料在暴露在相对湿度45％的空气中会逐渐失去磷光，实现对商品的真实出厂时间进行有效甄别的目的。Prepared by copolymerization method, acriflavine hydrochloride and water-absorbing polymer polyvinyl alcohol are co-dissolved in solvent water for grafting, and the mass ratio of acriflavine hydrochloride and polyvinyl alcohol is controlled to be 1:7000, acridine The mass fraction of the orange hydrochloride solution is 0.8%, and the solvent water is removed to obtain a time-effective room temperature phosphorescence anti-counterfeiting material. The room temperature phosphorescence anti-counterfeiting material exhibits fluorescence under the ultraviolet lamp, and long-life phosphorescence appears after the light is turned off, and the room temperature phosphorescence anti-counterfeiting material will gradually lose its phosphorescence when exposed to the air with a relative humidity of 45%, so as to realize the real factory time of the product. The purpose of effective screening.
实施例10Example 10
1、一种具有时效性的室温磷光防伪材料的制备方法，包括以下步骤：1. A preparation method of an aging room temperature phosphorescence anti-counterfeiting material, comprising the following steps:
采用溶液溶胀法制备，将吖啶黄盐酸盐与吸水性聚合物纤维素共同溶解于溶剂乙醇中进行复合反应，控制吖啶黄盐酸盐与纤维素的质量比为1：6000，吖啶橙盐酸盐溶液的质量分数为0.7％，去除溶剂，得到具有时效性的室温磷光防伪材料。该室温磷光防伪材料在紫外灯下呈现荧光，关灯后出现长寿命的磷光，而且该室温磷光防伪材料在暴露在相对湿度60％的空气中会逐渐失去磷光，实现对商品的真实出厂时间进行有效甄别的目的。Prepared by solution swelling method, acriflavine hydrochloride and water-absorbing polymer cellulose are co-dissolved in solvent ethanol for compound reaction, the mass ratio of acriflavine hydrochloride and cellulose is controlled to be 1:6000, acridine The mass fraction of the orange hydrochloride solution is 0.7%, and the solvent is removed to obtain a time-effective room temperature phosphorescence anti-counterfeiting material. The room temperature phosphorescent anti-counterfeiting material exhibits fluorescence under the ultraviolet lamp, and long-life phosphorescence appears after the light is turned off, and the room temperature phosphorescent anti-counterfeiting material will gradually lose its phosphorescence when exposed to the air with a relative humidity of 60%, so as to realize the real production time of the product. The purpose of effective screening.
本发明的室温磷光材料具有时效性，在完全干燥时体现出最强的磷光性质，而在接触空气后逐渐吸收水分而失去磷光，从而实现一般防伪标签所不具有的时效性；而且具有水性印刷性，可以通过简单的水溶液印刷获得图案，因此具有低成本、易加工的优点。The room temperature phosphorescent material of the present invention has the time-resistance, shows the strongest phosphorescent property when it is completely dried, and gradually absorbs moisture and loses phosphorescence after contacting the air, thereby realizing the time-resistance that general anti-counterfeiting labels do not have; and has water-based printing properties. The pattern can be obtained by simple aqueous solution printing, so it has the advantages of low cost and easy processing.
本发明将室温磷光物质复合到吸水性聚合物之中，通过聚合物的吸水性，使得防伪材料在密封包装打开后，吸收空气中的水份从而失去磷光，达到对商品包装是否被开封过进行甄别性防伪，以及对商品出厂真实时间进行指示性防伪的功能，在贵重的烟酒、药品、食品等具有时效性防伪需求的行业中，具有重要的应用价值和广阔的应用前景。In the invention, the room temperature phosphorescent substance is compounded into the water-absorbing polymer, and through the water absorption of the polymer, the anti-counterfeiting material absorbs the moisture in the air after the sealed package is opened, thereby losing the phosphorescence, so as to determine whether the product package has been opened. The function of discriminating anti-counterfeiting and indicating the real time of the goods leaving the factory has important application value and broad application prospects in industries with time-sensitive anti-counterfeiting requirements such as valuable tobacco, alcohol, medicine, and food.
申请人声明，以上具体实施方式为便于理解本发明而说明的较佳实施例，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the above specific embodiments are preferred embodiments to facilitate understanding of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the selected raw materials of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims (10)
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| CN202010230200.1A CN111253933B (en) | 2020-03-27 | 2020-03-27 | A kind of room temperature phosphorescence anti-counterfeiting material with aging and its preparation method and application |
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Cited By (7)
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| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot composite and preparation method thereof |
| CN111763512A (en) * | 2020-06-24 | 2020-10-13 | 中山大学 | Application of polyvinylbenzenesulfonic acid or its salt as room temperature phosphorescent material |
| CN112707922A (en) * | 2020-12-24 | 2021-04-27 | 河北工业大学 | Color-adjustable hectorite and 4,4' -biphenyldicarboxylic acid hybridized room temperature phosphorescent material |
| CN113025325A (en) * | 2021-03-25 | 2021-06-25 | 盐城工学院 | Preparation method and application of room-temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113789168A (en) * | 2021-10-08 | 2021-12-14 | 中山大学 | A thermally activated delayed fluorescent material and its preparation method and application |
| CN114621752A (en) * | 2021-12-03 | 2022-06-14 | 昆明理工大学 | A room temperature phosphorescent water-based polymer anti-counterfeiting material and its preparation method and application |
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot composite and preparation method thereof |
| CN111763512A (en) * | 2020-06-24 | 2020-10-13 | 中山大学 | Application of polyvinylbenzenesulfonic acid or its salt as room temperature phosphorescent material |
| CN112707922A (en) * | 2020-12-24 | 2021-04-27 | 河北工业大学 | Color-adjustable hectorite and 4,4' -biphenyldicarboxylic acid hybridized room temperature phosphorescent material |
| CN113025325A (en) * | 2021-03-25 | 2021-06-25 | 盐城工学院 | Preparation method and application of room-temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113025325B (en) * | 2021-03-25 | 2022-11-01 | 盐城工学院 | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113789168A (en) * | 2021-10-08 | 2021-12-14 | 中山大学 | A thermally activated delayed fluorescent material and its preparation method and application |
| CN114621752A (en) * | 2021-12-03 | 2022-06-14 | 昆明理工大学 | A room temperature phosphorescent water-based polymer anti-counterfeiting material and its preparation method and application |
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115161014B (en) * | 2022-06-09 | 2023-04-07 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
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Application publication date: 20200609 Assignee: Guangzhou Shuangyingli Biotechnology Co.,Ltd. Assignor: SUN YAT-SEN University Contract record no.: X2023440000011 Denomination of invention: An aging room temperature phosphorescent anti-counterfeiting material and its preparation method and application Granted publication date: 20210813 License type: Common License Record date: 20230302 |