CN114907660B - 一种用于防伪的温湿致变色复合膜的制备方法 - Google Patents
一种用于防伪的温湿致变色复合膜的制备方法 Download PDFInfo
- Publication number
- CN114907660B CN114907660B CN202210544011.0A CN202210544011A CN114907660B CN 114907660 B CN114907660 B CN 114907660B CN 202210544011 A CN202210544011 A CN 202210544011A CN 114907660 B CN114907660 B CN 114907660B
- Authority
- CN
- China
- Prior art keywords
- thermochromic
- gel
- color
- composite film
- pnipam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/02—Dextran; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
本发明公开了一种用于防伪的温湿致变色复合膜的制备方法,将PNIPAM或HPC引入到水凝胶基干膜中,利用膜吸水溶胀的性质创造温致变色的湿环境,利用PNIPAM的温致变色性质构建可逆温致变色防伪图案;将水凝胶基干膜和PNIPAM或HPC组装起来,共同构建起用于防伪的温湿致变色膜。该防伪膜在水中溶胀一定时间后,在一定的温度条件下,即可显示出防伪图案。
Description
技术领域
本发明属于防伪技术领域,具体涉及一种用于防伪的温湿致变色复合膜及其制备方法。
背景技术
防伪技术在社会商业领域发挥着重要作用,在防治和打击假冒伪劣产品方面发挥着重要作用。根据《2018年度全球品牌假冒和商标侵权报告》指出,在2022年,全球假冒商品市场规模将达到1.95万亿美元。市面上常见防伪标签有激光全息图防伪标签、荧光防伪标签、二维码防伪标签、数码防伪标签和规矩揭穿式复合防伪标签等,这些防伪存在制作成本高、识别成本高和不环保的问题,甚至存在被仿制的风险。因此,开发出一种制作成本低、识别成本低、环保且不易被仿制的新型防伪材料具有重要的意义。
发明内容
本发明的目的在于提供一种用于防伪的温湿致变色复合膜及其制备方法,通过将温致变色材料与水凝胶基质溶液混合得到变色材料与水凝胶混合溶液,浇筑并冷却制得温致变色凝胶;将未掺杂温致变色材料的水凝胶基质溶液浇筑在温致变色凝胶上,冷却构成温致变色复合凝胶;将上述温致变色复合凝胶进行热压干燥,即得所述的温湿致变色复合膜;该温湿致变色复合膜包含未掺杂温致变色材料的非变色区与温湿致变色区,通过浸泡在水中溶胀形成凝胶,在加热条件下可实现加密信息的获取,可以用于构建防伪系统。
为实现上述目的,本发明采用如下技术方案:
一种温湿致变色复合膜的制备方法:将温致变色材料与水凝胶基质溶液混合得到变色材料与水凝胶混合溶液,浇筑并冷却制得温致变色凝胶;将未掺杂温致变色材料的水凝胶基质溶液浇筑在温致变色凝胶上,冷却构成温致变色复合凝胶;将上述温致变色复合凝胶进行热压干燥,即得所述的温湿致变色复合膜。
所述的温致变色材料是聚异丙基丙烯酰胺或羟丙基纤维素,其中聚异丙基丙烯酰胺的平均粒径为650 nm;羟丙基纤维素为高取代度型,羟丙基含量为30~70%。
所述的水凝胶基质包括KGM、KCA、PVA-1799、PAA、PEO和SA中的一种或两种。
所述的温湿致变色复合膜的变色区中,温致变色材料占干重质量的3~70%。
所述的温湿致变色复合膜的变色区中,水凝胶基质占干重质量的30~97%。
所述的温湿致变色复合膜由温致变色复合凝胶经热压干燥制成,干燥温度为30~70℃,干燥时间为30~60 min。
所述的温湿致变色复合膜的厚度为0.01~0.2 mm。
所述的温湿致变色复合膜在水中浸泡时间为5~30 min。
在获取加密信息过程中,凝胶的加热温度为30~60℃,加热时间为20~50 s。
一种如上所述的方法制得的温湿致变色复合膜在防伪功能上的应用:将温湿致变色复合膜浸泡在水中溶胀后,在加热条件下进行加热,进行防伪应用,其中加热温度为30~60℃,加热时间为20~50 s。
本发明的有益效果在于:本发明提供了一种用于防伪的温湿致变色复合膜,利用PNIPAM/水凝胶基膜或HPC/水凝胶基膜在温湿条件下由透明转变为白色的现象,利用透光率差异设计出包含防伪信息的复合膜。该防伪膜具有绿色、廉价、可循环使用且难仿制的优点。
聚异丙基丙烯酰胺(PNIPAM)和羟丙基纤维素(HPC)是研究较为广泛的温致变色材料。当PNIPAM或HPC处在水分充盈的环境中,能够在受热时发生物理相变,使所在的体系由透明状态变为乳白色,透光率大大下降。利用这一性质,将PNIPAM或HPC在基材上呈现一定形状的分布,从而可以在温湿条件下展示出一定图案,用于防伪信息的识别。葡甘聚糖(KGM)、卡拉胶(KCA)、聚乙烯醇(PVA-1799)、聚丙烯酸(PAA)、聚环氧乙烷(PEO)和海藻酸钠(SA)是生产水凝胶的原料,这些原料成本低廉,具有可降解性,对环境友好。此外,这些原料含有大量的羟基和羰基等亲水基团,其制成的水凝胶基干膜可以在短时间内吸水溶胀成为水凝胶,构建出静态的水环境。另外,可以通过吸水溶胀和热压失水的方式,实现其形态在凝胶和膜之间的循环转变。本发明将PNIPAM或HPC与水凝胶基干膜结合起来,利用非温湿致变色膜和温湿致变色膜在温湿条件的透光率差异,制备出可以携带加密信息的可循环温湿致变色防伪复合膜。
附图说明
图1是本发明所述的温湿致变色复合膜在35℃环境中,在干膜和复水成为凝胶状态的应用示意图,其中五角星状区域是含有PNIPAM或HPC的温湿致变色区域,五角星状以外的区域是不含PNIPAM或HPC的非温湿致变色区域。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1:
(1)以异丙基丙烯酰胺单一为原料,利用N,N'-双丙基丙烯酰胺作为交联剂,以过硫酸铵为催化剂,采用无皂乳液聚合法合成PNIPAM;通过透析、干燥和研磨得到平均粒径为650 nm的PNIPAM;
(2)配置KGM/KCA溶液,其中KGM干重质量分数为33.3%,KCA干重质量分数为66.7%;
(3)将制备好的PNIPAM加入到已配置的KGM/KCA溶液中,搅拌均匀,得到PNIPAM/KGM/KCA溶液,其中PNIPAM干重质量分数为65.1%,KGM干重质量分数为11.6%,KCA干重质量分数为23.3%;
(4)将PNIPAM/KGM/KCA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的PNIPAM/KGM/KCA温致变色凝胶;
(5)将PNIPAM/KGM/KCA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用KGM/KCA溶液浸没PNIPAM/KGM/KCA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(6)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为90.7%和91.5%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为87.8%,非变色区透光率为88.6%;在35℃时,测得变色区透光率为13.4%,非变色区透光率为87.4%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有74.0%的透光率差异,可以显示出加密信息,且易于观察。
实施例2:
(1)配置KGM/KCA溶液,其中KGM干重质量分数为33.3%,KCA干重质量分数为66.7%;
(2)配置HPC溶液,加入到已配置的KGM/KCA溶液中,搅拌溶解,得到HPC/KGM/KCA溶液,其中HPC干重质量分数为66.7%,KGM干重质量分数为11.1%,KCA干重质量分数为22.2%;
(3)将HPC/KGM/KCA溶液注射在深度为2mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的HPC/KGM/KCA温致变色凝胶;
(4)将HPC/KGM/KCA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用KGM/KCA溶液浸没HPC/KGM/KCA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(5)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为90.0%和89.8%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为88.4%,非变色区透光率为88.5%;在35℃时,测得变色区透光率为33.5%,非变色区透光率为87.4%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有53.9%的透光率差异,可以显示出加密信息,且易于观察。
实施例3:
(1)以异丙基丙烯酰胺单一为原料,利用N,N'-双丙基丙烯酰胺作为交联剂,以过硫酸铵为催化剂,采用无皂乳液聚合法合成PNIPAM;通过透析、干燥和研磨得到平均粒径为650 nm的PNIPAM;
(2)配置PVA溶液,将制备好的PNIPAM加入到已配置的PVA溶液中,搅拌均匀,得到PNIPAM/PVA溶液,其中PNIPAM干重质量分数为6.4%,PVA干重质量分数为93.6%;
(3)将PNIPAM/PVA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的HPC/KGM/KCA温致变色凝胶;
(4)将PNIPAM/PVA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PVA溶液浸没PNIPAM/PVA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(5)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为91.0%和91.2%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为87.6%,非变色区透光率为88.1%;在35℃时,测得变色区透光率为13.5%,非变色区透光率为88.2%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有74.7%的透光率差异,可以显示出加密信息,且易于观察。
实施例4:
(1)分别配置HPC溶液与PVA溶液,将其混合得到HPC/PVA溶液,其中HPC干重质量分数为27.2%,KCA干重质量分数为72.8%;
(2)将HPC/PVA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2mm且具有一定形状的HPC/PVA温致变色凝胶;
(3)将HPC/PVA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PVA溶液浸没HPC/PVA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(4)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为89.2%和88.7%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为88.4%,非变色区透光率为87.8%;在35℃时,测得变色区透光率为40.2%,非变色区透光率为88.4%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有48.2%的透光率差异,可以显示出加密信息,且易于观察。
实施例5:
(1)以异丙基丙烯酰胺单一为原料,利用N,N'-双丙基丙烯酰胺作为交联剂,以过硫酸铵为催化剂,采用无皂乳液聚合法合成PNIPAM;通过透析、干燥和研磨得到平均粒径为650 nm的PNIPAM;
(2)配置PAA溶液,将制备好的PNIPAM加入到已配置的PAA溶液中,搅拌均匀,得到PNIPAM/PAA溶液,其中PNIPAM干重质量分数为3%,PAA干重质量分数为97%;
(3)将PNIPAM/PAA溶液注射在深度为2mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的PNIPAM/PAA温致变色凝胶;
(4)将PNIPAM/PAA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PAA溶液浸没PNIPAM/PAA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(5)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为88.5%和88.6%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为83.5%,非变色区透光率为82.5%;在35℃时,测得变色区透光率为10.7%,非变色区透光率为82.7%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有72.0%的透光率差异,可以显示出加密信息,且易于观察。
实施例6:
(1)分别配置HPC溶液与PAA溶液,将其混合得到HPC/PAA溶液,其中HPC干重质量分数为30%,PAA干重质量分数为70%;
(2)将HPC/PAA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2mm且具有一定形状的HPC/PAA温致变色凝胶;
(3)将HPC/PAA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PAA溶液浸没HPC/PAA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(4)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为87.5%和87.3%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为82.7%,非变色区透光率为81.7%;在35℃时,测得变色区透光率为35.0%,非变色区透光率为81.6%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有46.6%的透光率差异,可以显示出加密信息,且易于观察。
实施例7:
(1)以异丙基丙烯酰胺单一为原料,利用N,N'-双丙基丙烯酰胺作为交联剂,以过硫酸铵为催化剂,采用无皂乳液聚合法合成PNIPAM;通过透析、干燥和研磨得到平均粒径为650 nm的PNIPAM;
(2)配置PEO溶液,将制备好的PNIPAM加入到已配置的PEO溶液中,搅拌均匀,得到PNIPAM/PEO溶液,其中PNIPAM干重质量分数为12.1%,PEO干重质量分数为87.9%;
(3)将PNIPAM/PAA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的PNIPAM/PAA温致变色凝胶;
(4)将PNIPAM/PAA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PAA溶液浸没PNIPAM/PAA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(5)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为87.5%和88.5%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为83.3%,非变色区透光率为82.8%;在35℃时,测得变色区透光率为15.0%,非变色区透光率为82.8%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有67.8%的透光率差异,可以显示出加密信息,且易于观察。
实施例8:
(1)分别配置HPC溶液与PEO溶液,将其混合得到HPC/PEO溶液,其中HPC干重质量分数为50%,PEO干重质量分数为50%;
(2)将HPC/PEO溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2mm且具有一定形状的HPC/PEO温致变色凝胶;
(3)将HPC/PEO凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用PEO溶液浸没HPC/PEO凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(4)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为86.8%和87.5%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为84.0%,非变色区透光率为82.5%;在35℃时,测得变色区透光率为21.4%,非变色区透光率为82.0%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有60.6%的透光率差异,可以显示出加密信息,且易于观察。
实施例9:
(1)以异丙基丙烯酰胺单一为原料,利用N,N'-双丙基丙烯酰胺作为交联剂,以过硫酸铵为催化剂,采用无皂乳液聚合法合成PNIPAM;通过透析、干燥和研磨得到平均粒径为650 nm的PNIPAM;
(2)配置SA溶液,将制备好的PNIPAM加入到已配置的SA溶液中,搅拌均匀,得到PNIPAM/SA溶液,其中PNIPAM干重质量分数为12.1%,SA干重质量分数为87.9%;
(3)将PNIPAM/SA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2 mm且具有一定形状的PNIPAM/SA温致变色凝胶;
(4)将PNIPAM/SA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用SA溶液浸没PNIPAM/SA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(5)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550 nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为85.6%和86.4%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为82.2%,非变色区透光率为83.5%;在35℃时,测得变色区透光率为17.4%,非变色区透光率为83.2%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有65.8%的透光率差异,可以显示出加密信息,且易于观察。
实施例10:
(1)分别配置HPC溶液与SA溶液,将其混合得到HPC/SA溶液,其中HPC干重质量分数为50%,SA干重质量分数为50%;
(2)将HPC/SA溶液注射在深度为2 mm图形模具中,经室温冷却,使之形成厚度为2mm且具有一定形状的HPC/SA温致变色凝胶;
(3)将HPC/SA凝胶从深度为2 mm模具中取出,转移至深度为3 mm的模具中,用SA溶液浸没HPC/SA凝胶,冷却形成3 mm厚的温致变色复合凝胶;
(4)将3 mm厚的凝胶从模具中取出,经30℃热压得到厚度为0.03 mm的温湿致变色膜。
利用紫外可见光-分光光度计,在波长等于550nm处,测试温湿致变色复合膜干膜的透光率;测试温湿致变色复合膜复水后温致变色区和非温致变色区在25℃和35℃时的透光率。在干膜状态下,测得变色区和非变色区的透光率分别为91.4%和92.3%。在浸泡溶胀成为凝胶后,在25℃时,测得变色区透光率为86.8%,非变色区透光率为87.4%;在35℃时,测得变色区透光率为22.5%,非变色区透光率为87.0%。结果表明,在干膜状态下,变色区和非变色区透光率差异很小,具有隐藏加密信息的功能;在25℃时,干膜吸水溶胀后转变为温致变色凝胶,变色区和非变色区仍然具有隐藏加密信息的功能;在35℃时,温致变色凝胶的变色区和非变色区有64.5%的透光率差异,可以显示出加密信息,且易于观察。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (2)
1.一种用于防伪的温湿致变色复合膜的制备方法,其特征在于:将温致变色材料与水凝胶基质溶液混合得到混合溶液,浇筑并冷却制得温致变色凝胶;将未掺杂温致变色材料的水凝胶基质溶液浇筑在温致变色凝胶上,冷却构成温致变色复合凝胶;将温致变色复合凝胶进行热压干燥,即得到所述的温湿致变色复合膜;该温湿致变色复合膜包含未掺杂温致变色材料的非变色区与温湿致变色区,通过浸泡在水中溶胀形成凝胶,在加热条件下实现加密信息的获取,用于构建防伪系统;
温致变色材料是聚异丙基丙烯酰胺PNIPAM或羟丙基纤维素HPC,其中PNIPAM的平均粒径为650 nm;HPC为高取代度型,羟丙基含量为30~70%;
水凝胶基质包括葡甘聚糖KGM、卡拉胶KCA、聚乙烯醇PVA-1799、聚丙烯酸PAA、聚环氧乙烷PEO和海藻酸钠SA中的一种或两种;
温湿致变色复合膜的变色区中,温致变色材料占干重质量的3~70%;
温湿致变色复合膜的变色区中,水凝胶基质占干重质量的30~97%;
温湿致变色复合膜由温致变色复合凝胶经热压干燥制成,干燥温度为30~70℃,干燥时间为30~60 min;
温湿致变色复合膜的厚度为0.01~0.2 mm;
温湿致变色复合膜在水中浸泡时间为5~30 min;
获取加密信息过程中,凝胶的加热温度为30~60℃,加热时间为20~50 s。
2.一种如权利要求1所述的方法制得的温湿致变色复合膜在防伪领域中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210544011.0A CN114907660B (zh) | 2022-05-19 | 2022-05-19 | 一种用于防伪的温湿致变色复合膜的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210544011.0A CN114907660B (zh) | 2022-05-19 | 2022-05-19 | 一种用于防伪的温湿致变色复合膜的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114907660A CN114907660A (zh) | 2022-08-16 |
CN114907660B true CN114907660B (zh) | 2023-10-03 |
Family
ID=82768431
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210544011.0A Active CN114907660B (zh) | 2022-05-19 | 2022-05-19 | 一种用于防伪的温湿致变色复合膜的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114907660B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008063701A (ja) * | 2006-09-08 | 2008-03-21 | Oji Paper Co Ltd | 偽造防止用紙 |
CN110563965A (zh) * | 2019-08-09 | 2019-12-13 | 华南理工大学 | 一种具有一过性加密信息的温度敏感变色水凝胶及其制备方法 |
CN112126082A (zh) * | 2020-08-18 | 2020-12-25 | 浙江大学衢州研究院 | 一种自修复多重光响应的双层超分子水凝胶、其制备方法和应用 |
CN113990176A (zh) * | 2021-11-19 | 2022-01-28 | 中山大学 | 基于温致相变水凝胶的防伪标签的制备方法及应用 |
-
2022
- 2022-05-19 CN CN202210544011.0A patent/CN114907660B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008063701A (ja) * | 2006-09-08 | 2008-03-21 | Oji Paper Co Ltd | 偽造防止用紙 |
CN110563965A (zh) * | 2019-08-09 | 2019-12-13 | 华南理工大学 | 一种具有一过性加密信息的温度敏感变色水凝胶及其制备方法 |
CN112126082A (zh) * | 2020-08-18 | 2020-12-25 | 浙江大学衢州研究院 | 一种自修复多重光响应的双层超分子水凝胶、其制备方法和应用 |
CN113990176A (zh) * | 2021-11-19 | 2022-01-28 | 中山大学 | 基于温致相变水凝胶的防伪标签的制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN114907660A (zh) | 2022-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Polychrome photonic crystal stickers with thermochromic switchable colors for anti-counterfeiting and information encryption | |
Li et al. | Pressure/temperature dual‐responsive cellulose nanocrystal hydrogels for on‐demand schemochrome patterning | |
Zhang et al. | Photonic plasticines with uniform structural colors, high processability, and self‐healing properties | |
CN102703092A (zh) | 一种纳米纤维素液晶膜及其应用 | |
CN114907660B (zh) | 一种用于防伪的温湿致变色复合膜的制备方法 | |
Liao et al. | Temperature/pH dual sensitive Hericium erinaceus residue carboxymethyl chitin/poly (N-isopropyl acrylamide) sequential IPN hydrogels | |
CN108276590A (zh) | 可3d打印的琼脂/聚丙烯酰胺双氢键协同交联高韧性水凝胶的制备方法 | |
Bei et al. | Recent progress of biomass based self‐healing polymers | |
Xia et al. | Tough, freestanding, and colorless photonic paper using water as ink | |
Verma et al. | Cellulose nanocrystals for environment-friendly self-assembled stimuli doped multisensing photonics | |
CN113321827B (zh) | 一种纤维素基手性液晶薄膜的制备方法 | |
CN112851972B (zh) | 一种纳米纤维素聚合物光学复合水凝胶的制备方法和应用 | |
Wang et al. | Environmentally friendly optical multi-color rewritable paper based on inverse photonic glass | |
CN116253820B (zh) | 一种光致变色凝胶及其制备的多重响应变色干凝胶和变色方法 | |
CN112301452A (zh) | 一种光致变色超高分子量聚乙烯纤维的制备方法 | |
CN109942878A (zh) | 一种热压成型制备反蛋白结构高分子材料的方法 | |
CN114044924B (zh) | 一种温度敏感型变色水凝胶及其制备方法 | |
Jia et al. | Photo-induced multi-color fluorescent hydrogels for optical information coding and encryption | |
Gao et al. | Lanthanides-based invisible multicolor luminescent hydrogels and films for anti-counterfeiting | |
Wei et al. | An efficient method for improving the stability of Monascus pigments using ionic gelation | |
CN113831669A (zh) | 一种防伪用一维光子晶体膜及其制备方法 | |
Chen et al. | One-pot preparation of physical hydrogel-based photonic crystal | |
Chu et al. | Non-gelated polymeric photonic crystal films | |
ZAINAL et al. | Cellulose-based hydrogel as Halal agricultural medium | |
CN116392452B (zh) | 一种羟丙甲纤维素空心胶囊及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |