光（温）致变色材料的合成及其在防伪纸中的应用研究
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摘要
近年来,由于防伪技术的不断发展以及新材料的不断开发,为我国造纸工业的纸张防伪领域提供了全新的发展机遇。化学防伪领域是防伪领域最基础的技术之一,在防伪领域占据相当重要的位置。因此,对防伪新材料的合成及其在纸张上的应用研究具有非常重要的意义。
本论文第一部分首先进行了可逆温致变色材料合成及应用研究。针对当前无碳复写纸和传真纸都是不可逆微胶囊产品在造纸工业的应用,并且是一次性使用,国内造纸工业尚无可逆变色微胶囊应用的报道。本文分别以十四醇、十六醇和十八醇为溶剂,以内酯型化合物热敏红为隐色染料,以双酚A为显色剂,制备了变色温度分别为36.0～39.5℃,44.5～46.5℃51.0～53.5℃的可逆温致变色材料。通过大量实验表明:可逆温致变色材料中隐色染料、显色剂、溶剂三组份的最佳配比分别为1∶4∶30(十四醇)、1∶3∶40(十六醇)、1∶2∶20(十八醇),并利用红外谱图分析了可逆温致变色材料可能的变色机理。为了增强可逆温致变色材料的耐老化性能,本文采用相分离法和界面聚合法合成低温(100℃以下)可逆温致变色微胶囊,通过实验选择最优微囊化工艺,包括囊心的最佳配制比例、最佳壁材囊心比的确定以及诸多影响因素的研究,并对其进行了微胶囊化,研究了可逆温致变色材料及其微胶囊制品的耐疲劳性、抗氧化性以及对酸、碱、溶剂等化学环境的稳定性,从而扩展了可逆温致变色微胶囊材料在纸张防伪领域的应用。
鉴于目前国内外可逆温致变色材料大多在油墨或油漆中使用,本文将合成的可逆温致变色微胶囊材料应用于纸料体系和涂布纸涂料体系,并对防伪纸的防伪变色机理及留着机理进行系统研究,测定了防伪纸张的纸页性能、防伪涂布纸的印刷性能以及其防伪性能。将低温可逆温致变色微胶囊应用于纸料体系和纸张涂料体系制成温致变色防伪纸,填补了国内可逆低温温致变色防伪纸张的空白。
本论文第二部分对稀土配合物光致变色材料进行了合成及应用研究。稀土有机配合物发光是无机发光、有机发光和生物发光研究的交叉学科,有着重要的理论研究意义及实际应用研究价值。针对目前光致变色材料在纸张上的应用仅限于纸张的后加工处理—防伪油墨在钞票以及有价证券等中的印刷应用,本论文对光致变色稀土配合物的合成进行了研究,包括配体种类的选择、稀土与各配体的最佳比例以及配合物的稳定性等,并利用荧光光谱图定量测定了稀土配合物光致变色材料及其在防伪纸中的应用的防伪性能,从而扩展了稀土配合物光致变色材料在纸张防伪领域的应用性能。
鉴于目前国内外稀土配合物光致变色材料大多在油墨或油漆油性介质中
In recent years, the progressive development of anti-counterfeit technology and exploitation of new materials supplies the anti-counterfeit paper field in China paper industry with a bran-new developmental opportunity. Chemical anti-counterfeit is one of the most fundamental technologies and occupies a quite important position in anti-counterfeit field. Therefore, it is very important to study the synthesis of new anti-counterfeit materials.The synthesis and application of reversible thermochromic materials were studied in the first part of this paper. Considering the fact of the current carbonless paper and facsimile paper are the applications of irreversible thermochromic microcapsule technology in paper industry, and they are one-off materials, and it is never reported that the technology of reversible thermochromic microcapsule has been applied in native paper industry. So, using the tetradecanol, hexadecanol and octadecanol as corresponding solvents, with letlacton compound of 3-diethylamino-7,8-phenyl-fluoran as procrypsis dye, H_(15)H_(16)O_2 as color agent, these reversible thermochromic materials which can turn color when temperature range at respectively 36.0～39.5℃, 44.5～46.5℃, 51.0～53.5℃were prepared. A number of trials showed that the optimal ratios of procrypsis dye, color agent and solvent are 1:4:30(tetradecanol), 1:3:40(hexadecanol), 1:2:20(octadecanol). And by infrared spectrum technology, their chromic mechanisms of this kind of reversible thermochromic materials were analyzed. In order to strengthen the resisting capability of aging of these materials the phase disengagement and interphase polymerization were adopted to synthesize the low temperature (<100 ℃) reversible thermochromic microcapsule. By repeating experiments, the preparation technological conditions of microcapsule were determined considering their respective optimal compositions of the core and shell of microcapsule, and other factors. And some properties of reversible thermochromic materials and microcapsules were studied including the resisting capabilities of fatigue and oxidation, the stability to chemical ambiences such as acid, alkali and solvents, etc.Presently, in home and abroad, reversible thermochromic materials are mostly used in ink and paint. However, in this paper, they were firstly applied in the system of pulp and coating paper, and the anti-counterfeit mechanism of this kind of paper and the retention mechanism of reversible thermochromic materials were investigated systematically, the strength properties of anti-counterfeit paper and
printing properties of anti-counterfeit coating paper were tested. The low temperature reversible thermochromic microcapsule was successfully applied to prepare the thermochromic anti-counterfeit paper for the first time, which supplies a native gap of the low temperature reversible thermochromic anti-counterfeit paper.In the second part, rare earth polymer complex photochromic materials were synthesized and applied. Rare earth polymer complex photochromic is the interdisciplinary of inorganic, organic and biological, and has important research significance in theory and application value in practice. Presently, applications of photochromic materials in paper are limited to process banknote and bond paper. In this paper, the synthesis factors of rare earth polymer complex were studied, including the option of ligand, the optimal ratio of ligand and rare earth, the stability of ligand and so on. The anti-counterfeit properties of anti-counterfeit paper by fluorescent spectrum were studied, consequently extending the application of rare earth polymer complex photochromic materials in anti-counterfeit paper field.Presently, in the world, rare earth polymer complex thermochromic materials are commonly used in ink and paint. But, in our experiments, they were firstly applied in the system of pulp and coating paper, the anti-counterfeit mechanism of this kind of paper and the retention mechanism of rare earth polymer complex thermochromic materials were investigated systematically, the strength properties of anti-counterfeit paper were tested, the resisting capability of aging, the anti-counterfeit and printing properties of anti-counterfeit coating paper. The development of this kind of anti-counterfeit paper supplies a native gap of the photochromic anti-counterfeit paper, and supplies reliably theoretical reference to develop comprehensive anti-counterfeit paper, and has definite guiding significance to practical production.
本论文第一部分首先进行了可逆温致变色材料合成及应用研究。针对当前无碳复写纸和传真纸都是不可逆微胶囊产品在造纸工业的应用,并且是一次性使用,国内造纸工业尚无可逆变色微胶囊应用的报道。本文分别以十四醇、十六醇和十八醇为溶剂,以内酯型化合物热敏红为隐色染料,以双酚A为显色剂,制备了变色温度分别为36.0～39.5℃,44.5～46.5℃51.0～53.5℃的可逆温致变色材料。通过大量实验表明:可逆温致变色材料中隐色染料、显色剂、溶剂三组份的最佳配比分别为1∶4∶30(十四醇)、1∶3∶40(十六醇)、1∶2∶20(十八醇),并利用红外谱图分析了可逆温致变色材料可能的变色机理。为了增强可逆温致变色材料的耐老化性能,本文采用相分离法和界面聚合法合成低温(100℃以下)可逆温致变色微胶囊,通过实验选择最优微囊化工艺,包括囊心的最佳配制比例、最佳壁材囊心比的确定以及诸多影响因素的研究,并对其进行了微胶囊化,研究了可逆温致变色材料及其微胶囊制品的耐疲劳性、抗氧化性以及对酸、碱、溶剂等化学环境的稳定性,从而扩展了可逆温致变色微胶囊材料在纸张防伪领域的应用。
鉴于目前国内外可逆温致变色材料大多在油墨或油漆中使用,本文将合成的可逆温致变色微胶囊材料应用于纸料体系和涂布纸涂料体系,并对防伪纸的防伪变色机理及留着机理进行系统研究,测定了防伪纸张的纸页性能、防伪涂布纸的印刷性能以及其防伪性能。将低温可逆温致变色微胶囊应用于纸料体系和纸张涂料体系制成温致变色防伪纸,填补了国内可逆低温温致变色防伪纸张的空白。
本论文第二部分对稀土配合物光致变色材料进行了合成及应用研究。稀土有机配合物发光是无机发光、有机发光和生物发光研究的交叉学科,有着重要的理论研究意义及实际应用研究价值。针对目前光致变色材料在纸张上的应用仅限于纸张的后加工处理—防伪油墨在钞票以及有价证券等中的印刷应用,本论文对光致变色稀土配合物的合成进行了研究,包括配体种类的选择、稀土与各配体的最佳比例以及配合物的稳定性等,并利用荧光光谱图定量测定了稀土配合物光致变色材料及其在防伪纸中的应用的防伪性能,从而扩展了稀土配合物光致变色材料在纸张防伪领域的应用性能。
鉴于目前国内外稀土配合物光致变色材料大多在油墨或油漆油性介质中
In recent years, the progressive development of anti-counterfeit technology and exploitation of new materials supplies the anti-counterfeit paper field in China paper industry with a bran-new developmental opportunity. Chemical anti-counterfeit is one of the most fundamental technologies and occupies a quite important position in anti-counterfeit field. Therefore, it is very important to study the synthesis of new anti-counterfeit materials.The synthesis and application of reversible thermochromic materials were studied in the first part of this paper. Considering the fact of the current carbonless paper and facsimile paper are the applications of irreversible thermochromic microcapsule technology in paper industry, and they are one-off materials, and it is never reported that the technology of reversible thermochromic microcapsule has been applied in native paper industry. So, using the tetradecanol, hexadecanol and octadecanol as corresponding solvents, with letlacton compound of 3-diethylamino-7,8-phenyl-fluoran as procrypsis dye, H_(15)H_(16)O_2 as color agent, these reversible thermochromic materials which can turn color when temperature range at respectively 36.0～39.5℃, 44.5～46.5℃, 51.0～53.5℃were prepared. A number of trials showed that the optimal ratios of procrypsis dye, color agent and solvent are 1:4:30(tetradecanol), 1:3:40(hexadecanol), 1:2:20(octadecanol). And by infrared spectrum technology, their chromic mechanisms of this kind of reversible thermochromic materials were analyzed. In order to strengthen the resisting capability of aging of these materials the phase disengagement and interphase polymerization were adopted to synthesize the low temperature (<100 ℃) reversible thermochromic microcapsule. By repeating experiments, the preparation technological conditions of microcapsule were determined considering their respective optimal compositions of the core and shell of microcapsule, and other factors. And some properties of reversible thermochromic materials and microcapsules were studied including the resisting capabilities of fatigue and oxidation, the stability to chemical ambiences such as acid, alkali and solvents, etc.Presently, in home and abroad, reversible thermochromic materials are mostly used in ink and paint. However, in this paper, they were firstly applied in the system of pulp and coating paper, and the anti-counterfeit mechanism of this kind of paper and the retention mechanism of reversible thermochromic materials were investigated systematically, the strength properties of anti-counterfeit paper and
printing properties of anti-counterfeit coating paper were tested. The low temperature reversible thermochromic microcapsule was successfully applied to prepare the thermochromic anti-counterfeit paper for the first time, which supplies a native gap of the low temperature reversible thermochromic anti-counterfeit paper.In the second part, rare earth polymer complex photochromic materials were synthesized and applied. Rare earth polymer complex photochromic is the interdisciplinary of inorganic, organic and biological, and has important research significance in theory and application value in practice. Presently, applications of photochromic materials in paper are limited to process banknote and bond paper. In this paper, the synthesis factors of rare earth polymer complex were studied, including the option of ligand, the optimal ratio of ligand and rare earth, the stability of ligand and so on. The anti-counterfeit properties of anti-counterfeit paper by fluorescent spectrum were studied, consequently extending the application of rare earth polymer complex photochromic materials in anti-counterfeit paper field.Presently, in the world, rare earth polymer complex thermochromic materials are commonly used in ink and paint. But, in our experiments, they were firstly applied in the system of pulp and coating paper, the anti-counterfeit mechanism of this kind of paper and the retention mechanism of rare earth polymer complex thermochromic materials were investigated systematically, the strength properties of anti-counterfeit paper were tested, the resisting capability of aging, the anti-counterfeit and printing properties of anti-counterfeit coating paper. The development of this kind of anti-counterfeit paper supplies a native gap of the photochromic anti-counterfeit paper, and supplies reliably theoretical reference to develop comprehensive anti-counterfeit paper, and has definite guiding significance to practical production.
引文
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