CN108004789B - 一种纺织品用电致变色液晶微胶囊的制备方法 - Google Patents

一种纺织品用电致变色液晶微胶囊的制备方法 Download PDF

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CN108004789B
CN108004789B CN201711404913.XA CN201711404913A CN108004789B CN 108004789 B CN108004789 B CN 108004789B CN 201711404913 A CN201711404913 A CN 201711404913A CN 108004789 B CN108004789 B CN 108004789B
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付少海
张丽平
盛明非
田安丽
李敏
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Jiangnan University
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Abstract

本发明公开了一种纺织品用电致变色液晶微胶囊的制备方法，属于精细化工和材料科学技术领域。采用该方法制备的电致变色液晶微胶囊不仅颜色艳丽多变，能够满足人们对服装个性化和多样性的要求；而且具有良好的耐溶剂性和耐水性，粒径均匀，高芯材载量，驱动电压低，经过纺织品加工处理后仍能保持原有的颜色性能。并且应用时，液晶微胶囊的壳层结构不仅能够对液晶起到保护的作用，而且能够参与成膜，更加适用于纺织品的要求。

Description

一种纺织品用电致变色液晶微胶囊的制备方法
技术领域
本发明涉及一种纺织品用电致变色液晶微胶囊的制备方法，属于精细化工和材料科学技术领域。
背景技术
向列相液晶具有相当大的流动性，外场的变化会引起向列相分子取向的波动。这种波动在微观上调制了材料的折射率，并导致强烈的光散射。对向列相液晶主材料，掺杂一些二色性染料(这种染料因分子方向的改变而改变吸收光谱，具有光吸收各向异性)构成一对宾主材料。一般而言，二色性染料在液晶环境中的指向矢与液晶的指向矢一致。因此，掺杂二色性染料的向列型液晶在电路断开时为有色状态，导通时为无色状态。这种可逆电致变色模式具有响应速度快、变色灵敏度高、颜色鲜艳、耐光稳定性好、寿命长等优点。因此，掺杂二色性染料的向列相液晶显示有利于应用于贴近人体的产品，如人体心跳精密测量、柔性显示、电子纸、防伪包装、医用、有害静电检测、电致变色纺织品等。
液晶容易被污染，从而影响其光电效应，对其微胶囊化能够有效降低环境对向列相液晶的干扰作用，从而扩大其应用。国内针对液晶微胶囊的研究较少，主要采用复凝聚法、原位聚合等方法。例如，中国专利CN 201510237158.5、CN201410514834.4均涉及复凝聚法对液晶进行微胶囊化。吕奎等人通过溶剂蒸发法合成出高芯材载量的液晶微胶囊，并对其形貌调控机理进行了探究。郝鸿飞等人通过原位聚合法制备出表面光滑且粒径分布均匀的液晶微胶囊，用于制作变色涂料，并应用到纺织领域。然而，以上方法均不适用于染料掺杂型液晶微胶囊的制备，原因在于染料自身的易受污染特性和在制备微胶囊过程中染料较容易掺杂在聚合物基质中导致沾色现象，制备难度较大。国外Do Hyun Kim课题组通过隔膜乳化技术，制备了一种染料掺杂型液晶微胶囊，并应用于智能变色窗户，但该微胶囊的芯材载量较小，驱动电压过高，不适用于纺织品领域。
发明内容
为了解决上述问题，本发明目的在于提供一种纺织品用电致变色液晶微胶囊的制备方法，通过筛选合适的共聚单体，采用乳液聚合法制备染料掺杂型液晶微胶囊，染料掺杂型液晶微胶囊囊壁材料透明性、耐溶剂性和耐水性好，使得染料掺杂型液晶微胶囊在经过纺织品印花加工和后整理处理后仍然保持了的颜色性能，对染料掺杂型液晶起到了良好的保护作用。本发明制备的染料掺杂型液晶微胶囊可以满足纺织品的变色要求，颜色艳丽多变，耐光稳定性好，成膜性好，驱动电压低。
本发明的第一个目的是提供一种纺织品用电致变色液晶微胶囊，所述液晶微胶囊的制备是：(1)先将一定比例的二色性染料与向列型液晶充分混合制备染料掺杂型液晶材料；(2)染料掺杂型液晶材料制备乳液分散体，将软单体和硬单体按照软单体对硬单体的质量分数为50～200％的比例混匀后包覆染料掺杂型液晶材料。
在本发明的一种实施方式中，所述二色性染料对向列型液晶的质量分数为0.1～6％。
在本发明的一种实施方式中，所述染料掺杂型液晶占乳液分散体总体系质量分数1～15％。
在本发明的一种实施方式中，乳液分散体中乳化剂含量对染料掺杂型液晶质量分数为10-50％。
在本发明的一种实施方式中，软单体和硬单体混匀后的混合单体对染料掺杂型液晶质量分数为10～400％。
在本发明的一种实施方式中，包覆反应过程中逐滴加入对单体总量0.1-15％的引发剂。
在本发明的一种实施方式中，所述的引发剂是过硫酸钾、过硫酸铵或偶氮二异丁基脒盐酸盐中的一种。
在本发明的一种实施方式中，所述软单体为丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、甲基丙烯酸月桂酯、甲基丙烯酸正辛酯中的一种或两种。
在本发明的一种实施方式中，所述软单体为链长在2～8个碳原子的丙烯酸酯类。
在本发明的一种实施方式中，所述硬单体为苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、醋酸乙烯酯、甲基乙烯基醚、丙稀腈、丙烯酰胺、异戊二烯、双环戊二烯中的一种或两种。
在本发明的一种实施方式中，所述液晶为反式-丁基环己基甲酸、羟基联苯氰、4-丁基环己基甲酸-4‘-氰基联苯酚酯、N-4-甲氧基苄叉-正丁基苯胺、甲基丙烯酸β-羟乙酯(HEMA)、甲基丙烯酸卞醇酯(BMA)中的一种或多种。
在本发明的一种实施方式中，所述染料为蒽醌染料、偶氮染料或韭类染料。
在本发明的一种实施方式中，所述染料为C.I.分散黄119、C.I.分散红135、C.I.分散红343、C.I.分散蓝79、C.I.分散蓝165、C.I.分散蓝257、C.I.分散蓝148、C.I.分散红167或C.I.分散棕1。
在本发明的一种实施方式中，所述的乳化剂是阴离子型、非离子型或反应型表面活性剂中的一种；阴离子型表面活性剂为十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、油酸钾、烷基萘磺酸钠或松香酸钠中的一种；非离子型为聚氧乙烯烷基酚缩合物：OP-7、OP-10或OP-15，或聚氧乙烯脂肪醇缩合物：平平加O-10、平平加O-20、平平加O-25或平平加A-20，或聚氧乙烯多元醇醚脂肪酸酯：Tween40、Tween60、Tween65或Tween80；或脂肪酸的聚氧乙烯酯类：SG-10、SE-10或OE-15；反应型表面活性剂为1-烯丙氧基-3-(4-壬基苯酚)-2-丙醇聚氧乙烯(10)醚硫酸铵DNS-86。
在本发明的一种实施方式中，所述染料掺杂型液晶的混合方法是先将一定比例的液晶与二色性染料加热到全部溶解，搅拌0.5～3h后，降温到染料掺杂型液晶出现浑浊后，再升温至恰好透明，恒温搅拌0.5～5h，即得染料掺杂型液晶。
在本发明的一种实施方式中，所制备的液晶微胶囊大小为1.5-15μm，粒径可控，粒度分布窄，显色鲜艳，驱动电压低，耐水性和耐溶剂性好。
在本发明的一种实施方式中，所选用的染料应在主体向列型液晶基体中呈现出高的有序参数、高二色性和良好的溶解性。
本发明的第二个目的是提供上述液晶微胶囊的制备方法，所述方法具体是：将一定比例的二色性染料与向列型液晶充分混合制备染料掺杂型液晶，其中染料对液晶的质量分数为0.1～6％；保持一定温度在机械搅拌作用下，将染料掺杂型液晶滴加到相同温度下乳化剂水溶液中制备混合体系，其中染料掺杂型液晶占总体系质量分数1～15％，水溶液中乳化剂含量对染料掺杂型液晶质量分数为10-50％；高速乳化制备乳液分散体，将混合单体逐滴添加到液晶分散体中，继续乳化30～120分钟，其中混合单体对染料掺杂型液晶质量分数为10～400％，混合单体中软单体对硬单体的质量分数为50～200％；随后将乳化好的分散体转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气5～30分钟后，在250-1000转/分钟的搅拌速度下，升温至40～90℃，到达反应温度后，逐滴加入对单体总量0.1-15％的引发剂，保持温度反应2～12小时，反应完全后反复离心过滤，干燥后即可得到染料掺杂型液晶微胶囊。
本发明的有益效果是提供一种纺织品用电致变色液晶微胶囊的制备方法，采用该方法制备的电致变色液晶微胶囊不仅颜色艳丽多变，能够满足人们对服装个性化和多样性的要求，而且具有良好的耐溶剂性和耐水性，粒径均匀，高芯材载量，驱动电压低(低于人体安全电压)，经过纺织品加工处理后仍能保持原有的颜色性能。并且应用时，液晶微胶囊的壳层结构不仅能够对液晶起到保护的作用，而且能够参与成膜，更加适用于纺织品的要求。
具体实施方式
为了能够更清楚地理解本发明的技术内容，特举以下实施例详细说明，其目的仅在于更好理解本发明的内容而非限制本发明的保护范围。
实施例1：
将0.001gC.I.分散红60和1g混合液晶E7混合后加热到刚好全部溶解并成透明状，在此温度下搅拌0.5h后，降温到混合物出现颜色或浑浊后，再升温至恰好透明，恒温搅拌0.5h,即得染料掺杂型液晶。
将所得的染料掺杂型液晶保持在清亮点温度，并将其在机械搅拌作用下滴加到相同温度下含有0.1g分散剂0402的水溶液中，高速乳化形成均匀的分散体；将0.15g丙烯酸正丁酯和0.15g甲基丙烯酸甲酯，均匀混合后逐滴添加到液晶分散体中，继续乳化60分钟。随后转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气5分钟，在800转/分钟的搅拌速度下，升温至40℃，逐滴加入10g含有0.001g过硫酸铵的水溶液，反应2小时，恢复到室温后反复离心过滤，干燥后即得到染料掺杂型液晶微胶囊。该染料掺杂型液晶微胶囊粒径为3μm，25℃下显示明亮的红色，颜色随电压变化规律为红→无色。其它性能见表1、2。
实施例2：
将0.01gC.I.分散蓝60与液晶5CB混合后加热到刚好全部溶解，在此温度下搅拌1h后，降温到混合物出现浑浊后，再升温至恰好透明，恒温搅拌2h，即得染料掺杂型液晶。
将得到的混合液晶保持在清亮点温度在机械搅拌作用下滴加到相同温度下含有0.5g OP-10的水溶液中，高速乳化形成均匀的分散体；将2g苯乙烯和1g丙烯酸乙酯，均匀混合后逐滴添加到液晶分散体中，然后逐滴添加到液晶分散体中，继续乳化30分钟。随后转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气10分钟，在400转/分钟的搅拌速度下，升温至80℃，逐滴加入10g含有0.05g过硫酸钾的水溶液，反应2小时，恢复到室温后反复离心过滤，干燥后即得到染料掺杂型液晶微胶囊。该染料掺杂型液晶微胶囊粒径为10μm，25℃下显示蓝色，颜色随电压变化规律为蓝→无色。其它性能见表1、2。
实施例3：
将0.005g C.I.分散蓝359、0.005g C.I.分散红1及1g液晶7CB混合后加热到刚好全部溶解，在此温度下搅拌3h后，降温到混合物出现浑浊后，再升温至恰好透明，恒温搅拌5h,即得染料掺杂型液晶。
将得到的混合液晶保持在清亮点温度在机械搅拌作用下滴加到相同温度下含有0.2g Tween80的水溶液中，高速乳化形成均匀的液晶分散体；将1g甲基丙烯酸正辛酯和1g丙烯酸-2-乙基丁酯，混合均匀后逐滴添加到液晶分散体中，继续乳化120分钟。随后转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气20分钟，在1000转/分钟的搅拌速度下，升温至75℃，逐滴加入10g含有0.3g过硫酸钾的水溶液，反应5小时，恢复到室温后反复离心过滤，干燥后即得到染料掺杂型液晶微胶囊。该染料掺杂型液晶微胶囊粒径为1.5μm，25℃下显示紫色，颜色随电压变化规律为紫→无色。其它性能见表1、2。
实施例4：
将0.02gC.I.分散蓝359、0.02g C.I.分散红1、0.02gC.I.散黄119及1g液晶E7混合后加热到刚好全部溶解，在此温度下搅拌1h后，降温到混合物出现浑浊后，再升温至恰好透明，恒温搅拌2h，即得染料掺杂型液晶。
将得到的染料掺杂型液晶保持在清亮点温度在机械搅拌作用下滴加到相同温度下含有0.3g分散剂DNS-86的水溶液中，高速乳化形成均匀的分散体；将0.015g偶氮二异丁基脒盐酸盐溶解于0.5g醋酸乙烯酯和1g丙烯酸月桂酯，混合均匀后逐滴添加到分散体中，继续乳化60分钟。随后转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气30分钟，在250转/分钟的搅拌速度下，升温至90℃，反应12小时，恢复到室温后反复离心过滤，干燥后即得到染料掺杂型液晶微胶囊。该染料掺杂型液晶微胶囊粒径为15μm，25℃下显示棕色，颜色随温度变化规律为棕→无色。其它性能见表1、2。
对照例1：
单体采用3g苯乙烯和0.1g丙烯酸乙酯，均匀混合后逐滴添加到液晶分散体中，其他条件与实施例2一致，结果见表1、2；由于硬单体比例大，微胶囊硬度较大，成膜后手感较硬，不利于其在纺织品上应用。同时由于单体量过多，导致制备的微胶囊壳材较厚，微胶囊驱动电压过高。
对照例2：
单体采用0.5g苯乙烯和8g丙烯酸乙酯，均匀混合后逐滴添加到液晶分散体中，其他条件与实施例2一致，结果见表1、2；由于软单体比例大，微胶囊在纺织品上较易成膜，但成膜后手感较为粘稠，不利于其在纺织品上应用。同时由于单体量过多，导致制备的微胶囊壳材较厚，微胶囊驱动电压过高。
表1染料掺杂型液晶微胶囊的颜色性能
表2染料掺杂型液晶微胶囊的耐水性和耐溶剂性
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (8)

1.一种纺织品用电致变色液晶微胶囊，其特征在于，所述液晶微胶囊的制备是：(1)先将一定比例的二色性染料与向列型液晶充分混合制备染料掺杂型液晶材料；(2)染料掺杂型液晶材料制备乳液分散体，将软单体和硬单体按照软单体对硬单体的质量分数为50～200％的比例混匀后包覆染料掺杂型液晶材料；所述的软单体和硬单体混匀后的混合单体对染料掺杂型液晶质量分数为10～400％；所述染料为C.I.分散黄119、C.I.分散红135、C.I.分散红343、C.I.分散蓝79、C.I.分散蓝165、C.I.分散蓝257、C.I.分散蓝148、C.I.分散红167或C.I.分散棕1。
2.根据权利要求1所述的液晶微胶囊，其特征在于，所述软单体为丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、甲基丙烯酸月桂酯、甲基丙烯酸正辛酯中的一种或两种。
3.根据权利要求1所述的液晶微胶囊，其特征在于，所述硬单体为苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、醋酸乙烯酯、甲基乙烯基醚、丙稀腈、丙烯酰胺、异戊二烯、双环戊二烯中的一种或两种。
4.根据权利要求1所述的液晶微胶囊，其特征在于，所述二色性染料对向列型液晶的质量分数为0.1～6％。
5.根据权利要求1所述的液晶微胶囊，其特征在于，所述染料掺杂型液晶占乳液分散体总体系质量分数1～15％。
6.根据权利要求1所述的液晶微胶囊，其特征在于，所述液晶为反式-丁基环己基甲酸、羟基联苯氰、4-丁基环己基甲酸-4‘-氰基联苯酚酯、N-4-甲氧基苄叉-正丁基苯胺、甲基丙烯酸β-羟乙酯(HEMA)、甲基丙烯酸卞醇酯(BMA)中的一种或多种。
7.权利要求1所述的液晶微胶囊的制备方法，其特征在于，所述方法具体是：将一定比例的二色性染料与向列型液晶充分混合制备染料掺杂型液晶，其中染料对液晶的质量分数为0.1～6％；保持一定温度在机械搅拌作用下，将染料掺杂型液晶滴加到相同温度下乳化剂水溶液中制备混合体系，其中染料掺杂型液晶占总体系质量分数1～15％，水溶液中乳化剂含量对染料掺杂型液晶质量分数为10-50％；高速乳化制备乳液分散体，将混合单体逐滴添加到液晶分散体中，继续乳化30～120分钟，其中混合单体对染料掺杂型液晶质量分数为10～400％，混合单体中软单体对硬单体的质量分数为50～200％；随后将乳化好的分散体转移至带有冷凝回流和搅拌装置的四口烧瓶中，通氮气5～30分钟后，在250-1000转/分钟的搅拌速度下，升温至40～90℃，到达反应温度后，逐滴加入对单体总量0.1-15％的引发剂，保持温度反应2～12小时，反应完全后反复离心过滤，干燥后即可得到染料掺杂型液晶微胶囊。
8.权利要求1所述的液晶微胶囊在纺织领域的应用。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104765A (zh) * 1985-06-14 1986-06-10 中国人民解放军国防科技大学 液晶乳液快速微胶囊制法
CN105765449A (zh) * 2014-02-26 2016-07-13 株式会社Lg化学 液晶胶囊的制备方法
CN106749871A (zh) * 2016-12-19 2017-05-31 江南大学 一种纺织品印花用液晶微胶囊的制备方法
CN106890607A (zh) * 2017-01-19 2017-06-27 中国科学院化学研究所 一种液晶微胶囊的制备方法及液晶微胶囊

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104765A (zh) * 1985-06-14 1986-06-10 中国人民解放军国防科技大学 液晶乳液快速微胶囊制法
CN105765449A (zh) * 2014-02-26 2016-07-13 株式会社Lg化学 液晶胶囊的制备方法
CN106749871A (zh) * 2016-12-19 2017-05-31 江南大学 一种纺织品印花用液晶微胶囊的制备方法
CN106890607A (zh) * 2017-01-19 2017-06-27 中国科学院化学研究所 一种液晶微胶囊的制备方法及液晶微胶囊

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