WO2021008346A1 - 一种电、温双控型双稳态变色染料及微胶囊的制备方法 - Google Patents

一种电、温双控型双稳态变色染料及微胶囊的制备方法 Download PDF

Info

Publication number
WO2021008346A1
WO2021008346A1 PCT/CN2020/099093 CN2020099093W WO2021008346A1 WO 2021008346 A1 WO2021008346 A1 WO 2021008346A1 CN 2020099093 W CN2020099093 W CN 2020099093W WO 2021008346 A1 WO2021008346 A1 WO 2021008346A1
Authority
WO
WIPO (PCT)
Prior art keywords
dual
color
changing
control
temperature
Prior art date
Application number
PCT/CN2020/099093
Other languages
English (en)
French (fr)
Inventor
付少海
张丽平
王成成
盛明非
田安丽
Original Assignee
江南大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 江南大学 filed Critical 江南大学
Publication of WO2021008346A1 publication Critical patent/WO2021008346A1/zh
Priority to US17/395,793 priority Critical patent/US11655373B2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B9/00—Esters or ester-salts of leuco compounds of vat dyestuffs

Definitions

  • the invention relates to a method for preparing electricity and temperature dual-control bistable color-changing dyes and microcapsules, and belongs to the technical field of fine chemicals and materials science.
  • Leucome refers to white.
  • Color-changing leuco dye refers to a type of dye that changes color through the action of a color developer; or is obtained through a non-reduced intramolecular cyclization reaction (reaction restricted by heating, light, change, etc.) Colorless form of dye.
  • shifft bases spirocyclics, bisanthrones, phenothiazines, phthalides, triarylmethanes, and fluorans.
  • Thermochromic dyes are generally a mixture of color-changing leuco dyes, color developers, and solid solvents. Leuco dyes are chromogenic groups. The color-developing agent determines the color depth and the solvent determines the color-changing temperature. For example, in CN109667196A, from 4,4'-dihydroxydiphenyl sulfone, colorless thermosensitive dye, 1,2-diphenoxyethane, and auxiliary materials, replace bisphenol A with bisphenol S, and use 1,2 -Diphenoxyethane is used as a sensitizer, and a small amount of stearate is added to reduce the color temperature of thermal paper, and at the same time solve the problem of low thermal sensitivity of bisphenol S.
  • CN104228385A several polyisocyanates and their prepolymers are used to microencapsulate recessive thermosensitive dyes in the thermosensitive color developing layer to form microcapsules, and the softening temperature of different microcapsules is used to increase the color developing temperature range of the thermosensitive layer.
  • the lowest color temperature range is 100°C ⁇ 150°C.
  • Some leuco dyes used for thermochromic color can also change color under the action of an electric field.
  • the color change principle is: the leuco dye gains and loses electrons through the on-off of the voltage, so that the structure of the dye changes (lactone ring opening and closing ), which is expressed as a color change.
  • this type of leuco dye is electrical stimulation or temperature stimulation, when the stimulus value changes to the original value, the color of this single control discoloration element immediately changes to the original color, and cannot stabilize the color state after the stimulation.
  • the present invention finds and screens suitable electrolytes, leuco dyes and organic solid materials, and mixes them in a certain proportion to prepare the color change temperature at -5°C ⁇ +80°C and the driving voltage at A series of electric and temperature dual-control bistable color-changing microcapsules in the range of 1 ⁇ 10V.
  • the color-changing microcapsules need to change color under the coordinated control of electricity and temperature, and can achieve a certain color change under low temperature and power failure. The continuous steady state of the state.
  • the first object of the present invention is to provide an electric and temperature dual-control bistable color-changing dye, which includes a leuco dye, an electrolyte and an organic solid material.
  • the leuco dye includes 1,3-dimethyl-6-diethylaminofluoran, 2'-chloro-6'-(diethylamino)-3'-methylfluoran Alkanes, 2'-chloro-6'-(diethylamino)fluoran, 6'-(diethylamino)-1',3'-dimethylfluoran, triarylmethanes and spiropyrans.
  • the selected electrolyte is tetrabutylammonium perchlorate (TBAP), tetraethylammonium perchlorate, ferric nitrate, barium sulfate, calcium carbonate, mercury chloride, lead acetate and the like.
  • TBAP tetrabutylammonium perchlorate
  • ferric nitrate ferric nitrate
  • barium sulfate ferric nitrate
  • barium sulfate calcium carbonate
  • mercury chloride mercury chloride
  • the selected organic solid materials are one or more of small molecular organic alkyl alcohols and alkyl acids, and macromolecular ethers and esters.
  • the organic solid materials include but are not limited to the following Material: stearyl alcohol, cetyl alcohol, myristyl alcohol, myristic acid, palmitic acid, stearyl acid, glyceryl monostearate, glyceryl monostearate, phenyl salicylate, laurel Acid glycerides, azoanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate, benzyl benzoate.
  • the organic solid material is one or more of macromolecular ethers and esters, including glyceryl monostearate and glycerol monostearate. Ester, phenyl salicylate, glyceryl laurate, azoanisole, diphenyl carbonate, phenyl salicylate, phenyl stearate, benzyl benzoate.
  • the ratio of leuco dye, electrolyte and organic solid material is 1: (2-10): (15-50).
  • the second object of the present invention is to provide an electric and temperature dual-control bistable color-changing microcapsule, which uses the above-mentioned electric and temperature dual-control color-changing dye as the core material to obtain an electric and temperature dual-control bistable color-changing microcapsule capsule.
  • the third object of the present invention is to provide a method for preparing electricity and temperature dual-control bistable color-changing microcapsules, which includes the following steps:
  • Dual-control compound heat the above-mentioned electric and temperature dual-control color-changing dye and stir it by magnetic force to form a uniform mixed solution, that is, a dual-control compound;
  • the dual-control compound obtained in step (1) is added dropwise to the aqueous solution containing emulsifier, the emulsifier accounts for 25- of the mass fraction of the dual-control compound 100%, high-speed emulsification to form a uniform dye dispersion; add the monomer with a mass fraction of 20-100% of the dye compound to the dye dispersion drop by drop, continue to emulsify for 10-20 minutes; then disperse the emulsified
  • the body is transferred to a four-necked flask with a condensing reflux and stirring device. After nitrogen gas for 5-30 minutes, the temperature is raised to 55-75°C at a stirring speed of 250-500r/min. After reaching the reaction temperature, add dropwise For the initiator with the total monomer content of 0.1-1%, keep the temperature and react for 2-6 hours, wash with water after the reaction is completed, and dry to obtain dual-control bistable microcapsules.
  • the selected monomers are methyl methacrylate, styrene, ethyl methacrylate, butyl methacrylate, vinyl acetate, methyl vinyl ether, acrylonitrile, One or two of acrylamide, isoprene, and dicyclopentadiene.
  • the selected initiator is one of potassium persulfate, ammonium persulfate, and azobisisobutylamidine hydrochloride.
  • the selected emulsifier is one or more of non-ionic surfactants, anionic surfactants, and polymer surfactants, including but not limited to the following materials: Gum Laber , Sodium dodecylbenzene sulfonate, styrene-maleic anhydride copolymer, Tween, Span.
  • the fourth object of the present invention is to provide an application of the above-mentioned electric and temperature dual-control bistable color-changing microcapsules in color-changing materials.
  • the present invention provides a method for preparing electricity and temperature dual control type steady-state color-changing microcapsules.
  • the electricity and temperature dual-control color-changing microcapsules prepared by the method need to change color under the synergistic conditions of specific voltage and temperature, and the color change temperature is at -5°C ⁇ +80°C, and according to different conditions, it can realize a continuous and stable state of a certain discoloration state, and finally achieve controllable discoloration conditions and a stable state of discoloration; and the driving voltage is lower than 10V (much lower than the human body The safety voltage is 36V). After the color is changed, the power is turned off, which can reach a steady state time of 5 days. It has a broad application prospect in the fields of color-changing textiles and glass.
  • the color-changing microcapsules are coated on a rigid substrate with electrodes. After the coating is completely dried, another rigid electrode is added on the film, and the upper and lower electrodes are bonded together with a colloid to obtain a display device.
  • DC steady-state power supplies were used to drive the devices, and the driving voltage of the color-changing microcapsules was verified based on the color-changing phenomenon.
  • 0.1g of 2'-chloro-6'-(diethylamino)fluoran, 0.8g of tetrabutylammonium perchlorate (TBAP), and 5g of phenyl salicylate were magnetically stirred at 80°C for 1 hour to obtain A homogeneous mixed solution.
  • TBAP tetrabutylammonium perchlorate
  • phenyl salicylate 5g was magnetically stirred at 80°C for 1 hour to obtain A homogeneous mixed solution.
  • the voltage When the voltage is applied, it is colorless when it is lower than 80°C; when the temperature is higher than 80°C, it becomes orange-red; when the temperature is lower than 80°C, the voltage remains orange-red when the temperature is lowered; and the temperature is returned to colorless. When no voltage is applied, it is colorless under any conditions.
  • Example 1 The 0.8 g of tetrabutylammonium perchlorate (TBAP) in Example 1 is omitted, and other conditions or parameters are consistent with those in Example 1, to obtain a microcapsule product. Weigh 0.2g of the product and press it into a tablet as a research object. It is colorless under any conditions, and cannot realize electric and temperature dual control discoloration.
  • TBAP tetrabutylammonium perchlorate
  • Example 1 The diphenyl carbonate in Example 1 was replaced with cetyl alcohol, and other conditions or parameters were consistent with those in Example 1, to obtain a microcapsule product. Weigh 0.2 g of the product, press the tablet, and use it as the research object. When the voltage is applied, it is colorless when it is lower than 28°C; when the temperature is higher than 28°C, it becomes orange-red; when the temperature is lower than 28°C, then the voltage remains orange-red, which has an energy-saving effect; color. When no voltage is applied, it is colorless under any conditions. However, the color of the sample is uneven, and the color is lighter, and the driving voltage is larger.
  • Example 1 Replace the 0.1g 2'-chloro-6'-(diethylamino)fluoran in Example 1 with 0.1g N-[4-[2-(4-methoxyphenyl)diazenyl]benzene Yl]-2-nitroaniline, and other conditions or parameters are the same as in Example 1, to obtain a microcapsule product. Weigh 0.2g of the product and press it into a tablet as a research object. It is colorless under any conditions, and cannot realize electric and temperature dual control discoloration.
  • fluoran dyes such as 1,3-dimethyl-6-diethylaminofluoran, 2'-chloro-6'-(diethylamino)-3'-methylfluoran Alkane, 2'-chloro-6'-(diethylamino)fluoran, 6'-(diethylamino)-1',3'-dimethylfluoran or crystal violet lactone or spiropyran leuco Body dyes can better realize the dual control of electricity and temperature.
  • the selected organic solid materials are one or more of macromolecular ethers and esters, including glyceryl monostearate, glycerol monostearate, and salicylic acid.
  • the obtained microcapsule product can realize electricity and temperature.
  • Control discoloration, and the driving voltage is less than 10V; other types of organic solid phase materials (such as: small molecule organic alkyl alcohol and alkyl acid, stearyl alcohol, cetyl alcohol, tetradecyl alcohol, tetradecanoic acid, hexadecyl Acid, octadecanoic acid, etc.) Either electric and temperature dual control discoloration cannot be realized, or the driving voltage is too high, or the color rendering effect is not good.
  • organic solid phase materials such as: small molecule organic alkyl alcohol and alkyl acid, stearyl alcohol, cetyl alcohol, tetradecyl alcohol, tetradecanoic acid, hexadecyl Acid, octadecanoic acid, etc.
  • the ratio of leuco dye, electrolyte and organic solid material is 1: (2-10): (15-50).
  • the electrical and temperature dual-control bistable color-changing microcapsules prepared by organic solid phase materials have better color-changing performance.
  • the driving voltage is less than 10V, which is lower than the safe voltage of the human body. Steady state time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Color Printing (AREA)

Abstract

一种电、温双控型双稳态变色染料，电、温双控型双稳态变色微胶囊及其制备方法和应用，通过将电解质、隐色体染料和有机固体材料按1：(2-10)：(15-50)混合后，可以制备变色温度在-5℃-+80℃范围内的一系列电、温双控双稳态变色染料复配物，由该电、温双控双稳态变色染料复配物制备得到的电、温双控型双稳态变色微胶囊在电压和温度的驱动下，实现变色性能和变色稳定状态可控，驱动电压低于10V。

Description

一种电、温双控型双稳态变色染料及微胶囊的制备方法 技术领域
本发明涉及一种电、温双控型双稳态变色染料及微胶囊的制备方法，属于精细化工和材料科学技术领域。
背景技术
“隐色体”指白色。变色隐色体染料，指通过与显色剂的作用而变的有颜色的一类染料；或是通过如非还原的分子内环化反应(受加热、光照、变化等制约的反应)得到的无色形式的染料。一般有shifft碱类、螺环类、双蒽酮类、吩噻嗪类、苯酞类三芳甲烷类和荧烷类等。
温致变色染料一般变色隐色体染料、显色剂和固体溶剂的混合物，隐色体染料为发色基团，显色剂决定颜色深浅和溶剂决定变色温度。如：CN109667196A中，由4，4’-二羟基二苯砜、无色热敏染料、1，2-二苯氧基乙烷、和辅料，用双酚S替换双酚A，用1，2-二苯氧基乙烷作为增感剂，再配合上少量硬脂酸盐达到降低热敏纸的显色温度，同时解决了双酚S热感度低问题。CN104228385A中，在热敏显色层中运用几种多异氰酸酯及其预聚体微包裹隐性热敏染料形成微胶囊，利用不同微胶囊的软化温度来增大热敏层的显色温度范围，其最低显色温度范围在100℃～150℃。
有些用于温致变色的隐色体染料还可以在电场作用下发生变色，其变色原理是：通过电压的通断控制隐色体染料得失电子，使得染料的结构发生变化(内酯环开闭)，从而表现为颜色变化。但是，这类隐色体染料不论是电刺激还是温度刺激，这种单一控制变色元素在刺激值变为原始数值时，颜色立即变为原始颜色，不能稳定在刺激后所呈现的颜色状态。在特定场合下，需要一直施加电压和温度来维持某一种需要的颜色，影响了变色材料应用的轻便性，并具有不节能、不绿色环保等缺点。
发明内容
为了解决上述问题，本发明通过寻找和筛选合适的电解质、隐色体染料和有机固体材料，将其将其按一定比例混合后，可以制备变色温度在-5℃～+80℃、驱动电压在1～10V范围内的一系列电、温双控制双稳态变色微胶囊，这种变色微胶囊需要电和温度的协同控制作用下变色，并能在低温和断电情况下，实现某种变色状态的持续稳定态。
本发明的第一个目的是提供一种电、温双控型双稳态变色染料，所述电、温双控制型双稳态变色染料包括隐色体染料、电解质和有机固体材料。
在本发明一种实施方式中，隐色体染料包括1,3-二甲基-6-二乙氨基荧烷、2’-氯-6’-(二乙氨基)-3’-甲基荧烷、2’-氯-6’-(二乙氨基)荧烷、6’-(二乙氨基)-1’,3’-二甲基 荧烷、三芳甲烷类和螺吡喃类。
在本发明一种实施方式中，所选用的电解质为四丁基高氯酸铵(TBAP)、四乙基高氯酸铵、硝酸铁、硫酸钡、碳酸钙、氯化汞、醋酸铅等。
在本发明一种实施方式中，所选用的有机固体材料为小分子有机烷基醇和烷基酸、大分子的醚类和酯类中的一种或者几种，有机固体材料包括但不限于以下材料：十八醇、十六醇、十四醇、十四酸、十六酸、十八酸、单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯。
在本发明一种实施方式中，优选地，所述有机固体材料为大分子的醚类和酯类中的一种或者几种，包括单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯。
在本发明一种实施方式中，隐色体染料、电解质和有机固体材料的比例为1：(2-10)：(15-50)。
本发明的第二个目的是提供一种电、温双控型双稳态变色微胶囊，采用上述电、温双控型变色染料为芯材制备得到电、温双控型双稳态变色微胶囊。
本发明的第三个目的是提供一种电、温双控型双稳态变色微胶囊的制备方法，包括以下步骤：
(1)双控型复配物：将上述电、温双控型变色染料加热并通过磁力搅拌，形成均匀的混合溶液，即双控型复配物；
(2)制备双控制型双稳态微胶囊：将步骤(1)得到的双控型复配物滴加到含有乳化剂的水溶液中，乳化剂占双控型复配物质量分数的25-100％，高速乳化形成均匀的染料分散体；将对染料复配物质量分数20～100％的单体，逐滴添加到染料分散体中，继续乳化10-20分钟；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250-500r/min的搅拌速度下，升温至55-75℃，到达反应温度后，逐滴加入对单体总量0.1-1％的引发剂，保持温度反应2-6小时，反应完全后水洗，干燥后即可得到双控制型双稳态微胶囊。
在本发明一种实施方式中，所选用的单体是甲基丙烯酸甲酯、苯乙烯、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。
在本发明一种实施方式中，所选用的引发剂是过硫酸钾、过硫酸铵，偶氮二异丁基脒盐酸盐中的一种。
在本发明一种实施方式中，所选用的乳化剂为非离子表面活性剂、阴离子表面活性剂、 高分子类表面活性剂中的一种或者几种，包括但不限于以下材料：拉伯树胶、十二烷基苯磺酸钠、苯乙烯-马来酸酐共聚物、吐温、司盘。
本发明第四个目的是提供一种上述电、温双控型双稳态变色微胶囊在变色材料方面的应用。
本发明的有益效果：
本发明提供了一种电、温双控型稳态变色微胶囊的制备方法，采用该方法制备的电、温双控制变色微胶囊需要在特定电压和温度的协同作用条件下变色，变色温度在-5℃～+80℃范围，并能根据条件的不同，实现某种变色状态的持续稳定态，最终达到变色条件可控和变色稳定状态可控；且驱动电压低于10V(远低于人体安全电压36V)，变色后，再断电，可达到5天稳态时间，在变色纺织品及变色玻璃等领域应用前景广阔。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
将变色微胶囊涂覆在带有电极的刚性基板上，待涂层完全干燥后在薄膜上面加盖另外一块刚性电极，并采用胶体将上下两块电极粘结起来，进行封装处理得到显示器件。分别采用直流稳态电源对器件进行驱动，根据变色现象验证变色微胶囊的驱动电压。
实施例1
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、5g碳酸二苯酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于31℃，无色；高于31℃，无色变为橙红色；降温至31℃以下，然后去电压，仍然保持为橙红色，具有节能的作用；升温变回无色。不加电压状态下，任意条件下都无色。
实施例2
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、5g水杨酸苯酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于25℃，无色；高于25℃，无色变为橙红色；降温至25℃以下，再去电压，仍然保持为橙红色；升温变回无色。不加电 压状态下，任意条件下都无色。
实施例3
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、5g硬脂酸苯酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于31℃，无色；高于31℃，无色变为橙红色；降温至31℃以下，再去电压仍然保持为橙红色；升温变回无色。不加电压状态下，任意条件下都无色。
实施例4
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、5g苯甲酸苄酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于5℃，无色；高于5℃，无色变为橙红色；降温至5℃以下，再去电压仍然保持为橙红色；升温回到无色。不加电压状态下，任意条件下都无色。
实施例5
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、5g单十八烷酸丙三醇酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于80℃，无色；高于80℃，无色变为橙红色；降温至80℃以下，再去电压仍然保持为橙红色；升温回到无色。不加电压状态下，任意条件下都无色。
实施例6
将0.1g 2’-氯-6’-(二乙氨基)荧烷、0.8g四丁基高氯酸铵(TBAP)、2.7g十六醇、2.3g单十八烷酸丙三醇酯在80℃条件下，磁力搅拌1小时，得到均匀的混合溶液。1.8g十二烷基苯磺酸钠、95.2g水、在70℃、6000r/min条件下乳化20分钟，边乳化边滴加油相(2g均匀复配物和1g聚甲基丙烯酸甲酯)，再加入0.01g过硫酸铵，80℃条件下机械搅拌(500r/min)3小时，最后水洗干燥得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状 态下，低于60℃，无色；高于60℃，无色变为橙红色；降温至60℃以下，再去电压仍然保持为橙红色；升温回到无色。不加电压状态下，任意条件下都无色。与实施例5相比，将十六醇与单十八烷酸丙三醇酯进行复配，变色温度由80℃降至60℃；而单独采用单十八烷酸丙三醇酯，变色温度为80℃，说明十六醇与单十八烷酸丙三醇酯进行复配能显著降低变色温度20℃。
对比例1
省略实施例1中的0.8g四丁基高氯酸铵(TBAP)，其他条件或者参数与实施例1一致，得到微胶囊产物。称取0.2g产物，压片后，作为研究对象，任意条件下都是无色，不能实现电、温双控变色。
对比例2
将实施例1中的碳酸二苯酯替换成十六醇，其他条件或者参数与实施例1一致，得到微胶囊产物。称取0.2g产物，压片后，作为研究对象。加电压状态下，低于28℃，无色；高于28℃，无色变为橙红色；降温至28℃以下，然后去电压，仍然保持为橙红色，具有节能的作用；升温变回无色。不加电压状态下，任意条件下都无色。但是，该样品变色不均匀，且颜色较浅，驱动电压较大。
对比例3
将实施例1中的0.1g 2’-氯-6’-(二乙氨基)荧烷替换成0.1g N-[4-[2-(4-甲氧基苯基)二氮烯基]苯基]-2-硝基苯胺，其他条件或参数与实施例1一致，得到微胶囊产物。称取0.2g产物，压片后，作为研究对象，任意条件下都是无色，不能实现电、温双控变色。发明人经过多次实验发现，荧烷类染料如：1,3-二甲基-6-二乙氨基荧烷、2’-氯-6’-(二乙氨基)-3’-甲基荧烷、2’-氯-6’-(二乙氨基)荧烷、6’-(二乙氨基)-1’,3’-二甲基荧烷或结晶紫内酯或螺吡喃类隐色体染料能够较好地实现电、温双控变色。
表1电、温双控型变色染料微胶囊的变色性能
Figure PCTCN2020099093-appb-000001
Figure PCTCN2020099093-appb-000002
发明人经过多次实验发现，选用的有机固体材料为大分子的醚类和酯类中的一种或者几种，包括单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯，得到的微胶囊产物能实现电、温双控变色，且驱动电压低于10V；单独采用其他种类的有机固相材料(如：小分子有机烷 基醇和烷基酸，十八醇、十六醇、十四醇、十四酸、十六酸、十八酸等)要么不能实现电、温双控变色，要么驱动电压过高，要么显色效果不好。但是，将十八醇、十六醇、十四醇、十四酸、十六酸、十八酸等小分子有机烷基醇和烷基酸与单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯等醚类和酯类进行复配，能显著降低变色温度。
发明人经过多次实验摸索，得出隐色体染料、电解质和有机固体材料的比例为1：(2-10)：(15-50)范围内，选用电解质、隐色体染料和酯类的有机固相材料制备得到的电、温双控型双稳态变色微胶囊的变色性能较好，驱动电压均小于10V，低于人体安全电压，且变色后，再断电，能维持5天的稳态时间。
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 (13)

  1. 一种电、温双控型双稳态变色染料，其特征在于，所述电、温双控制型双稳态变色染料包括隐色体染料、电解质和有机固体材料；所述隐色体染料为2’-氯-6’-(二乙氨基)荧烷；所述电解质为四丁基高氯酸铵；有机固体材料选自十八醇、十六醇、十四醇、十四酸、十六酸、十八酸、单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯中的一种或几种；所述隐色体染料、电解质和有机固体材料的比例为1：(2-10)：(15-50)。
  2. 一种电、温双控型双稳态变色染料，其特征在于，所述电、温双控制型双稳态变色染料包括隐色体染料、电解质和有机固体材料。
  3. 根据权利要求1所述的双控型双稳态变色染料，其特征在于，隐色体染料、电解质和有机固体材料的比例为1：(2-10)：(15-50)。
  4. 根据权利要求1所述的双控型双稳态变色染料，其特征在于，隐色体染料为1,3-二甲基-6-二乙氨基荧烷、2’-氯-6’-(二乙氨基)-3’-甲基荧烷、2’-氯-6’-(二乙氨基)荧烷、6’-(二乙氨基)-1’,3’-二甲基荧烷、结晶紫内酯或螺吡喃类。
  5. 根据权利要求1所述的双控型双稳态变色染料，其特征在于，电解质为四丁基高氯酸铵、四乙基高氯酸铵、硝酸铁、硫酸钡、碳酸钙、氯化汞或醋酸铅。
  6. 根据权利要求1所述的双控型双稳态变色染料，其特征在于，有机固体材料为小分子有机烷基醇和烷基酸、大分子的醚类和酯类中的一种或者几种，有机固体材料选自十八醇、十六醇、十四醇、十四酸、十六酸、十八酸、单硬脂酸甘油酯、单十八烷酸丙三醇酯、水杨酸苯酯、月桂酸甘油酯、对氧化偶氮苯甲醚、碳酸二苯酯、水杨酸苯酯，硬脂酸苯酯、苯甲酸苄酯中的一种或几种。
  7. 一种电、温双控型双稳态变色微胶囊，其特征在于，采用权利要求1～6任一所述的双控型变色染料为芯材制备得到电、温双控型双稳态变色微胶囊。
  8. 权利要求7所述的电、温双控型双稳态变色微胶囊在变色材料方面的应用。
  9. 一种电、温双控型双稳态变色微胶囊的制备方法，其特征在于，包括以下步骤：
    (1)双控型复配物：将权利要求1～6任一所述的双控型变色染料加热搅拌，形成均匀的混合溶液，即双控型复配物；
    (2)制备双控制型双稳态微胶囊：将步骤(1)得到的双控型复配物滴加到含有乳化剂的水溶液中，乳化剂占双控型复配物质量分数的25-100％，高速乳化形成均匀的染料分散体；将对染料复配物质量分数20～100％的单体，逐滴添加到染料分散体中，继续乳化10-20分钟；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250-500r/min的搅拌速度下，升温至55-75℃，到达反应温度后，逐滴加入对单体总量0.1-1％ 的引发剂，保持温度反应2-6小时，反应完全后水洗，干燥后即可得到双控制型双稳态微胶囊。
  10. 根据权利要求9所述的双控型双稳态变色微胶囊的制备方法，其特征在于，所选用的单体是甲基丙烯酸甲酯、苯乙烯、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。
  11. 根据权利要求9所述的双控型双稳态变色微胶囊的制备方法，其特征在于，所选用的引发剂是过硫酸钾、过硫酸铵、偶氮二异丁基脒盐酸盐中的一种。
  12. 根据权利要求9所述的双控型变色微胶囊的制备方法，其特征在于，所选用的乳化剂为非离子表面活性剂、阴离子表面活性剂、高分子类表面活性剂中的一种或者几种。
  13. 根据权利要求9所述的双控型变色微胶囊的制备方法，其特征在于，所选用的乳化剂选自拉伯树胶、十二烷基苯磺酸钠、苯乙烯-马来酸酐共聚物、吐温、司盘。
PCT/CN2020/099093 2019-07-18 2020-06-30 一种电、温双控型双稳态变色染料及微胶囊的制备方法 WO2021008346A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/395,793 US11655373B2 (en) 2019-07-18 2021-08-06 Method of preparing electric and temperature dual-control bi-stable color-changing dyes and microcapsules

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910648872.1 2019-07-18
CN201910648872.1A CN110330809B (zh) 2019-07-18 2019-07-18 一种电、温双控型变色染料及其微胶囊的制备方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/395,793 Continuation US11655373B2 (en) 2019-07-18 2021-08-06 Method of preparing electric and temperature dual-control bi-stable color-changing dyes and microcapsules

Publications (1)

Publication Number Publication Date
WO2021008346A1 true WO2021008346A1 (zh) 2021-01-21

Family

ID=68145869

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/099093 WO2021008346A1 (zh) 2019-07-18 2020-06-30 一种电、温双控型双稳态变色染料及微胶囊的制备方法

Country Status (3)

Country Link
US (1) US11655373B2 (zh)
CN (1) CN110330809B (zh)
WO (1) WO2021008346A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330809B (zh) * 2019-07-18 2020-07-07 江南大学 一种电、温双控型变色染料及其微胶囊的制备方法
CN111505880B (zh) * 2020-05-25 2023-05-30 哈尔滨工程大学 一种热响应电解质材料及其制备方法和应用

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054889A (ja) * 1983-09-05 1985-03-29 Alps Electric Co Ltd 電圧書込型記録媒体
JPS6268880A (ja) * 1985-09-20 1987-03-28 Pilot Ink Co Ltd 熱変色性材料
JPH0772441A (ja) * 1993-09-01 1995-03-17 Dainippon Printing Co Ltd 表示用組成物
CN1861607A (zh) * 2006-05-10 2006-11-15 浙江工业大学 一种荧烷类衍生物及其制备和应用
CN101755029A (zh) * 2007-04-16 2010-06-23 弗劳恩霍弗实用研究促进协会 具有反向热致变色性能的复合物、含有它的复合材料及用途
WO2014002292A1 (ja) * 2012-06-27 2014-01-03 三菱鉛筆株式会社 色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物
CN104910714A (zh) * 2015-06-23 2015-09-16 南昌添丽特实业有限责任公司 一种可温变的微胶囊涂料及其制备方法
CN105950077A (zh) * 2016-04-01 2016-09-21 合肥第六元素光电科技有限公司 温致变色胶及其制备方法及其制得的胶带
CN107216718A (zh) * 2017-07-22 2017-09-29 厦门市诚安毅科技有限公司 一种温控变色油墨的制备方法
CN108468096A (zh) * 2018-03-20 2018-08-31 江南大学 一种温致变色夜光纤维及其制备方法
CN108873537A (zh) * 2018-06-25 2018-11-23 常州铱视光电科技有限公司 一种电致变色薄膜、其制备方法和应用以及电致变色器件
CN109575911A (zh) * 2018-12-29 2019-04-05 江南大学 草莓形热致变色储能材料及其制备方法与应用
CN110330809A (zh) * 2019-07-18 2019-10-15 江南大学 一种电、温双控型变色染料及其微胶囊的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054889B2 (ja) 1981-10-05 1985-12-02 ホ−ヤ株式会社 板ガラスを成形する方法
JPH0772441B2 (ja) 1989-08-03 1995-08-02 株式会社熊谷組 高層建築物に於けるごみ排出装置
CN105017807B (zh) * 2015-07-30 2017-03-29 苏州雄鹰笔墨科技有限公司 一种可逆温敏变色染料、制备方法及其应用

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054889A (ja) * 1983-09-05 1985-03-29 Alps Electric Co Ltd 電圧書込型記録媒体
JPS6268880A (ja) * 1985-09-20 1987-03-28 Pilot Ink Co Ltd 熱変色性材料
JPH0772441A (ja) * 1993-09-01 1995-03-17 Dainippon Printing Co Ltd 表示用組成物
CN1861607A (zh) * 2006-05-10 2006-11-15 浙江工业大学 一种荧烷类衍生物及其制备和应用
CN101755029A (zh) * 2007-04-16 2010-06-23 弗劳恩霍弗实用研究促进协会 具有反向热致变色性能的复合物、含有它的复合材料及用途
WO2014002292A1 (ja) * 2012-06-27 2014-01-03 三菱鉛筆株式会社 色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物
CN104910714A (zh) * 2015-06-23 2015-09-16 南昌添丽特实业有限责任公司 一种可温变的微胶囊涂料及其制备方法
CN105950077A (zh) * 2016-04-01 2016-09-21 合肥第六元素光电科技有限公司 温致变色胶及其制备方法及其制得的胶带
CN107216718A (zh) * 2017-07-22 2017-09-29 厦门市诚安毅科技有限公司 一种温控变色油墨的制备方法
CN108468096A (zh) * 2018-03-20 2018-08-31 江南大学 一种温致变色夜光纤维及其制备方法
CN108873537A (zh) * 2018-06-25 2018-11-23 常州铱视光电科技有限公司 一种电致变色薄膜、其制备方法和应用以及电致变色器件
CN109575911A (zh) * 2018-12-29 2019-04-05 江南大学 草莓形热致变色储能材料及其制备方法与应用
CN110330809A (zh) * 2019-07-18 2019-10-15 江南大学 一种电、温双控型变色染料及其微胶囊的制备方法

Also Published As

Publication number Publication date
US20210363355A1 (en) 2021-11-25
US11655373B2 (en) 2023-05-23
CN110330809A (zh) 2019-10-15
CN110330809B (zh) 2020-07-07

Similar Documents

Publication Publication Date Title
WO2021008346A1 (zh) 一种电、温双控型双稳态变色染料及微胶囊的制备方法
JP5484630B2 (ja) エレクトロウェッティング素子の製造方法、及びエレクトロウェッティングディスプレイ
Fameau et al. Stimuli-responsive liquid foams: From design to applications
CN110317473B (zh) 一种光致温致协同变色微胶囊的制备方法
JPS5951587B2 (ja) サ−モクロミズム材料
JPH0839936A (ja) 感温変色性色彩記憶性組成物
CN110964498A (zh) 一种热致变色胶囊及其制备方法
JPH04267190A (ja) 可逆性熱変色材料
WO2022257684A1 (zh) 一种高灵敏度的感温可逆变色微胶囊的制备方法
CN114456643A (zh) 一种基于三芳基乙烯体系的光热双响应变色墨水及制备方法和应用
WO2000016985A1 (en) Microcapsules comprising solvent for chromogenic material
ES2305647T3 (es) Adhesivo y cinta adhesiva de transferencia sensible a la presion.
CN115869867B (zh) 一种含有硅氧烷的聚氨酯/脲树脂壁材的微胶囊及其制备方法
CN110317472B (zh) 一种双稳态温致变色染料及微胶囊的制备方法
US3642514A (en) Pressure-sensitive copying sheet utilizing stabilized crystal violet lactone, method of making and method of making composition
JP3460001B2 (ja) 可逆熱変色性材料及びそれを内包した可逆熱変色性マイクロカプセル顔料
JPH02252576A (ja) 発色材料
JP4048722B2 (ja) 電気泳動表示装置
ES2277101T3 (es) Procedimiento para encapsular correactantes coloreados disueltos de sistemas de reaccion cromatica, las capsulas obtenidas posteriormente, asi como su uso en papeles de reaccion cromatica.
KR950002237B1 (ko) 캪슐형 감온성 안료조성물
JP4104410B2 (ja) 熱可逆性発消色粉粒体
CN111100604A (zh) 一种复合变色储能胶囊及其制备方法
KR100853088B1 (ko) 광색성 염료의 나노 캡슐화 방법
JPH01283183A (ja) フルオラン化合物の液状組成物
CN115888572A (zh) 一种具有多色域指示和调温功能的微胶囊

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20839865

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20839865

Country of ref document: EP

Kind code of ref document: A1