CN112898992A - Temperature-sensitive chromogenic liquid crystal microcapsule and preparation and application methods thereof - Google Patents
Temperature-sensitive chromogenic liquid crystal microcapsule and preparation and application methods thereof Download PDFInfo
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- CN112898992A CN112898992A CN201911227123.8A CN201911227123A CN112898992A CN 112898992 A CN112898992 A CN 112898992A CN 201911227123 A CN201911227123 A CN 201911227123A CN 112898992 A CN112898992 A CN 112898992A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims abstract description 37
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- 239000005140 Cholesterol Oleyl Carbonate Substances 0.000 description 4
- 239000005158 Cholesterol Pelargonate Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- XMPIMLRYNVGZIA-TZOMHRFMSA-N cholesteryl oleyl carbonate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)OCCCCCCCC\C=C/CCCCCCCC)C1 XMPIMLRYNVGZIA-TZOMHRFMSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 2
- XUGISPSHIFXEHZ-UHFFFAOYSA-N 3beta-acetoxy-cholest-5-ene Natural products C1C=C2CC(OC(C)=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 XUGISPSHIFXEHZ-UHFFFAOYSA-N 0.000 description 2
- CSQPODPWWMOTIY-UHFFFAOYSA-N 4-(4-octylphenyl)benzonitrile Chemical compound C1=CC(CCCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 CSQPODPWWMOTIY-UHFFFAOYSA-N 0.000 description 2
- VYYZMIPOAWOHAI-UHFFFAOYSA-N 5-amino-2-methoxybenzenesulfonamide Chemical compound COC1=CC=C(N)C=C1S(N)(=O)=O VYYZMIPOAWOHAI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- 239000005155 Cholesterol Propionate Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 239000002775 capsule Substances 0.000 description 2
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- UVZUFUGNHDDLRQ-LLHZKFLPSA-N cholesteryl benzoate Chemical compound O([C@@H]1CC2=CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)C(=O)C1=CC=CC=C1 UVZUFUGNHDDLRQ-LLHZKFLPSA-N 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CKDZWMVGDHGMFR-GTPODGLVSA-N [(3s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] butanoate Chemical class C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCC)C1 CKDZWMVGDHGMFR-GTPODGLVSA-N 0.000 description 1
- XMPIMLRYNVGZIA-CCEZHUSRSA-N [10,13-dimethyl-17-(6-methylheptan-2-yl)-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] [(e)-octadec-9-enyl] carbonate Chemical compound C12CCC3(C)C(C(C)CCCC(C)C)CCC3C2CC=C2C1(C)CCC(OC(=O)OCCCCCCCC/C=C/CCCCCCCC)C2 XMPIMLRYNVGZIA-CCEZHUSRSA-N 0.000 description 1
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- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XUGISPSHIFXEHZ-VEVYEIKRSA-N cholesteryl acetate Chemical class C1C=C2C[C@@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-VEVYEIKRSA-N 0.000 description 1
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/36—Steroidal liquid crystal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a temperature-sensitive chromogenic liquid crystal microcapsule, which takes cholesteric liquid crystal as a core material and acrylic resin as a wall material, wherein the glass transition temperature of the acrylic resin is less than 80 ℃, and the temperature-sensitive chromogenic liquid crystal microcapsule has a flat structure when being dried. The invention also provides a method for preparing and applying the temperature-sensitive chromogenic liquid crystal microcapsule. The temperature-sensitive chromogenic liquid crystal microcapsule disclosed by the invention can develop color along with temperature change in different temperature ranges, can obviously improve the reflectivity and has bright display color. Meanwhile, the preparation and application processes can be greatly simplified, so that the production cost is saved, and the method is safe and environment-friendly.
Description
Technical Field
The invention relates to a liquid crystal microcapsule and preparation thereof, in particular to a temperature-sensitive color development liquid crystal microcapsule capable of improving reflectivity and a preparation and application method thereof.
Background
Cholesteric liquid crystal molecules are basically in a flat shape, are arranged in parallel to each other by virtue of the interaction of end groups to form a layered structure, are arranged in a manner that long axes are basically parallel in each plane, and are gradually deviated from the long axis orientation between layers to form a spiral structure. The distance between two nearest layers with the long axes in the same orientation is called the pitch P of the cholesteric liquid crystal, the wavelength of incident light capable of being reflected by the cholesteric liquid crystal is related to the pitch P, and the Bragg reflection formula can be used as follows: λ =2nPsin Φ, where λ is the wavelength of the reflected light, n is the average refractive index of the cholesteric liquid crystal, and Φ is the angle of the reflected light with the liquid crystal surface. The pitch of most cholesteric liquid crystals is greatly influenced by temperature, a magnetic field, a chemical environment and the like, and when the external temperature changes, the pitch of the cholesteric liquid crystals can be greatly changed, so that the color of the surface of the liquid crystal is obviously changed. The temperature-sensitive cholesteric liquid crystal is easily influenced by external temperature, solvent and the like due to the sensitivity of the temperature-sensitive cholesteric liquid crystal and the intersolubility of mixed liquid crystal in the using process, so that the performance of the temperature-sensitive cholesteric liquid crystal is changed. The microencapsulated liquid crystal can better protect the core material liquid crystal, thereby widening the application range of the liquid crystal.
When the temperature-sensitive cholesteric liquid crystal is used for preparing a temperature-sensitive coating or a film, the reflectivity of the temperature-sensitive cholesteric liquid crystal to visible light is an important index influencing the color brightness degree of the temperature-sensitive cholesteric liquid crystal. When the microcapsule is prepared into a liquid crystal microcapsule, the particle size, the particle distribution, the light transmittance, the shape and the stability of the wall material all have important influences on the reflectivity, and the choice of the wall material is often a decisive factor. In the prior art, the prepared liquid crystal microcapsule has the defects of insufficient reflectivity, complex process, difficult industrial production, high raw material toxicity or low reflectivity caused by easy doping of liquid crystal and the like.
Therefore, it is required to provide a temperature-sensitive chromogenic liquid crystal microcapsule with significantly improved reflectivity, simple preparation process and low cost.
Disclosure of Invention
In order to solve the above problems, an aspect of the present invention provides a temperature-sensitive color-developing liquid crystal microcapsule, which uses cholesteric liquid crystal as a core material and acrylic resin as a wall material, wherein the glass transition temperature of the acrylic resin is less than 80 ℃, and the temperature-sensitive color-developing liquid crystal microcapsule has a flat structure when dried. In a preferred embodiment, the average particle size of the temperature-sensitive color-developing liquid crystal microcapsule is 3-15 microns.
In a preferred embodiment, the acrylic resin comprises a homopolymer or copolymer of an acrylate and a methacrylate.
In a preferred embodiment, the cholesteric liquid crystal is a cholesteric ester liquid crystal or a chiral nematic liquid crystal. In a more preferred embodiment, the cholesteric ester liquid crystal comprises one or more of cholesterol oleyl carbonate, cholesterol pelargonate, cholesterol benzoate, cholesterol chloride ester, cholesterol propionate ester, cholesterol acetate ester, cholesterol n-butyrate ester and cholesterol alkenyl carbonate.
In a preferred embodiment, the mass ratio of the core material to the wall material is 5:1 to 15: 1.
On the other hand, the invention also discloses a method for preparing the temperature-sensitive chromogenic liquid crystal microcapsule, which comprises the following steps: mixing cholesteric liquid crystal and acrylic resin according to a ratio, and dissolving the cholesteric liquid crystal and the acrylic resin in an organic solvent to form a uniform and transparent oil phase; slowly adding the oil phase into the water phase containing the emulsifier, and stirring to obtain a dispersion liquid containing oil phase droplets; slowly heating to evaporate the organic solvent; and (4) centrifugal washing.
In a preferred embodiment, the organic solvent comprises one or more of acetone, ethyl acetate, n-hexane, dichloromethane and cyclohexane.
In a preferred embodiment, the mass ratio of the oil phase to the water phase is 1:1 to 1: 4.
In a preferred embodiment, the emulsifier comprises one or more of a nonionic surfactant, an ionic surfactant, and a natural macromolecule.
The invention also discloses a method for applying the temperature-sensitive chromogenic liquid crystal microcapsule, which comprises the following steps: uniformly mixing the temperature-sensitive color developing liquid crystal microcapsule and the aqueous solution of the high polymer resin according to a certain proportion to obtain slurry; uniformly coating the slurry on a substrate; and heating and curing the slurry to form a dry film containing the temperature-sensitive chromogenic liquid crystal microcapsule.
The invention provides a temperature-sensitive color development liquid crystal microcapsule, which can develop color along with temperature change in different temperature ranges, can obviously improve reflectivity and provide more vivid display color. Meanwhile, the preparation and application processes can be greatly simplified, so that the production cost is saved, and the method is safe and environment-friendly.
Drawings
The invention may be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic view (a) and an SEM image (b) of the structure of a spherical liquid crystal microcapsule when dried;
fig. 2 is a schematic structural view (a) and an SEM image (b) of a liquid crystal microcapsule according to an embodiment of the present invention when dried;
FIG. 3 is a microscopic view of a liquid crystal microcapsule prepared according to a comparative example of the present invention in an aqueous solution (a) and dried (b);
FIG. 4 is a microscopic view of a liquid crystal microcapsule prepared according to example 1 of the present invention in an aqueous solution (a) and when dried (b);
FIG. 5 is a microscopic image of a liquid crystal microcapsule prepared according to example 2 of the present invention in an aqueous solution (a) and when dried (b);
FIG. 6 is a microscopic image of a liquid crystal microcapsule prepared according to example 3 of the present invention in an aqueous solution (a) and when dried (b);
FIG. 7 is a microscopic image of a liquid crystal microcapsule prepared according to example 4 of the present invention in an aqueous solution (a) and when dried (b);
fig. 8 is a microscopic view of the liquid crystal microcapsule prepared according to example 5 of the present invention in an aqueous solution (a) and when dried (b).
Detailed Description
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details. The illustrated example embodiments have been set forth only for the purposes of example and that it is not intended to be limiting. Therefore, it is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthetic techniques are conventional and the resulting compounds are tested for compliance with electronic standards.
The invention discloses a temperature-sensitive chromogenic liquid crystal microcapsule which takes cholesteric liquid crystal as a core material and acrylic resin as a wall material, wherein the glass transition temperature (T) of the acrylic resin forming the capsule wallG) Less than 80 degrees. The average grain diameter of the liquid crystal microcapsule is 3-15 microns. Generally, the cholesteric liquid crystal microcapsule maintains a spherical shape when dried, and thus, as shown in fig. 1, light reflected by cholesteric liquid crystal of the core material is dispersed in all directions along a radial direction, thereby reducing the reflectance when the liquid crystal microcapsule is applied. The temperature-sensitive chromogenic liquid crystal microcapsules of the present invention have a flat structure when dried, as shown in fig. 2, such that the helical axis of the cholesteric liquid crystal tends to align toward the shorter axis of the microcapsule, i.e., substantially perpendicular to the coated surface of the substrate when applied, and the alignment of the liquid crystal is similar to the planar texture of cholesteric liquid crystal, with higher reflectance. In a preferred embodiment, the acrylic resin forming the capsule wall has a glass transition temperature of less than 70 degrees, which further improves the reflectivity.
The mass ratio of the core material to the wall material of the temperature-sensitive color-developing liquid crystal microcapsule is 5: 1-15: 1. The acrylic resin includes commonly used homo-or copolymers of acrylic and methacrylic esters, such as polymethyl acrylate, polymethyl methacrylate, polyglycidyl methacrylate, polyethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, copolymers of methyl methacrylate and n-butyl methacrylate, and the like. The cholesteric liquid crystal is cholesterol ester liquid crystal or chiral nematic liquid crystal, wherein the cholesterol ester liquid crystal comprises one or more of cholesterol oleyl carbonate, cholesterol pelargonate, cholesterol benzoate, chlorinated cholesterol ester, cholesterol propionate, cholesterol acetate, cholesterol n-butyrate and cholesterol alkenyl carbonate. The chiral nematic liquid crystal is a mixture of a nematic liquid crystal and a chiral agent, wherein the nematic liquid crystal is 5CB, 7CB, 8CB, E7 and the like, and the chiral agent is S811, S1011, R811, R6N, R5011, R1011, CB15 and the like.
The invention also discloses a method for preparing the temperature-sensitive chromogenic liquid crystal microcapsule, which specifically comprises the following steps.
First, cholesteric liquid crystal and acrylic resin are mixed in proportion and dissolved in an organic solvent to form a uniform transparent oil phase. Wherein the mass ratio of the cholesteric liquid crystal to the acrylic resin is 5: 1-15: 1. The organic solvent is a solvent capable of dissolving the cholesteric liquid crystal and the acrylic resin, such as one or more of acetone, ethyl acetate, n-hexane, dichloromethane and cyclohexane.
And secondly, slowly adding the oil phase into the water phase containing the emulsifier, and stirring to obtain a dispersion liquid containing oil phase droplets. Wherein the mass ratio of the oil phase to the water phase is 1: 1-1: 4, and the emulsifier comprises one or more of common nonionic surfactants (such as alkylphenol polyoxyethylene, polyvinyl alcohol PVA, and the like), ionic surfactants (such as alkyl sulfate, alkylbenzene sulfonate, and the like) and natural polymers (such as gelatin, Arabic gum, starch, and the like). The mass percentage of the emulsifier in the water phase is 0.5-10%.
Then, the organic solvent was evaporated by slowly raising the temperature. Specifically, the dispersion liquid can be placed in an evaporation container, the temperature is slowly increased to 5-20 ℃ below the boiling point of the organic solvent, and the organic solvent is evaporated under continuous stirring until the organic solvent is completely volatilized. In the process, the cholesteric liquid crystal of the core material and the acrylic resin of the wall material are mutually incompatible to generate phase separation, and the acrylic resin forms a polymer film on the surface of the cholesteric liquid crystal, so that the cholesteric liquid crystal is wrapped in the polymer film to form a core-wall structure.
Finally, centrifugal washing. The emulsifier and the unreacted reactant can be removed by washing, and finally the dispersion liquid containing the temperature-sensitive chromogenic liquid crystal microcapsule is formed.
The invention also discloses a method for applying the temperature-sensitive chromogenic liquid crystal microcapsule, which comprises the following steps: uniformly mixing the temperature-sensitive chromogenic microcapsules with the aqueous solution of the high polymer resin according to a certain proportion to obtain slurry; uniformly coating the slurry on a substrate; and heating and curing the slurry to form a dry film containing the temperature-sensitive chromogenic liquid crystal microcapsule. The polymer resin can be common water-soluble polymer resin, such as water-soluble acrylic resin, acrylic emulsion, water-soluble polyurethane resin, etc. The substrate is any substrate needing printing, such as glass, cloth, polymer materials and the like. In the following examples, the substrates are all black PET.
The structure, performance and preparation and application method of the temperature-sensitive chromogenic liquid crystal microcapsule will be described in detail with reference to the specific examples.
Comparative example
2.55g of cholesteryl nonanoate, 0.45g of cholesteryl propionate and 0.3g of polymethyl methacrylate (T) were weighed outGValue 105 ℃ C.), and dissolved in 40g of ethyl acetate. The prepared solution was added to 60g of a 2% aqueous PVA solution under stirring, and stirring was continued for 10 minutes. And then heating the emulsified solution to 60 ℃, stirring and volatilizing for 3 hours to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. The liquid crystal microcapsules were centrifuged at 8000rpm and washed with water for 2 times and then centrifuged to remove the residual PVA solution, to obtain liquid crystal microcapsules having an average particle diameter of 6.0. mu.m, which were in an aqueous solution and dried, and the morphology thereof was as shown in FIGS. 3 (a) and (b), from which it was seen that the liquid crystal microcapsules remained substantially perfectly spherical both in an aqueous solution and when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 55-65 ℃, the color-changing film shows changes of red, green and blue along with the temperature rise, but the color is darker, and the measured reflectivity is only 13.67%.
Example 1
2.55g of cholesteryl nonanoate, 0.45g of cholesteryl propionate, 0.3g of a copolymer of methyl methacrylate and n-butyl methacrylate (T)GValue 43 ℃ C.), was dissolved in 40g of ethyl acetate. The prepared solution was added to 60g of a 2% aqueous PVA solution under stirring, and stirring was continued for 10 minutes. And then heating the emulsified solution to 60 ℃, stirring and volatilizing for 3 hours to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. Centrifuging at 8000rpm, washing with water for 2 times, centrifuging to remove residual PVA solution to obtain liquid crystal microcapsule with average particle diameter of 4.9 μm, which is shown in FIG. 4 (a) and (b)b) As shown, it can be seen from the figure that the liquid crystal microcapsules are all spherical in the aqueous solution, but the liquid crystal microcapsules are flat when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 55-65 ℃, the color-changing film shows the change of red, green and blue along with the temperature rise, the color is bright, and the measured reflectivity is 42.67%.
Example 2
2.8377g of 4-octyl-4' -cyanobiphenyl, 0.1623gR5011, 0.4g of a copolymer of methyl methacrylate and n-butyl methacrylate (T)GValue 75 ℃ C.), and dissolved in 40g of a mixed solvent of ethyl acetate and cyclohexane (volume ratio: 3: 1). The prepared solution was added to 100g of a 2% aqueous PVA solution under stirring, and stirring was continued for 10 minutes. And then heating the emulsified solution to 60 ℃, stirring and volatilizing for 2h, then heating to 70 ℃, and continuing stirring and volatilizing for 2h to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. The liquid crystal microcapsules were centrifuged at 8000rpm, washed with water for 2 times, and centrifuged to remove the residual PVA solution, to obtain liquid crystal microcapsules having an average particle diameter of 5.2 μm, and the shapes of the liquid crystal microcapsules in an aqueous solution and after drying were as shown in FIGS. 5 (a) and (b), and it was found from the figure that the liquid crystal microcapsules were spherical in the aqueous solution, but the liquid crystal microcapsules were flat when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 8-12 ℃, the color-changing film shows the change of red, green and blue along with the temperature rise, the color is bright, and the measured reflectivity is 20.24%.
Example 3
1.50g of cholesterol oleyl carbonate, 1.50g of cholesterol pelargonate, 0.25g of a copolymer of methyl methacrylate and n-butyl methacrylate (T)GValue 62 ℃ C.), and dissolved in 40g of a mixed solvent of ethyl acetate and methylene chloride (volume ratio 1: 1). The prepared solution was added to 150g of 5% gelatin aqueous solution under stirring, and stirring was continued for 10 minutes. Then heating the emulsified solution to 30 ℃, stirring and volatilizing for 2h, then heating to 60 ℃, and then continuing toStirring and volatilizing for 2h to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. The liquid crystal microcapsules were centrifuged at 8000rpm, washed with water for 2 times, and centrifuged to remove the residual PVA solution, to obtain liquid crystal microcapsules having an average particle diameter of 8.5 μm, and the shapes of the liquid crystal microcapsules in an aqueous solution and after drying were as shown in FIGS. 6 (a) and (b), and it was found from the figure that the liquid crystal microcapsules were spherical in the aqueous solution, but the liquid crystal microcapsules were flat when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 34-59 ℃, the color-changing film shows the change of red, green and blue along with the temperature rise, the color is bright, and the measured reflectivity is 25.32%.
Example 4
1.50g of cholesteryl oleyl carbonate, 1.50g of cholesteryl nonanoate, 0.3g of polyisobutyl methacrylate (T)GValue 65 ℃ C.), dissolved in 40g of ethyl acetate. The prepared solution was added to 150g of a 2% aqueous PVA solution under stirring, and stirring was continued for 10 minutes. And then heating the emulsified solution to 60 ℃, stirring and volatilizing for 3 hours to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. The liquid crystal microcapsules were centrifuged at 8000rpm, washed with water for 2 times, and centrifuged to remove the residual PVA solution, to obtain liquid crystal microcapsules having an average particle diameter of 7.0 μm, and the shapes thereof in an aqueous solution and after drying were as shown in FIGS. 7 (a) and (b), from which it was seen that the liquid crystal microcapsules were spherical in the aqueous solution, but were flat when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 34-59 ℃, the color-changing film shows the change of red, green and blue along with the temperature rise, the color is bright, and the measured reflectivity is 24.77%.
Example 5
1.50g of cholesterol oleyl carbonate, 1.50g of cholesterol pelargonate and 0.3g of polyethyl methacrylate (T)GValue 63 ℃ C.), dissolved in 40g of ethyl acetate. The prepared solution was added to 150g of a 2% aqueous PVA solution under stirring, and stirring was continued for 10 minutes.And then heating the emulsified solution to 60 ℃, stirring and volatilizing for 3 hours to obtain the liquid crystal microcapsule dispersion liquid with uniform particle size. The liquid crystal microcapsules were centrifuged at 8000rpm, washed with water for 2 times, and centrifuged to remove the residual PVA solution, to obtain liquid crystal microcapsules having an average particle diameter of 6.5 μm, and the shapes thereof in an aqueous solution and after drying were as shown in FIGS. 8 (a) and (b), from which it was seen that the liquid crystal microcapsules were spherical in the aqueous solution, but were flat when dried. The color-changing film is mixed with polyurethane resin (Anda Huatai 1704B type resin) according to a certain proportion, coated and heated to be cured to obtain the color-changing film with the thickness of 170 micrometers, the color-changing temperature of the color-changing film is 34-59 ℃, the color-changing film shows the change of red, green and blue along with the temperature rise, the color is bright, and the measured reflectivity is 24.93%.
It can be seen from the above comparative examples and examples that the temperature-sensitive chromogenic liquid crystal microcapsule disclosed by the invention can not only display different colors in different temperature ranges along with temperature changes, but also greatly improve the reflectivity (by at least 50%), and increase the vividness of the colors.
Although several exemplary embodiments have been described above in detail, the disclosed embodiments are merely exemplary and not limiting, and those skilled in the art will readily appreciate that many other modifications, adaptations, and/or alternatives are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of the present disclosure. Accordingly, all such modifications, adaptations, and/or alternatives are intended to be included within the scope of the present disclosure as defined by the following claims.
Claims (10)
1. The temperature-sensitive color developing liquid crystal microcapsule takes cholesteric liquid crystal as a core material and acrylic resin as a wall material, wherein the glass transition temperature of the acrylic resin is less than 80 ℃, and the temperature-sensitive color developing liquid crystal microcapsule has a flat structure when being dried.
2. The temperature-sensitive chromogenic liquid crystal microcapsule according to claim 1, wherein the acrylic resin is a homopolymer or a copolymer of an acrylate or a methacrylate.
3. The temperature-sensitive chromogenic liquid crystal microcapsule according to claim 1, wherein the cholesteric liquid crystal is a cholesteric ester liquid crystal or a chiral nematic liquid crystal.
4. The temperature-sensitive chromogenic liquid crystal microcapsule according to claim 1, wherein the mass ratio of the core material to the wall material is 5:1 to 15: 1.
5. The temperature-sensitive chromogenic liquid crystal microcapsule according to claim 1, wherein the average particle size of the temperature-sensitive chromogenic liquid crystal microcapsule is 3 to 15 μm.
6. A method of preparing a temperature-sensitive chromogenic liquid crystal microcapsule comprising:
1) mixing cholesteric liquid crystal and acrylic resin according to a ratio, and dissolving the cholesteric liquid crystal and the acrylic resin in an organic solvent to form a uniform and transparent oil phase;
2) slowly adding the oil phase into a water phase containing an emulsifier, and stirring to obtain a dispersion liquid containing oil phase droplets;
3) slowly heating to evaporate the organic solvent;
4) and (4) centrifugal washing.
7. The method of claim 6, wherein the organic solvent comprises one or more of acetone, ethyl acetate, n-hexane, dichloromethane, and cyclohexane.
8. The method of claim 6, wherein the oil phase and the water phase are present in a mass ratio of 1:1 to 1: 4.
9. The method of claim 6, wherein the emulsifier comprises one or more of a non-ionic surfactant, an ionic surfactant, and a natural polymer.
10. A method of applying a temperature sensitive chromogenic liquid crystal microcapsule comprising:
1) uniformly mixing the temperature-sensitive color developing liquid crystal microcapsule and the aqueous solution of the high polymer resin according to a certain proportion to obtain slurry;
2) uniformly coating the slurry onto a substrate;
3) and heating and curing the slurry to form a dry film containing the temperature-sensitive chromogenic liquid crystal microcapsule.
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