CN109293821A - A kind of dyestuff doping type liquid crystal microcapsule material and preparation method thereof - Google Patents
A kind of dyestuff doping type liquid crystal microcapsule material and preparation method thereof Download PDFInfo
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- CN109293821A CN109293821A CN201811152977.XA CN201811152977A CN109293821A CN 109293821 A CN109293821 A CN 109293821A CN 201811152977 A CN201811152977 A CN 201811152977A CN 109293821 A CN109293821 A CN 109293821A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention discloses a kind of preparation methods of dyestuff doping type liquid crystal microcapsule, belong to fine chemistry industry and material science and technology field.The dyestuff doping type liquid crystal of the method for the present invention preparation has multilayered structure; outer layer dyestuff doping type liquid crystal and polymeric shell layer subtract color matching as color layer and core material dyestuff doping type liquid crystal microcapsule; it is used as protective layer simultaneously, protects internal layer dyestuff doping type liquid crystal from external environmental.Not only color is gorgeous changeable for the liquid crystal microcapsule prepared using this method, and driving voltage is low, and there is good solvent resistance and water resistance, original color characteristics are still able to maintain after working process, people be can satisfy to liquid crystal colour developing personalization and multifarious requirement in Flexible Displays and intelligent textile, had a extensive future.
Description
Technical field
The invention belongs to fine chemistry industries and material science and technology field, and in particular to a kind of dyestuff doping type liquid crystal microcapsule
Material and preparation method thereof.
Background technique
Liquid crystal display is had a wide range of applications in practice with its excellent optical property and electrooptic effect.Meanwhile to open up
Application of the liquid crystal under particular demands is opened up, such as the preparation of flexible display technologies, intelligent fiber, liquid crystal microcapsule chemical industry skill play this
Vital effect is arrived.On the one hand, the dispersion, protection and cause for realizing liquid crystal by coating function are steady, prevent liquid crystal from existing
Flowing during device flexure, ensures that the feasibility of liquid crystal Flexible Displays；On the other hand, pass through control microcapsules
Size and distribution carry out the size of liquid crystal droplet in regulation system, to improve the electro-optical properties of display device.In recent years,
Hanyang University achieves biggish breakthrough on liquid crystal microcapsule, and explores nematic liquid crystal microcapsule product
Application in PDLC.Fuji Xerox Co., Ltd report a kind of liquid crystal microcapsule with internal approach layer structure,
By the molecules align of liquid crystal droplet inside specification microcapsules, so that LC/polymer system shows preferable electro-optical properties,
Device displays contrast up to 40:1.Southern Yangtze University closes jade etc. and prepares cholesteric liquid crystal microcapsules, and benefit using complex coacervation
Temperature induced color changing intelligent fiber of the response temperature between 35-38 DEG C is prepared with electrostatic spinning technique.
However, it is micro- to focus primarily upon a small number of regional and company, liquid crystal about the report of liquid crystal microcapsule up to now
The preparation method of capsule is based on core-shell structure.The electrochromism liquid crystal microcapsule of these methods preparation is using cholesteric phase liquid
When crystalline substance is used as core material, the driving voltage of liquid crystal microcapsule is higher；And use dichroic dye doping nematic liquid crystal as core material,
It can not accomplish the color-developing of single liquid crystal microcapsule；When being such as used in combination according to a variety of monotropic dichroic liquid crystal microcapsules, due to
The difference of liquid crystal microcapsule partial size, light scattering effect is obvious, and color developing effect is bad.Therefore, a kind of physical and chemical and optics how is prepared
The liquid crystal microcapsule for haveing excellent performance and meeting low driving voltage and colorful color-changeable performance is in the urgent need to address in industry asks
Topic.
Summary of the invention
To solve the above-mentioned problems, the present invention devises a kind of dyestuff doping type liquid crystal microcapsule of multilayered structure, realizes
Using nematic liquid crystal a kind of good translucency, high mechanical strength, liquid crystal microcapsule resistant to chemical etching is prepared, simultaneously should
Liquid crystal microcapsule need to meet lower driving voltage and colorful electrochromism ability.And the multilayered structure dyestuff doping type is probed into
The specific preparation method of liquid crystal microcapsule is used by screening suitable monomer, liquid crystal, dichroic dye and surfactant
Seed emulsion polymerization prepares multilayered structure dyestuff doping type liquid crystal microcapsule.
The first purpose of the invention is to provide a kind of preparation method of dyestuff doping type liquid crystal microcapsule, the method packets
It includes:
(1) dichroic dye and nematic crystal are sufficiently mixed to the dyestuff doping type liquid for preparing different colours variation respectively
Brilliant material；
(2) a kind of dyestuff doping type liquid crystal material organic monomer of color is uniformly mixed, organic monomer includes and soft list
Body, hard monomer, cross-linking monomer and the high adhesive force of low-surface-energy organic monomer, be added non-ionic class surfactant be made
Evenly dispersed emulsion dispersion；
(3) initiator is added and causes polymerization, the liquid crystal microcapsule of polymer overmold dyestuff doping type liquid crystal material is made, mentions
Lotion after pure reaction obtains the uniform dyestuff doping type liquid crystal microcapsule lotion of size distribution；
(4) using the dyestuff doping type liquid crystal microcapsule prepared in above-mentioned (3) as seed, the dyestuff of another different colours is mixed
Miscellaneous type liquid crystal material and soft monomer and hard monomer are mixed to get oil and are added in lotion, mass fraction of the soft monomer to hard monomer
It is 50~200%, temperature (be first warming up in surfactant cloud point, then be cooled to emulsifying temperature) and revolving speed is controlled, so that table
Face activating agent changes with water molecules ability, to make being adsorbed on microcapsules seed of oil phase；
(5) initiator heating is added and causes polymerization, makes the oil for being adsorbed on internal layer liquid crystal microcapsule surface that polymerization mutually occur anti-
It answers, releaser phase separation, is prepared into polymer overmold dyestuff doping type liquid crystal coated polymer cladding dyestuff doping type liquid
Brilliant multilayered structure dyestuff doping type liquid crystal microcapsule.
In one embodiment of the invention, quality point of the dichroic dye to nematic crystal in the step (1)
Number is 0.1~6%.
In one embodiment of the invention, in the step (2) soft monomer to the mass fraction of hard monomer be 50~
200%, crosslinking agent is 10~50% to the mass fraction of soft or hard monomer total amount, and the organic monomer of the high adhesive force of low-surface-energy is to soft
The mass fraction of hard monomer total amount is 5~30%.
In one embodiment of the invention, dyestuff doping type liquid crystal accounts for emulsion dispersion totality in the step (2)
It is mass fraction 1~15%.
In one embodiment of the invention, emulsifier content mixes dyestuff in emulsion dispersion in the step (2)
Miscellaneous type liquid crystal mass fraction is 10-50%.
In one embodiment of the invention, mix monomer divides dyestuff doping type liquid crystal quality in the step (2)
Number is 10~400%.
In one embodiment of the invention, mass fraction of the crosslinking agent to soft or hard monomer total amount in the step (2)
It is 10~50%.
In one embodiment of the invention, in the step (2) organic monomer of the high adhesive force of low-surface-energy to soft
The mass fraction of hard monomer total amount is 5~30%.
In one embodiment of the invention, it is added dropwise during coating reaction and monomer total amount 0.1-15% is drawn
Send out agent.
In one embodiment of the invention, the initiator is potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide
Or one of azo diisobutyl amidine hydrochloride.
In one embodiment of the invention, the soft monomer includes that ethyl acrylate, butyl acrylate, acrylic acid are different
One of monooctyl ester, lauryl acrylate, acrylic acid-2-ethyl caproite, lauryl methacrylate, n octyl methacrylate
Or two kinds.
In one embodiment of the invention, the soft monomer includes acrylate of the chain length in 2~8 carbon atoms
Class.
In one embodiment of the invention, the hard monomer includes styrene, methyl acrylate, methyl methacrylate
Ester, ethyl methacrylate, butyl methacrylate, vinylacetate, methyl vinyl ether, acrylonitrile, acrylamide, isoamyl
One or both of diene, dicyclopentadiene.
In one embodiment of the invention, the cross-linking monomer includes acrylic acid, hydroxy-ethyl acrylate, acrylic acid hydroxyl
Propyl ester, methacrylic acid, hydroxyethyl methacrylate, hydroxy propyl methacrylate, divinylbenzene, dimethacrylate second two
One or both of alcohol vinegar, N hydroxymethyl acrylamide or Diacetone Acrylamide.
In one embodiment of the invention, the organic monomer of the high adhesive force of the low-surface-energy includes methacrylic acid
Trifluoro ethyl ester, trifluoroacetyl triflate, 3- fluorophenyl acetate, dodecafluoroheptyl methacrylate, (perfluoro hexyl)
One or both of ethylene, Hexafluorobutyl mathacrylate.
In one embodiment of the invention, the nematic crystal includes trans--butylcyclohexyl formic acid, hydroxyl connection
Benzene cyanogen, 4- butylcyclohexyl formic acid -4 '-cyanobiphenyl phenolic ester, N-4- methoxyl group benzal-n-butyl aniline, methacrylic acid β -
One of hydroxyl ethyl ester (HEMA), methacrylic acid Bian alcohol ester (BMA) are a variety of.
In one embodiment of the invention, the dyestuff includes anthraquinone dye, azo dyes or fragrant-flowered garlic class dyestuff.
In one embodiment of the invention, the dyestuff includes C.I. disperse yellow 119, C.I. DISPERSE Red 13 5, C.I.
Disperse Red 343, C.I. Disperse Blue-79, C.I. disperse blue 165, C.I. disperse blue 257, C.I. disperse blue 148, C.I. disperse red
167 or C.I. disperse brown 1.
In one embodiment of the invention, the emulsifier includes one of nonionic surface active agent；
It is described non-ionic including polyoxyethylene alkylphenol condensation product: OP-7, OP-10 or OP-15 or polyoxyethylene fatty alcohol condensation
Object: paregal O -10, paregal O -20, peregal O-25 or peregal A-20 or polyoxyethylene polyols ether fatty acid ester:
Tween40, Tween60, Tween65 or Tween80；Or the polyoxyethylene esters of fatty acid: SG-10, SE-10 or OE-15；
In one embodiment of the invention, the preparation method of step (1) the dyestuff doping type liquid crystal is first by one
The liquid crystal and dichroic dye of certainty ratio are heated to whole dissolutions, after stirring 0.5~3h, cool to the appearance of dyestuff doping type liquid crystal
After muddiness, then be warming up to just it is transparent, constant temperature stir 0.5~5h to get dyestuff doping type liquid crystal.
In one embodiment of the present invention, the method specifically comprises the following steps:
(1) a certain proportion of dichroic dye and nematic crystal are sufficiently mixed and prepare dyestuff doping type liquid crystal, wherein
Dyestuff is 0.1~6% to the mass fraction of liquid crystal, prepares the dyestuff doping type liquid crystal system of different colours respectively；
(2) it keeps certain temperature under mechanical agitation, a kind of dyestuff doping type liquid crystal is added drop-wise at identical temperature
Mixed system is prepared in emulsifier aqueous solution, wherein dyestuff doping type liquid crystal accounts for total system mass fraction 1~15%, in aqueous solution
Emulsifier content is 10-50% to dyestuff doping type liquid crystal mass fraction；High speed emulsification prepares emulsion dispersion, by mix monomer
It is added dropwise in Liquid Crystal dispersion, continues emulsification 30~120 minutes, wherein mix monomer is to dyestuff doping type liquid crystal quality point
Number is 10~400%, and soft monomer is 50~200% to the mass fraction of hard monomer in mix monomer, and crosslinking agent is to soft or hard monomer
The mass fraction of total amount is 10~50%, and the organic monomer of the high adhesive force of low-surface-energy is to the mass fraction of soft or hard monomer total amount
5~30%；Then the dispersion emulsified is transferred to being condensed back in the four-hole boiling flask with agitating device, leads to nitrogen 5
After~30 minutes, under 250-1000 revs/min of mixing speed, be warming up to 40~90 DEG C, after reaching reaction temperature, dropwise plus
Enter the initiator to monomer total amount 0.1-15%, is kept for thermotonus 2~12 hours, purify, obtain by diaphragm after fully reacting
Obtain the dyestuff doping type liquid crystal microcapsule lotion of even particle size distribution；
(3) miscella of another dyestuff doping type liquid crystal and monomer is added into above-mentioned dye-doped liquid crystal microcapsule emulsion
Phase, wherein monomer is 10~400% to dyestuff doping type liquid crystal mass fraction, mass fraction of the soft monomer to hard monomer in monomer
It is 50~200%.Adjusting revolving speed is 250-1000 revs/min, raises simultaneously system temperature and reaches non-ionic surface active used
The cloud point of agent emulsifies the dye that 4-8h makes oil phase be adsorbed on internal layer so that surfactant dies down with water molecules power
Expect doping type liquid crystal microcapsule surface.System temperature is then slowly reduced to room temperature, while reducing revolving speed is 250-500 revs/min
Clock continues to keep emulsification 0.5-2h；Then the dispersion emulsified is transferred to four mouthfuls be condensed back with agitating device
In flask, lead to nitrogen after 5~30 minutes, under 250-500 revs/min of mixing speed, is warming up to 40~90 DEG C, reaches reaction
After temperature, the initiator to monomer total amount 0.1-15% is added dropwise, is kept for thermotonus 2~12 hours；It is dry through centrifugation purification
After dry, required multilayered structure dyestuff doping type liquid crystal microcapsule is obtained.
Second object of the present invention is to provide a kind of dyestuff doping type liquid crystal microcapsule using the above method.
Third object of the present invention is to provide a kind of intelligent fiber, the preparation method of the intelligent fiber is using above-mentioned
Dyestuff doping type liquid crystal microcapsule.
Fourth object of the present invention is that the dyestuff doping type liquid crystal microcapsule is applied to flexible display technologies, intelligence
In energy fiber art.
Beneficial effects of the present invention:
The multilayered structure dyestuff doping type liquid crystal microcapsule that the method for the present invention is prepared, the outer layer dyestuff doping type liquid crystal
It subtracts color matching with polymeric shell layer as color layer and core material dyestuff doping type liquid crystal microcapsule, while as protective layer,
Protect internal layer dyestuff doping type liquid crystal from external environmental.The dyestuff used in this method is in host nematic liquid crystal matrix
In show high order parameter, high dichroism and good dissolubility.Not only color is gorgeous changeable for gained liquid crystal microcapsule, shows
Color is bright-coloured, can satisfy people to clothes personalization and multifarious requirement, and liquid crystal microcapsule size is 5-20 μm, partial size
Controllably, epigranular has good solvent resistance and water resistance, and high core material carrying capacity, driving voltage is low (to be lower than human-body safety electricity
Pressure), original color characteristics are still able to maintain after working process.And in application, the shell structurre of liquid crystal microcapsule is not only
It can play the role of protection to liquid crystal, and can participate in forming a film, good film-forming property is more applicable for the requirement of coating.This hair
The liquid crystal microcapsule display performance that bright method obtains has obtained significant raising, and stability is more preferable, has preferable physical and chemical
And optical property, it has a extensive future.
Detailed description of the invention
The transmission electron microscope picture of Fig. 1 dyestuff doping type liquid crystal microcapsule；
The petrographic microscope figure of Fig. 2 dyestuff doping type liquid crystal microcapsule；
The transmission electron microscope picture of Fig. 3 multilayered structure dyestuff doping type liquid crystal microcapsule；
The petrographic microscope figure of Fig. 4 layer structure dyestuff doping type liquid crystal microcapsule；
The transmission electron microscope picture of the microcapsule product prepared in Fig. 5 comparative example 1；
The transmission electron microscope picture of the microcapsule product prepared in Fig. 6 comparative example 2.
Specific embodiment
In order to be more clearly understood that technology contents of the invention, spy lifts following embodiment and is described in detail, and purpose is only
It is to be best understood from the protection scope that the contents of the present invention are not intended to limit the present invention.
Photoelectric properties test:
By prepared multilayer dyestuff doping type liquid crystal microcapsule lotion with electrode rigid substrates on film, it is to be coated
Layer covers other one piece of rigid electrode on film after being completely dried, and upper and lower two pieces of electrode adhesions are got up using colloid,
It is packaged processing, to obtain rigid liquid crystal microcapsule display device.DC Steady voltage is respectively adopted to the micro- glue of liquid crystal
Capsule device is driven, and the electrochromism phenomenon of display device is verified.Display effect, electro-optical properties to liquid crystal microcapsule device
Characterized respectively: display effect of the device under voltage driving passes through real-time photographic recording；Using fiber spectrometer, with device
Center reflection wavelength of the part under color status is fixed test wavelength, and it is saturating to test incident light of the device under different applied voltages
Cross rate curve.In test process, using two-layer electrode as blank reference.
Water-fast/solvent nature test:
Referring to GB/T 5211.5-2008, selected solvent includes second for water resistance testing method and solvent resistance test method
Alcohol, ethylene glycol, acetone.
Embodiment 1
Will 0.01g C.I. disperse red 60 and 1g mixed liquid crystal E7 mix after be heated to just all dissolutions and at transparence,
After stirring 0.5h at this temperature, cool to after color or muddiness occurs in mixture, then be warming up to just transparent, constant temperature stirring
0.5h, up to red based dye doping type liquid crystal.
Resulting red based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.2g ethoxylated dodecyl alcohol at identical temperature, high speed emulsification forms uniform dispersion；It will
0.5g butyl methacrylate and 0.5g isoprene, 0.1g divinylbenzene and 0.05g trifluoroethyl methacrylate,
It is added dropwise in Liquid Crystal dispersion after even mixing, continues emulsification 60 minutes.It is subsequently transferred to condensing reflux and stirring dress
In the four-hole boiling flask set, leads to nitrogen 5 minutes, under 500 revs/min of mixing speed, be warming up to 60 DEG C, 10g is added dropwise and contains
There is the aqueous solution of 0.001g ammonium persulfate, react 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dye is arrived
Expect doping type liquid crystal microcapsule lotion.The dyestuff doping type liquid crystal microcapsule partial size is to show bright red at 15 μm, 25 DEG C.
Transmission electron microscope observing is carried out to the dyestuff doping type liquid crystal microcapsule of preparation, transmission electron microscope photo is as shown in Figure 1.It is right
The liquid crystal microcapsule with core-shell structure of above-mentioned preparation carries out polarized light microscope observing, and polarisation photo is as shown in Figure 2.
It is heated to just all dissolve and at transparent after 0.01g C.I. disperse blue 359 and 1g mixed liquid crystal E7 are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
0.5g Hexyl 2-propenoate and 0.5g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 90 DEG C, 700 turns/
The emulsified 5h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 0.5h under 400 revs/min of mixing speed.With
It is transferred to afterwards with being condensed back in the four-hole boiling flask with agitating device, is led to nitrogen 5 minutes, in 500 revs/min of mixing speed
Under, be warming up to 60 DEG C, be added dropwise the aqueous solution that 10g contains 0.001g ammonium persulfate, react 6h, be restored to after room temperature by every
Film repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.The multilayered structure dyestuff doping type liquid
Brilliant Microcapsules Size is to show purple at 20 μm, 25 DEG C.
Transmission electron microscope observing is carried out to the liquid crystal microcapsule with multi-layer structure of above-mentioned preparation, transmission electron microscope photo is as schemed
Shown in 3.Polarized light microscope observing, polarisation photo such as Fig. 4 institute are carried out to the liquid crystal microcapsule with core-shell structure of above-mentioned preparation
Show.By the uniform particle sizes of the liquid crystal microcapsule of Fig. 3, Fig. 4 core-shell structure for knowing to prepare by above-mentioned preparation method, controllably.It is right
The liquid crystal microcapsule with multi-layer structure of above-mentioned preparation carries out photoelectric properties test (being shown in Table 1) and water-fast, solvent resistance is surveyed
It tries (being shown in Table 2).
Embodiment 2
It is heated to just all dissolve and at transparent after 0.01g C.I. disperse blue 359 and 1g mixed liquid crystal E7 are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.1g OP-10 at identical temperature, high speed emulsification forms uniform dispersion；By 0.5g methyl-prop
The own ester of olefin(e) acid and 0.25g styrene, 0.375g divinylbenzene and 0.225g trifluoroacetyl triflate uniformly mix
After be added dropwise in Liquid Crystal dispersion, continue emulsification 60 minutes.It is subsequently transferred to four with condensing reflux and agitating device
In mouth flask, leads to nitrogen 5 minutes, under 500 revs/min of mixing speed, be warming up to 60 DEG C, 10g is added dropwise and contains
The aqueous solution of 0.001g ammonium persulfate reacts 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dyestuff is arrived
Doping type liquid crystal microcapsule lotion.The dyestuff doping type liquid crystal microcapsule partial size is to show bright blue at 15 μm, 25 DEG C.
Will 0.01g C.I. disperse red 60 and 1g mixed liquid crystal E7 mix after be heated to just all dissolutions and at transparence,
After stirring 0.5h at this temperature, cool to after color or muddiness occurs in mixture, then be warming up to just transparent, constant temperature stirring
0.5h, up to red based dye doping type liquid crystal.
Resulting red based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
0.5g Hexyl 2-propenoate and 0.5g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 80 DEG C, 700 turns/
The emulsified 5h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 2h under 400 revs/min of mixing speed.Then
It is transferred to being condensed back in the four-hole boiling flask with agitating device, leads to nitrogen 5 minutes, in 500 revs/min of mixing speed
Under, be warming up to 70 DEG C, be added dropwise the aqueous solution that 10g contains 0.001g ammonium persulfate, react 6h, be restored to after room temperature by every
Film repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.The multilayered structure dyestuff doping type liquid
Brilliant Microcapsules Size is to show purple at 20 μm, 25 DEG C.
The liquid crystal microcapsule with multi-layer structure of above-mentioned preparation is carried out photoelectric properties test (being shown in Table 1) and water-fast, resistance to
Solvent nature tests (being shown in Table 2).
Embodiment 3
It is heated to just all dissolve and at transparent after 0.001g C.I. disperse blue 60 and 1g mixed liquid crystal 5CB are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.5g SE-10 at identical temperature, high speed emulsification forms uniform dispersion；By 0.1g acrylic acid
Butyl ester and 0.2g methyl methacrylate, 0.003g Diacetone Acrylamide and 0.003g Hexafluorobutyl mathacrylate are uniform
It is added dropwise in Liquid Crystal dispersion after mixing, continues emulsification 60 minutes.It is subsequently transferred to condensing reflux and agitating device
Four-hole boiling flask in, lead to nitrogen 5 minutes, under 1000 revs/min of mixing speed, be warming up to 70 DEG C, 10g is added dropwise and contains
The aqueous solution of 0.045 azo-bis-isobutyl cyanide reacts 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dye is arrived
Expect doping type liquid crystal microcapsule lotion.The dyestuff doping type liquid crystal microcapsule partial size is to show bright blue at 8 μm, 25 DEG C.
Just all dissolutions are heated to after 0.001g C.I. disperse yellow 119 and 1g mixed liquid crystal xenol cyanogen are mixed
And at transparence, after stirring 0.5h at this temperature, cool to after color or muddiness occurs in mixture, then be warming up to just thoroughly
Bright, constant temperature stirs 0.5h to get yellow based dye doping type liquid crystal.
Resulting yellow based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
0.5g Hexyl 2-propenoate and 0.5g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 95 DEG C, 700 turns/
The emulsified 4h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 1h under 250 revs/min of mixing speed.Then
It is transferred to being condensed back in the four-hole boiling flask with agitating device, leads to nitrogen 15 minutes, in 500 revs/min of mixing speed
Under, be warming up to 60 DEG C, be added dropwise the aqueous solution that 10g contains 0.001g ammonium persulfate, react 8h, be restored to after room temperature by every
Film repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.The multilayered structure dyestuff doping type liquid
Brilliant Microcapsules Size is to show green at 15 μm, 25 DEG C.
The liquid crystal microcapsule with multi-layer structure of above-mentioned preparation is carried out photoelectric properties test (being shown in Table 1) and water-fast, resistance to
Solvent nature tests (being shown in Table 2).
Embodiment 4
It is heated to just all dissolve and at transparent after 0.05g C.I. disperse yellow 119 and 1g mixed liquid crystal 7CB are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to yellow based dye doping type liquid crystal.
Resulting yellow based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.2g Tween 80 at identical temperature, high speed emulsification forms uniform dispersion；By 0.05g acrylic acid
Own ester and 0.05g methyl acrylate, 0.002g ethylene glycol dimethacrylate vinegar and 0.002g (perfluoro hexyl) ethylene are uniform
It is added dropwise in Liquid Crystal dispersion after mixing, continues emulsification 60 minutes.It is subsequently transferred to condensing reflux and agitating device
Four-hole boiling flask in, lead to nitrogen 30 minutes, under 1500 revs/min of mixing speed, be warming up to 40 DEG C, 10g is added dropwise and contains
There is the aqueous solution of 0.001g ammonium persulfate, react 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dye is arrived
Expect doping type liquid crystal microcapsule lotion.The dyestuff doping type liquid crystal microcapsule partial size is to show bright yellow at 3 μm, 25 DEG C.
It is heated to just all dissolve and at transparent after 0.05g C.I. disperse blue 60 and 1g mixed liquid crystal 5CB are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
2.0g Hexyl 2-propenoate and 2.0g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 80 DEG C, 700 turns/
The emulsified 8h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 0.5h under 400 revs/min of mixing speed.With
It is transferred to afterwards with being condensed back in the four-hole boiling flask with agitating device, is led to nitrogen 30 minutes, in 500 revs/min of stirrings speed
Under degree, be warming up to 40 DEG C, be added dropwise the aqueous solution that 10g contains 0.6g potassium peroxydisulfate, react 12h, be restored to after room temperature by
Diaphragm repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.The multilayered structure dyestuff doping type
Liquid crystal microcapsule partial size is to show green at 5 μm, 25 DEG C.
The liquid crystal microcapsule with multi-layer structure of above-mentioned preparation is carried out photoelectric properties test (being shown in Table 1) and water-fast, resistance to
Solvent nature tests (being shown in Table 2).
The color characteristics of 1 multilayered structure dyestuff doping type liquid crystal microcapsule of table
The water resistance and solvent resistance of 2 multilayered structure dyestuff doping type liquid crystal microcapsule of table
Comparative example 1
Influence of the low-surface-energy monomer to preparation Multi-layer microcapsule is investigated:
Will 0.01g C.I. disperse red 60 and 1g mixed liquid crystal E7 mix after be heated to just all dissolutions and at transparence,
After stirring 0.5h at this temperature, cool to after color or muddiness occurs in mixture, then be warming up to just transparent, constant temperature stirring
0.5h, up to red based dye doping type liquid crystal.
Resulting red based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.2g ethoxylated dodecyl alcohol at identical temperature, high speed emulsification forms uniform dispersion；It will
0.5g butyl methacrylate and 0.5g isoprene, 0.1g divinylbenzene are added dropwise to dispersed liquid crystal after evenly mixing
In body, continue emulsification 60 minutes.It is subsequently transferred to lead to nitrogen 5 minutes with being condensed back in the four-hole boiling flask with agitating device,
Under 500 revs/min of mixing speed, 60 DEG C are warming up to, the aqueous solution that 10g contains 0.001g ammonium persulfate is added dropwise, instead
It answers 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dyestuff doping type liquid crystal microcapsule lotion is arrived.The dye
Material doping type liquid crystal microcapsule partial size is to show bright red at 15 μm, 25 DEG C.
It is heated to just all dissolve and at transparent after 0.01g C.I. disperse blue 359 and 1g mixed liquid crystal E7 are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
0.5g Hexyl 2-propenoate and 0.5g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 90 DEG C, 700 turns/
The emulsified 5h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 0.5h under 400 revs/min of mixing speed.With
It is transferred to afterwards with being condensed back in the four-hole boiling flask with agitating device, is led to nitrogen 5 minutes, in 500 revs/min of mixing speed
Under, be warming up to 60 DEG C, be added dropwise the aqueous solution that 10g contains 0.001g ammonium persulfate, react 6h, be restored to after room temperature by every
Film repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.
Transmission electron microscope observing is carried out to the liquid crystal microcapsule with multi-layer structure of above-mentioned preparation, transmission electron microscope photo is as schemed
Shown in 5.Due to the missing of low-surface-energy monomer, even if interior microcapsule is built into type, but the oleophylic ability of shell material is poor, so that inhaling
Attached oily phasor is few, can not form required multilayer liquid crystal microcapsule structure.
Comparative example 2
Influence of the cross-linking monomer to preparation Multi-layer microcapsule is investigated:
It is heated to just all dissolve and at transparent after 0.05g C.I. disperse yellow 119 and 1g mixed liquid crystal 7CB are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to yellow based dye doping type liquid crystal.
Resulting yellow based dye doping type liquid crystal is maintained at clearing point temperature, and it is dripped under mechanical agitation
It is added in the aqueous solution containing 0.2g Tween 80 at identical temperature, high speed emulsification forms uniform dispersion；By 0.05g acrylic acid
Own ester and 0.05g methyl acrylate and 0.002g (perfluoro hexyl) ethylene are added dropwise to Liquid Crystal dispersion after evenly mixing
In, continue emulsification 60 minutes.It is subsequently transferred to lead to nitrogen 30 minutes with being condensed back in the four-hole boiling flask with agitating device,
Under 1500 revs/min of mixing speed, 40 DEG C are warming up to, the aqueous solution that 10g contains 0.001g ammonium persulfate is added dropwise, instead
It answers 2 hours, is washed by diaphragm repeated filtration after being restored to room temperature to get dyestuff doping type liquid crystal microcapsule lotion is arrived.The dye
Material doping type liquid crystal microcapsule partial size is to show bright yellow at 2 μm, 25 DEG C.
It is heated to just all dissolve and at transparent after 0.05g C.I. disperse blue 60 and 1g mixed liquid crystal 5CB are mixed
Shape after stirring 0.5h at this temperature, cools to after color or muddiness occurs in mixture, then is warming up to just transparent, and constant temperature stirs
0.5h is mixed, up to blue based dye doping type liquid crystal.
Resulting blue based dye doping type liquid crystal is maintained at clearing point temperature, and it is added dropwise under mechanical agitation
2.0g Hexyl 2-propenoate and 2.0g methyl methacrylate to identical temperature form mixed rear oily phase, dropwise after evenly mixing
It is added in the dyestuff doping type liquid crystal microcapsule lotion of above-mentioned preparation.Mixed system temperature is increased to 80 DEG C, 700 turns/
The emulsified 8h of mixing speed of minute.It then is cooled to room temperature, continues to emulsify 0.5h under 400 revs/min of mixing speed.With
It is transferred to afterwards with being condensed back in the four-hole boiling flask with agitating device, is led to nitrogen 30 minutes, in 500 revs/min of stirrings speed
Under degree, be warming up to 40 DEG C, be added dropwise the aqueous solution that 10g contains 0.6g potassium peroxydisulfate, react 12h, be restored to after room temperature by
Diaphragm repeated filtration washs to arrive multilayered structure dyestuff doping type liquid crystal microcapsule lotion.There is multilayer to above-mentioned preparation
The liquid crystal microcapsule of structure carries out transmission electron microscope observing, and transmission electron microscope photo is as shown in Figure 6.Due to the missing of crosslinking agent, cause
Interior microcapsule constructs that rear shell material intensity is low, it is oily mutually adsorb when organic solvent to the swelling of shell material and phase separation China and foreign countries
For one polymer under the collective effect of the pressure of internal layer shell material, microcapsules or rupture or swelling set can not form the micro- glue of multilayer
Capsule structure.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (10)
1. a kind of preparation method of dyestuff doping type liquid crystal microcapsule, which is characterized in that the described method includes:
(1) dichroic dye and nematic crystal are sufficiently mixed to the dyestuff doping type liquid crystal material for preparing different colours variation respectively
Material；
(2) a kind of dyestuff doping type liquid crystal material of color and organic monomer are copolymerized, wherein organic monomer include soft monomer, it is hard
Then the organic monomer of monomer, cross-linking monomer and the high adhesive force of low-surface-energy is added surfactant and evenly dispersed cream is made
Liquid dispersion；The organic monomer of the high adhesive force of low-surface-energy includes trifluoroethyl methacrylate, trifluoroacetyl fluoroform
Sulphonic acid ester, 3- fluorophenyl acetate, dodecafluoroheptyl methacrylate, (perfluoro hexyl) ethylene, Hexafluorobutyl mathacrylate
One or more of；
(3) initiator is added and causes polymerization, the liquid crystal microcapsule of polymer overmold dyestuff doping type liquid crystal material is made, purification is anti-
Lotion after answering obtains the dyestuff doping type liquid crystal microcapsule lotion of even particle size distribution；
(4) using the dyestuff doping type liquid crystal microcapsule lotion prepared in above-mentioned (3) as seed, the dyestuff of another different colours is mixed
Miscellaneous type liquid crystal material is mixed to get oily phase with soft monomer and hard monomer, is added in lotion, and make oil phase is adsorbed on micro- glue
On capsule seed；
(5) initiator is added and causes polymerization, make the oil for being adsorbed on internal layer liquid crystal microcapsule surface that polymerization reaction, releaser mutually occur
The polymer overmold dyestuff doping type liquid crystal coated polymer cladding dyestuff doping type of multilayered structure is prepared in phase separation
The dyestuff doping type liquid crystal microcapsule of liquid crystal.
2. method according to claim 1, which is characterized in that the crosslinking agent is 10 to the mass fraction of soft or hard monomer total amount
~50%.
3. method according to claim 1, which is characterized in that the organic monomer of the high adhesive force of low-surface-energy is to soft or hard list
The mass fraction of body total amount is 5~30%.
4. method according to claim 1, which is characterized in that the soft monomer to the mass fraction of hard monomer be 50~
200%.
5. method according to claim 1, which is characterized in that cross-linking monomer includes acrylic acid, acrylic acid in the step (2)
Hydroxyl ethyl ester, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxy propyl methacrylate, divinylbenzene,
One or both of ethylene glycol dimethacrylate vinegar, N hydroxymethyl acrylamide or Diacetone Acrylamide.
6. -5 any the method according to claim 1, which is characterized in that dichroic dye is to nematic in the step (1)
The mass fraction of liquid crystal is 0.1~6%.
7. -5 any the method according to claim 1, which is characterized in that dyestuff doping type liquid crystal accounts for cream in the step (2)
Liquid dispersion total system mass fraction 1~15%.
8. the dyestuff doping type liquid crystal microcapsule that any the method for claim 1-5 is prepared.
9. a kind of intelligent fiber, which is characterized in that the preparation method of the intelligent fiber is to utilize dyestuff according to any one of claims 8
Doping type liquid crystal microcapsule.
10. dyestuff doping type liquid crystal microcapsule according to any one of claims 8 answering in flexible display technologies or intelligent field of textiles
With.
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