CN104226213A - Method for making styrene-containing multi-shell liquid crystal microcapsule - Google Patents
Method for making styrene-containing multi-shell liquid crystal microcapsule Download PDFInfo
- Publication number
- CN104226213A CN104226213A CN201410514834.4A CN201410514834A CN104226213A CN 104226213 A CN104226213 A CN 104226213A CN 201410514834 A CN201410514834 A CN 201410514834A CN 104226213 A CN104226213 A CN 104226213A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- shell
- capsule
- solution
- gelatin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Abstract
The invention relates to a method for making a multi-shell liquid crystal microcapsule through the interaction of different classes of styrene-containing capsule shell substances and different classes of polymerization methods. The method is characterized in that polystyrene with the high-strength outermost layer is formed in the capsule shell through polymerization. Another characteristic lies in the uniqueness of the structure, and a capsule form adopting multi-shell protection is adopted in order to effectively protect the specific optical color of liquid crystal. The structural characteristics lie in that two hydrophilic colloids with different charges are used as the wall material in the first shell layer, a polymer of organic compound monomers is used in the second shell layer, a high molecular alloy transition layer of an interpenetrating network structure is built between the first shell layer and the second shell layer, and the strength is obviously improved. The liquid crystal is effectively protected from the corrosion of ambient acid and alkaline, the durability and the mechanical pressure bearing capability are improved, the application safety is high, the microcapsule can be truly used in print ink for example for bearing print pressure, and the specific optimal color of the liquid crystal is effectively protected.
Description
Technical field
The present invention relates to a kind of different types of softgel shell material and different types of polymerization interacts and manufactures the method for many shells liquid crystal microcapsule
Background technology
In order to prevent that Cucumber (gas, liquid, solid) is oxidized, variable color, corrosion and loss of stability, relevant art means will be taked to protect.Adopt filmogen to be wrapped up in it, include and wherein form different tiny capsules, interior bag thing is core, and external coating is shell material, and the method for this kind of tiny capsules technology of preparing is a high-end technology of being shown great attention to this century, and purposes is very extensive.
The quality being protection medicine at field of medicaments at present adopts capsule technique, but the particle diameter of medicine class capsule is larger.But industry and high-end technology field application very few, in fact in the urgent need to.As developer, function long-acting sustained-release agent, anticorrisive agent etc. have microcapsules technology to be taken to implement protection.
Current field of medicaments many employings high temperature spray-drying technology, although technique is simple, high temperature evaporation, can destroy active material, cyst wall breaks, and compactness is poor, and protectiveness is poor.
The core of current manufacture capsule mostly is pressed powder and high concentration liquid, become capsule opaque.Relate to the few of liquid crystal.The current overwhelming majority adopts the capsule of the coated formation of individual layer, shaky, dangerous, but because it is final products, therefore it doesn't matter.But applying it is in the industry intermediate products, and it will be subject to the effect of various power, can be damaged, therefore infeasible, do not reach the protection objects such as the colour developing of expection and slowly-releasing.
Liquid crystal makes it have unique optical characteristics due to special molecular structure and in the arrangement conformation in space, and presents distinctive optical color.Little about the relevant report of liquid crystal applications at present, liquid crystal display is only limitted at applied technical field, and temperature display meter, reason is that liquid crystal can be subject to changing and disappearing in solvent, soda acid, pressure and collision this distinctive optical characteristics in surrounding medium.Also it applies difficult reason on ink just for this.Therefore the document of this respect is little.Because the form of liquid crystal is very special, be the 4th state of the non-solid non-gas of non-liquid, between fluid and solid, so comparatively large to its coated difficulty, conventional single layer is coated, and cyst wall is solid not, soft and soggy, easy adhesion.All can break under collision and extruding, exert pressure to the process of the printing ink transfer of pressure as: printing is one, thus capsule shaky be must break undoubtedly.Instant invention overcomes application number in 2013 is that in the preparation of the cigarette wrapping paper of a CN103233397A reversible temperature-sensitive, its encapsulated particles size is to 5-1000 μm, and it is all higher than layer of ink, cannot realize the shortcoming of printing; Clad is one deck, and capsule easily breaks and adds the materials such as clay, silicate, aluminium in its capsule shell, causes the shortcomings such as the optical color of liquid crystal cannot represent.
The CN102675958A clad that instant invention overcomes application in 2012 is one deck, the shortcoming that capsule easily breaks.But the liquid crystal that the CN1062744A that instant invention overcomes application in 1992 adopts is double walled capsule internal layer is that grease is difficult to polymerization, between ground floor shell and second layer shell, bond shortcoming loosely.
The present invention is technical method effectively coated for liquid crystal capsule specially, increases cyst wall intensity and soft firm conjugation, and is multilayer softgel shell, ensure that the security and stability of application, therefore can apply in gravure and serigraphy.
Summary of the invention
The present invention be directed to the special 4th form product of one of material, have the feature of fluidised form and crystalline state concurrently, there is the small molecule liquid crystal of dynamic molecular combination conformation, be prepared into microemulsion, carry out variety classes material and variety classes polymerization being polymerized of blending property mutually, it is characterized by many shell structurres of having constructed microcapsules uniqueness.Form many shells microcapsules.Based on the gravitation of liquid crystal molecule two terminal polar group, not easily disperse, therefore introducing three components dissolves.Adopt natural electronegative gum arabic and positively charged gelatin, by positive and negative charge attract each other interact and progressively deposit to around capsule-core, the gelatin that the gum arabic first enclosed and rear absorption are got on is coated on the surface of capsule-core in double-deck multiple state of aggregation, achieves that to carry out the first shell to liquid crystal coated.Before the second shell is coated, centre is constructed and is defined swelling grafting transition zone, and adopt natural gelatin, gum arabic respectively accounts for 50%.This layer is the grafting by various radical reaction, forms the alloy structure layer passing network mutually in bulk polymerization.The last radical polymerization carrying out styrene monomer under the effect of emulsifying agent, initator, forms the second shell.Form microcapsules fine uniform; solid, not inter-adhesive; good stability; security is high; liquid crystal is protected wherein; its distinctive Birefringent optical characteristic and color are protected, and lose its distinctive optical signature and color under avoiding the effect such as burn into light, stress of the PH change in coated do not caused applied environment, solvent.
The present invention for the technical scheme realizing above-mentioned technical goal and take is:
The manufacture method of many shells liquid crystal microcapsule of A, a kind of cross polymerization is characterised in that following reactions steps and technological process.First add the electronegative hydrophilic colloid aqueous solution in the reactor, add liquid crystal solution under high velocity agitation, form microemulsion, and then under specific temperature-time, then add the positively charged hydrophilic colloid aqueous solution, two kinds of different charge interactions, form multiple coacervate, then lower the temperature gradually, reduce mixing speed, under certain hour stability, then by the effect of curing agent and promoter, multiple coacervate is converted into undissolved cross-linked structure first shell.
B, then add the swelling grafting transition zone that colloidal solution forms the first shell layer surface, that is to say the swelling grafting transition zone between ground floor and the second layer.Because the first shell completes post bake below freezing, epidermis consolidation is smooth, is difficult to other foreign peoples's materials of attachment, is namely difficult to the coated polymerization carrying out second layer shell.Therefore heating makes that the first shell epidermis is swelling to be clamminess, then adds the fusion grafting that colloid of the same race is just easy on swelling epidermis attachment and then realizes molecule, here except physical action, also has ionization, the effect of hydroxyl and other group.The grafting transition zone of such preparation is conducive to the coated of the second shell.Grafting molecules chain is caused in follow-up polymerization, to form inierpeneirating network structure with the organic compound of the second shell, suitable high polymer alloy layer, so layer intensity is very large.
C, under the protection of emulsifying agent, then realize the radical polymerization of styrene monomer further, form the second shell.After cleaning is separated, form the microcapsule product of about 2-20 μm, product fully shows the distinctive optical characteristics of liquid crystal and color.
This manufacturing system is one and condenses the small parcel shell of formation from emulsion again through positive and negative charge effect, and then it is crosslinked, then realize the radical polymerization of the styrene monomer of secondary emulsion by the swelling grafting layer of middle interpenetrating networks, form the class emulsion polymerization systems of many shells tiny capsules.Its holds the multiple excellent characteristics having drawn together emulsion and solution, ion and free radical, interpenetrating networks and hud polymerization.
This its core of manufacturing system material therefor is Small molecular cholesteryl liquid crystal, and this kind of liquid crystal is a kind of non-solid, non-liquid, non-gas form, is the 4th state outside tri-state, has characteristic that is liquid and crystalline state concurrently, present fluidised form and solid-state between form.Possess birefringent characteristic specific to optical anisotropy crystal, by temperature, the impact of light and angle, makes its various optical property variations in light, presents different color.But any one or any combination done in core cholesteryl liquid crystal.Liquid crystal is the mixture of slichem-79 and BDH2281. or cholesterine cinnamate, cholesteryl nonanoate, cholesteryl benzoate, benzoic acid acetic acid esters.
In this manufacture method, the first shell shell material is gum arabic and gelatin, is natural environmental protection colloid.The swelling grafting transition zone that centre is constructed is also gum arabic and gelatin, and the second shell material is distyryl compound monomer.Mounting medium is water. therefore production process is harmless, Product Green, safety.
The emulsifying agent of formation second shell polymerization used in this manufacture method is enuatrol, neopelex, lauryl sodium sulfate.
The initator of formation second shell polymerization used in this manufacture method is potassium peroxydisulfate, ammonium persulfate, dibenzoyl peroxide.
The curing agent making coacervate form cross-linked structure in this manufacture method is the one in formaldehyde, sulfuryl ethyl sulfonate, Alpha-hydroxy sulfuryl, pyridine salt, and hardening accelerator is that 1,3,5-trihydroxybenzene, hybar X, uracil, sodium hydrogen tartrate are wherein a kind of.
From capsule-core to the material usage of multilayer softgel shell in manufacturing technology of the present invention:
Capsule-core
Liquid crystal and acetone, butanone ratio are account for 4.25% of total system weight at 1: 1
First shell
Concentration is that the Arabic gum aqueous solution of 15-20% accounts for 1.59% of total system weight.
Concentration is that the aqueous gelatin solution of 15-20% accounts for 1.59% of total system weight.
System PH=4 is adjusted, (do not participate in reaction, ignore) with the HAc of concentration 50%.
Carry out system dilution with distilled water, distilled water accounts for 74.4% of total system weight
The curing agents such as the formaldehyde of 37% concentration or sulfuryl ethyl sulfonate, account for 0.637% of total system weight
The hardening accelerator 1,3,5-trihydroxybenzene of 1% concentration or hybar X etc. account for 0.03% of total system weight.
With the NaHCo of concentration 10%
3tune about system PH=8, (do not participate in reaction, ignore).
Swelling grafting transition zone in the middle of first and second shell
Formed by the colloidal solution of 15-20% concentration, gum arabic/gelatin is: 50%/50%. accounts for 1% of total system weight
Emulsifying agent enuatrol accounts for 0.03% of total system weight.
The solvent of dissolved emulsifier is distilled water, accounts for 5.3% of total system weight
Second shell
Add emulsifying agent (enuatrol or the neopelex etc.) aqueous solution and form emulsion protection, 0.021% of total system weight
Add initator (potassium peroxydisulfate or ammonium persulfate or dibenzoyl peroxide etc.), account for 0.053% of total system weight
Add monomer styrene, account for 0.9% of total system weight
The solvent dissolving above-mentioned three kinds of auxiliary agents is distilled water, accounts for 10% of total system weight
In the core of liquid crystal, introduce a solvent composition, namely formed in microemulsion and introduce three components butanone or acetone, they play the effect of dissolving liquid crystal, make it to become liquid crystal solution.And contribute to diffusion and the flowing of liquid crystal.
The technique particularity forming the first shell step in manufacture method is: the high rotating speed 1400-2200 rev/min stirring from liquid crystal dispersion, and be progressively down to 100-500 rev/min, established ground floor clad is stablized in effect, makes it not collide non-caked.Temperature from 40 DEG C-70 DEG C of dispersed liquid crystal be down to encystation time 0 DEG C of point below, effect forms physical constriction to obtain solid rete.
In the step of constructing intermediate swellings grafting layer, mixing speed is 200-700 rev/min, and temperature, from the 35-50 DEG C of colloidal solution adding 50%/50% gelatin/gum arabic, is adjusted to the 50-70 DEG C when putting into emulsifying agent, and emulsion dispersion is accelerated in effect.
In the step of formation second shell, the second shell mixing speed remains on 200-700 rev/min, and temperature is transferred to the 60-90 DEG C of polyaddition monomer monomer from 50-70 DEG C that adds emulsifying agent. and effect promotes polymerization.Reaction time is 2-3.5 hour, and wherein monomer adds employing dropping mode.
The pH value of manufacturing system by from dispersed liquid crystal in gum arabic gelatin, form microemulsion time PH=2-4, effect is the dispersion that acidity is conducive to system, is adjusted to PH=8-12 during last encystation, and effect is that alkalescence is conducive to the stable of softgel shell.
Beneficial effect of the present invention:
Importantly by under first step high-speed stirred; formed and be full of the colloid of negative electrical charge and the microemulsion of liquid crystal solution; just because of the protection of electric charge; make formed microemulsion very even; trickle; so that afterwards can both uniform particle sizes to the formation of microcapsules from small glue-line inclusion enclave, tiny, can 2-20 μm be reached.
Just because of the adding of curing agent and hardening accelerator; system is made to define the cross-linked structure of ground floor in the reaction; and constructed the swelling grafting layer of one deck in the first shell layer surface; the alloy structure layer of interpenetrating networks is formed after polymerization; finally under the protective effect of emulsifying agent, define the second shell; the microcapsules formed are stablized, solid, safely, do not reveal.The protection object of expection can be reached.
Condition above-mentioned just ensures, fully can show the distinctive optical birefringence feature of liquid crystal and color to make the microcapsules obtained.
Detailed description of the invention:
Embodiment 1.
By concentration be first 20% Arabic gum aqueous solution 15ml add reaction bulb, add liquid crystal solution (20g Liquid crystal pour 20ml acetone) under high velocity agitation again, accelerate be stirred to 2200 revs/min.Form microemulsion at 70 DEG C, after stablizing 5 minutes, add the aqueous gelatin solution 15ml that concentration is 15%.System PH=4 is adjusted with the HAc of concentration 50%, stir speed (S.S.) is down to 500 revs/min, stablize 5 minutes, adding distil water (40 DEG C) 200ml dilutes, now mixing speed is down to 200 revs/min, the outer positive and negative charge effect of system core produces multiple cohesion, stablize 10 minutes, the distilled water 500ml adding 35 DEG C again dilutes, and system temperature is 35 DEG C, about 10 minutes, then solution system is cooled to-5 DEG C, and add the curing agent formaldehyde 20ml of 37%, 3ml hardening accelerator 1,3,5-trihydroxybenzene, with the NaHCo of concentration 10%
3tune about system PH=8; react 60 minutes; by stirring modulation 600 revs/min; be warming up to 40 DEG C again; add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml; form swelling grafting transition zone; the 60ml aqueous solution containing 0.5 gram of emulsifying agent (enuatrol) is added when 55 DEG C; formation emulsion is protected; drip when 65 DEG C and there is 0.3 gram of initiator potassium persulfate; the emulsifying agent enuatrol of 0.2 gram, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 200-300 rev/min.80 DEG C of reactions terminate for 3.5 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.
Embodiment 2.
By concentration be first 15% Arabic gum aqueous solution 18ml add reaction bulb stir.Then the solution of (20g liquid crystal+20ml butanone) is injected, stir and be down to 1400 revs/min, form microemulsion under temperature 60 C, stablize about 10 minutes, add the gelatin solution 15ml that concentration is 20% concentration.PH=3.5 is adjusted with the HAc of concentration 50%, stirring reduction of speed rate is 500 revs/min, stablize 5-10 minute, the distilled water 170ml adding (50 DEG C) dilutes, now mixing speed is down to 300 revs/min, system core outer casing charge effect forms multiple cohesion, stablize 5 minutes, then the distilled water 4500ml adding 30 DEG C dilutes, temperature is 30-40 DEG C, about 10 minutes, afterwards system is cooled to-5 DEG C below freezing, and adds curing agent and enter sulfuryl ethyl sulfonate 20ml, hardening accelerator hybar X 3ml, stir 40 minutes, with the NaHCo of concentration 10%
3tune about system PH=8.By stirring modulation 100 revs/min, react 50 minutes.Be warming up to 30 DEG C again; add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml; form swelling grafting transition zone; the aqueous solution of the 50ml containing 0.3 gram of neopelex is added when 45 DEG C; formation emulsion is protected, and adds and has 0.3 gram of ammonium persulfate, 0.2 gram of neopelex when 60 DEG C; the 100ml aqueous solution of 9ml styrene monomer, mixing speed remains on 200-300 rev/min.React end in 3.5 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.
Embodiment 3.
By concentration be first 20% Arabic gum aqueous solution 15ml add reaction bulb, add liquid crystal solution (20g Liquid crystal pour 20ml acetone) under high velocity agitation again, accelerate be stirred to 1700 revs/min.Form microemulsion at 50 DEG C, after stablizing 5 minutes, add the aqueous gelatin solution 18ml that concentration is 15%.System PH=4 is adjusted with the HAc of concentration 50%, stir speed (S.S.) is down to 1000 revs/min, stablize 5 minutes, adding distil water (40 DEG C) 200ml dilutes, now mixing speed is down to 200 revs/min, the effect of system core surfaces positive and negative charge produces multiple cohesion, stablize 10 minutes, the distilled water 500ml adding 35 DEG C again dilutes, and system temperature is 35 DEG C, about 10 minutes, then solution system is cooled to-5 DEG C, and add the curing agent Alpha-hydroxy sulfuryl 20ml of 37%, 3ml hardening accelerator uracil, with the NaHCo of concentration 10%
3tune about system PH=8; react 45 minutes, by stirring modulation 600 revs/min, then be warming up to 45 DEG C; add colloidal solution 10ml; form swelling grafting transition zone, when 50 DEG C, add the 60ml aqueous solution containing 0.5 gram of emulsifier sodium lauryl sulfate, form emulsion protection; add when 75 DEG C and there is 0.3 gram of initiator potassium persulfate; 0.2 gram of lauryl sodium sulfate, the 100ml miscible fluid of the styrene monomer of 9ml, mixing speed remains on 200 revs/min.React end in 3.5 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.
Embodiment 4.
By concentration be first 20% Arabic gum aqueous solution 15ml add reaction bulb, add liquid crystal solution (20g Liquid crystal pour 20ml acetone) under high velocity agitation again, accelerate be stirred to 1800 revs/min.Form microemulsion at 50 DEG C, after stablizing 5 minutes, add the aqueous gelatin solution 15ml that concentration is 15%.System PH=4 is adjusted with the HAc of concentration 50%, stir speed (S.S.) is down to 1000 revs/min, stablize 5 minutes, adding distil water (40 DEG C) 200ml dilutes, now mixing speed is down to 250 revs/min, the outer positive and negative charge effect of system core produces multiple cohesion, stablize 10 minutes, the distilled water 450ml adding 35 DEG C again dilutes, and system temperature is 35 DEG C, about 10 minutes, then solution system is cooled to-2 DEG C, and add the curing agent pyridiniujm 20ml of 37%, 3ml hardening accelerator sodium hydrogen tartrate, with the NaHCo of concentration 10%
3tune about system PH=8; react 65 minutes, by stirring modulation 450 revs/min, then be warming up to 45 DEG C; add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml; form swelling grafting transition zone, when 60 DEG C, add the 60ml aqueous solution containing 0.5ml emulsification enuatrol, form emulsion protection; add when 70 DEG C and there is 0.3 gram of initiator potassium persulfate; 0.2 gram of enuatrol, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 300 revs/min.React end in 3 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.
Embodiment 5.
By concentration be first 20% Arabic gum aqueous solution 15ml add reaction bulb, add liquid crystal solution (20g Liquid crystal pour 20ml acetone) under high velocity agitation again, accelerate be stirred to 1700 revs/min.Form microemulsion at 50 DEG C, after stablizing 5 minutes, add the aqueous gelatin solution 18ml that concentration is 15%.System PH=4 is adjusted with the HAc of concentration 50%, stir speed (S.S.) is down to 1000 revs/min, stablize 5 minutes, adding distil water (40 DEG C) 185ml dilutes, now mixing speed is down to 200 revs/min, the outer positive and negative charge effect of system core produces multiple cohesion, stablize 10 minutes, the distilled water 515ml adding 35 DEG C again dilutes, and system temperature is 35 DEG C, about 10 minutes, then solution system is cooled to-5 DEG C, and adding the curing agent Alpha-hydroxy sulfone 20ml of 37%, 3ml hardening accelerator uracil, with the NaHCo of concentration 10%
3tune about system PH=8; react 35 minutes; by stirring modulation 600 revs/min; be warming up to 40 DEG C again; add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml; form swelling grafting transition zone; the 60ml aqueous solution containing 0.5 gram of emulsifying agent (enuatrol) is added when 55 DEG C; formation emulsion is protected; add when 70 DEG C and there is 0.3 gram of initator dibenzoyl peroxide, 0.2 gram of enuatrol; the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 200-300 rev/min.React end in 3.5 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.About minute, then solution system is cooled to-5 DEG C, and adds the curing agent formaldehyde 20ml of 37%, 3ml hardening accelerator 1,3,5-trihydroxybenzene, with the NaHCo of concentration 10%
3tune about system PH=8; react 45 minutes; by stirring modulation 600 revs/min; be warming up to 45 DEG C again; add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml; form swelling grafting transition zone; the 60ml aqueous solution containing 0.5 gram of emulsifying agent neopelex is added when 65 DEG C; formation emulsion is protected; add when 70 DEG C and there is 0.3 gram of initator dibenzoyl peroxide; 0.2 gram of neopelex, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 200-300 rev/min.React end in 3.5 hours.After room temperature places 24 hours, distilled water cleans, and is separated.Obtain the microcapsules that particle diameter is 2-20 μm.Product fully shows optical signature and the color of liquid crystal.
Product photo is as accompanying drawing; can find out that from accompanying drawing the distinctive Birefringent optical characteristic of above-mentioned many shells liquid crystal and color are protected, under avoiding the effect such as burn into light, stress of the PH change in coated do not caused applied environment, solvent, lose its distinctive optical signature and color.(see photo).
Claims (12)
1. the manufacture method of the many shells liquid crystal capsule containing polystyrene, its feature comprises the following steps: (1) forms capsule-core and the first shell: first add the electronegative gum arabic hydrophilic colloid aqueous solution in the reactor, then the liquid crystal solution with butanone or acetone solution is added under high velocity agitation, form microemulsion, then at 40-60 DEG C, after 3-15 minute, add the positively charged gelatin hydrophilic colloid aqueous solution again, two kinds of different charge interactions, the capsule-core that liquid crystal is formed forms multiple coacervate.Then lower the temperature gradually, reduce mixing speed, under 20-50 minute stable state, by the effect of curing agent and promoter, multiple coacervate is converted into undissolved cross-linked structure first shell again, (2) swelling grafting transition zone is formed: at heating 35-50 DEG C, add concentration is 15-25%, consumption is the swelling grafting transition zone that 50%/50% gelatin/gum arabic colloidal solution forms the first shell layer surface, because the first shell compacts, smooth surface is very difficult adheres to other materials, but rear surface is swelling is clamminess in heating, just adhere to surface after adding a small amount of gelatin/Arab easily and form grafting through reaction, this plays positive role by the second the coated of shell material, grafting molecules chain is caused in follow-up polymerization, to form inierpeneirating network structure with the organic compound of the second shell, suitable high polymer alloy, (3) the second shell is formed: be warming up to 35-60 DEG C more afterwards, add quantitative emulsifier solution, under the protection of emulsifying agent, when system is warming up to 60-90 DEG C, by the solution instillation system containing initator, emulsifying agent, styrene monomer, react and achieve styrene monomer radical polymerization in 2-3.5 hour, form the second shell, (4) cleaning obtains the microcapsule product of about 2-20 μm after being separated.
2. liquid crystal capsule manufacture method as claimed in claim 1, it is characterized in that, formed in the step of the first shell: (1) is in formation capsule-core and the first shell step, rotating speed is by the high rotating speed 1400-2200 rev/min making dispersed liquid crystal, effect makes the more tiny dispersion of the microemulsion of formation.Progressively be down to 100-500 rev/min, established first shell is stablized in effect, makes it not collide non-caked.Temperature from 40 DEG C-70 DEG C of dispersed liquid crystal be down to less than 0 DEG C; Effect forms physical constriction to obtain solid rete;
(2) in the step forming swelling grafting layer, the mixing speed of swelling grafting layer is 200-700 rev/min, temperature is from the 35-50 DEG C when adding the colloidal solution of 50%/50% gelatin/gum arabic, and be adjusted to the 50-70 DEG C when putting into emulsifying agent, emulsion dispersion is accelerated in effect.
(3) in the step of formation second shell, the second shell mixing speed remains on as 200-700 rev/min, is transferred to the 60-90 DEG C of polyaddition monomer monomer. and effect promotes polymerization.Reaction time is 2-3.5 hour, and wherein monomer adds employing dropping mode.
3. liquid crystal capsule manufacture method as claimed in claim 1, regulate in reactor the pH value manufacturing standby system, will to form liquid crystal be capsule-core, PH=2-4 when gelatin-gum arabic is the microemulsion dispersion of clad, effect is the dispersion that acidity is conducive to system, be adjusted to PH=8-12 during last encystation, effect is that alkalescence is conducive to the stable of softgel shell.
4. the liquid crystal microcapsule of shell more than, is characterized in that many shells liquid crystal microcapsule comprises capsule-core, the first shell, swelling grafting transition zone and the second shell; First shell and swelling grafting layer comprise the material be made up of pure natural substance, second shell comprises the material be made up of polymerisable organic compound, in first shell, the material of pure natural substance composition is the hydrophilic colloid aqueous solution utilizing the electric charge of gum arabic, gelatin different, the clad of quick formation liquid crystal surfactant, with formaldehyde, sulfuryl ethyl sulfonate, Alpha-hydroxy sulfuryl, pyridine salt wherein one do curing agent, with 1,3,5-trihydroxybenzene, hybar X, uracil, sodium hydrogen tartrate wherein one do hardening accelerator and carry out Quick cross-linking formation; Second shell is polymer, it is made up of polymerisable organic compound styrene, second shell initator used is potassium peroxydisulfate or ammonium persulfate or dibenzoyl peroxide, and the emulsifying agent wherein used is enuatrol, neopelex or lauryl sodium sulfate one wherein; Also construct between first and second shell and in heating process, formed swelling grafting transition zone with 50% gelatin/50% gum arabic; Capsule-core layer is the liquid crystal with butanone or acetone solution, and increase the effect of microemulsion diffusion and flowing with butanone or acetone solution, above-mentioned capsule is evenly small, and particle diameter is 2 μm about-20 μm.
5. liquid crystal capsule as claimed in claim 4, it is characterized in that core is Small molecular cholesteryl liquid crystal, this cholesteryl liquid crystal is the combination of single kind liquid crystal or several liquid crystal.
6. liquid crystal capsule as claimed in claim 4, is characterized in that liquid crystal 50% butanone that core is used or 50% acetone dissolve, thus increases the effect of microemulsion diffusion and flowing, and the core material solution of liquid crystal and butanone or acetone accounts for 4.25% of total system weight.
7. liquid crystal capsule as claimed in claim 4, it is characterized in that the Arabic gum aqueous solution that the hydrophilic solution that the first housing uses is 15-20% for concentration, the 1.5910-20% aqueous gelatin solution concentration accounting for system gross weight this layer of weight total solid content is 15-20%, accounts for the 10-20% that 1.59% of system gross weight accounts for this layer of total solid content.
8. liquid crystal capsule as claimed in claim 4, it is characterized in that with concentration being that the one wherein such as 37% formaldehyde or sulfuryl ethyl sulfonate is for sclerosis crosslinking agent, account for a kind of 0.03% of total system weight that accounts for wherein such as hardening accelerator 1,3,5-trihydroxybenzene or hybar X of 0.637%1% concentration of total system weight, for the distilled water of diluted system, account for 74.4% of total system weight.
9. liquid crystal capsule as claimed in claim 4, it is characterized in that the swelling grafting transition zone in first and second shell, it is formed by 15-20% (gum arabic 50%/gelatin 50%) colloidal solution.Both account for 1% of total system weight, the 80-95% of this layer of solid content altogether, and emulsifying agent enuatrol accounts for 0.03% of total system weight.The solvent of dissolved emulsifier is distilled water, accounts for 5.3% of overall weight.
10. liquid crystal capsule as claimed in claim 4, is characterized in that the second shell contains emulsifying agent enuatrol or neopelex etc., accounts for 0.021% of total system weight.
11. liquid crystal capsules as claimed in claim 4, is characterized in that the initiator potassium persulfate of styrene monomer or ammonium persulfate or dibenzoyl peroxide wherein a kind of accounts for 0.053% of total system weight.
12. liquid crystal capsules as claimed in claim 4, is characterized in that styrene monomer accounts for 0.9% of total system weight, being distilled water, accounting for 10% of total system weight for dissolving the solvent of initator, emulsifying agent and monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514834.4A CN104226213B (en) | 2014-09-30 | 2014-09-30 | A kind of manufacture method containing cinnamic many shells liquid crystal microcapsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514834.4A CN104226213B (en) | 2014-09-30 | 2014-09-30 | A kind of manufacture method containing cinnamic many shells liquid crystal microcapsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104226213A true CN104226213A (en) | 2014-12-24 |
| CN104226213B CN104226213B (en) | 2016-05-18 |
Family
ID=52215640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410514834.4A Active CN104226213B (en) | 2014-09-30 | 2014-09-30 | A kind of manufacture method containing cinnamic many shells liquid crystal microcapsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104226213B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317064A (en) * | 2018-09-30 | 2019-02-12 | 江南大学 | A kind of preparation method of the liquid crystal microcapsule of carbon black doping |
| CN110243788A (en) * | 2018-03-09 | 2019-09-17 | 江苏集萃智能液晶科技有限公司 | A kind of method and its system detecting gaseous compound concentration |
| CN114100538A (en) * | 2020-08-26 | 2022-03-01 | 北京化工大学 | Preparation method of self-assembled microcapsule |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2800457A (en) * | 1953-06-30 | 1957-07-23 | Ncr Co | Oil-containing microscopic capsules and method of making them |
| JPS6228284A (en) * | 1985-07-30 | 1987-02-06 | Mitsui Toatsu Chem Inc | Microcapsule support |
| CN1062744A (en) * | 1991-12-21 | 1992-07-15 | 深圳北方投资开发公司 | Liquid crystal heat colour-changed printing ink |
| US20030129247A1 (en) * | 2001-10-19 | 2003-07-10 | Ju Hee Kyung | Thermotropic liquid crystal polymer microcapsules, a method for preparing the same, and cosmetic compositions containing the same |
| CN101319108A (en) * | 2007-06-07 | 2008-12-10 | 中国印钞造币总公司 | Round-polarization novel printing ink and method of producing the same |
| CN101530769A (en) * | 2009-03-09 | 2009-09-16 | 浙江大学 | Method for preparing electronic ink microcapsule |
| CN102847495A (en) * | 2011-06-30 | 2013-01-02 | 广州奥熠电子科技有限公司 | Electrophoretic display microcapsule and its manufacturing method |
-
2014
- 2014-09-30 CN CN201410514834.4A patent/CN104226213B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2800457A (en) * | 1953-06-30 | 1957-07-23 | Ncr Co | Oil-containing microscopic capsules and method of making them |
| JPS6228284A (en) * | 1985-07-30 | 1987-02-06 | Mitsui Toatsu Chem Inc | Microcapsule support |
| CN1062744A (en) * | 1991-12-21 | 1992-07-15 | 深圳北方投资开发公司 | Liquid crystal heat colour-changed printing ink |
| US20030129247A1 (en) * | 2001-10-19 | 2003-07-10 | Ju Hee Kyung | Thermotropic liquid crystal polymer microcapsules, a method for preparing the same, and cosmetic compositions containing the same |
| CN101319108A (en) * | 2007-06-07 | 2008-12-10 | 中国印钞造币总公司 | Round-polarization novel printing ink and method of producing the same |
| CN101530769A (en) * | 2009-03-09 | 2009-09-16 | 浙江大学 | Method for preparing electronic ink microcapsule |
| CN102847495A (en) * | 2011-06-30 | 2013-01-02 | 广州奥熠电子科技有限公司 | Electrophoretic display microcapsule and its manufacturing method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110243788A (en) * | 2018-03-09 | 2019-09-17 | 江苏集萃智能液晶科技有限公司 | A kind of method and its system detecting gaseous compound concentration |
| CN109317064A (en) * | 2018-09-30 | 2019-02-12 | 江南大学 | A kind of preparation method of the liquid crystal microcapsule of carbon black doping |
| CN114100538A (en) * | 2020-08-26 | 2022-03-01 | 北京化工大学 | Preparation method of self-assembled microcapsule |
| CN114100538B (en) * | 2020-08-26 | 2022-11-25 | 北京化工大学 | Preparation method of self-assembled microcapsule |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226213B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3691090A (en) | Encapsulation method | |
| Yu et al. | Preparation and characterization of acrylic-based electronic inks by in situ emulsifier-free emulsion polymerization for electrophoretic displays | |
| CN104307445B (en) | A kind of manufacture method of many shells liquid crystal microcapsule of cross polymerization | |
| CN103193916B (en) | Preparation method of polymeric microspheres for electrophoretic display | |
| CN104226213A (en) | Method for making styrene-containing multi-shell liquid crystal microcapsule | |
| JP2009544052A (en) | Particles for use in electrophoretic displays | |
| CN104624124A (en) | Liquid crystal microcapsule and preparation method thereof | |
| JP7280041B2 (en) | Nanoemulsion optical materials | |
| CN104231725A (en) | Optical extraordinary splendor ink composition consisting of multi-shell liquid crystal, and preparation method of optical extraordinary splendor ink | |
| Tawiah et al. | An overview of the science and art of encapsulated pigments: Preparation, performance and application | |
| JP5313388B2 (en) | Switchable particle-based display and manufacturing method thereof | |
| WO2010071002A1 (en) | Bicolored particles having improved display performance | |
| CN1919940A (en) | Electron ink microcapsule and preparation method thereof | |
| Hong et al. | Hollow capsules prepared from all block copolymer micelle multilayers | |
| JP2022520049A (en) | Composite electrophoretic particles and variable permeable film containing them | |
| CN102585676A (en) | Electrophoretic display coating liquid and preparation method thereof | |
| CN101130661A (en) | Electrostatic resistance applying liquid composition and manufacture of high penetrance electrostatic resistance film | |
| CN101417221A (en) | Preparation method of micro-capsules for electrophoretic display | |
| Donbrow | Developments in phase separation methods, aggregation control, and mechanisms of microencapsulation | |
| JP5709268B2 (en) | Method for producing composite fine particles having heterogeneous surface | |
| CN1185048C (en) | Method for covering high polymer gel microsphere by using emulsion method | |
| CN102641704B (en) | Manufacture method of microcapsule for electrophoresis display | |
| JP3527167B2 (en) | Display device manufacturing method and display device | |
| JP2010207813A (en) | Particle and method of preparing the same | |
| JP4678591B2 (en) | Microcapsules for ultrasonic destruction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |