CN1299159C - Preparation method of microcapsule - Google Patents
Preparation method of microcapsule Download PDFInfo
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- CN1299159C CN1299159C CNB2004100392235A CN200410039223A CN1299159C CN 1299159 C CN1299159 C CN 1299159C CN B2004100392235 A CNB2004100392235 A CN B2004100392235A CN 200410039223 A CN200410039223 A CN 200410039223A CN 1299159 C CN1299159 C CN 1299159C
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Abstract
The present invention relates to a preparation method for microcapsules. The preparation method comprises the following steps: (1) pigments, background dyes and electrostatic charging agents are dispersed in organic solvents to form an oil phase electrophoresis liquid; (2) an aqueous solution of first capsule wall materials and an aqueous solution of second capsule wall materials are prepared; (3) the oil phase electrophoresis liquid is added in the aqueous solution of the second capsule wall materials to be dispersed first, then the second capsule wall materials are deposited on the surfaces of oil drops under the conditions of certain reaction temperatures, mixing speeds and pH values, and the aqueous solution of the first capsule wall materials is added; crosslinking agents are added in a dropping mode to make the molecules of the first capsule wall materials polymerized in molecule gaps of the first capsule wall materials to form an aqueous phase insoluble polymer, and a microcapsule can be obtained. Microcapsules prepared by the method of the present invention have the advantages of round and complete capsule shapes, transparent capsule walls, high tightness and easy separation, and requirements of electronic paper for electrophoretic display can be met.
Description
Technical field
The present invention relates to a kind of preparation method of microcapsules.
Technical field
Microcapsules technology research approximately starts from the thirties in last century, enters climax the fifties, now applies to fields such as biomedicine, pharmacy, printing and dyeing, food processing, tackifier widely.Microcapsules technology is meant solid particle, liquid droplet or the gas core material as capsule, forms the process of the continuous and thin packing of one deck outside it.Microcapsules are made up of core materials and cyst material, wherein capsule-core can be liquid, solid or gas, cyst wall can be inorganic material and organic material, but the most frequently used is macromolecular material, as water-soluble polymers, oil-soluble polymers, thermosetting polymer, thermoplastic polymer, polyureas, polyamine and derivant, polyvinyl alcohol (PVA) etc.The manufacture method of microcapsules is a lot, is broadly divided into chemical method, physics method and chemicals logos from principle, and commonly used have situ aggregation method, complex coacervation, interfacial polymerization, single coacervation, spray-on process, a hypobaric drying method etc.
Electronic Paper, as a kind of novel display material, it has wide visual angle, high brightness, hard contrast, low energy consumption, does not stimulate characteristics such as eyes, can link to each other with computing machine, the content of update displayed can be stirred, can be write arbitrarily, possess paper and electronic device characteristics simultaneously, the visual custom that had both met people, convenient, fast again, can Digital Control.Can be applicable to show, show, write, print and duplicate etc.The principle of electrophoresis display electronic paper, be with pigment, dyestuff and charge control agent etc., be dispersed in the transparent organic solvent, and with the color of dyestuff look as a setting, mixed solution is encapsulated in constitutes display device between the electrode, under the extra electric field effect, charged particle moves to anti-electrical electrode, replace near the colour particles of this electrode, thereby demonstrate certain color.
Compare with the business-like lcd technology that technology and manufacture craft are all very ripe, electrophoresis showed has characteristics such as high brightness, hard contrast, wide visual angle, bistable state, low energy consumption, but, after eliminating extra electric field, prolongation along with the time, its color that demonstrates often takes off change, and this defective has greatly been limited to the application of electrophoretic display technology.
Cause the reason that color takes off change to mainly contain two: first, often particle diameter is very little for colored electrophoresis particle, normally several microns to tens microns, also has the nanometer fineness, these particles have very high specific surface area, are in the dynamics non-steady state, and very easy spontaneous gathering is agglomerating between the particle, at this moment the density of electrophoresis showed image and brightness becomes irregular, and visual effect is coarse; The second, Particle Density or diameter are excessive, and slowly sedimentation of particle under action of gravity causes the density of electrophoresis showed image and brightness to become irregular or fades.
The introducing of microcapsules technology is the important breakthrough of electrophoretic display technology: (1) in limited range, makes particle dispersion, confinement the diffusion of particulate and gathering obtain restriction, has solved the instability problem of electrophoresis showed.(2) after electrophoresis liquid is made microcapsules, can also directly be coated with or be printed on softness, frivolous (approaching with paper) material, just because of these characteristics, electrophoretic image shows just can be used to make e-book.
A kind of method of making microcapsules by complex coacervation is disclosed among the U.S. Pat P6262833, method according to this patent introduction, can realize the microcapsules of oil-soluble core material are coated, but, this method exists in the shortcoming that has crosslinked in a large number epoxy glue between the microcapsules, microcapsules therefrom can't be separated, thereby can't be applied in the making of electrophoresis display electronic paper.
Introduced a kind of method that realizes the microcapsules coating by situ aggregation method in the U.S. Pat 3516846, but, in this method, can't guarantee that all polymerizations all take place on the surface of liquid microballoon, the microcapsules cyst wall rough surface that this method is produced, bad and the microcapsules of leakproofness are distributed in the bulk polymer that is polymerized, and can't make it to be separated from each other or evenly disperse, and make the follow-up use of microcapsules or manufacture a product quite difficulty.
In addition, all disclose the preparation method of microcapsules among U.S. Pat 3985840, US3577517, the US4046741, but all had shortcomings such as cyst wall rough surface, leakproofness be bad according to the microcapsules that the method that these patents provide is produced.
Summary of the invention
The objective of the invention is, a kind of microcapsule preparation method is provided, microcapsules scrotiform rounding, the cyst wall of preparing according to this method is transparent, good leak tightness, separate easily, can satisfy the requirement of electrophoresis display electronic paper.
Technical scheme of the present invention is:
A kind of microcapsule preparation method is characterized in that its preparation method comprises the steps:
(1) pigment, background dye, charge control agent are scattered in form oil phase electrophoresis liquid in the organic solvent;
(2) the preparation first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution;
(3) elder generation joins oil phase electrophoresis liquid in the second microcapsule wall material aqua aqueous solution and disperses, be that 0～40 ℃, stirring rate are 100～150 rev/mins, pH value pH=3～6 times in temperature of reaction then, make second microcapsule wall material aqua be deposited on oil droplets, and add the first microcapsule wall material aqua aqueous solution, add crosslinking chemical by the dropping mode, the molecule of first microcapsule wall material aqua forms the polymkeric substance that is insoluble to water at the molecule interstitial polymerization of second microcapsule wall material aqua, obtains microcapsules.
A kind of preferred version, wherein said first microcapsule wall material aqua is polyacrylonitrile, polyvinyl acetate (PVA), polystyrene or urea-formaldehyde prepolymer, preferred urea-formaldehyde prepolymer.
A kind of preferred version, wherein said second microcapsule wall material aqua is aqueous solution, gum arabic, sodium carboxymethyl cellulose (CMC) or the cellulose acetate-phthalate ester of gelatin, haemoglobin polysaccharide, sodium alginate, mosanom, agar, poly-second pyrrolidone and formaldehyde-naphthalene sulfonic acids condensed polymer (sodium methylene bis-naphthalene sulfonate), preferred gelatin and gum arabic.
Among the present invention, the step of preparation microcapsules is:
1. preparation oil phase electrophoresis liquid
Oil phase electrophoresis liquid, its component comprises pigment, organic solvent, background dye, charge control agent.
Pigment
Pigment is one of important component part of electrophoresis liquid, and its stable dispersion itself has electric charge or charged under the charge control agent effect in organic solvent, and under the extra electric field effect electrophoresis takes place, and realizes showing.Pigment can be organic pigment, also can be inorganic pigment or organic/inorganic pigment composite pigment.
Organic pigment mainly comprises C.I.PY14 pigment series, uses a certain kind sometimes, the composite use of a plurality of sometimes pigment.
Inorganic pigment comprises titania, titanium is black, the oxide of titan yellow and silicon, and cadmium yellow, lithopone, iron oxide yellow, the titanium baryta yellow, the cadmium silver yellow, cadmium red, cadmium lithopone orange, the cadmium lithopone is red, the molybdic acid orange, iron oxide red, plumbous red, the silver orange, cadmium orange, amber, iron oxide brown, the zinc chrome cologne earth, chrome green, chromium oxide, cobalt green, turkey blue, the cobalt titanium is green, Prussian blue, cobalt blue, celestine blue, sky blue, cobalt aluminium cadmium indigo plant, cobalt violet, mineral violet, carbon black, iron black, ferromanganese is black, ferro-cobalt is black, copper-chrome black, copper chromium manganese black, copper powder, aluminium powder, glass putty, zinc powder etc., wherein, dark pigment is mainly used in absorption light, light pigment reflection ray.
Pigment has following Essential Performance Requirements:
The high scattered power of optical characteristics, high reflectance
Electrology characteristic is charged stable, non-conductive
Dissolution characteristics is poor
The character of surface chemical inertness
0.01～5 micron of particle diameter
The shape ball-type is best
Density and suspending liquid are complementary
Organic solvent
Organic solvent wherein contains auxiliary agents such as extinction dyestuff, stabilizing agent, antioxidant as the suspending medium of pigment.
Organic solvent should meet following characteristic:
Specific inductive capacity ≈ 2
Resistivity＞10
12Ω cm, nonconductor
Viscosity＜5cPs is suitable for the particle migration
Nontoxic or the low toxicity of toxicity, no environmental protection problem
Water solubility＜10ppm
Refractive index＜1.2 are complementary with electrophoresis particle
Density＞1.5 are complementary with electrophoresis particle
Temperature require operating temperature :-10 ℃～70 ℃; Storing temperature :-40 ℃～100 ℃.
Organic solvent mainly comprises: tetrafluoro dibromoethane, zellon, trifluoro-ethylene, 1,2,4, trichloro-benzenes, phenixin, dodecane, the tetradecane, aliphatic hydrocarbon series, silanes, decyl siloxane and high molecular cyclosiloxane, polyphenol radical siloxane, heptyl siloxane etc., in addition, olive oil and other edible oils also can be used as suspending medium, and characteristics are nontoxic.
Suspending medium can be the liquid of one-component, but potpourri normally.
Background dye
The background dye of dissolving in the organic solvent can effectively reduce the light reflection, improves to show contrast.The dyestuff performance requirement: easily dissolving in organic solvent, stable chemical performance is not adsorbed on electrode and pigment, high optical density (OD), high fastness to light, color is moderate, cost is low.General azo, anthraquinone and the triarylmethane compound dyestuff selected can be black dyestuff, fluorescent dye, light-sensitive coloring agent (UV-irradiation becomes colourless or other colors), and these dyestuffs also can be aggregated on the capsule shells, form solid absorption-type polymkeric substance.
Known suitable background dye has: azo dyes, oil red, tonyred and sudan black series; Anthraquinone dye, solvent blue, Macrolex Blue series; Triarylmethane dyes, peacock green, crystal violet etc.
Charge control agent
Charge control agent gives pigment good electrophoretic characteristic, and it can be low molecular compound, oligomer or superpolymer.Charge control agent generally is divided into positive charge control agent, negative charge controlling agent etc.
Positive charge control agent generally is an acid compound; The negativity charge control agent generally is the surfactant of basic character.For example dinonyl adipate (acid of naphthalene ester), tygon pyrimidine, pyrimidine, quaternary ammonium salt, polyisobutylene dicarboxylic anhydride, zinc octoate, calcium octoate, PVA, polyacrylic acid, polymethylacrylic acid, Polyvinylchloride, tygon ethyl acetate, poly-isobutyl succinimide, poly N-ethylene pyrrolinone, barium sulfonate, dinonyl naphthols, barium sulfonate etc.
Other charge control agents also have, block polymer, and organic phosphate and phosphoric acid fat, for example, two (2-ethylhexyl) amber sodium sulfonate, calcium dodecyl benzene sulfonate, calcium mahogany sulfonate, neutral or alkaline dinonyl naphtholsulfonic acid barium/calcium.Dodecyl benzene sulfonate, bay amidosulphuric acid salt.Soap, the cobalt of naphthenic acid, calcium, copper, manganese, nickel, zinc and molysite.Stearic barium, aluminium, zinc, copper, lead salt etc.Polymkeric substance has two sections polymkeric substance of AB (A) 2-(N, N) the methyl P-TOLUENE SULFO ACID 99 quaternary ammonium salt of dimethyl amino ethyl methacrylate, (B) 2-ethylhexyl methacrylate, the graft polymer and the molecular weight 1800 that have ten dihydroxystearic acids of side chain have the polymethacrylate-methacrylic acid of sagging group.
2. prepare the first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution
Microcapsules are made up of core materials and cyst material, and cyst material can be inorganic material and organic material, but the most frequently used be macromolecular material.For solve microcapsules cyst wall rough surface, leakproofness is bad and microcapsules are distributed in the medium shortcoming of the bulk polymer that is polymerized, make it to be separated from each other or evenly dispersion, two microcapsule wall material aqua have been adopted among the present invention, being fit to first microcapsule wall material aqua of the present invention can be polyacrylonitrile, polyvinyl acetate (PVA), polystyrene or urea-formaldehyde prepolymer, preferred urea-formaldehyde prepolymer; Being fit to second microcapsule wall material aqua of the present invention can be aqueous solution, gum arabic, sodium carboxymethyl cellulose (CMC) or the cellulose acetate-phthalate ester of gelatin, haemoglobin polysaccharide, sodium alginate, mosanom, agar, poly-second pyrrolidone and formaldehyde-naphthalene sulfonic acids condensed polymer (sodium methylene bis-naphthalene sulfonate), preferred gelatin and gum arabic.
Among the present invention, first microcapsule wall material aqua is dispersed in the water, obtains the first microcapsule wall material aqua aqueous solution, standby; Second microcapsule wall material aqua is dispersed in the water, obtains the first microcapsule wall material aqua aqueous solution, standby.
3. the preparation of microcapsules
Capsule wall should have high resistivity, though the material of low-resistivity also can be used as capsule wall, driving voltage is increased, U.S. Pat 4,605, and 284 pairs of capsule wall electrical properties have been done detailed discussion; Capsule wall also should have enough physical strengths, can bear the mechanical force in a series of last handling processes such as centrifugal, washing, filtration, coating; Capsule wall should be transparent, its refractive index near suspending liquid and when coating used tackifier; In addition, capsule wall also should be a leakproofness, leaks to prevent electrophoresis liquid, also requires capsule to have single particle diameter that disperses in some cases.
Among the present invention, earlier oil phase electrophoresis liquid is joined in the second microcapsule wall material aqua aqueous solution and disperse, then under certain reaction temperature, stirring rate, pH value and wall concentration, make second microcapsule wall material aqua be deposited on oil droplets, and add the first microcapsule wall material aqua aqueous solution, add crosslinking chemical by the dropping mode, make the molecule of first microcapsule wall material aqua form the polymkeric substance that is insoluble to water, obtain microcapsules at the molecule interstitial polymerization of second microcapsule wall material aqua.Wherein, temperature of reaction is 0～40 ℃; Stirring rate is 100～150 rev/mins; PH=3～6.Be fit to crosslinking chemical of the present invention and can be formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, alum, zirconates, polyisocyanate salt etc., the rate of addition of crosslinking chemical is 0.2～1 ml/min.
In the present invention, the concrete operations of microcapsules preparation are: oil phase electrophoresis liquid is joined in the second microcapsule wall material aqua aqueous solution disperse earlier, in temperature of reaction is that 0～40 ℃, stirring rate are under 100～150 rev/mins, the reaction conditions of PH=3～6, make second microcapsule wall material aqua be deposited on oil droplets, add the first microcapsule wall material aqua aqueous solution, drip crosslinking chemical, the control rate of addition is 0.2～1 ml/min, make the molecule of first microcapsule wall material aqua form the polymkeric substance that is insoluble to water, obtain microcapsules at the molecule interstitial polymerization of second microcapsule wall material aqua.
By the microcapsules that above method is produced, can reach the goal of the invention of this patent, the microcapsules of the big particle diameter that detects by an unaided eye, profile is satisfactorily bright and clean, favorable dispersibility; Examine under a microscope, the skin that can see microcapsules is transparent shinny cyst wall, and scrotiform is full, after making the Electronic Paper display layer, can be according to the control program displaying contents, and displaying contents can preserve more than three months, show that the intensity of microcapsules, permanance are better.
Description of drawings
Accompanying drawing 1 is the microcapsules electromicroscopic photograph of comparative example 1;
Accompanying drawing 2 is the microcapsules electromicroscopic photograph of comparative example 2;
Accompanying drawing 3 is embodiment 1 an isolated single microcapsules electromicroscopic photograph;
Accompanying drawing 4 is the microcapsules electromicroscopic photograph of embodiment 2;
Accompanying drawing 5 is the electromicroscopic photograph with the microencapsulation coating of the microcapsules making of embodiment 2;
Accompanying drawing 6 is the photo that the microencapsulation coating of embodiment 2 is realized electrophoresis showed;
Accompanying drawing 7 is the microcapsules electromicroscopic photograph of embodiment 3;
Accompanying drawing 8 is the photo that the microencapsulation coating of embodiment 3 is realized electrophoresis showed;
Accompanying drawing 9 is the microcapsules electromicroscopic photograph of embodiment 4.
Specific implementation method
The present invention is described further below by specific embodiment.
Comparative example 1 (conventional complex coacervation)
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris, to wherein adding 1.8 gram titania R-900 (Beijing Orient sky Gui development in science and technology company limited), 0.78 restrain 8%1292 solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmer instrument co.Chicago) at 30 ℃, handle after 5 minutes under 5000 rev/mins of conditions, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare gelatin-gum arabic solution
Get gelatin 5 grams and join in 45 ml deionized water, dissolved rising 40 minutes stirs, is heated to 40 ℃ then, all dissolves until gelatin;
Get gum arabic 5 grams and join in 45 ml deionized water, stir, be heated to 40 ℃ then, all dissolve until gum arabic;
Two kinds of glues are filtered the back mixing for standby use with nylon cloth.
III. prepare microcapsules
Aqueous gelatin solution and Arabic gum aqueous solution that dissolving is good join in 500 milliliters of there-necked flasks that have water bath with thermostatic control, start stirring, 100 rev/mins of stirring rates, 25 milliliters of the oil phase electrophoresis liquid that continues the above-mentioned preparation of adding under the stirring, at 40 ℃, under the condition that stirring rate is 100 rev/mins, stir after 30 minutes, add 250 ml deionized water, the pH value of the hydrochloric acid regulation system with 1% is 4, the formalin 8 milliliters (Tianjin chemical reagent two factories) that adds 37% concentration then continues reaction 2 hours, and the pH value of the sodium hydroxide solution regulation system with 10% is 10, continues reaction 30 minutes, naturally after cooling to room temperature, obtain microcapsules.
Comparative example 2 (conventional situ aggregation method)
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris and put into one 50 milliliters polypropylene centrifuge tube, to wherein adding 1.8 gram titania R-900 (Beijing Orient sky Gui development in science and technology company limited), 0.78 restrain 8% 1292 solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmer instrumentco.Chicago) 30 ℃ handle 5 minutes after, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare urea-formaldehyde prepolymer
Formalin 245 grams of 37% concentration (are contained formaldehyde 3mol, Tianjin chemical reagent two factories) at room temperature mixed 30 minutes with 120 gram urea (Beijing Chemical Plant), then mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, under 100 rev/mins stirring rate, add triethanolamine and regulate pH=8, and in 20 minutes, temperature is risen to 70 ℃, insulation continues stirring reaction 3 hours, obtain the liquid of thickness, dilute with 1200 ml deionized water, obtain urea-formaldehyde prepolymer, 2000 rev/mins of centrifugal impurity of removing in the performed polymer in 10 minutes of 30 ℃ of insulations, standby.
III. prepare microcapsules
Get 100 milliliters of above-mentioned urea-formaldehyde prepolymer solution, join in 500 milliliters the there-necked flask, under 200 rev/mins stirring rate, in 30 seconds, at the uniform velocity slowly join in the prepolymer solution electrophoresis liquid of 20 milliliters of above-mentioned preparations, and add 5 milliliter 8% 1283 aqueous solution (fine chemicals company of Chinese Lekai Film Group Co), continue to stir 20 minutes, temperature is raised to 50 ℃, regulate emulsion pH=4 with 1% aqueous hydrochloric acid solution, keep temperature and stirring rate constant, stir cool to room temperature after 3 hours, remove remaining unreacted components for 3 times with water rinse, filter the large capsule agglomerate of removing flocculation with 100 order sub-sieves again, obtain microcapsules.
Embodiment 1
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris, to wherein adding yellow pigment PY-14 (the Xiaoshan victory reaches the chemical plant), 0.78 restrain 8%1292 aqueous solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmer instrumentco.Chicago) at 30 ℃, handle after 5 minutes under 5000 rev/mins of conditions, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare the first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution
(1) preparation gelatin-Arabic gum aqueous solution
Get gelatin 3.5 grams and join in 46.5 ml deionized water, dissolved rising 40 minutes is stirred and heated to 40 ℃ then, all dissolves until gelatin;
Get gum arabic 3.5 grams and join in 46.5 ml deionized water, be stirred and heated to 40 ℃ then, all dissolve until gum arabic;
Two kinds of glues are filtered the back with nylon cloth mix, obtain gelatin-Arabic gum aqueous solution, standby.
(2) preparation urea-formaldehyde prepolymer aqueous solution
Formalin 245 grams of 37% concentration (are contained formaldehyde 3mol, Tianjin chemical reagent two factories) with 120 gram urea (2mol, the Beijing Chemical Plant) at room temperature mixes 30 minutes, then mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 100 rev/mins of stirring rates, continue to stir and add triethanolamine adjusting pH=8 down, and in 20 minutes, temperature is risen to 70 ℃, insulation continues stirring reaction 3 hours, obtain the liquid of thickness,, obtain urea-formaldehyde prepolymer with the dilution of 2500 ml deionized water, 2000 rev/mins of centrifugal impurity of removing in the performed polymer in 10 minutes of 30 ℃ of insulations, standby.
III. prepare microcapsules
Gelatin-gum arabic mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, under 100 rev/mins stirring rate, add 25 milliliters of oil phase electrophoresis liquid, then at 40 ℃, under 100 rev/mins the stirring rate, continue to stir 30 minutes, add 250 ml deionized water again, the pH value of the hydrochloric acid regulation system with 1% is 3, continue reaction 2 hours, the pH value of the sodium hydroxide solution regulation system with 10% is 10, continues reaction 30 minutes, adds 120 milliliters in urea-formaldehyde prepolymer aqueous solution, the pH value that continues with 1% hydrochloric acid regulation system is 3, the temperature and the stirring rate of maintenance system are constant, drip 8 milliliters of the formalins (Tianjin chemical reagent two factories) of 37% concentration then with the speed of 0.2 ml/min, react after 60 minutes, naturally cool to room temperature, the microcapsules that coated.
Getting 30 gram microcapsule suspensions joins in 30 grams, 5% polyvinyl alcohol (PVA) (Beijing Organic Chemical Plant) aqueous solution and mixes, the potpourri that obtains is applied on the thick 0.7 millimeter transparent conducting glass, and the glass smear is integral with another electro-conductive glass applying after 30 minutes 60 ℃ of dryings.Add the electrical testing electrophoretic effects, during test result sees Table.
Embodiment 2
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris, to wherein adding yellow pigment PY-14 (the Xiaoshan victory reaches the chemical plant), 0.78 restrain 8%1292 aqueous solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmer instrumentco.Chicago) at 30 ℃, handle after 5 minutes under 5000 rev/mins of conditions, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare the first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution
(1) aqueous solution of the poly-second pyrrolidone of preparation and formaldehyde-naphthalene sulfonic acids condensed polymer (sodium methylene bis-naphthalene sulfonate)
Get the poly-second pyrrolidone (model: K-30, chemical reagent purchasing station, Shanghai) of 10 grams and join in 40 ml deionized water, be stirred and heated to 50 ℃ then, until its whole dissolvings;
Get 10 gram formaldehyde-naphthalene sulfonic acids condensed polymers (Beijing weaving scientific research institution) and join in 40 ml deionized water, be stirred and heated to 40 ℃ then, until its whole dissolvings;
Two kinds of solution are filtered the back with nylon cloth mix, obtain the aqueous solution of poly-second pyrrolidone and formaldehyde-naphthalene sulfonic acids condensed polymer (sodium methylene bis-naphthalene sulfonate), standby.
(2) preparation urea-formaldehyde prepolymer aqueous solution
Formalin 245 grams of 37% concentration (are contained formaldehyde 3mol, Tianjin chemical reagent two factories) with 120 gram urea (2mol, the Beijing Chemical Plant) at room temperature mixes 30 minutes, then mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 100 rev/mins of stirring rates, continue to stir and add triethanolamine adjusting pH=8 down, and in 20 minutes, temperature is risen to 70 ℃, insulation continues stirring reaction 3 hours, obtain the liquid of thickness,, obtain urea-formaldehyde prepolymer with the dilution of 1200 ml deionized water, 2000 rev/mins of centrifugal impurity of removing in the performed polymer in 10 minutes of 30 ℃ of insulations, standby.
III. prepare microcapsules
The aqueous solution of poly-second pyrrolidone and formaldehyde-naphthalene sulfonic acids condensed polymer is moved on in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 120 rev/mins of stirring rates, continue to stir and add 25 milliliters of oil phase electrophoresis liquid down, keep (20 ℃, 120 rev/mins of stirring rates) 30 minutes, add 100 ml deionized water, the pH value of the hydrochloric acid regulation system with 1% is 5, continue reaction 2 hours, the pH value of the sodium hydroxide solution regulation system with 10% is 10, continue reaction 30 minutes, add 200 milliliters in urea-formaldehyde prepolymer aqueous solution, the pH value that continues with 1% hydrochloric acid regulation system is 5, the temperature of maintenance system and stirring rate, the pH value that drips 8 milliliters of (the Tianjin chemical reagent two factories) regulation system of formalin that add 37% concentration with the speed of 0.5 ml/min is 5 then, continue the temperature of maintenance system and stirring rate reaction 60 minutes, cool to room temperature naturally after, coated microcapsules.
Getting 30 gram microcapsule suspensions joins in 30 grams, 5% polyvinyl alcohol (PVA) (Beijing Organic Chemical Plant) aqueous solution and mixes, the potpourri that obtains is applied on the thick 0.7 millimeter transparent conducting glass, and the glass smear is integral with another electro-conductive glass applying after 30 minutes 60 ℃ of dryings.Add the electrical testing electrophoretic effects, during test result sees Table.
Embodiment 3
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris, to wherein adding yellow pigment PY-14 (the Xiaoshan victory reaches the chemical plant), 0.78 restrain 8%1292 aqueous solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmerinstrument co.Chicago) at 30 ℃, handle after 5 minutes under 5000 rev/mins of conditions, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare the first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution
(1) preparation gelatin-Arabic gum aqueous solution
Get gelatin 10 grams and add in deionized water 40 grams, dissolved rising 40 minutes is stirred and heated to 40 ℃ then, all dissolves until gelatin;
Get gum arabic 10 grams and add in deionized water 40 grams, be stirred and heated to 40 ℃ then, all dissolve until gum arabic;
Two kinds of glues are filtered the back with nylon cloth mix, obtain gelatin-Arabic gum aqueous solution, standby.
(2) preparation urea-formaldehyde prepolymer aqueous solution
Formalin 245 grams of 37% concentration (are contained formaldehyde 3mol, Tianjin chemical reagent two factories) with 120 gram urea (2mol, the Beijing Chemical Plant) at room temperature mixes 30 minutes, then mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 100 rev/mins of stirring rates, continue to stir and add triethanolamine adjusting pH=8 down, and in 20 minutes, temperature is risen to 70 ℃, insulation continues stirring reaction 3 hours, obtain the liquid of thickness,, obtain urea-formaldehyde prepolymer with the dilution of 2000 ml deionized water, 2000 rev/mins of centrifugal impurity of removing in the performed polymer in 10 minutes of 30 ℃ of insulations, standby.
III. prepare microcapsules
Gelatin-Arabic gum aqueous solution is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, at 40 ℃, under the stirring of 150 rev/mins stirring rate, add 35 milliliters of oil phase electrophoresis liquid, continue to stir 30 minutes, the pH value of the hydrochloric acid regulation system with 1% is 6, the temperature of reaction system is reduced to 0 ℃, keep 150 rev/mins of stirring rates, continue reaction 2 hours, the pH value of the sodium hydroxide solution regulation system with 10% is 10, continues reaction 30 minutes, adds 150 milliliters in urea-formaldehyde prepolymer aqueous solution, the pH value that hydrochloric acid with 1% is regulated the maintenance system is 6, speed with 1.0 ml/min drips 150 milliliters of 3% glyoxal water solutions (Tianjin chemical reagent two factories) then, and keeping temperature is 150 rev/mins of 0 ℃ and stirring rates, reacts 60 minutes, naturally after being warmed up to room temperature, the microcapsules that coated.
Getting 30 gram microcapsule suspensions joins in 30 grams, 5% polyvinyl alcohol (PVA) (Beijing Organic Chemical Plant) aqueous solution and mixes, the potpourri that obtains is applied to (precoating ITO layer) on the thick 0.2 millimeter clear PET film, and smear is integral with another electro-conductive glass applying after 30 minutes 60 ℃ of dryings.Add the electrical testing electrophoretic effects, during test result sees Table.
Embodiment 4
I. prepare oil phase electrophoresis liquid
In 1 liter of flask, add 0.5 gram 7B type tonyred dyestuff (the Xiaoshan victory reaches the chemical plant), 417.25 gram dimethylbenzene (Tianjin Xin Tong Fine Chemical Co., Ltd) and 73.67 gram zellons (University Of Tianjin chemical experimental factory), said components was stirred 6 hours at 60 ℃, cool to room temperature then, get 50.13 gram potpourris, to wherein adding yellow pigment PY-14 (the Xiaoshan victory reaches the chemical plant), 0.78 restrain 8%1292 aqueous solution (Chinese Lekai fine chemicals company) and 0.15 gram Span 80 (the favorable to the people company limited in Zhejiang), with said mixture ultrasound wave (model: 4710 Ultrasonic Homogenizer, Cole-Parmer instrumentco.Chicago) at 30 ℃, handle after 5 minutes under 5000 rev/mins of conditions, filter with 400 order stainless steel sub-sieves, remove mechanical impurity, obtain oil phase electrophoresis liquid, standby.
II. prepare the first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution
(1) preparation gelatin-Arabic gum aqueous solution
Get gelatin 8 grams and join in 42 ml deionized water, dissolved rising 40 minutes is stirred and heated to 40 ℃ then, all dissolves until gelatin;
Get gum arabic 8 grams and join in 42 ml deionized water, be stirred and heated to 40 ℃ then, all dissolve until gum arabic;
Two kinds of glues are filtered the back with nylon cloth mix, obtain gelatin-Arabic gum aqueous solution, standby.
(2) preparation urea-formaldehyde prepolymer aqueous solution
Formalin 245 grams of 37% concentration (are contained formaldehyde 3mol, Tianjin chemical reagent two factories) with 120 gram urea (2mol, the Beijing Chemical Plant) at room temperature mixes 30 minutes, then mixed liquor is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 100 rev/mins of stirring rates, continue to stir and add triethanolamine adjusting pH=8 down, and in 20 minutes, temperature is risen to 70 ℃, insulation continues stirring reaction 3 hours, obtain the liquid of thickness,, obtain urea-formaldehyde prepolymer with the dilution of 1200 ml deionized water, 2000 rev/mins of centrifugal impurity of removing in the performed polymer in 10 minutes of 30 ℃ of insulations, standby.
III. prepare microcapsules
Gelatin-Arabic gum aqueous solution is transferred in 500 milliliters of there-necked flasks that have water bath with thermostatic control, 150 rev/mins of stirring rates, continue to stir and add 35 milliliters of oil phase electrophoresis liquid down, keep (10 ℃, 150 rev/mins of stirring rates) 30 minutes, add 400 ml deionized water, the pH value of the hydrochloric acid regulation system with 1% is 4, continue reaction 2 hours, the pH value of the sodium hydroxide solution regulation system with 10% is 12, continue reaction 30 minutes, add 200 milliliters in urea-formaldehyde prepolymer aqueous solution, the pH value of the hydrochloric acid regulation system with 1% is 4, keeping temperature is 150 rev/mins of 10 ℃ and stirring rates, drip 8 milliliters of the formalins (Tianjin chemical reagent two factories) of 37% concentration then with the speed of 0.6 ml/min, continue the pH value and the temperature of maintenance system, reacted 60 minutes, naturally after being warmed up to room temperature, the microcapsules that coated.
Getting 30 gram microcapsule suspensions joins in 30 grams, 5% polyvinyl alcohol (PVA) (Beijing Organic Chemical Plant) aqueous solution and mixes, the potpourri that obtains is applied to (precoating ITO layer) on the thick 0.2 millimeter clear PET film, and smear is integral with another electro-conductive glass applying after 30 minutes 60 ℃ of dryings.Add the electrical testing electrophoretic effects, during test result sees Table.
Each embodiment result relatively
| Embodiment | White autohemagglutination microlith | Smoothness, transparency | The capsule physical strength | The capsule leakproofness | Remarks |
| Comparative example 1 | ★ | ● | ▲ | ◆ | See Fig. 1 |
| Comparative example 2 | ★★ | ●● | ▲▲ | ◆◆ | See Fig. 2 |
| Embodiment 1 | --- | ○ | --- | ◆ | See Fig. 3 |
| Embodiment 2 | --- | ○ | --- | ◆ | See Fig. 4 |
| Embodiment 3 | --- | ○ | --- | ◆ | See Fig. 7 |
| Embodiment 4 | --- | ○ | --- | ◆ | See Fig. 9 |
White autohemagglutination microlith
★ ★: the subsidiary reaction degree is very high, and white microlith is a lot; ★: subsidiary reaction degree height, white microlith is many; ☆ has subsidiary reaction to take place, and a small amount of microlith is only arranged; The no subsidiary reaction of---: takes place, and does not have white microlith.
Smoothness and transparency
With observation by light microscope surface of microcapsule smoothness and transparency, microscope model: LEICA DMR. evaluation method: ● ●: the coarse thorniness of surface of microcapsule, be white in color, adhesion is serious between the capsule; ●: surface of microcapsule is coarse, and shallow white has adhesion but not serious; Zero: surface of microcapsule is level and smooth inadequately, and white is alternate with transparent region, does not have adhesion between the capsule substantially;---: microcapsule granule is strong, does not have adhesion each other, surface smoothing and transparent.
The capsule physical strength
Microcapsules were broken when ▲ ▲: washing was handled, and electrophoresis liquid leaks outside;
▲: broken when washing is handled, but scratched by screen cloth when filtering;
△: not broken when washing is handled and filtered, have on a small quantity in the preparation coating fluid process and break;
Microcapsules crack-free phenomenon in---: the last handling process.
The capsule leakproofness
Two kinds of evaluation methods are arranged.
One. the heated baking method, the microcapsules of all the other components of nothing behind the washing filtering are evenly tiled in surface plate into about the thick one deck of 1mm, put into drying box, under 55 ℃ of calm states, it is toasted, lose the used time of color after being heated according to microcapsules fully to estimate its leakproofness.
Two. the alcohol immersion method, 20 gram microcapsules are put into the 100ml absolute ethyl alcohol carry out static immersion, the sample that the capsule shells leakproofness is bad, can be penetrated into by the micro chink on the capsule wall in the absolute ethyl alcohol with immiscible organic solvent and the background dye of water in its capsule core, make water white ethanol become the color of electrophoresis liquid, estimate its leakproofness according to ethanol variable color speed.
◆ ◆: leakproofness is very poor, and electrophoresis liquid is exosmosed soon; ◆: electrophoresis liquid is exosmosed slower; ◇: electrophoresis liquid is exosmosed very slow;---: electrophoresis liquid does not have and exosmoses.
Beneficial effect
Can be found out by data in the table: the microcapsules that adopt the inventive method to prepare, scrotiform rounding, cyst wall are transparent, good leak tightness, separate easily. Its apparent smoothness and transparency, mechanical strength are all satisfactory, and it is coarse to have overcome the microcapsules micro-capsule wall surface that open method obtains, and bad, the not segregative shortcoming of seal can satisfy the requirement of electrophoresis display electronic paper.
Claims (5)
1. a microcapsule preparation method is characterized in that its preparation method comprises the steps:
(1) pigment, background dye, charge control agent are scattered in form oil phase electrophoresis liquid in the organic solvent;
(2) the preparation first microcapsule wall material aqua aqueous solution and the second microcapsule wall material aqua aqueous solution;
(3) elder generation joins oil phase electrophoresis liquid in the second microcapsule wall material aqua aqueous solution and disperses, be that 0～40 ℃, stirring rate are under 100～150 rev/mins, the condition of PH=3～6 in temperature of reaction then, make second microcapsule wall material aqua be deposited on oil droplets, and add the first microcapsule wall material aqua aqueous solution, add crosslinking chemical by the dropping mode, wherein, the crosslinking chemical rate of addition is 0.2～1 ml/min, make the molecule of first microcapsule wall material aqua form the polymkeric substance that is insoluble to water, obtain microcapsules at the molecule interstitial polymerization of second microcapsule wall material aqua.
2. microcapsule preparation method according to claim 1 is characterized in that, wherein said first microcapsule wall material aqua is polyacrylonitrile, polyvinyl acetate (PVA), polystyrene or urea one formaldehyde prepolymer.
3. microcapsule preparation method according to claim 2 is characterized in that, wherein said first microcapsule wall material aqua is the urea-formaldehyde performed polymer.
4. microcapsule preparation method according to claim 1, it is characterized in that wherein said second microcapsule wall material aqua is aqueous solution, gum arabic, sodium carboxymethyl cellulose or the cellulose acetate-phthalate ester of gelatin, haemoglobin polysaccharide, sodium alginate, mosanom, agar, poly-second pyrrolidone and sodium methylene bis-naphthalene sulfonate.
5. microcapsule preparation method according to claim 4 is characterized in that, wherein said second microcapsule wall material aqua is gelatin or gum arabic.
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| CN101239296B (en) * | 2008-03-07 | 2010-04-21 | 清华大学 | Method for preparing solvent microcapsule |
| CN102046281A (en) * | 2008-06-02 | 2011-05-04 | 国立大学法人新泻大学 | Microcapsules, method of producing the microcapsules and food and drink containing the microcapsules |
| TWI477266B (en) * | 2009-11-05 | 2015-03-21 | Taiwan Biotech Co Ltd | Mehtod and device of continuously preparing microspheres, and collection unit thereof |
| US9993019B2 (en) * | 2010-03-26 | 2018-06-12 | Philip Morris Usa Inc. | Method for making particle of a hydrophobic additive and a polysaccharide coating and tobacco products containing particle of a hydrophobic additive and a polysaccharide coating |
| CN102059084B (en) * | 2010-12-07 | 2016-05-18 | 江南大学 | A kind of preparation method of the Phthalocyanine Green G Microcapsules with electric field response behavior |
| CN102146218B (en) * | 2011-01-19 | 2013-04-24 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN104307445B (en) * | 2014-09-30 | 2016-03-30 | 永发印务(东莞)有限公司 | A kind of manufacture method of many shells liquid crystal microcapsule of cross polymerization |
| CN104559422B (en) * | 2014-12-18 | 2016-08-17 | 益阳市资阳区明乐士涂料厂 | A kind of similar immiscible particle for ornament materials and preparation method thereof |
| US11886090B2 (en) * | 2018-12-12 | 2024-01-30 | E Ink Corporation | Edible electrodes and uses in electrophoretic displays |
| CN113041230B (en) * | 2021-03-23 | 2022-06-24 | 浙江尖峰健康科技有限公司 | Capsule shell of soft capsule and soft capsule prepared from capsule shell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3516846A (en) * | 1969-11-18 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsule-containing paper |
| US6262833B1 (en) * | 1998-10-07 | 2001-07-17 | E Ink Corporation | Capsules for electrophoretic displays and methods for making the same |
| JP2003290647A (en) * | 2002-03-29 | 2003-10-14 | Toyo Ink Mfg Co Ltd | Method for producing microcapsule encapsulating electrophoretic particle dispersion and reversible display medium using the capsule |
| JP2003315993A (en) * | 2002-04-23 | 2003-11-06 | Mitsubishi Electric Corp | Photosensitive recording material |
| US20040012839A1 (en) * | 2002-05-23 | 2004-01-22 | E Ink Corporation | Capsules, materials for use therein and electrophoretic media and displays containing such capsules |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3516846A (en) * | 1969-11-18 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsule-containing paper |
| US6262833B1 (en) * | 1998-10-07 | 2001-07-17 | E Ink Corporation | Capsules for electrophoretic displays and methods for making the same |
| JP2003290647A (en) * | 2002-03-29 | 2003-10-14 | Toyo Ink Mfg Co Ltd | Method for producing microcapsule encapsulating electrophoretic particle dispersion and reversible display medium using the capsule |
| JP2003315993A (en) * | 2002-04-23 | 2003-11-06 | Mitsubishi Electric Corp | Photosensitive recording material |
| US20040012839A1 (en) * | 2002-05-23 | 2004-01-22 | E Ink Corporation | Capsules, materials for use therein and electrophoretic media and displays containing such capsules |
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