CN101850229B - Electrophoretic microcapsules formed by complex coacervation of carboxyl butyronitrile/gelatin and Arabic gum and preparation method thereof - Google Patents
Electrophoretic microcapsules formed by complex coacervation of carboxyl butyronitrile/gelatin and Arabic gum and preparation method thereof Download PDFInfo
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Abstract
The invention relates to electrophoretic particle microcapsules formed by complex coacervation of carboxyl butyronitrile/gelatin and Arabic gum and a preparation method thereof. The preparation method comprises the following steps: enabling carboxyl butyronitrile latex and gelatin to carry out blending reaction, and respectively dissolving the carboxyl butyronitrile/gelatin blending material and the Arabic gum and then preparing into a water solution; adding an electrophoretic suspension into the carboxyl butyronitrile/gelatin solution and the Arabic gum solution under the condition of stirring; continuously stirring to enable the carboxyl butyronitrile/gelatin solution and the Arabic gum solution to be fully mixed uniformly; meantime, forming stable oil-in-water emulsion which is condensated into capsules in the system to be separated out; and simultaneously, embedding dispersive capsule cores in the solution to form electrophoretic display microcapsules. In the capsules, the carboxyl butyronitrile/gelatin and the Arabic gum are used as wall materials, and the electrophoretic suspension is a black-and-white bicolor electrophoretic suspension. By improving processes and conditions, microcapsules which have regular geometrical appearance, uniform particle size distribution, smooth and regular surfaces and good transparency and flexibility and can not break easily are prepared.
Description
Technical field
The present invention relates to electrophoresis particle microcapsules and preparation method that carboxyl butyronitrile/gelatin and Arabic gum condense again, belong to the microcapsules preparing technical field.
Background technology
Electrophoretic display technology is charged corpuscle to be dispersed in constitute colloid in the suspension liquid; When this dispersion was applied electric field, electrophoresis will take place in charged particle under the effect of Coulomb force, through changing voltage; Make the directed swimming of particle of different colours, constitute demonstration through transparency electrode.Electrophoresis showed is display element with the electric ink, under the driving of extra electric field, realizes reversible, bistable state, the flexible demonstration.The microcapsules electrophoretic display technology is to be proposed a kind of Electronic Paper Display Technique that is grown up by U.S. E Ink company subsequently by the Massachusetts Institute of Technology (MIT) Media Lab the earliest.The introducing of microcapsules is important breakthrough of electrophoretic display technology, and it disperses electrophoresis liquid, confine in limited volume range, and the diffusion and the aggregation limited that make particulate have solved the instability problem of electrophoresis showed in very little scope.
The microcapsule-type electrophoretic display device (EPD) is that electrophoresis liquid is coated in the smooth microcapsules of the spherical transparent of diameter 30～150 μ m; These capsules are distributed in constitute dispersion in the adhesive; Coating perhaps is printed on the transparent battery lead plate, forms the microcapsule-type electrophoresis showed.Microcapsule-type electrophoretic display device (EPD) bad mechanical property, to environment sensitive, high and complicated to the microcapsules manufacturing process requirement.
Since " microcapsules electrophoresis showed " notion proposed in 1996, the microcapsules display and the Philips of U.S. E Ink company had obtained the achievement that attracts people's attention.But domestic microcapsules electrophoretic display technology also is in the stage at the early-stage.With external electrophoretic display technology contrast, the research of domestic electrophoretic display technology mainly is confined to fundamental research and equipment preliminary design phase, the narrow range of research.The main contents of research relate to the technology of preparing of microcapsules in the electric ink and the modification work of electrophoresis particle, do not relate to the actual application problem of electrophoresis showed.
With the gelatin Arabic gum is that the wall material prepares the representative instance that microcapsules are complex coacervations, and Dong Chunling has studied the influence that power value, isoelectric point and pH value etc. form microcapsules of freezing of gelatin.Xie Jianyu has studied gelatin and the Arabic gum complex coacervation prepares microcapsules; Investigated the influence of wall material concentration, mixing speed, crosslinking time to microcapsules clad ratio, surface topography, particle diameter; And add of the influence of small amount of toluene vulcabond in the wall material to microcapsule wall intensity, the breakage of microcapsules is descended.
Prepare in the method for electrophoresis microcapsule at present, the microcapsule wall material intensity that gelatin Arabic gum complex coacervation obtains is low, in microcapsules classification and coating process, breaks easily; And the surface of microcapsule that the urea-formaldehyde situ aggregation method obtains is more coarse, and the transparency is bad.Therefore, research has higher wall material intensity and toughness, smooth surface, the transparent good microcapsules technology that is applicable to electrophoresis showed and has important in theory meaning and using value widely.
Summary of the invention
This paper proposes electrophoresis particle microcapsules and the preparation method that carboxyl butyronitrile/gelatin and Arabic gum condense again; Prepared that how much patterns, particle diameters with rule are evenly distributed, smooth surface, rule, good transparency and pliability have been arranged through the improvement of technology and condition, be difficult for breaking.And this technology applied in the preparation of double-colored particle microcapsules, this capsule can be used in the Display Technique of electric ink, can anti-solvent, better seal property is arranged, and compatibility is preferably arranged with electrophoresis particle.The electron ink microcapsule pliability is good, and capsule is difficult for breaking, and makes it that arranged longer service life under External Electrical Field.The present invention has tangible electrophoresis showed response when the voltage of transformation with the electrophoresis microcapsule of carboxyl butyronitrile/gelatin and Arabic gum complex coacervation preparation.
The present invention realizes through following technical proposals.
The preparation method of the electrophoresis particle microcapsules that a kind of carboxyl butyronitrile/gelatin and Arabic gum condense again adopts carboxyl butyronitrile/gelatin and Arabic gum complex coacervation, and step is following:
1) gelatin being mixed with concentration is 2.5%～15% the aqueous solution; At 60 ℃～80 ℃; With carboxylic acrylonitrile butadiene rubber latex: gelatin carried out blending reaction at 100: 80～100: 120; The sodium tetraborate or the citric acid that add 1%～3% content, reaction 20min～40min, 35 ℃～45 ℃ insulations of reaction back blend solution are subsequent use;
2) carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 35 ℃～45 ℃ water, are mixed with mass concentration and are 0.5%～6% the carboxyl butyronitrile/gelatin aqueous solution and mass concentration and be 0.5%～6% the Arabic gum aqueous solution;
3) under 40 ℃～50 ℃ water bath condition, under 600rpm～1100rpm stirring condition, electrophoresis suspensioning liquid is joined in the carboxyl butyronitrile/gelatin solution of step 1), stir gently; In mixed solution, add step 2 behind 10min～20min) gumwater, continue to stir carboxyl butyronitrile/gelatin solution and gumwater fully mixed, form stable O/w emulsion at this moment; Again under agitation, Dropwise 5 %～20% acetum, multiple aggregation takes place 3.0～4.5 in regulator solution pH value; The cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution is carried out embedding and forms electrophoretic display microcapsule.
The preparation method of electrophoresis particle microcapsules of the present invention; Electrophoresis suspensioning liquid is the double-colored electrophoresis suspensioning liquid of black and white; The mass ratio of white electrophoretic particles and black electrophoretic particles is 5: 1～30: 1, and the electrophoresis suspensioning liquid of mixing is prepared into the double-colored electrophoresis dispersion of uniform black and white under Ball milling.
Electrophoresis particle microcapsules of the present invention, capsule is the wall material with carboxyl butyronitrile/gelatin and Arabic gum.Electrophoresis suspensioning liquid in the microcapsules is the double-colored electric ink of black and white, and particle size range is 50～120mm.
This paper adopts the microcapsules of carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation; Prepared that how much patterns, particle diameters with rule are evenly distributed, smooth surface, smooth surface, rule, good transparency and pliability have been arranged through the improvement of technology and condition, be difficult for breaking.And this technology applied in the preparation of the double-colored particle microcapsules of black and white, this capsule can be used in the Display Technique of electric ink, can anti-solvent, better seal property is arranged, and compatibility is preferably arranged with electrophoresis particle.The electron ink microcapsule pliability is good, and capsule is difficult for breaking, and has crush resistance strength preferably, makes it that arranged longer service life under External Electrical Field.The present invention has tangible electrophoresis showed response when the voltage of transformation with the double-colored electrophoresis microcapsule of black and white of carboxyl butyronitrile/gelatin and Arabic gum complex coacervation preparation.
Adopt electrophoresis particle microcapsules of the present invention to prepare the microcapsules device: common microcapsules device method can adapt to the present invention.
The present invention explains as follows for example: the 140mm～160mm polyester film that at first will cut into square shape sticks on the conducting surface of electro-conductive glass with adhesive.Take out a certain amount of electrophoresis microcapsule then,, remove part water with the filter paper suction because the capsule appearance possibly have more water; Make it contain a spot of water as far as possible, it is evenly mixed with the adhesive that has added 40wt%～60wt% polyvinylpyrrolidone K30 (PVP), glycerine, in air, place a period of time; With spreader it is coated in the middle of the groove of polyester film and ito glass; Coating speed should be slow, and when body to be mixed will be dry, the electro-conductive glass that another piece is scribbled adhesive was above it bonding; Dry 1h～2h in 70 ℃～90 ℃ baking oven makes the microcapsules display device.
The microcapsules of gelatin and the preparation of Arabic gum complex coacervation are seen Fig. 2; Fig. 3 is the microcapsules of carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation; Microcapsules pliability before the carboxyl butyronitrile modification is poor, very easily break, and the bright and Arabic gum surface of microcapsule after the modification is Paint Gloss; Toughness is better, is difficult for breaking.
Carbon black isoparaffin system, titanium oxide tetrachloro-ethylene system and the titanium oxide concentration that Fig. 4, Fig. 5 and Fig. 6 are respectively the preparation of carboxyl butyronitrile/gelatin and Arabic gum complex coacervation is 10% electrophoresis microcapsule; Show the anti-solvent of prepared electrophoresis microcapsule, better seal property is arranged, and compatibility is preferably arranged with electrophoresis particle.The electron ink microcapsule pliability is good, and capsule is difficult for breaking, and has crush resistance strength preferably, and particle size range satisfies the requirement of electrophoresis displaying particle roughly at 50～120mm.
Fig. 7 is the pattern and the wall thickness of the electrophoresis microcapsule of carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation.The cyst wall that can find out the prepared electrophoresis microcapsule of the present invention is approximately 4mm, and the particle internal diameter is about 60mm.
Fig. 8 shows that titanium dioxide concentration is that electrophoresis particle in 10% the electrophoresis microcapsule has tangible electrophoresis response when voltage of transformation.
The electrophoresis microcapsule display device can prepare according to Fig. 9, wherein: the 1st, transparency electrode, the 2nd, adhesive, the 3rd, microcapsules, the 4th, electrophoresis particle, the 5th, electrophoresis disclosing solution M representes that microcapsules are in not added electric field state; L representes that microcapsules are in the bottom and apply positive electric field status; N representes that microcapsules are in the state that the bottom applies negative electric field.
Description of drawings
The technological process that Fig. 1 carboxyl butyronitrile/gelatin and Arabic gum complex coacervation prepare electrophoresis microcapsule;
The blank microcapsules of Fig. 2 gelatin and the preparation of Arabic gum complex coacervation;
The blank microcapsules of Fig. 3 carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation;
The carbon black isoparaffin system electrophoresis microcapsule of Fig. 4 carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation;
The titanium oxide tetrachloro-ethylene system electrophoresis microcapsule of Fig. 5 carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation;
The titanium dioxide concentration of Fig. 6 carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation is 10% electrophoresis microcapsule;
The pattern and the wall thickness of the electrophoresis microcapsule of Fig. 7 carboxyl butyronitrile/gelatin and the preparation of Arabic gum complex coacervation;
Fig. 8 titanium dioxide concentration is the electrophoresis response diagram of electrophoresis particle when voltage of transformation in 10% the electrophoresis microcapsule;
The cross-sectional structure sketch map of Fig. 9 electrophoresis microcapsule display device.
Specific embodiments
A kind of preparation method who contains the double-colored particle electrophoresis microcapsules of black and white of the present invention, as shown in Figure 1: as to comprise following preparation process:
1, the preparation of carboxyl butyronitrile/gelatin intermingling material
The preparation of carboxyl butyronitrile/gelatin intermingling material: it is 2.5%～15% the aqueous solution that gelatin is mixed with concentration; At 60 ℃～80 ℃; According to carboxylic acrylonitrile butadiene rubber latex: gelatin carried out blending reaction at 100: 80～100: 120; The sodium tetraborate or the citric acid that add 1%～3% content are promoter, reaction 20min～40min.35 ℃～45 ℃ insulations of reaction back blend solution are subsequent use.
2, the preparation of electrophoresis suspensioning liquid
Electrophoresis particle (is comprised TiO
2, all black and white pigment particles such as TiO or carbon black) join in the tetrachloro-ethylene; Be made into mass fraction and be 1%～20% dispersion liquid; The surfactant that in dispersion liquid, adds liquid quality fraction 0.5%～2%; Described surfactant is sorbitan trioleate series (Span series) or polyethenoxy sorbitan list oleic acid series (Tween series), in dispersion liquid, add the charge control agent polyisobutene mono butonediimide series (T151, T152 etc.) of liquid quality fraction 0.1%～2%; Add the zirconium pearl again; Under 300rpm～600rpm, grind 12h～24h, remove the zirconium pearl then and obtain stable white electrophoresis suspensioning liquid or black electrophoresis suspensioning liquid, sealing is preserved subsequent use.
3, the preparation of black and white electronic ink microcapsule
1. carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 35 ℃～45 ℃ water, are mixed with mass concentration respectively and are 0.5%～6% the carboxyl butyronitrile/gelatin aqueous solution and the Arabic gum aqueous solution;
2. be 5: 1～30: 1 ratio in the mass ratio of white electrophoretic particles and black electrophoretic particles, the electrophoresis suspensioning liquid of getting two kinds of blend of colors of certain mass is prepared into the double-colored electrophoresis dispersion of uniform black and white under Ball milling;
3. under 40 ℃～50 ℃ water bath condition, the double-colored electrophoresis dispersion of black and white that under 600rpm～1100rpm stirring condition, will 2. prepare joins step 1. in the carboxyl butyronitrile/gelatin solution, stirs gently.In mixed solution, add gumwater (mass ratio of the carboxyl butyronitrile/gelatin and the Arabic gum aqueous solution is 1.8～2.2 ratio) behind 10min～20min; Continue stirring carboxyl butyronitrile/gelatin solution and gumwater are fully mixed, form stable O/w emulsion this moment.At last, under constantly stirring, Dropwise 5 %～20% acetum, regulator solution pH value makes it that multiple aggregation take place 3.0～4.5.Carboxyl butyronitrile/gelatin and Arabic gum are because of the charged formation compound that neutralizes on the contrary mutually, and its solubility reduces, and the cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution are carried out embedding and form electrophoretic display microcapsule;
4. under constantly stirring, when solution naturally cools to 20 ℃～30 ℃, be placed in the ice bath, continuing to be stirred to temperature is below 10 ℃; When reaction mixture cools to 0 ℃～10 ℃, be 0.8～1.2 by gelatin and glutaraldehyde mass ratio, add glutaraldehyde to reaction mixture; Continue to stir 10min～20min, make it curing cross-linked, using 5%～15%NaOH solution to regulate again and making its pH is 8～9; Continue to stir 10min～30min, observe till separate out, leave standstill and treat the microcapsules sedimentation.Microcapsules after solidifying are washed with distilled water, sieve, obtain containing the double-colored electrophoresis microcapsule of black and white.
Specify as follows:
1, the preparation of carboxyl butyronitrile/gelatin intermingling material
It is 2.5% the aqueous solution that gelatin is mixed with concentration, at 60 ℃, according to carboxylic acrylonitrile butadiene rubber latex: gelatin carried out blending reaction at 100: 80, and the sodium tetraborate that adds 1% content is a promoter, reaction 30min.40 ℃ of insulations of reaction back blend solution are subsequent use.
2, the preparation of electrophoresis suspensioning liquid
The carbon black electrophoresis particle is joined in the tetrachloro-ethylene; Be made into mass fraction and be 1% dispersion liquid, in dispersion liquid, add the surfactant of liquid quality fraction 1%, described surfactant is sorbitan trioleate, in dispersion liquid, add the charge control agent polyisobutene mono butonediimide series of liquid quality fraction 1%; Add the zirconium pearl again; Under 300rpm, grind 12h, remove the zirconium pearl then and obtain stable white electrophoresis suspensioning liquid or black electrophoresis suspensioning liquid, sealing is preserved subsequent use.
3, the preparation of black and white electronic ink microcapsule
1. carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 40 ℃ of water, are mixed with mass concentration respectively and are 3% the carboxyl butyronitrile/gelatin aqueous solution and the Arabic gum aqueous solution;
2. be 5: 1 ratio in the mass ratio of white electrophoretic particles and black electrophoretic particles, the electrophoresis suspensioning liquid of getting two kinds of blend of colors of certain mass is prepared into the double-colored electrophoresis dispersion of even black and white under Ball milling;
3. under 40 ℃～50 ℃ water bath condition, the double-colored electrophoresis dispersion of the black and white that under the 600r/min stirring condition, will 2. prepare joins step 1. in the carboxyl butyronitrile/gelatin solution, stirs gently.In mixed solution, add gumwater (mass ratio of the carboxyl butyronitrile/gelatin and the Arabic gum aqueous solution is 1.8 ratio) behind the 15min; Continue stirring carboxyl butyronitrile/gelatin solution and gumwater are fully mixed, form stable O/w emulsion this moment.At last, under constantly stirring, drip 10% acetum, regulator solution pH value makes it that multiple aggregation take place 3.0～4.5.Carboxyl butyronitrile/gelatin and Arabic gum are because of the charged formation compound that neutralizes on the contrary mutually, and its solubility reduces, and the cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution are carried out embedding and form electrophoretic display microcapsule;
4. under constantly stirring, when solution naturally cools to 30 ℃ of left and right sides, be placed in the ice bath, continuing to be stirred to temperature is below 10 ℃; When reaction mixture cools to 0～10 ℃, be 1: 1 by gelatin and glutaraldehyde mass ratio, add glutaraldehyde to reaction mixture; Continue to stir 15min, make it curing cross-linked, using 10%NaOH solution to regulate again and making its pH is 8～9; Continue to stir 20min, observe till separate out, leave standstill and treat the microcapsules sedimentation.Microcapsules after solidifying are washed with distilled water, sieve, obtain containing the double-colored electrophoresis microcapsule of black and white.
4, microcapsules device preparation: the 150mm polyester film that at first will cut into square shape sticks on the conducting surface of electro-conductive glass with adhesive.Take out a certain amount of electrophoresis microcapsule then,, remove part water with the filter paper suction because the capsule appearance possibly have more water; Make it contain a spot of water as far as possible, it is evenly mixed with the adhesive that has added 50wt% polyvinylpyrrolidone K30 (PVP), glycerine, in air, place a period of time; With spreader it is coated in the middle of the groove of polyester film and ito glass; Coating speed should be slow, and when body to be mixed will be dry, the electro-conductive glass that another piece is scribbled adhesive was above it bonding; In 80 ℃ baking oven, dry by the fire 1h, make the microcapsules display device.
Instance 2
1, the preparation of carboxyl butyronitrile/gelatin intermingling material
It is 10% the aqueous solution that gelatin is mixed with concentration, at 70 ℃, according to carboxylic acrylonitrile butadiene rubber latex: gelatin carried out blending reaction at 100: 100, and the sodium tetraborate or the citric acid that add 2% content are promoter, reaction 20min.30 ℃ of insulations of reaction back blend solution are subsequent use.
2, the preparation of electrophoresis suspensioning liquid
With TiO
2Electrophoresis particle joins in the tetrachloro-ethylene; Be made into mass fraction and be 10% dispersion liquid, in dispersion liquid, add the surfactant of liquid quality fraction 2%, described surfactant is polyethenoxy sorbitan list oleic acid, in dispersion liquid, add the charge control agent polyisobutene mono butonediimide of liquid quality fraction 2%; Add the zirconium pearl again; Under 300rpm, grind 18h, remove the zirconium pearl then and obtain stable white electrophoresis suspensioning liquid or black electrophoresis suspensioning liquid, sealing is preserved subsequent use.
3, the preparation of black and white electronic ink microcapsule
1. carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 30 ℃ of water, are mixed with mass concentration respectively and are 6% the carboxyl butyronitrile/gelatin aqueous solution and the Arabic gum aqueous solution;
2. be 15: 1 ratio in the mass ratio of white electrophoretic particles and black electrophoretic particles, the electrophoresis suspensioning liquid of getting two kinds of blend of colors of certain mass is prepared into the double-colored electrophoresis dispersion of uniform black and white under Ball milling;
3. under 40 ℃～50 ℃ water bath condition, the double-colored electrophoresis dispersion of the black and white that under the 900rpm stirring condition, will 2. prepare joins step 1. in the carboxyl butyronitrile/gelatin solution, stirs gently.In mixed solution, add gumwater (mass ratio of the carboxyl butyronitrile/gelatin and the Arabic gum aqueous solution is 2.0 ratio) behind the 10min; Continue stirring carboxyl butyronitrile/gelatin solution and gumwater are fully mixed, form stable O/w emulsion this moment.At last, under constantly stirring, Dropwise 5 % acetum, regulator solution pH value makes it that multiple aggregation take place 3.0～4.5.Carboxyl butyronitrile/gelatin and Arabic gum are because of the charged formation compound that neutralizes on the contrary mutually, and its solubility reduces, and the cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution are carried out embedding and form electrophoretic display microcapsule;
4. under constantly stirring, when solution naturally cools to 30 ℃ of left and right sides, be placed in the ice bath, continuing to be stirred to temperature is below 10 ℃; When reaction mixture cools to 0～10 ℃, be 0.8: 1 by gelatin and glutaraldehyde mass ratio, add glutaraldehyde to reaction mixture; Continue to stir 10min, make it curing cross-linked, using 10%NaOH solution to regulate again and making its pH is 8～9; Continue to stir 10min, observe till separate out, leave standstill and treat the microcapsules sedimentation.Microcapsules after solidifying are washed with distilled water, sieve, obtain containing the double-colored electrophoresis microcapsule of black and white.
4, microcapsules device preparation: the 140mm polyester film that at first will cut into square shape sticks on the conducting surface of electro-conductive glass with adhesive.Take out a certain amount of electrophoresis microcapsule then,, remove part water with the filter paper suction because the capsule appearance possibly have more water; Make it contain a spot of water as far as possible, it is evenly mixed with the adhesive that has added 40wt% polyvinylpyrrolidone K30 (PVP), glycerine, in air, place a period of time; With spreader it is coated in the middle of the groove of polyester film and ito glass; Coating speed should be slow, and when body to be mixed will be dry, the electro-conductive glass that another piece is scribbled adhesive was above it bonding; In 80 ℃ baking oven, dry by the fire 1h, make the microcapsules display device.
1, the preparation of carboxyl butyronitrile/gelatin intermingling material
It is 10% the aqueous solution that gelatin is mixed with concentration, at 80 ℃, according to carboxylic acrylonitrile butadiene rubber latex: gelatin carried out blending reaction at 100: 120, added the sodium tetraborate of 1% content, reaction 30min.45 ℃ of insulations of reaction back blend solution are subsequent use.
2, the preparation of electrophoresis suspensioning liquid
The TiO electrophoresis particle is joined in the tetrachloro-ethylene; Be made into mass fraction and be 20% dispersion liquid; The surfactant that in dispersion liquid, adds liquid quality fraction 2%; Described surfactant is polyethenoxy sorbitan list oleic acid, in dispersion liquid, adds the charge control agent polyisobutene mono butonediimide of liquid quality fraction 2%, adds the zirconium pearl again, under 300rpm, grinds 24h; Remove the zirconium pearl then and obtain stable white electrophoresis suspensioning liquid or black electrophoresis suspensioning liquid, sealing is preserved subsequent use.
3, the preparation of black and white electronic ink microcapsule
1. carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 40 ℃ of water, are mixed with mass concentration respectively and are 6% the carboxyl butyronitrile/gelatin aqueous solution and the Arabic gum aqueous solution;
2. be 30: 1 ratio in the mass ratio of white electrophoretic particles and black electrophoretic particles, the electrophoresis suspensioning liquid of getting two kinds of blend of colors of certain mass is prepared into the double-colored electrophoresis dispersion of uniform black and white under Ball milling;
3. under 40 ℃～50 ℃ water bath condition, the double-colored electrophoresis dispersion of the black and white that under the 1100rpm stirring condition, will 2. prepare joins step 1. in the carboxyl butyronitrile/gelatin solution, stirs gently.In mixed solution, add gumwater (mass ratio of the carboxyl butyronitrile/gelatin and the Arabic gum aqueous solution is 2.2 ratio) behind the 20min; Continue stirring carboxyl butyronitrile/gelatin solution and gumwater are fully mixed, form stable O/w emulsion this moment.At last, under constantly stirring, drip 20% acetum, regulator solution pH value makes it that multiple aggregation take place 3.0～4.5.Carboxyl butyronitrile/gelatin and Arabic gum are because of the charged formation compound that neutralizes on the contrary mutually, and its solubility reduces, and the cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution are carried out embedding and form electrophoretic display microcapsule;
4. under constantly stirring, when solution naturally cools to 30 ℃ of left and right sides, be placed in the ice bath, continuing to be stirred to temperature is below 10 ℃; When reaction mixture cools to 0～10 ℃, be 1.2: 1 by gelatin and glutaraldehyde mass ratio, add glutaraldehyde to reaction mixture; Continue to stir 20min, make it curing cross-linked, using 10%NaOH solution to regulate again and making its pH is 8～9; Continue to stir 30min, observe till separate out, leave standstill and treat the microcapsules sedimentation.Microcapsules after solidifying are washed with distilled water, sieve, obtain containing the double-colored electrophoresis microcapsule of black and white.
4, microcapsules device preparation: the 160mm polyester film that at first will cut into square shape sticks on the conducting surface of electro-conductive glass with adhesive.Take out a certain amount of electrophoresis microcapsule then,, remove part water with the filter paper suction because the capsule appearance possibly have more water; Make it contain a spot of water as far as possible, it is evenly mixed with the adhesive that has added 60wt% polyvinylpyrrolidone K30 (PVP), glycerine, in air, place a period of time; With spreader it is coated in the middle of the groove of polyester film and ito glass; Coating speed should be slow, and when body to be mixed will be dry, the electro-conductive glass that another piece is scribbled adhesive was above it bonding; In 80 ℃ baking oven, dry by the fire 1h, make the microcapsules display device.
Claims (2)
1. the preparation method of the electrophoresis particle microcapsules that condense again of carboxyl butyronitrile/gelatin and Arabic gum is characterized in that adopting carboxyl butyronitrile/gelatin and Arabic gum complex coacervation, and step is following:
1) preparation of carboxyl butyronitrile/gelatin intermingling material: it is 2.5%～15% the aqueous solution that gelatin is mixed with concentration; Under 60～80 ℃; With carboxylic acrylonitrile butadiene rubber latex: gelatin carries out blending reaction at 100 ︰, 80～100 ︰ 120; The sodium tetraborate or the citric acid that add 1%～3% content, reaction 20min～40min, 35 ℃～45 ℃ insulations of reaction back blend solution are subsequent use;
2) carboxyl butyronitrile/gelatin intermingling material and Arabic gum are dissolved in respectively in 35 ℃～45 ℃ water, are mixed with mass concentration and are 0.5%～6% the carboxyl butyronitrile/gelatin aqueous solution and mass concentration and be 0.5%～6% the Arabic gum aqueous solution;
3) under 40 ℃～50 ℃ water bath condition, under 600rpm～1100rpm stirring condition, electrophoresis suspensioning liquid is joined step 2) the carboxyl butyronitrile/gelatin aqueous solution in, stir gently; In mixed solution, add step 2 behind 10min～20min) gumwater, continue to stir carboxyl butyronitrile/gelatin solution and gumwater fully mixed, form stable O/w emulsion at this moment; Constantly stirring down again, Dropwise 5 %～20% acetum, regulator solution pH value is 3.0～4.5, and aggregation is answered in generation; The cohesion encystation is separated out in system, simultaneously the capsule-core that disperses in the solution is carried out embedding and forms electrophoretic display microcapsule.
2. the preparation method of electrophoresis particle microcapsules as claimed in claim 1; It is characterized in that described electrophoresis suspensioning liquid is the double-colored electrophoresis suspensioning liquid of black and white; The mass ratio of white electrophoretic particles and black electrophoretic particles is 5 ︰, 1～30 ︰ 1, and the electrophoresis suspensioning liquid of mixing is prepared into the double-colored electrophoresis dispersion of uniform black and white under Ball milling.
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| CN111226163B (en) * | 2017-11-03 | 2021-10-22 | 伊英克公司 | Process for producing electro-optic displays |
| CN113960846A (en) * | 2021-09-30 | 2022-01-21 | 中国科学院重庆绿色智能技术研究院 | Flexible electronic paper and preparation and application thereof |
| CN114191405B (en) * | 2021-11-06 | 2023-02-03 | 山东润德生物科技有限公司 | Preparation method and application of gel type glucosamine preparation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1371410A1 (en) * | 2002-06-14 | 2003-12-17 | NIZO food research | Complex coacervates containing whey proteins |
| CN1730572A (en) * | 2005-08-02 | 2006-02-08 | 天津大学 | Yellow electronic ink microcapsule preparation method |
| CN1772364A (en) * | 2005-10-27 | 2006-05-17 | 天津大学 | Prepn process of microcapsule containing Hansa yellow 100 electrophoresis liquid |
| CN1978557A (en) * | 2005-12-01 | 2007-06-13 | 北京化工大学 | Electronic ink microcapsule, and its preparing method |
-
2010
- 2010-02-05 CN CN2010103012784A patent/CN101850229B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1371410A1 (en) * | 2002-06-14 | 2003-12-17 | NIZO food research | Complex coacervates containing whey proteins |
| CN1730572A (en) * | 2005-08-02 | 2006-02-08 | 天津大学 | Yellow electronic ink microcapsule preparation method |
| CN1772364A (en) * | 2005-10-27 | 2006-05-17 | 天津大学 | Prepn process of microcapsule containing Hansa yellow 100 electrophoresis liquid |
| CN1978557A (en) * | 2005-12-01 | 2007-06-13 | 北京化工大学 | Electronic ink microcapsule, and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 李承明等.明胶/XNBR复合膜的制备及其性能研究.《明胶/XNBR复合膜的制备及其性能的研究》.2004,第24卷(第3期),121-125. * |
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