CN102757681A - Electronic ink and preparation method thereof - Google Patents

Electronic ink and preparation method thereof Download PDF

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Publication number
CN102757681A
CN102757681A CN2012102125905A CN201210212590A CN102757681A CN 102757681 A CN102757681 A CN 102757681A CN 2012102125905 A CN2012102125905 A CN 2012102125905A CN 201210212590 A CN201210212590 A CN 201210212590A CN 102757681 A CN102757681 A CN 102757681A
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coating layer
zinc oxide
suspension
zinc
electric ink
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王雪岚
薛建设
刘宸
舒适
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BOE Technology Group Co Ltd
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BOE Technology Group Co Ltd
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Priority to PCT/CN2012/084978 priority patent/WO2013189151A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Abstract

The invention relates to electronic ink and a preparation method of the electronic ink. The electronic ink disclosed by the invention comprises electrophoresis liquid, oil-soluble dyes and electrophoresis particles, wherein the electrophoresis particles comprise zinc oxide microspheres and ionized cladding layers coated on the zinc oxide microspheres. According to the electronic ink, the zinc oxide microspheres with the ionized cladding layers are taken as electrophoresis particles, so that the formed electronic ink has good stability.

Description

A kind of electric ink and preparation method
Technical field
The present invention relates to the demonstration field, relate in particular to a kind of electric ink and preparation method.
Background technology
At present, the preparation method of Electronic Paper has screw technology, microcapsulary, minute-pressure membrane technique and electrowetting technology.Sipix company adopts accurate grinding tool on plastic substrate, to extrude little glass of array of regular arrangement in length and breadth, and each little glass of size is loaded suspension-s and realized electrophoresis showed about 50-200 μ m in little cup.U.S. MIT and E-ink company adopt microcapsulary, in transparent microcapsule, put into materials such as the suspension-s of industry dark dye, charged light particle.In the end of the year 2003, PHILIPS Co. proposes electric moistening technique of display and prepares Electronic Paper.
Microcapsulary is the general demonstration means (U.S. US5961804 and US5930026) of current Electronic Paper research and commerical prod, but this method still has many technology to remain to be broken through.For example microcapsule are difficult to preparation evenly, the non-constant width of size-grade distribution, and mechanical property is difficult to controlled, and the cyst wall easy ageing is broken etc., thereby causes problems such as the display unit contrast gradient is low, the life-span is relatively shorter.Also have, the inner colour developing electrophoresis particle distribution of sizes broad of filling of microcapsule, shape is not spherical, it is irregular therefore to cause surface charge to distribute, and is easy to sedimentation; And non-sphere is moved under electric field action and is prone to cause intergranular bridging, influences other particulate motions, causes resolving power lower.
Little cup is a kind of electrophoresis microchamber that adopts fabrication techniques such as photoetching or minute-pressure film, because controllable size, material property is stable, has overcome the shortcoming of microcapsule effectively; And, more be prone to reach bistable structure because the restriction of microchamber makes electrophoretic image show that the turbulent susceptibility lowers to external world; Wall thickness also can be adjusted between little cup, improves performances such as withstand voltage, scratch resistance greatly.But above-mentioned technology also requires high for employed electric ink, needs electric ink to have very high stability.
Summary of the invention
The present invention provides a kind of electric ink, comprises electrophoresis liquid, oil-soluble colourant and electrophoresis particle, and said electrophoresis particle comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide microballoon.
Concrete, said ionize coating layer is Ionized polyethylene wax.
Concrete, said ionize coating layer is Ionized epoxide group.
Concrete, said ionize coating layer is Ionized pyridine group.
Concrete, said ionize coating layer is Ionized Vinylpyrrolidone polymer.
Concrete, said ionize coating layer is Ionized PS.
Concrete, said electrophoresis liquid is one or more in the group of liquid ester more than 7 of liquid alcohol 7 or more of liquid aliphatic hydrocarbon, carbonatoms, carbonatoms, the liquid organic acid composition of carbonatoms more than 4.
Concrete, said oiliness dyestuff comprises solvent blue, Oil Yellow, oil red, solvent green or Oil Violet; The mass percent of said oiliness dyestuff is 0.5-10%.
The present invention also provides a kind of preparation method of electric ink, may further comprise the steps:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, the zinc oxide that said preparation has coating layer may further comprise the steps:
S1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
S2) said suspension-s is heated to 80 ~ 120 ° of C, polyethylene wax is added in the said suspension-s, after the stirring, reduce to room temperature, obtain the said zinc oxide suspension that has coating layer.
Concrete, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
The S I) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
The S II) under the condition of stirring and the existence of protection gas, adds oxidizing agent solution; Add mixed liquor I and reductant solution; After accomplishing, reaction regulates pH value scope 6.0 ~ 8.0; Obtain the said zinc oxide suspension that has coating layer, said mixed liquor I is the mixed solution that comprises Vinylstyrene and SY-Monomer G.
Concrete, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
K1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
K2) under agitation condition, add oxidizing agent solution, feed protection gas, add Vinylstyrene pyridine and 4-vinylpridine mixed solution and reductant solution, obtain the said zinc oxide suspension that has coating layer.
Concrete, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
Q1) the zinc-oxide nano microballoon is dispersed in the solvent that contains Sodium hexametaphosphate 99, regulates pH value scope 6.0 ~ 8.0, form suspension-s;
Q2) Vinylpyrrolidone polymer is added in the said suspension-s,, obtain the said zinc oxide that has coating layer the suspension-s ultrasonic dispersing of said adding Vinylpyrrolidone polymer.
Concrete, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
D1) the zinc-oxide nano microballoon is dispersed in the mixed solvent of second alcohol and water composition, disperses to form suspension-s;
The monomer styrene that D2) will be dissolved with initiator azo diethyl butyronitrile is added dropwise to 50 ~ 90 ℃ of reactions in the said suspension-s, obtains the said zinc oxide that has coating layer.
Electric ink provided by the invention and preparation method thereof adopts the zinc oxide microballoon that has the ionize coating layer as electrophoresis particle, and the electric ink of formation has good stability, can satisfy the requirement of little glass of Electronic Paper to electric ink stability.
Description of drawings
Fig. 1 is the synoptic diagram of electric ink provided by the invention;
Fig. 2 representes the synoptic diagram of the little glass of contrast gradient experimental apparatus for testing in the electrophoresis showed experiment;
Fig. 3 representes the driving voltage/contrast curves figure of the little glass of Electronic Paper that electric ink that the embodiment of the invention 1 provides is processed.
Embodiment
The mensuration of zinc oxide fine particles granularity:
The zinc oxide fine particles granularity for preparing among the present invention is to adopt laser light scattering screen analysis appearance to measure.That is, get an amount of zinc-oxide nano microballoon, add terepthaloyl moietie, ultra-sonic dispersion 15 minutes is got 1.1mL sample suspension liquid in sample pool, measures the elastic collision rate of laser and sample, makes it remain on 1 * 10 4～2.64 * 10 6Inferior/s, then the sample particle diameter is carried out autoscan, obtain sample granularity, prepare the suspension of 10 lot sample article altogether.
Electric ink stably dispersing property testing:
Adopt 712 type spectrophotometers, measure the system transmittance over time.Analyze the dispersion stabilization of modification front and back nano zine oxide microballoon in electric ink in view of the above.The solid-liquid interface that bright particle of transmittance novel and liquid form is stable, is difficult between the particle reuniting, and powder is stable dispersion in liquid easily; Otherwise the big explanation solid-liquid interfacial tension of transmitance is big, reunites easily between the particle and sinks, and powder can not form stabilising system in liquid.The zinc oxide microballoon that takes by weighing the modification front and back of equivalent mixes with electrophoretic medium, all leaves standstill and places 90 days, extracts the turbid liquid in upper strata, does reference solution with electrophoretic medium, uses wavelength to be got turbid liquid by the rayed of 580nm, the record transmittance.Test every day in week that begins was most once tested once, was observed altogether 3 months in later per 1 month.
The present invention provides a kind of electric ink, and is as shown in Figure 1, comprises electrophoresis liquid 2, oil-soluble colourant and electrophoresis particle 1, and electrophoresis particle comprises zinc oxide microballoon 12 and is coated on the ionize coating layer 11 on the zinc oxide microballoon.
Electric ink provided by the invention has stability preferably, can satisfy the requirement of little glass of Electronic Paper to electrophoresis liquid.
Concrete, the ionize coating layer that is coated on the zinc oxide microballoon is Ionized polyethylene wax.Adopt Ionized polyethylene wax following as the concrete preparation method of ionize coating layer:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, step 1) may further comprise the steps:
S1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
S2) said suspension-s is heated to 80 ~ 120 ° of C, polyethylene wax is added in the said suspension-s, after the stirring, reduce to room temperature, obtain the said zinc oxide suspension that has coating layer.
At step S2) in, Heating temperature is 80 ~ 120 ° of C, is preferably 80 ° of C, 100 ° of C, 120 ° of C, following mask body is that example is elaborated with 120 ° of C.
Embodiment 1
1) the preparation the first step of zinc-oxide nano microballoon: compound concentration is the zinc acetate ethanolic soln of 0.25mol/L; Compound concentration is the sodium hydroxide ethanolic soln of 5mol/L; 8 weight part sodium hydroxide ethanolic solns are joined in the 4 weight part zinc acetate ethanolic solns, stir to react fully in 50 minutes under 120 ℃ and carry out, reaction finishes the back and use the filter membrane suction filtration, and washs.After 80 ℃ of vacuum-dryings, be dispersed in 25 parts by weight of ethanol, this mixing solutions is designated as a 3, strength of solution is 0.035mol/L;
Second step: compound concentration is the zinc acetate glycol ether solution of 0.5mol/L, adopts the method for crystal growth to prepare the zinc oxide microballoon.Zinc acetate glycol ether solution is designated as solution b 3, with 2 parts by weight solution a 3Join 100 parts by weight solution b 3In, 220 ℃ are stirred after 3 hours 10000rpm rotating speed centrifugal treating down; Remove supernatant liquid and washing, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 50nm, and adopts above-mentioned testing graininess method to measure granularity; The result is as shown in table 1, and its particle size distribution mv is less than 7%.
For easy difference, will be also referred to as 50nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of these embodiment 3 preparations.That is, other meaning of the 50nm level that the 50nm here representes not is strict 50nm.
Table 1 zinc-oxide nano microspherulite diameter distribution table
Figure BDA00001796765300051
2) coat polyethylene wax
Further modify as core with the extraordinary 50nm zinc-oxide nano of the monodispersity of method for preparing microballoon.Concrete steps are following.
With 0.5 weight part zellon is dispersion solvent, under ultrasonic oscillation, slowly adds 0.05 weight part 50nm zinc oxide microballoon.Ultrasonic oscillation 70 minutes; Be warming up to 120 ℃, under ultrasonic oscillation, slowly add the polyethylene wax of relative quantity of solvent 0.005 weight part, after continuing ultrasonic oscillation then it fully being spread; Cooling; Obtain the zinc oxide sphere that the surface coats polyethylene wax, promptly electrophoresis particle is accomplished the preparation of the compound ball of zinc oxide function.With above-mentioned zellon suspension-s with after the 0.44 weight part zellon dilution; Sonic oscillation 80 minutes, elder generation slowly adds the BYK112 electric charge dispersing agent of 0.02 weight part in batches under ultrasonic oscillation, adds the solvent blue of 0.02 weight part then; Ultrasonic oscillation 70 minutes obtains electric ink.Leave standstill and placed 90 days, extract the turbid liquid in upper strata, do reference solution, the record transmittance with liquid at the bottom of the electric ink.The result is shown in following table 2.
Comparative Examples 1
Taking by weighing the 50nm zinc oxide microballoon with embodiment 1 moderate, is solvent with the zellon, the zellon solution of preparation and the 50nm zinc oxide microballoon of embodiment 1 same concentrations; Leave standstill and placed 90 days; Extract the turbid liquid in upper strata, do reference solution, the record transmittance with zellon.The result is shown in following table 2.
The microsphere modified front and back of table 2 particle diameter 50nm zinc oxide electric ink stability test
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 8.1 48.2 76.7 87.6 87.5 87.7 87.9 87.8 87.7 87.6
The electric ink transmittance 6.1 7.5 8.0 9.1 9.3 8.9 9.0 9.0 9.3 9.2
From table, can find out that the electric ink transmittance for preparing in the present embodiment changes basicly stable in time, explain that electric ink is highly stable.
3) little glass of electrophoresis showed experiment
The electric ink of embodiment 1 preparation is injected in little cup, is packaged into microchamber.Driving circuit fits together with the microchamber that has encapsulated, and accomplishes the assembling of whole principle device.The contrast gradient experimental apparatus for testing is as shown in Figure 2, and its driving pulse voltage is provided frequency adjustable by function generator/telltale.During test, selecting the driving voltage frequency is 1kHz.Diameter be the helium neon laser beam of 0.8mm through the later on vertical sample that gets into of light transmission shaft polaroid in the horizontal direction, after the light that comes out from sample is the diaphragm restriction of 2.5 degree through aperture angle, received by silicon photodetector.Driving voltage/the contrast curves that records is as shown in Figure 3.Under electric field action, when driving voltage was higher than 4V, contrast gradient raise very soon, and when driving voltage was 8V, contrast gradient can reach 20:1, and was as shown in Figure 3.
Above-mentioned application experiment result shows, the electric ink that obtains according to the inventive method, and good dispersibility not only, and also other each item performances are also good, can be effective as Electronic Paper and use electric ink.
Embodiment 2
1) preparation of zinc-oxide nano microballoon
The first step: prepare 0.002mol/L tungstophosphoric acid ethanolic soln respectively; 0.015mol/L the trolamine aqueous solution; Zinc acetate aqueous solution with 0.02mol/L;
Second step: measure 60 weight part tungstophosphoric acid ethanolic solns, 60 weight part zinc acetate aqueous solutions, the 60 weight part trolamine aqueous solution respectively, under agitation zinc acetate aqueous solution slowly is added drop-wise in the tungstophosphoric acid ethanolic soln; Stir after 30 minutes, agitation condition slowly drips the trolamine aqueous solution down, after dropwising; Being warming up to 80 ℃ continues to stir after 3 hours; 8000rpm rotating speed centrifugal treating, after removing supernatant liquid and washing the infrared vacuum-drying of bottom solid, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 160nm; The result is as shown in table 3, and its particle size distribution mv is less than 6%.
For easy difference, will be also referred to as 160nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of these embodiment 5 preparations.That is, other meaning of the 160nm level that the 160nm here representes not is strict 160nm.
Table 3 zinc-oxide nano microspherulite diameter distribution table
Batch 1 2 3 4 5 6 7 8 9 10
Particle diameter (nm) 160.38 162.69 165.32 154.66 160.98 152.39 158.96 165.33 161.25 151.18
The particle diameter deviation 0.23% 1.68% 3.32% 3.34% 0.61% 4.76% 0.65% 3.33% 0.78% 5.51%
2) coat polyethylene wax
Further modify as core with the extraordinary 160nm zinc-oxide nano of the monodispersity of method for preparing microballoon.Concrete steps are following.
With 0.5 weight part zellon is dispersion solvent, under ultrasonic concussion, slowly adds the 160nm zinc oxide microballoon of 0.1 weight part.Behind the ultrasonic oscillation 90 minutes; Be warming up to 150 ℃, under ultrasonic concussion, slowly add the polyethylene wax of relative quantity of solvent 0.015 weight part, continue ultrasonic concussion after 180 minutes; Cooling; Obtain the zinc oxide sphere that the surface coats polyethylene wax, promptly electrophoresis particle is accomplished the preparation of the compound ball of zinc oxide function.With of the zellon dilution of above-mentioned zellon suspension-s with 0.38 weight part; Sonic oscillation 120 minutes; BYK 9076 electric charge dispersing agents that under ultrasonic concussion, slowly in batches add 0.08 weight part earlier; Slowly add the oil red of 0.1 weight part then, ultrasonic oscillation 100 minutes obtains electric ink in batches.Leave standstill and placed 90 days, extract the turbid liquid in upper strata, do reference solution, the record transmittance with liquid at the bottom of the electric ink.The result is shown in following table 4.
Comparative Examples 2
Taking by weighing the 160nm zinc oxide microballoon with embodiment 2 moderates, is solvent with the zellon, the zellon solution of preparation and the 160nm zinc oxide microballoon of embodiment 2 same concentrations; Leave standstill and placed 90 days; Extract the turbid liquid in upper strata, do reference solution, the record transmittance with zellon.The result is shown in following table 4.
The microsphere modified front and back of table 4 particle diameter 160nm zinc oxide electric ink stability test
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 8.9 48.7 76.2 87.5 87.9 88.2 88.0 88.1 88.2 88.1
The electric ink transmittance 5.8 7.2 7.9 8.9 9.0 8.8 9.1 9.3 9.3 9.2
From table, can find out that the electric ink transmittance for preparing in the present embodiment changes basicly stable in time, explain that electric ink is highly stable.
Concrete, the ionize coating layer that is coated on the zinc oxide microballoon is Ionized epoxide group.
Adopt Ionized epoxide group following as the concrete preparation method of ionize coating layer:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, step 1) may further comprise the steps:
The S I) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
The S II) under the condition of stirring and the existence of protection gas, adds oxidizing agent solution; Add mixed liquor I and reductant solution; After accomplishing, reaction regulates pH value scope 6.0 ~ 8.0; Obtain the said zinc oxide suspension that has coating layer, said mixed liquor I is the mixed solution that comprises Vinylstyrene and SY-Monomer G.
Embodiment 3
1) preparation of zinc-oxide nano microballoon
The first step: compound concentration is the zinc acetate ethanolic soln of 0.1mol/L; Compound concentration is the sodium hydroxide ethanolic soln of 2mol/L; 8 weight part sodium hydroxide ethanolic solns are joined in the 4 weight part zinc acetate ethanolic solns, stir to react fully in 45 minutes under 100 ℃ and carry out, reaction finishes the back and use the filter membrane suction filtration, and washs.After 80 ℃ of vacuum-dryings, be dispersed in 15 parts by weight of ethanol, obtain a that strength of solution is 0.015mol/L 2
Second step: compound concentration is the zinc acetate glycol ether solution of 0.25mol/L; Adopt the method for crystal growth to prepare the zinc oxide microballoon.Zinc acetate glycol ether solution is designated as solution b 2, with 2 parts by weight solution a 2Join 500 parts by weight solution b 2In, 200 ℃ are stirred after 3 hours 8000rpm rotating speed centrifugal treating down; Remove supernatant liquid and washing, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 80nm, and adopts above-mentioned testing graininess method to measure granularity; The result is as shown in table 5, and its particle size distribution mv is less than 6%.
For easy difference, will be also referred to as 80nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of these embodiment 2 preparations.That is, other meaning of the 80nm level that the 80nm here representes not is strict 80nm.
Table 5 zinc-oxide nano microspherulite diameter distribution table
Figure BDA00001796765300091
2) coat epoxide group
Adopt the extraordinary 80nm zinc-oxide nano of the monodispersity microballoon of method for preparing.40 part by weight of zinc oxide and 120 parts by weight of deionized water are mixed, its mixed solution was disperseed on ball mill 4 hours; Scattered emulsion is imported in the reactor drum, add 0.3 weight part ammonium persulphate and the formulated oxidizing agent solution of 40 parts by weight of deionized water while stirring; Feed argon gas as protection gas; Under maximum stir speed (S.S.) 800rpm, stirred 40 minutes under the normal temperature; In argon atmosphere, be warming up to 35 ℃ then and continue stir, alternately drip the mixed solution of monomer 0.4 weight part Vinylstyrene and 2.5 weight part SY-Monomer Gs and be the reductant solution of the dodecyl benzyl dimethyl ammonium chloride preparation of 1.5CMC by 0.015 weight part sodium sulfite anhy 96,40 weight part concentration; 3 hours dropping time.After dropwising, continued stirring reaction 2 hours; At last with the pH value of the sodium bicarbonate aqueous solution of 10wt% adjustment system to neutral.Reaction finishes, and makes zinc oxide nuclear-shell microballoon dispersion liquid, and its structure is that internal layer is the global structure of white zinc oxide microballoon, and skin is an epoxide group.
Then microballoon is carried out ionize.Be specially, in 120 parts of zinc oxide nuclear-shell microballoon dispersion liquids, drip the trimethylammonium ethyl amide hydrochloride of 80 parts of 12wt% while stirring; Dropwise, after stirring 40 minutes under the maximum stir speed (S.S.) 800rpm, slowly be warming up to 80 ℃, continue to stir 5 hours; Be cooled to normal temperature, finish reaction, the epoxy group(ing) of microsphere surface is opened, and forms hydroxyl and hydrochloride ion, has realized the ionize of microsphere surface.Use Rotary Evaporators that the water in the above-mentioned solution is removed, and vacuum-drying, obtain the zinc oxide nuclear-shell microballoon after the ionize, i.e. the electrophoresis microballoon.
10 parts of electrophoresis microballoons are joined in 100 parts of tetradecanes, and sonic oscillation fully disperseed it in 150 minutes, obtained electric ink.Leave standstill and placed 90 days, extract the turbid liquid in upper strata, do reference solution, the record transmittance with the tetradecane.The result is shown in following table 6.
Comparative Examples 3
Take by weighing with the above-mentioned extraordinary 80nm zinc-oxide nano of the monodispersity microballoon for preparing by the preparation method one of zinc-oxide nano microballoon of embodiment 3 moderates and mix with 100 parts of tetradecanes; Sonic oscillation 150 minutes; Leave standstill and placed 90 days; Extract the turbid liquid in upper strata, do reference solution, the record transmittance with the tetradecane.The result is shown in following table 6.
The microsphere modified front and back of table 6 80nm zinc oxide electric ink stability test
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 9.2 47.9 86.5 87.1 87.1 86.5 86.4 87.1 86.2 87.2
The electric ink transmittance 4.0 4.5 6.0 6.3 6.4 7.0 7.2 7.0 7.2 7.0
Can find out that from last table the zinc oxide suspension liquid transmittance before and after the modification alters a great deal, explain behind the modified zinc oxide that because its surperficial ionize of realization has the biphase affinity, dispersion stabilization obtains very big improvement; Transmittance changes basicly stablely in time in addition, explains that the electric ink system is highly stable.
Concrete, the ionize coating layer that is coated on the zinc oxide microballoon is Ionized pyridine group.
Adopt Ionized pyridine group following as the concrete preparation method of ionize coating layer:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, step 1) may further comprise the steps:
K1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
K2) under agitation condition, add oxidizing agent solution, feed protection gas, add Vinylstyrene pyridine and 4-vinylpridine mixed solution and reductant solution, obtain the said zinc oxide suspension that has coating layer.
Embodiment 4
1) preparation of zinc-oxide nano microballoon
The first step: prepare 0.002mol/L tungstophosphoric acid ethanolic soln respectively; 0.025mol/L the trolamine aqueous solution; Zinc acetate aqueous solution with 0.05mol/L;
Second step: measure 60 weight part tungstophosphoric acid ethanolic solns, 60 weight part zinc acetate aqueous solutions, the 60 weight part trolamine aqueous solution respectively, under agitation zinc acetate aqueous solution slowly is added drop-wise in the tungstophosphoric acid ethanolic soln; Stir after 60 minutes, agitation condition slowly drips the trolamine aqueous solution down, after dropwising; Being warming up to 120 ℃ continues to stir after 4.5 hours; 12000rpm rotating speed centrifugal treating, after removing supernatant liquid and washing the infrared vacuum-drying of bottom solid, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 100nm; The result is as shown in table 7, and its particle size distribution mv is less than 5%.
For easy difference, will be also referred to as 100nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of this embodiment preparation.That is, other meaning of the 100nm level that the 100nm here representes not is strict 100nm.
Table 7 zinc-oxide nano microspherulite diameter distribution table
Batch 1 2 3 4 5 6 7 8 9 10
Particle diameter (nm) 100.52 103.75 96.01 102.35 95.11 101.69 102.38 98.63 101.97 97.93
The particle diameter deviation 0.52% 3.75% 3.99% 2.35% 4.89% 1.69% 2.38% 1.37% 1.97% 2.07%
2) coat the pyridine group
Adopt the extraordinary 100nm zinc-oxide nano of the monodispersity microballoon of method for preparing.40 part by weight of zinc oxide and 120 parts by weight of deionized water are mixed, its mixed solution was disperseed on ball mill 6 hours; Scattered emulsion is imported in the reactor drum, add 0.4 weight part hydrogen peroxide, the formulated oxidizing agent solution of 50 parts by weight of deionized water while stirring; Feed argon gas as protection gas; Under maximum stir speed (S.S.) 800rpm, stirred 60 minutes under the normal temperature; In argon atmosphere, be warming up to 60 ℃ then and continue stir, the reductant solution of the X 2073 preparation that alternately drips the mixed solution of monomer 0.4 weight part Vinylstyrene and 2.0 weight part 4-vinylpridines and be 5CMC by the iron vitriol and the 40 weight part concentration of 0.025 weight part sodium sulfite anhy 96,0.025 weight part; 3 hours dropping time.After dropwising, continued stirring reaction 3 hours; Adjust the pH value to 7.0 of system at last with the sodium bicarbonate aqueous solution of 10wt%.Reaction finishes, and makes zinc oxide nuclear-shell microballoon dispersion liquid, and its structure is that internal layer is the global structure of white zinc oxide microballoon, and skin is the pyridine group.
Then microballoon is carried out ionize.Particularly, in 120 part by weight of zinc oxide nuclear-shell microballoon dispersion liquids, drip the aqueous hydrochloric acid of 40 weight part 14wt% while stirring, maximum stir speed (S.S.) 800rpm stirred 40 minutes, slowly was warming up to 100 ℃, was incubated 5 hours; Be cooled to normal temperature, finish reaction, the pyridyl salify of microsphere surface forms pyridine hydrochloride, has realized the ionize of microsphere surface.Use Rotary Evaporators that the water in the above-mentioned solution is removed, and vacuum-drying, obtain the zinc oxide nuclear-shell microballoon after the ionize, i.e. the electrophoresis microballoon.
10 weight part electrophoresis microballoons are joined in the 90 weight part isoamyl heptylates, and sonic oscillation fully disperseed it in 100 minutes, thereby obtained electric ink.Leave standstill and placed 90 days, extract the turbid liquid in upper strata, do reference solution, the record transmittance with isoamyl heptylate.The result is shown in following table 8.
Comparative Examples 4
The extraordinary 100nm zinc-oxide nano of the monodispersity microballoon that takes by weighing above-mentioned preparing method's preparation of equivalent mixes with 90 isoamyl heptylates, and sonic oscillation 100 minutes leaves standstill and placed 90 days, extracts the turbid liquid in upper strata, does reference solution with isoamyl heptylate, the record transmittance.The result is shown in following table 8.
The microsphere modified front and back of table 8 particle diameter 100nm zinc oxide electric ink stability test
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 10.1 58.2 88.1 88.0 87.9 88.3 88.2 88.0 88.4 88.2
The electric ink transmittance 5.0 5.7 6.2 7.3 7.4 8.1 8.0 7.9 8.1 8.0
Can find out that from last table the zinc oxide suspension liquid transmittance before and after the modification alters a great deal, explain behind the modified zinc oxide that because its surperficial ionize of realization has the biphase affinity, dispersion stabilization obtains very big improvement; Transmittance changes basicly stablely in time in addition, explains that the electric ink system is highly stable.
Concrete, the ionize coating layer that is coated on the zinc oxide microballoon is Ionized Vinylpyrrolidone polymer.
Adopt Ionized Vinylpyrrolidone polymer following as the concrete preparation method of ionize coating layer:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, step 1) may further comprise the steps:
Q1) the zinc-oxide nano microballoon is dispersed in the solvent that contains Sodium hexametaphosphate 99, regulates pH value scope 6.0 ~ 8.0, form suspension-s;
Q2) Vinylpyrrolidone polymer is added in the said suspension-s,, obtain the said zinc oxide that has coating layer the suspension-s ultrasonic dispersing of said adding Vinylpyrrolidone polymer.
Embodiment 5
1) preparation of zinc-oxide nano microballoon
The first step: compound concentration is the zinc acetate ethanolic soln of 0.01mol/L; Compound concentration is the sodium hydroxide ethanolic soln of 0.5mol/L; 8 weight part sodium hydroxide ethanolic solns are joined in the 4 weight part zinc acetate ethanolic solns, stir to react fully in 30 minutes under 80 ℃ and carry out, reaction finishes the back and use the filter membrane suction filtration, and washs.After 80 ℃ of vacuum-dryings, be dispersed in 10 parts by weight of ethanol, obtaining concentration is the solution a of 0.003mol/L 1
Second step: compound concentration is the zinc acetate glycol ether solution of 0.01mol/L; Adopt the method for crystal growth to prepare the zinc oxide microballoon.Zinc acetate glycol ether solution is designated as solution b 1, with 2 parts by weight solution a 1Join 1000 parts by weight solution b 1In, 180 ℃ are stirred after 90 minutes 5000rpm rotating speed centrifugal treating down; Remove supernatant liquid and washing, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 120nm, and adopts above-mentioned testing graininess method to measure granularity; The result is as shown in table 9, and its particle size distribution mv is less than 7%.
For easy difference, will be also referred to as 120nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of this embodiment preparation.That is, other meaning of the 120nm level that the 120nm here representes not is strict 120nm.
Table 9 zinc-oxide nano microspherulite diameter distribution table
Figure BDA00001796765300131
2) coat Vinylpyrrolidone polymer
A certain amount of 120nm zinc-oxide nano microballoon is dissolved in the water that contains a small amount of Sodium hexametaphosphate 99, regulates pH value about 6, fully dissolve with sonic oscillation with 1%HCl.Add properties-correcting agent Vinylpyrrolidone polymer PVPK30, ultra-sonic dispersion 1h.Taking-up is dry 24h under 105 ℃, fully grinds and sieves, and obtains organically-modified zinc-oxide nano microballoon.With organically-modified zinc-oxide nano microballoon is the colour developing particle; With the zellon is dispersion medium, and organically-modified zinc-oxide nano microballoon weight part is 15%, sonic oscillation 1h; Add 2wt% oil red dyestuff; Add 3wt%byk 161 electric charge dispersing agent dispersion agents, ultrasonic oscillation 30 minutes, preparation electrophoresis disclosing solution.
Comparative Examples 5
Take by weighing zinc-oxide nano microballoon with the foregoing description equivalent; With the zellon is solvent, prepares the zellon solution of the zinc-oxide nano microballoon of concentration same as the previously described embodiments, sonic oscillation 30 minutes; Leave standstill and placed 90 days; Extract the turbid liquid in upper strata, do reference solution, the record transmittance with zellon.The result is shown in following table 10.
The microsphere modified front and back of zinc-oxide nano electric ink stability test among table 10 embodiment 3
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 7.3 45.6 76.1 86.9 87.3 87.1 86.8 87.1 86.9 87.1
The electric ink transmittance 6.4 7.1 8.4 9.4 9.2 9.1 9.2 9.3 9.2 9.1
From table, can find out that the electric ink transmittance for preparing in the present embodiment changes basicly stable in time, explain that electric ink is highly stable.
Concrete, the ionize coating layer that is coated on the zinc oxide microballoon is Ionized PS.
Adopt Ionized PS following as the concrete preparation method of ionize coating layer:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
Concrete, step 1) may further comprise the steps:
D1) the zinc-oxide nano microballoon is dispersed in the mixed solvent of second alcohol and water composition, disperses to form suspension-s;
The monomer styrene that D2) will be dissolved with initiator azo diethyl butyronitrile is added dropwise to 50 ~ 90 ℃ of reactions in the said suspension-s, obtains the said zinc oxide that has coating layer.
Embodiment 6
1) preparation of zinc-oxide nano microballoon
(1) prepares 0.001mol/L tungstophosphoric acid ethanolic soln respectively; 0.005mol/L the trolamine aqueous solution; Zinc acetate aqueous solution with 0.01mol/L;
(2) measure 60 weight part tungstophosphoric acid ethanolic solns, 60 weight part zinc acetate aqueous solutions, the 60 weight part trolamine aqueous solution respectively, under agitation zinc acetate aqueous solution slowly is added drop-wise in the tungstophosphoric acid ethanolic soln; Stir after 10 minutes, agitation condition slowly drips the trolamine aqueous solution down, after dropwising; Being warming up to 100 ℃ continues to stir after 2 hours; 5000rpm rotating speed centrifugal treating, after removing supernatant liquid and washing the infrared vacuum-drying of bottom solid, obtaining particle diameter is single zinc-oxide nano microballoon that disperses of 200nm; The result is as shown in table 11, and its particle size distribution mv is less than 7%.
For easy difference, will be also referred to as 200nm zinc-oxide nano microballoon among the present invention by the zinc-oxide nano microballoon of this embodiment preparation.That is, other meaning of the 200nm level that the 200nm here representes not is strict 200nm.
Table 11 zinc-oxide nano microspherulite diameter distribution table
Batch 1 2 3 4 5 6 7 8 9 10
Particle diameter (nm) 200.31 208.47 209.88 205.65 212.23 201.56 206.58 213.43 205.73 207.62
The particle diameter deviation 0.15% 4.23% 4.94% 2.82% 6.11% 0.78% 3.29% 6.71% 2.86% 3.86%
2) coat PS
Quantitative stablizer hydroxypropylcellulose and 200nm zinc-oxide nano microballoon are dissolved in the mixed solvent of being made up of the second alcohol and water; Ultra-sonic dispersion 30min is equipped with its input in the 250ml four-hole bottle of TM, whisking appliance and condensing surface, logical nitrogen protection; In 70 ℃ of pre-dispersed 30min; Slowly drip the monomer styrene that is dissolved with initiator azo diethyl butyronitrile then,, promptly get monodisperse polymer complex microsphere samples of latex at 70 ℃ of reaction 12h.Samples of latex is used centrifugal settling, discard supernatant liquid, centrifugal again with washing with alcohol lower floor microballoon, washing so repeats 5 times again.Microballoon after the washing is poured in the petridish, and dry 24h in 60 ℃ of vacuum drying ovens promptly gets zinc oxide/PS composite nano-microsphere, and promptly electrophoresis particle is accomplished the preparation of the compound ball of zinc oxide function.The above-mentioned zellon suspension-s sonic oscillation 50 minutes that will contain the electrophoresis particle of 10wt%.Under sonic oscillation, slowly add solvent blue and 2wt%byk 163 electric charge dispersing agents that account for suspension-s 1wt% earlier, ultrasonic oscillation 30 minutes obtains electric ink in batches.
Comparative Examples 6 takes by weighing the zinc-oxide nano microballoon with the foregoing description moderate; With the zellon is solvent, prepares the zellon solution of the zinc-oxide nano microballoon of concentration same as the previously described embodiments, and sonic oscillation fully spread it in 50 minutes; Leave standstill and placed 90 days; Extract the turbid liquid in upper strata, do reference solution, the record transmittance with zellon.The result is shown in following table.
The microsphere modified front and back of zinc oxide electric ink stability test among table 12 embodiment 6
Time (day) 1d 2d 3d 4d 5d 6d 7d 30d 60d 90d
Unmodified transmittance 7.5 45.1 76.3 86.7 87.5 87.6 87.8 87.9 87.7 87.6
The electric ink transmittance 5.6 6.8 7.8 7.9 8.0 8.2 8.1 8.3 8.2 8.0
From table, can find out that the electric ink transmittance for preparing in the present embodiment changes basicly stable in time, explain that electric ink is highly stable.
More than explanation is just illustrative for the purpose of the present invention; And nonrestrictive, those of ordinary skills understand, under the situation of spirit that does not break away from accompanying claims and limited and scope; Can make many modifications, variation or equivalence, but all will fall in protection scope of the present invention.

Claims (14)

1. an electric ink comprises electrophoresis liquid, oil-soluble colourant and electrophoresis particle, it is characterized in that, said electrophoresis particle comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide microballoon.
2. electric ink as claimed in claim 1 is characterized in that, said ionize coating layer is Ionized polyethylene wax.
3. electric ink as claimed in claim 1 is characterized in that, said ionize coating layer is Ionized epoxide group.
4. electric ink as claimed in claim 1 is characterized in that, said ionize coating layer is Ionized pyridine group.
5. electric ink as claimed in claim 1 is characterized in that, said ionize coating layer is Ionized Vinylpyrrolidone polymer.
6. electric ink as claimed in claim 1 is characterized in that, said ionize coating layer is Ionized PS.
7. like the described electric ink of claim 1 ~ 6; It is characterized in that one or more in the group that said electrophoresis liquid is a liquid ester more than 7 of liquid alcohol more than 7 of liquid aliphatic hydrocarbon, carbonatoms, carbonatoms, the liquid organic acid of carbonatoms more than 4 formed.
8. like the described electric ink of claim 1 ~ 6, it is characterized in that said oiliness dyestuff comprises solvent blue, Oil Yellow, oil red, solvent green or Oil Violet; The mass percent of said oiliness dyestuff is 0.5-10%.
9. the preparation method of an electric ink is characterized in that, may further comprise the steps:
1) the preparation particle diameter has the zinc oxide microsphere suspension liquid of coating layer uniformly;
The zinc oxide microballoon that has coating layer that 2) will prepare and the surface ion agent that the zinc oxide that has coating layer carries out surface ionization added in the organic solvent; Disperse the back to form the electrophoresis liquid that contains electrophoresis particle, the electrophoresis particle in the said electrophoresis liquid comprises the zinc oxide microballoon and is coated on the ionize coating layer on the zinc oxide kernel;
3) in the said electrophoresis liquid that contains electrophoresis particle, add oil-soluble colourant, form said electric ink behind the ultrasonic oscillation.
10. the preparation method of electric ink as claimed in claim 9 is characterized in that, the zinc oxide that said preparation has coating layer may further comprise the steps:
S1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
S2) said suspension-s is heated to 80 ~ 120 ° of C, polyethylene wax is added in the said suspension-s, after the stirring, reduce to room temperature, obtain the said zinc oxide suspension that has coating layer.
11. the preparation method of electric ink as claimed in claim 9 is characterized in that, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
The S I) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
The S II) under the condition of stirring and the existence of protection gas, adds oxidizing agent solution; Add mixed liquor I and reductant solution; After accomplishing, reaction regulates pH value scope 6.0 ~ 8.0; Obtain the said zinc oxide suspension that has coating layer, said mixed liquor I is the mixed solution that comprises Vinylstyrene and SY-Monomer G.
12. the preparation method of electric ink as claimed in claim 9 is characterized in that, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
K1) the zinc-oxide nano microballoon is dispersed in the solvent, forms suspension-s;
K2) under agitation condition, add oxidizing agent solution, feed protection gas, add Vinylstyrene pyridine and 4-vinylpridine mixed solution and reductant solution, obtain the said zinc oxide suspension that has coating layer.
13. the preparation method of electric ink as claimed in claim 9 is characterized in that, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
Q1) the zinc-oxide nano microballoon is dispersed in the solvent that contains Sodium hexametaphosphate 99, regulates pH value scope 6.0 ~ 8.0, form suspension-s;
Q2) Vinylpyrrolidone polymer is added in the said suspension-s,, obtain the said zinc oxide that has coating layer the suspension-s ultrasonic dispersing of said adding Vinylpyrrolidone polymer.
14. the preparation method of electric ink as claimed in claim 9 is characterized in that, the zinc oxide suspension that said preparation has coating layer may further comprise the steps:
D1) the zinc-oxide nano microballoon is dispersed in the mixed solvent of second alcohol and water composition, disperses to form suspension-s;
The monomer styrene that D2) will be dissolved with initiator azo diethyl butyronitrile is added dropwise to 50 ~ 90 ℃ of reactions in the said suspension-s, obtains the said zinc oxide that has coating layer.
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