CN101550288B - Preparation method of colourful electrophoresis disclosing solution for electronic ink display - Google Patents
Preparation method of colourful electrophoresis disclosing solution for electronic ink display Download PDFInfo
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- CN101550288B CN101550288B CN200910084221A CN200910084221A CN101550288B CN 101550288 B CN101550288 B CN 101550288B CN 200910084221 A CN200910084221 A CN 200910084221A CN 200910084221 A CN200910084221 A CN 200910084221A CN 101550288 B CN101550288 B CN 101550288B
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Abstract
The present invention relates to a preparation method of colorful electrophoresis disclosing solution for electronic ink display. Using anti-solvent re-crystallization method to proceed re-crystallization on coloring agent to get coloring agent particle small particle diameter, simultaneity in the re-crystallization process, adding modifying agent to improve dispersion stabilization of particles and improve charge properties. Particle diameter of the prepared electrophoresis particles can reach 50 nm-300 nm, and colorful electrophoresis solution prepared by using the coloring agent particles has excellent dispersancy and charge properties, which can be used in electronic ink display and can also be used as raw materials for preparing electronic ink microcapsule capsule-core.
Description
Technical field:
The present invention relates to the preparation method that a kind of color electrophoresis that is used for the electric ink demonstration shows liquid, belong to nano material preparation and surface modified field.
Background technology:
In recent years, the electric ink demonstration receives extensive concern as a kind of novel technique of display.The electric ink demonstration is to realize that through electrophoresis particle the moving in electric field that is dispersed in the medium this just requires particle in dispersion medium, to have good dispersion stabilization and charging property.
Realize that at present the method that electric ink shows mainly contains two kinds, the one, electrophoresis disclosing solution is wrapped in the microcapsule, the 2nd, directly be prepared into electrophoresis disclosing solution and carry out electrophoresis showed with the electrophoresis particle of modification.This patent is to the latter, has invented a kind of preparation method who is used for the colored electrophoresis disclosing solution of electrophoresis disclosing solution of electric ink demonstration.
Domestic many that demonstration is studied to the micro encapsulation electric ink.(Chinese publication number: disclose with stearylamine modification phthalocyanine green 1506416) is granules of pigments to people such as the Zhao Xiao of Northwestern Polytechnical University roc in " preparation method of environment-friendly electronic ink "; Zellon is a solvent; Span-80 is a tensio-active agent; Thiocarbamide and formalin are the wall material, and adopting situ aggregation method to prepare green, particle diameter is the microcapsule of 30～80 microns sizes.People such as Zhao Xiaopeng also disclose " blue preparing electronic ink microcapsule ", and (Chinese publication number: 1506153), prepared capsule size is 5～200 microns; " white electron ink microcapsule " (Chinese publication number: 1492275) its inventive features is: capsule is that the capsule wall material is a urea-formaldehyde resin with the situ aggregation method preparation, and electrophoretic particles is a nano titanium oxide.
External most of patent all is the research to microcapsule and electrophoretic display device, EDD.People such as YamamotoHitoshi disclose the patent (US20060234053A1) of microcapsule preparations, and the electrophoresis dispersion that coats in the microcapsule of its preparation has a large amount of electrophoresis particles, first tunic parcel electrophoresis dispersion.Second tunic wraps up first tunic, and second tunic is an organic polymer, contains a large amount of polar groups and hydrophobic grouping.
The characteristics of above-mentioned prior art: basically all be 1, about the preparation of microcapsule and the making of electrophoretic display device, EDD; 2, there is not the special research report that shows liquid to the color electrophoresis that directly is used for the electric ink demonstration.And the micro encapsulation electric ink exists that mechanical property is relatively poor, the time of response in electric field is long, to defectives such as environment sensitive, preparing technique process complicacies.
In order to overcome the problems referred to above; Someone has proposed directly electrophoresis particle to be dispersed in the method for doing demonstration in the electrophoresis disclosing solution, compares with electron ink microcapsule, and its advantage is: 1, need not carry out the coating of microcapsule again; Save a step experimentation, in actual production, can reduce cost; 2, do not have the obstruct of capsule wall, can improve the time of response of particle in electric field; 3, further improve the resolving power of electronic ink display.4, relatively poor with the mechanical property of electron ink microcapsule, relatively to the shortcoming of environment sensitive, directly show to overcome these deficiencies well with electrophoresis disclosing solution.
But when electrophoresis particle was dispersed in the electrophoresis disclosing solution, the problem of existence had: 1, electrophoresis particle sedimentation easily in electrophoresis disclosing solution; 2, particle diameter is bigger and inhomogeneous, so that the time of response is long and development contrast is not obvious.
Summary of the invention:
The purpose of this invention is to provide the preparation method that a kind of color electrophoresis that is used for the electric ink demonstration shows liquid; Through anti-solvent recrystallization method pigment is carried out recrystallization; Obtain the less pigment particles of particle diameter; In the process of recrystallization, add properties-correcting agent and improve the dispersion stabilization of pigment particles and improve charging property simultaneously.The prepared electrophoresis particles particle diameter can reach 50nm～300nm; The color electrophoresis for preparing with this pigment particles shows that liquid has good dispersiveness and charging property; Can directly be used for electric ink and show, also can be used as the raw material of electron ink microcapsule capsule-core preparation.
The present invention is the preparation method that a kind of color electrophoresis that is used for the electric ink demonstration shows liquid; It is characterized in that: adopt anti-solvent recrystallization method that pigment is carried out recrystallization; In recrystallization process, add the dispersing property that properties-correcting agent improves pigment particles, concrete steps are following:
A: pigment dissolved in solvent, is mixed with the solution of 1g/L～10g/L;
B: properties-correcting agent is joined in the anti-solvent of deionized water, fully dissolve, be mixed with the solution of 0.1g/L～10g/L;
C: under agitation condition, join the pigment solution that obtains among the A in the modifier solution of B, it is 1～25: 1 that the amount of adding makes the mass ratio of properties-correcting agent and pigment, reaction 15～35min;
D: in the suspension that the C step obtains, add dispersion medium, the pigment solution volume ratio in its add-on and the A step is 1～3: 1, continues under agitation condition reaction 10～20min;
E: with the mixing liquid that the D step obtains, leave standstill 10～30min layering, take off layer; Add dispersion agent, stir 20～30min, after treating to dissolve mixing fully; Add background particle again,, promptly obtain being used for the color electrophoresis demonstration liquid that electric ink shows through supersound process 10～20min.
The described pigment of above-mentioned A step is red pigment, veridian or blue pigments, and red pigment can adopt common toluidine red or red, and veridian can be used phthalocyanine green, and blue pigments can be used phthalocyanine blue.
Solvent described in the A step is the vitriol oil, perhaps is a kind of in the following solvent or their mixture: ethanol, DMSO 99.8MIN. (DMSO), THF, acetone.But be not limited to above-mentioned solvent.
Properties-correcting agent described in the above-mentioned B step can be alkyl hydroximic acid, sodium lauryl sulphate (SDS), cetyl trimethylammonium bromide (CTAB), polysorbas20, polysorbate60 or PVAC polyvinylalcohol-124.
Stirring velocity described in the above-mentioned C step is preferably 600rpm～1200rpm.
Dispersion medium can be tetracol phenixin, zellon, hexanaphthene, 1 in the above-mentioned D step, a kind of in 3-dioxane, vinylbenzene, the Virahol or their mixture.
Background particle is selected nano-titania particle for use in the above-mentioned E step, and particle diameter preferably is no more than 100nm, and its consumption is 5～20 times of pigment mass.Dispersion agent is selected UV681, CH-6, CH-13B, CH-13E, Dispers 650, Dispers 655 or Dispers 710 for use, is preferably CH-6 or UV681, and its consumption is 0.6～1.2 times of pigment mass.
Through aforesaid method, can obtain the good red white electrophoresis disclosing solution of stability and charging property, green white electrophoresis disclosing solution, blue white electrophoresis disclosing solution.
The properties-correcting agent that the present invention uses belongs to tensio-active agent, and being adsorbed on the granules of pigments surface can ionization go out reactive group, makes particle surface adsorb a certain amount of electric charge, has improved the particulate surface electrical behavior; The tensio-active agent hydrophobic chain forms the solvation film simultaneously, and it can reduce particulate through space steric effect and reunite.Static and sterically hindered synergy make granules of pigments can stable dispersion in medium.But not every tensio-active agent can both be used for electrophoresis displaying particle, and the remodeling agent that we selected for use is from numerous tensio-active agents, preferably to come out.
The molecular structure of the dispersion agent that the present invention adopts can be divided into two parts, and a part is an anchoring group, and it mainly acts on is that the dispersion agent adsorbed close is surperficial in granules of pigments, prevents the dispersion agent desorption; Another part is a solvent chain, and it mainly acts on is to form certain thickness resist on the granules of pigments surface, thereby effectively improves the dispersion stabilization of granules of pigments in organic medium.
Innovation part of the present invention is: 1, through anti-solvent recrystallization method coloured pigment is carried out recrystallization; Colored electrophoresis displaying particle size is 50nm～300nm in the demonstration liquid that obtains; Littler nearly 20 times than pigment raw material; Can improve the time of response on the one hand, also can improve the stability of particle in dispersion medium simultaneously; 2, preparation is simple, and easy handling is with low cost, and equipment is not had particular requirement, and the sepn process of its particle is prone to realize; 3, add under the 30V voltage, the color electrophoresis for preparing shows that the liquid time of response is about 2s, and modification TiO in the present prior art
2The demonstration time that particle eletrophoresis shows liquid usually more than 30s, as: people such as Peng Xuhui are at " the TiO of surface-treated
2Be used as the research of electrophoresis particle " " high chemical engineering journal " (2006, the 20 the 6th phases of volume: 893-897) reported Al
2O
3Modification TiO
2Particle is the colour developing particle, and under impressed voltage 50V/mm, its time of response is 35s with its electrophoresis disclosing solution for preparing.Show that the electrophoresis colour developing liquid colour developing particle that the present invention obtains has improved the time of response greatly.
Description of drawings:
Fig. 1 is the stereoscan photograph of toluidine red after toluidine red former state and embodiment 3 modifications, and the former state particle is bar-shaped, about size-grade distribution 2 μ m; Toluidine red after recrystallization and modification, particle is rounded, and size-grade distribution is 50nm～100nm;
Fig. 2 is the red white electrophoresis disclosing solution that embodiment 1 makes, and adds the forward and reverse electrophoresis showed effect behind the 30V voltage;
Fig. 3 is the stereoscan photograph of phthalocyanine green after phthalocyanine green former state and embodiment 7 modifications, and the former state particle size is uneven, and size-grade distribution is between 1 μ m-2 μ m, and it is more serious to reunite; Phthalocyanine green after recrystallization and modification, particle is rounded, and size-grade distribution is 100nm～200nm;
Fig. 4 is the green white electrophoresis disclosing solution that embodiment 6 makes, and adds the forward and reverse electrophoresis showed effect behind the 30V voltage;
Fig. 5 is the stereoscan photograph of phthalocyanine blue after phthalocyanine blue former state and embodiment 8 modifications, and it is bar-shaped that particle is, and it is very serious to reunite, about size-grade distribution 1 μ m; Phthalocyanine blue after recrystallization and modification, particle is rounded, and size-grade distribution is 50nm～300nm;
Fig. 6 is the blue white electrophoresis disclosing solution that embodiment 8 makes, and adds the forward and reverse electrophoresis showed effect behind the 30V voltage;
Fig. 1, Fig. 3, Fig. 5 are the pattern of particle before and after toluidine red, phthalocyanine green, the phthalocyanine blue pigment modification, the ESEM comparison diagram of size, and as can be seen from the figure, commercially available granules of pigments is micron order, and size distribution is inhomogeneous, serious agglomeration.The grain diameter that obtains after the process modification is about 50～300nm, and is littler nearly 20 times than raw material, helps shortening its time of response.
Fig. 2, Fig. 4, Fig. 6 are mixed with red white, green white, blue white electrophoresis disclosing solution after toluidine red, phthalocyanine green, the phthalocyanine blue pigment modification; Inject homemade electronic ink display respectively; After with voltage stabilized source indicating meter being applied 30V voltage, obtained the color word of the white background shown in the figure; When the positive and negative electrode that switches voltage stabilized source, the wrongly written or mispronounced character of the color end of getting back as shown in the figure.In the process that conversion shows, the time of response is about 2s, and the writing of demonstration is clear evenly.
Embodiment:
Embodiment 1:
(1) takes by weighing the 0.03g toluidine red, be dissolved in the 10mL absolute ethyl alcohol;
(2) take by weighing 0.05g sodium lauryl sulphate (SDS) and join in the 200mL deionized water, magnetic agitation 20min joins in the there-necked flask of 250mL after waiting to dissolve.The control stirring velocity is 600rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to toluidine red-ethanolic soln in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add the 10mL zellon, continue to stir 10min, leave standstill 10min then, toluidine red has been extracted in the zellon, and layer is taken off in layering.Promptly obtain the toluidine red-zellon suspension after the modification.
(5) add 0.02g hyper-dispersant CH-6 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.25g particle diameter is lower than 100nm.With the ultrasonic 10min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the red white electrophoresis disclosing solution that electric ink shows.
With the toluidine red that makes in (4)-zellon suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 30.6%.
Embodiment 2:
(1) takes by weighing the 0.05g toluidine red, be dissolved in the 10mL THF;
(2) measure 1mLSpan-80 (quality is 1.1g) and join in the 200mL deionized water, magnetic agitation 20min joins in the there-necked flask of 250mL after waiting to dissolve.The control stirring velocity is 900rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to toluidine red-tetrahydrofuran solution in (1) in (2) carries out recrystallization and modification, reaction 15min.
(4) in the suspension of above-mentioned (3), add 8mL zellon and 2.5mL hexanaphthene, as composite dispersion medium, continue to stir 10min, leave standstill 10min then, toluidine red has been extracted in the compound system, and layer is taken off in layering.Promptly obtain the toluidine red-zellon/hexanaphthene suspension after the modification.
(5) add 0.05g dispersion agent UV681 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.4g particle diameter is lower than 100nm.With the ultrasonic 20min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the red white electrophoresis disclosing solution that electric ink shows.
With the toluidine red-zellon that makes in (4)/hexanaphthene suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 28.5%.
Embodiment 3:
(1) takes by weighing the 0.03g toluidine red, be dissolved in the 5mL vitriol oil (mass concentration is 98%), it is fully dissolved with the glass stick stirring;
(2) measure the 100mL deionized water,, measure 1mL alkyl hydroximic acid (quality is 0.75g) and add in the 2mL ethanol as anti-solvent, treat that it dissolves fully after, add in the deionized water, add the mixing solutions that obtains in the there-necked flask of 250mL at last.The control stirring velocity is 800rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to toluidine red-concentrated sulfuric acid solution in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add the 8mL tetracol phenixin, continue to stir 10min, leave standstill 10min then, toluidine red has been extracted in the tetracol phenixin, and layer is taken off in layering.Promptly obtain the toluidine red-tetracol phenixin suspension after the modification.
(5) add 0.025g hyper-dispersant CH-6 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.3g particle diameter is lower than 100nm.With the ultrasonic 20min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the red white electrophoresis disclosing solution that electric ink shows.
With the toluidine red that makes in (4)-tetracol phenixin suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 12.5%.
Embodiment 4:
(1) takes by weighing the 0.04g red, be dissolved in the 10mL DMSO 99.8MIN.;
(2) measure the 200mL deionized water,, measure 1mL alkyl hydroximic acid (quality is 0.75g) and add in the 2mL ethanol as anti-solvent, treat that it dissolves fully after, add in the anti-solvent, add the mixing solutions that obtains in the there-necked flask of 250mL at last.The control stirring velocity is 900rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to red-dimethyl sulphoxide solution in (1) in (2) carries out recrystallization and modification, reaction 15min.
(4) in the suspension of above-mentioned (3), add 10mL zellon and 3mL Virahol, as compound system, continue to stir 10min, leave standstill 10min then, red has been extracted in the compound system of zellon and Virahol, and layer is taken off in layering.Promptly obtain the red-zellon/Virahol suspension after the modification.
(5) add 0.035g hyper-dispersant CH-6 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.45g particle diameter is lower than 100nm.With the ultrasonic 15min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the red white electrophoresis disclosing solution that electric ink shows.
With the red-zellon that makes in (4)/Virahol suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 22.4%.
Embodiment 5:
(1) takes by weighing the 0.1g red, be dissolved in the 15mL absolute ethyl alcohol;
(2) take by weighing 0.1g PVAC polyvinylalcohol-124 and join in the 200mL deionized water, stir 30min, wait to dissolve in the there-necked flask of back adding 250mL at 80 ℃ of lower magnetic forces.The control stirring velocity is 1000rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to red-ethanolic soln in (1) in (2) carries out recrystallization and modification, reaction 15min.
(4) in the suspension of above-mentioned (3), add the 20mL zellon, continue to stir 10min, leave standstill 10min then, toluidine red has been extracted in the zellon, and layer is taken off in layering.Promptly obtain the red-zellon suspension after the modification.
(5) add 0.08g dispersion agent Dispers 650 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 1.5g particle diameter is lower than 100nm.With the ultrasonic 15min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the red white electrophoresis disclosing solution that electric ink shows.
With the red that makes in (4)-zellon suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 31.7%.
Embodiment 6:
(1) take by weighing the 0.03g phthalocyanine green, be dissolved in the 5mL vitriol oil (mass concentration is 98%), stirring is fully dissolved it;
(2) measure the 100mL deionized water,, measure 1mL alkyl hydroximic acid (quality is 0.75g) and add in the 2mL ethanol as anti-solvent, treat that it dissolves fully after, add in the anti-solvent, add the mixing solutions that obtains in the there-necked flask of 250mL at last.The control stirring velocity is 800rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to phthalocyanine green-concentrated sulfuric acid solution in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add the 10mL zellon, continue to stir 10min, leave standstill 10min then, phthalocyanine green has been extracted in the zellon, and layer is taken off in layering.Promptly obtain the phthalocyanine green-zellon suspension after the modification.
(5) add 0.025g hyper-dispersant CH-6 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.5g particle diameter is lower than 100nm.With the ultrasonic 10min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the green white electrophoresis disclosing solution that electric ink shows.
With the phthalocyanine green that makes in (4)-zellon suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 16%.
Embodiment 7:
(1) take by weighing the 0.08g phthalocyanine green, be dissolved in the 8mL vitriol oil (mass concentration is 98%), stirring is fully dissolved it;
(2) take by weighing 0.1g cetyl trimethylammonium bromide (CTAB) and join in the 150mL deionized water, stir 20min, treat to dissolve fully in the there-necked flask of back adding 250mL at 40 ℃ of lower magnetic forces.The control stirring velocity is 900rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to phthalocyanine green-concentrated sulfuric acid solution in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add 10mL zellon and 9.8mL tetracol phenixin, as composite dispersion medium, continue to stir 20min, leave standstill 10min then, phthalocyanine green has been extracted in the compound system, and layer is taken off in layering.Promptly obtain the phthalocyanine green-zellon/tetracol phenixin suspension after the modification.
(5) add 0.06g dispersion agent Dispers 710 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 1.2g particle diameter is lower than 100nm.With the ultrasonic 20min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the green white electrophoresis disclosing solution that electric ink shows.
With the phthalocyanine green-zellon that makes in (4)/tetracol phenixin suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 14%.
Embodiment 8:
(1) take by weighing the 0.03g phthalocyanine blue, be dissolved in the 5mL vitriol oil (mass concentration is 98%), stirring is fully dissolved it;
(2) take by weighing 0.05g sodium lauryl sulphate (SDS) and join in the 100mL deionized water, magnetic agitation 20min treats to dissolve fully in the there-necked flask of back adding 250mL.The control stirring velocity is 800rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to phthalocyanine blue-concentrated sulfuric acid solution in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add the 10mL zellon, continue to stir 15min, leave standstill 10min then, phthalocyanine blue has been extracted in the zellon, and layer is taken off in layering.Promptly obtain the phthalocyanine blue-zellon suspension after the modification.
(5) add 0.03g hyper-dispersant CH-6 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 0.3g particle diameter is lower than 100nm.With the ultrasonic 10min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the blue white electrophoresis disclosing solution that electric ink shows.
With the phthalocyanine blue that makes in (4)-zellon suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 26.1%.
Embodiment 9:
(1) take by weighing the 0.08g phthalocyanine blue, be dissolved in the 10mL vitriol oil (mass concentration is 98%), stirring is fully dissolved it;
(2) take by weighing 0.4g cetyl trimethylammonium bromide (CTAB), join in the 200mL deionized water, magnetic agitation 20min treats to dissolve fully in the there-necked flask of back adding 250mL at normal temperatures.The control stirring velocity is 900rpm, begins to stir.
(3) under room temperature, agitation condition, the there-necked flask that is added drop-wise to phthalocyanine blue-concentrated sulfuric acid solution in (1) in (2) carries out recrystallization and modification, reaction 20min.
(4) in the suspension of above-mentioned (3), add 10mL tetracol phenixin and 3.7mL vinylbenzene, as composite dispersion medium, continue to stir 20min, leave standstill 10min then, phthalocyanine blue has been extracted in the compound system, and layer is taken off in layering.Promptly obtain the phthalocyanine blue-tetracol phenixin/vinylbenzene suspension after the modification.
(5) add 0.06g dispersion agent UV681 in the lower floor's solution that in (4), obtains, the normal temperature lower magnetic force stirs 30min, treats that fully the dissolving back adds the white nano-titania particle that the 1.5g particle diameter is lower than 100nm.With the ultrasonic 20min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
The suspension that make this moment is and can be used for the blue white electrophoresis disclosing solution that electric ink shows.
With the phthalocyanine blue-tetracol phenixin that makes in (4)/vinylbenzene suspension ultra-sonic dispersion 20min, pour in the sedimentation bottle and leave standstill observation, obtaining its rate of descent behind the 200h is 29.1%.
The display performance test:
(1) makes the electronic ink display spare that can be used for electrophoresis showed by oneself with ITO (nano indium tin MOX) glass; With two ito glasses as last bottom crown; Wherein an ito glass engraves the pattern that is shown; Stick with glue agent two glass conglutinates, and interpolation one deck mesh size is 200 purpose nylon wires in the middle of two blocks of glass, promptly obtains being used for the simple and easy electronic ink display spare of electrophoresis showed.
(2) carrying out before the electrophoresis showed measure of merit, red white, green white, the blue white electrophoresis disclosing solution that earlier the present invention is made carries out ultra-sonic dispersion to be handled.With the ultrasonic 10min of KQ5200DE type numerical control supersonic cleanser, ultransonic parameter setting is: ultrasonic pulse is 2sec on, 1sec off; Ultrasonic amplitude is 100%.
(3) get two glass sandwichs that above-mentioned red white electrophoresis disclosing solution 0.5mL after ultrasonic injects above-mentioned electronic ink display spare; (top crown adds cathode voltage with voltage stabilized source electronic ink display to be applied 30V voltage; Bottom crown adds cathode voltage), after the pattern of waiting to develop the color was stable, (top crown added cathode voltage to switch positive and negative electrode again; Bottom crown adds cathode voltage), indicating meter shows the pattern of different colours.In the voltage handoff procedure, the time of response is (to see table 1) about 2s, and the clear patterns that shows is even.
(4) change electrophoresis disclosing solution, repeat (3) process, can obtain the electrophoresis showed effect of green white electrophoresis disclosing solution, blue white electrophoresis disclosing solution respectively, its time of response is 2.3s-5.3s (seeing table 1).The clear patterns of its demonstration, effect is obvious.
Data can find out that the time of response best effects of the color electrophoresis liquid that the present invention makes in electrophoresis disclosing solution can reach 2s from table, average 3.67s, and significant raising has been arranged about the 30s than common prior art, and (people such as Peng Xuhui is at " the TiO of surface-treated
2Be used as the research of electrophoresis particle " " high chemical engineering journal " (2006, the 20 the 6th phases of volume: 893-897) reported Al
2O
3Modification TiO
2Particle is the colour developing particle, and under impressed voltage 50V/mm, its time of response is 35s with its electrophoresis disclosing solution for preparing.), shortened the time of response greatly, improved product performance.
The present invention is 29.1%, 26.1% through the phthalocyanine blue electrophoresis particle rate of descent in dispersion medium that obtains after the modification; Phthalocyanine green rate of descent after cetyl trimethylammonium bromide (CTAB), the modification of alkyl hydroximic acid is respectively 14%, 16%, and toluidine red rate of descent after the modification of alkyl hydroximic acid can reach 12.5%.The electrophoresis particle of three kinds of colors its rate of descent after the recrystallization modification all reduces, and prior art preferably also about 40%, has improved the stability of color electrophoresis liquid in dispersion medium usually.
Claims (6)
1. one kind is used for the preparation method that color electrophoresis that electric ink shows shows liquid; It is characterized in that: adopt anti-solvent recrystallization method that pigment is carried out recrystallization; In recrystallization process, add the dispersing property that properties-correcting agent improves pigment particles, concrete steps are following:
A: pigment dissolved in solvent, is mixed with the solution of 1g/L～10g/L;
B: properties-correcting agent is joined in the anti-solvent of deionized water, fully dissolve, be mixed with the solution of 0.1g/L～10g/L;
C: under agitation condition, join the pigment solution that obtains among the A in the modifier solution of B, it is 1～25: 1 that the amount of adding makes the mass ratio of properties-correcting agent and pigment, reaction 15～35min;
D: in the suspension that the C step obtains, add dispersion medium, the pigment solution volume ratio is 1～3: 1 among the dispersion medium of adding and the A, continues under agitation condition reaction 10～20min;
E: with the mixed solution that the D step obtains, leave standstill 10～30min layering, take off layer; Add dispersion agent, stir 20～30min, after treating to dissolve mixing fully; Add background particle again,, promptly obtain being used for the color electrophoresis demonstration liquid that electric ink shows through supersound process 10～20min;
The described pigment of A step is red pigment, veridian or blue pigments, and red pigment is toluidine red or red, and veridian is a phthalocyanine green, and blue pigments is a phthalocyanine blue;
Properties-correcting agent described in the B step is alkyl hydroximic acid, sodium lauryl sulphate, cetyl trimethylammonium bromide, polysorbas20, polysorbate60 or PVAC polyvinylalcohol-124;
Dispersion agent described in the E step is UV681, CH-6, CH-13B, CH-13E, Dispers 650, Dispers 655 or Dispers 710, and consumption is 0.6～1.2 times of pigment mass.
2. according to the method for claim 1, it is characterized in that: the solvent described in the A step is the vitriol oil, perhaps is a kind of in the following solvent or their mixture: ethanol, DMSO 99.8MIN., THF, acetone.
3. according to the method for claim 1, it is characterized in that: the stirring velocity described in the C step is controlled at 600rpm～1200rpm.
4. according to the method for claim 1, it is characterized in that: dispersion medium is tetracol phenixin, zellon, hexanaphthene, 1 in the D step, a kind of in 3-dioxane, vinylbenzene, the Virahol or their mixture.
5. according to the method for claim 1, it is characterized in that: background particle is the TiO 2 particles that particle diameter is no more than 100nm in the E step, and consumption is 5～20 times of pigment mass.
6. according to the method for claim 1, it is characterized in that: dispersion agent is CH-6 or UV681.
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| CN101819368B (en) * | 2010-04-21 | 2011-06-29 | 天津大学 | Red and white electronic ink microcapsule and preparation method thereof |
| CN101870827B (en) * | 2010-05-28 | 2013-04-10 | 北京化工大学 | Preparation method of stable double-particle system electronic ink display solution |
| CN102167885A (en) * | 2011-03-09 | 2011-08-31 | 东南大学 | High-intensity urea-formaldehyde resin microcapsule and preparation method thereof |
| CN102649880B (en) * | 2012-02-14 | 2014-12-17 | 京东方科技集团股份有限公司 | Nanometer pigment and manufacturing method, electronic ink microcapsules and electrophoretic display device |
| JP5978821B2 (en) * | 2012-07-13 | 2016-08-24 | セイコーエプソン株式会社 | Electrophoretic material, electrophoretic display device, and electronic apparatus |
| CN103483862A (en) * | 2013-09-18 | 2014-01-01 | 吴江市冰心文教用品有限公司 | Preparation method of pigment yellow 180 dispersion liquid |
| CN109880404B (en) * | 2019-01-21 | 2020-10-27 | 西安交通大学 | Blue electrophoretic particle for electronic ink display and preparation method thereof |
| CN111323983B (en) * | 2020-03-19 | 2021-12-03 | 深圳秋田微电子股份有限公司 | Electrophoresis liquid for improving low-temperature resistance of electronic paper |
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