CN101833217A - Modified yellow electrophoretic particle with shell-core composite structure and preparation method thereof - Google Patents
Modified yellow electrophoretic particle with shell-core composite structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified yellow electrophoretic particle with a shell-core composite structure and a preparation method thereof and belongs to the preparation technology of an electrophoretic particle, which is applied to electronic ink. The yellow electrophoretic particle has a core of yellow azo organic pigment and a shell layer of silica, wherein the surface of the silica has -NH2 or -COOH groups. The yellow electrophoretic particle is prepared by the steps of: cladding a compact silica shell layer on the surface of the organic pigment respectively through ethyl silicate hydrolysis and sodium silicate hydrolysis by using an electrostatic self-assembly method, and then carrying out grafting reaction respectively on gamma-aminopropyl triethoxysilane and succinic acid by using -OH on the surface of the silica to obtain the silica, the surface of which carries -NH2 or -COOH groups. The invention has the advantages of simple process and easy raw material obtaining; and the obtained yellow electrophoretic particle has good solvent resistance and good dispersion stability in tetrachloroethylene; and moreover, since the shell surface of the particle carries plenty of -NH2 or -COOH groups, and the yellow electrophoretic particle has strong surface charge ability when applied to the electronic ink.
Description
Technical field
The present invention relates to a kind of yellow electrophoretic particle and preparation method thereof of shell-shell-core composite structure of modification, belong to the electrophoresis particle technology of preparing that is applied to electric ink.
Background technology
Electric ink (microcapsules electrophoresis showed) is a kind of stock that is applied to electrophoresis showed, and it is coated in the microcapsules by charged particle and dispersion medium forms.Electrophoresis showed in order to realize its colorize, needs research Huang, pinkish red, the demonstration situation of blue or green three primary colors pigment applications in electric ink as a kind of reflective display.Organic pigment has advantages such as strong coloring force, lovely luster, chromatogram be complete, close with organic dispersion medium density, is suitable as the electrophoresis particle of realizing that color electrophoresis shows.
Compare with redness (color lake class) commonly used, blue (phthalocyanines) organic pigment, there is the shortcoming of thermotolerance, against weather, poor solvent resistance in yellow (azo class) organic pigment commonly used, and it is particularly outstanding particularly to be applied in the organic dispersion medium that electric ink shows shortcoming.The preparation of yellow particles electrophoresis liquid in the past is that yellow organic pigment, charge control agent, stabilizing agent etc. are dispersed in the medium, by physical method such as polishing, ball-milling method and supercritical ultrasonics technology preparation.People such as Li Luhai have studied C.I.Pigmeng Yellow 14 as yellow electrophoretic particle, the mixed solution of zellon and dimethylbenzene is as dispersion medium, organic amine prepares yellow electrophoretic liquid [1] [Li Luhai as charge control agent, Zhang Shufen, Yang Jinzong, Zou Jing, Zhao Qiang. spectroscopy and spectral analysis, 2005,25 (10): 1584～1587]; People such as Pei Guangling serve as the colour developing particle with benzidine yellow G (C.I.Pigmeng Yellow14), the mixed solution of zellon and toluene is a dispersion medium, the blue N of oil-soluble is a background dye, hyper-dispersant CH-2C is a stabilizing agent, has prepared ureaformaldehyde microcapsules [2] [Pei Guangling, Wang Tingjie that single-particle shows by situ aggregation method, Yang Yi, Jin Yong. Acta PhySico-Chimica Sinica, 2005,21 (4): 430～434]; People such as Feng Yaqing use Hansa yellow 100 (C.I.Pigmeng Yellow 3) to be electrophoresis particle, toluene, cyclohexane or zellon are dispersion medium, prepare electrophoresis liquid by adding the surfactant Ball milling, having coated the wall material respectively is the electron ink microcapsule [3 of polyureas and Arabic gum-gelatin, 4] [Li Gang, Feng Yaqing, Li Xianggao, Wang Jing, Xie Jianyu. application number: 200510014699.8, publication number: CN1730572A. Feng Ya green grass or young crops, Xie Jianyu, Li Xianggao, Wang Jing, Li Gang. application number: 200510015685.8, publication number: CN1772364A].
But yellow organic pigment (azo class) the electrophoresis particle less stable in organic solvent in the electrophoresis liquid of these method preparations, especially in nonpolar zellon (being suitable as very much the dispersion medium of electrophoresis liquid), exist tangible dissolving and swelling phenomenon, have a strong impact on the display quality of electric ink; And specific density is slightly little mutually with zellon for yellow organic pigment, and along with the prolongation of electrophoresis liquid time of repose, the pigment particles of dispersion floats gradually and is cotton-shaped gathering and is suspended in liquid surface.In order to overcome above shortcoming, must carry out surface modification to yellow organic pigment could be as the electrophoresis particle that is fit to be applied to electric ink.
Summary of the invention
The object of the present invention is to provide a kind of yellow electrophoretic particle and preparation method thereof of shell-shell-core composite structure of modification, described yellow electrophoretic particle solvent resistance in nonpolar zellon dispersion medium is good, have excellent dispersion stability, surperficial charged ability is strong.Its preparation method process is simple.
The present invention is realized by following technical proposals.A kind of yellow electrophoretic particle of shell-shell-core composite structure of modification, the particle diameter of this electrophoresis particle is 200～1000nm, its core is a kind of among benzidine yellow G (C.I.Pigmeng Yellow 12), permanent yellow GR (C.I.Pigmeng Yellow 13) and the Hansa yellow 100 (C.I.Pigmeng Yellow 3) or two kinds or three kinds, it is characterized in that, the shell of this yellow electrophoretic particle is a silicon dioxide, and silica surface has-NH
2Group or-the COOH group.
One of preparation method of the yellow electrophoretic particle of the shell-shell-core composite structure of above-mentioned modification is characterized in that comprising following process:
(1) a kind of among benzidine yellow G (C.I.Pigmeng Yellow 12), permanent yellow GR (C.I.Pigmeng Yellow 13) and the Hansa yellow 100 (C.I.Pigmeng Yellow 3) or two kinds or three kinds are dispersed in the isopropyl alcohol, the quality consumption of isopropyl alcohol is 20～30 times of yellow uitramarine consumption, behind soak time 12～36h, centrifuging goes out particle, and wash particle with ethanol, make yellow particles;
(2) yellow particles that step (1) is made adds in the ethanol, the quality consumption of ethanol is 40～60 times of yellow particles consumption, in yellow particles and alcohol mixeding liquid, add polyvinylpyrrolidone again, the quality consumption of polyvinylpyrrolidone is 3～4 times of yellow particles consumption, emulsification jitter time 0.5～1h forms emulsion, with emulsion heating-up temperature to 55～60 ℃, adding quality is 3～4 times ammoniacal liquor of yellow particles consumption, and the dropping mass concentration is 30～40% silester ethanolic solution, the quality consumption of the silester that drips is 3～4 times of yellow particles quality, the dropping time is 3～5h, keep 55～60 ℃ of reaction time 8～12h of temperature then, go out particle through centrifuging, particle is washed with deionized water and ethanol successively, obtain the yellow particles of surperficial coated silica shell again through temperature 60 ℃ of vacuum drying;
(3) be to form suspending liquid in 85～90% the ethanol water with the yellow particles of the surperficial coated silica shell of step (2) preparation with the ultrasonic mass concentration that is scattered in, the quality consumption of ethanol water is 90～100 times of yellow particles quality of surperficial coated silica shell; In suspending liquid, add gamma-aminopropyl-triethoxy-silane (KH-550) again, the quality consumption of gamma-aminopropyl-triethoxy-silane (KH-550) is 0.2～0.4 times of yellow particles quality of surperficial coated silica shell, the dilute sulfuric acid adjusting pH that also adds 5mol/L in suspending liquid is 3, at 60～80 ℃ of reaction time 8～12h of temperature, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through temperature 60 ℃ of vacuum drying, obtain having-NH at the silica shell laminar surface
2The yellow electrophoretic particle of group modified shell-shell-core composite structure, the particle diameter of particle are 200～1000nm;
(4) or with ultrasonic being scattered in of yellow particles of the surperficial coated silica layer of step (2) preparation form suspending liquid in the acetonitrile, the quality consumption of acetonitrile is 30～50 times of yellow particles consumption; Under 50～70 ℃ of temperature, it is 3～4% succinic acid acetonitrile solution that acetonitrile is dissolved in succinic acid preparation mass concentration, in the succinic acid acetonitrile solution, add the yellow particles of surperficial coated silica layer and the suspending liquid of acetonitrile, the quality consumption of succinic acid acetonitrile solution is 30～50 times of yellow particles quality of surperficial coated silica shell, keep 70～80 ℃ of reaction time 20～25h of temperature then, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through 60 ℃ of vacuum drying of temperature, obtain having on silica shell laminar surface surface-yellow electrophoretic particle of the group modified shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm.
The preparation method's of the yellow electrophoretic particle of the shell-shell-core composite structure of above-mentioned modification two is characterized in that comprising following process:
(1) a kind of among benzidine yellow G (C.I.Pigmeng Yellow 12), permanent yellow GR (C.I.Pigmeng Yellow 13) and the Hansa yellow 100 (C.I.Pigmeng Yellow 3) or two kinds or three kinds are dispersed in the isopropyl alcohol, the quality consumption of isopropyl alcohol is 20～30 times of yellow uitramarine consumption, behind soak time 12～36h, centrifuging goes out particle, and wash particle with ethanol, make yellow particles;
(2) yellow particles that step (1) is made adds in the deionized water, the quality consumption of deionized water is 100～110 times of yellow particles consumption, in the emulsion of yellow particles and water, add cetyl trimethyl ammonium bromide (CTAB) again, the quality consumption of cetyl trimethyl ammonium bromide (CTAB) is 0.18～2.20 times of yellow particles consumption, and emulsification jitter time 0.5～1h forms emulsion; With emulsion heating-up temperature to 85～95 ℃, drip mass concentration and be the aqueous solution of 30～40% sodium silicate, the quality consumption of sodium silicate is 4～5 times of yellow particles quality, the reactant liquor of the dilute sulfuric acid of Dropwise 5 mol/L control simultaneously pH is 9～10, the dropping time is 2～3h, keeps 85～95 ℃ of reaction time 5～8h of temperature then; Dilute sulfuric acid conditioned reaction liquid pH with 5mol/L is 3 then, keep 85～95 ℃ of temperature to continue reaction 2～3h, go out particle through centrifuging, particle is washed with ethanol with deionized water successively washed, obtain the yellow particles of surperficial coated silica shell again through 60 ℃ of vacuum drying of temperature;
(3) be to form suspending liquid in 85～90% the ethanol water with the yellow particles of the surperficial coated silica shell of step (2) preparation with the ultrasonic mass concentration that is scattered in, the quality consumption of ethanol water is 90～100 times of yellow particles quality of surperficial coated silica shell; In suspending liquid, add gamma-aminopropyl-triethoxy-silane (KH-550) again, the quality consumption of gamma-aminopropyl-triethoxy-silane (KH-550) is 0.2～0.4 times of yellow particles quality of surperficial coated silica shell, the dilute sulfuric acid adjusting pH that also adds 5mol/L in suspending liquid is 3, at 60～80 ℃ of reaction time 8～12h of temperature, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through temperature 60 ℃ of vacuum drying, obtain having-NH at the silica shell laminar surface
2The yellow electrophoretic particle of group modified shell-shell-core composite structure, the particle diameter of particle are 200～1000nm;
(4) or with ultrasonic being scattered in of yellow particles of the surperficial coated silica layer of step (2) preparation form suspending liquid in the acetonitrile, the quality consumption of acetonitrile is 30～50 times of yellow particles consumption; Under 50～70 ℃ of temperature, it is 3～4% succinic acid acetonitrile solution that acetonitrile is dissolved in succinic acid preparation mass concentration, in the succinic acid acetonitrile solution, add the yellow particles of surperficial coated silica layer and the suspending liquid of acetonitrile, the quality consumption of succinic acid acetonitrile solution is 30～50 times of yellow particles quality of surperficial coated silica shell, keep 70～80 ℃ of reaction time 20～25h of temperature then, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through 60 ℃ of vacuum drying of temperature, obtain having on silica shell laminar surface surface-yellow electrophoretic particle of the group modified shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm.
The invention has the advantages that procedure is simple, raw material is easy to get, and grain size and coated with silica layer thickness can be controlled by the consumption that changes raw material as required; The yellow electrophoretic particle of the shell-shell-core composite structure of prepared modification solvent resistance in nonpolar zellon dispersion medium is good, has excellent dispersion stability, and the particle shell surface has abundant-NH
2Or-the COOH charged functional groups, it is strong to be applied in the electric ink the charged ability of particle surface.
Embodiment
Example 1
Benzidine yellow G (C.I.Pigmeng Yellow 12) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, centrifuging goes out particle, obtains benzidine yellow G particle 1g after washing with ethanol.Benzidine yellow G particle 1g is transferred in the 100ml ethanol, adds the PVP of 5g, emulsification disperses 0.5h; Heating-up temperature to 70 ℃ adds 5ml ammoniacal liquor; Dropwise 5 g silester is dissolved in the solution of 50ml ethanol, drip 3h, keep 70 ℃ of reactions of temperature 12h, centrifuging goes out particle, with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the benzidine yellow G particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of benzidine yellow G particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent (for example calcium dodecyl benzene sulfonate etc.) and can make the particle surface positively charged.
Example 2
The method of the benzidine yellow G of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 12) particle is with example 1.In the ultrasonic 50ml of the being dispersed in acetonitrile of benzidine yellow G particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, successively with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add alkaline charge control agent (for example polyisobutenyl succinimide etc.) and can make particle surface electronegative.
Example 3
Benzidine yellow G (C.I.Pigmeng Yellow 12) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, the centrifuging particle obtains benzidine yellow G particle 1g after washing with deionized water.Benzidine yellow G particle 1g is transferred in the 100ml deionized water, adds the CTAB of 0.25g, emulsification disperses 0.5h; Heating-up temperature to 95 ℃ drips the solution that the 3g sodium silicate is dissolved in 50ml water, and the dilute sulfuric acid of Dropwise 5 mol/L control reaction pH drips 3h between 9～10, keeps 95 ℃ of reactions of temperature 8h; Regulate pH to 3 with the dilute sulfuric acid of 5mol/L then, keep 95 ℃ of temperature to continue reaction 3h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the benzidine yellow G particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of benzidine yellow G particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent and can make the particle surface positively charged.
Example 4
The method of the benzidine yellow G of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 12) particle is with example 3.In the ultrasonic 50ml of the being dispersed in acetonitrile of benzidine yellow G particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, and successively with the washing of deionized water, ethanol, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200.～1000nm, is dispersed in the zellon to add alkaline charge control agent and can make particle surface electronegative.
Example 5
Permanent yellow GR (C.I.Pigmeng Yellow 13) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, the centrifuging particle obtains permanent yellow GR particle 1g after washing with ethanol.1g is transferred in the 100ml ethanol with permanent yellow GR particle, adds the PVP of 5g, and emulsification disperses 0.5h; Heating-up temperature to 70 ℃ adds 5ml ammoniacal liquor; Dropwise 5 g silester is dissolved in the solution of 50ml ethanol, drip 3h, keep 70 ℃ of reactions of temperature 12h, centrifuging goes out particle, with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the permanent yellow GR particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of permanent yellow GR particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent and can make the particle surface positively charged.
Example 6
The method of the permanent yellow GR of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 13) particle is with example 5.In the ultrasonic 50ml of the being dispersed in acetonitrile of permanent yellow GR particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, and successively with the washing of deionized water, ethanol, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add alkaline charge control agent and can make particle surface electronegative.
Example 7
Permanent yellow GR (C.I.Pigmeng Yellow 13) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, the centrifuging particle obtains permanent yellow GR particle 1g after washing with deionized water.1g is transferred in the 100ml deionized water with permanent yellow GR particle, adds the CTAB of 0.25g, and emulsification disperses 0.5h; Heating-up temperature to 95 ℃ drips the solution that the 3g sodium silicate is dissolved in 50ml water, and the sulfuric acid of Dropwise 5 mol/L control reaction pH drips 3h between 9～10, keeps 95 ℃ of reactions of temperature 8h; Regulate pH to 3 with the dilute sulfuric acid of 5mol/L then, keep 95 ℃ of temperature to continue reaction 3h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the permanent yellow GR particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of permanent yellow GR particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent and can make the particle surface positively charged.
Example 8
The method of the permanent yellow GR of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 13) particle is with example 7.In the ultrasonic 50ml of the being dispersed in acetonitrile of permanent yellow GR particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, and successively with the washing of deionized water, ethanol, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add alkaline charge control agent and can make particle surface electronegative.
Example 9
Hansa yellow 100 (C.I.Pigmeng Yellow 3) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, the centrifuging particle obtains Hansa yellow 100 particle 1g after washing with ethanol.Hansa yellow 100 particle 1g is transferred in the 100ml ethanol, adds the PVP of 5g, emulsification disperses 0.5h; Heating-up temperature to 70 ℃ adds 5ml ammoniacal liquor; Dropwise 5 g silester is dissolved in the solution of 50ml ethanol, drip 3h, keep 70 ℃ of reactions of temperature 12h, centrifuging goes out particle, with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the Hansa yellow 100 particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of Hansa yellow 100 particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent and can make the particle surface positively charged.
Example 10
The method of the Hansa yellow 100 of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 3) particle is with example 9.In the ultrasonic 50ml of the being dispersed in acetonitrile of Hansa yellow 100 particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, and successively with the washing of deionized water, ethanol, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add alkaline charge control agent and can make particle surface electronegative.
Example 11
Hansa yellow 100 (C.I.Pigmeng Yellow 3) 1g is dispersed in the 50ml isopropyl alcohol soaks 24h, the centrifuging particle obtains Hansa yellow 100 particle 1g after washing with deionized water.Hansa yellow 100 particle 1g is transferred in the 100ml deionized water, adds the CTAB of 0.25g, emulsification disperses 0.5h; Heating-up temperature to 95 ℃ drips the solution that the 3g sodium silicate is dissolved in 50ml water, and the dilute sulfuric acid of Dropwise 5 mol/L control reaction pH drips 3h between 9～10, keeps 95 ℃ of reactions of temperature 8h; Regulate pH to 3 with the dilute sulfuric acid of 5mol/L then, keep 95 ℃ of temperature to continue reaction 3h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the Hansa yellow 100 particle 2g that the surface coats fine and close silica shell successively.In the mixed solution with the ultrasonic 90ml of the being dispersed in ethanol of Hansa yellow 100 particle 1g of the surperficial coated silica layer that makes and 10ml water; Add 0.5gKH-550, regulate pH=3 with the dilute sulfuric acid of 5mol/L, keep 80 ℃ of reactions of temperature 12h, centrifuging goes out particle, and with deionized water, ethanol washing, 60 ℃ of vacuum drying obtain the surface and have-NH successively
2The yellow electrophoretic particle 1.05g of the shell-shell-core composite structure of group, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add acid charge control agent and can make the particle surface positively charged.
Example 12
The method of the Hansa yellow 100 of the surperficial coated silica layer of this examples preparation (C.I.Pigmeng Yellow 3) particle is with example 11.In the ultrasonic 50ml of the being dispersed in acetonitrile of Hansa yellow 100 particle 1g with the surperficial coated silica layer that makes; Other gets the solution that the 5g succinic acid is dissolved in the 50ml acetonitrile, heating-up temperature to 60 ℃, treat that succinic acid dissolves the emulsion that the back adds particle and acetonitrile fully, keep 80 ℃ of reactions of temperature 30h, centrifuging goes out particle, and successively with the washing of deionized water, ethanol, 60 ℃ of vacuum drying obtain the surface and have-the yellow electrophoretic particle 1.1g of shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm, is dispersed in the zellon to add alkaline charge control agent and can make particle surface electronegative.
Claims (3)
1. the yellow electrophoretic particle of the shell-shell-core composite structure of a modification, the particle diameter of this electrophoresis particle is 200～1000nm, its core is a kind of among benzidine yellow G, permanent yellow GR and the Hansa yellow 100 or two kinds or three kinds, it is characterized in that, the shell of this yellow electrophoretic particle is a silicon dioxide, and silica surface has-NH
2Group or-the COOH group.
2. the method for the yellow electrophoretic particle of a shell-shell-core composite structure for preparing the described modification of claim 1 is characterized in that comprising following process:
(1) a kind of among benzidine yellow G, permanent yellow GR and the Hansa yellow 100 or two kinds or three kinds are dispersed in the isopropyl alcohol, the quality consumption of isopropyl alcohol is 20～30 times of yellow uitramarine consumption, and behind soak time 12～36h, centrifuging goes out particle, and wash particle with ethanol, make yellow particles;
(2) yellow particles that step (1) is made adds in the ethanol, the quality consumption of ethanol is 40～60 times of yellow particles consumption, in yellow particles and alcohol mixeding liquid, add polyvinylpyrrolidone again, the quality consumption of polyvinylpyrrolidone is 3～4 times of yellow particles consumption, emulsification jitter time 0.5～1h forms emulsion, with emulsion heating-up temperature to 55～60 ℃, adding quality is 3～4 times ammoniacal liquor of yellow particles consumption, and the dropping mass concentration is 30～40% silester ethanolic solution, the quality consumption of the silester that drips is 3～4 times of yellow particles quality, the dropping time is 3～5h, keep 55～60 ℃ of reaction time 8～12h of temperature then, go out particle through centrifuging, particle is washed with deionized water and ethanol successively, obtain the yellow particles of surperficial coated silica shell again through temperature 60 ℃ of vacuum drying;
(3) be to form suspending liquid in 85～90% the ethanol water with the yellow particles of the surperficial coated silica shell of step (2) preparation with the ultrasonic mass concentration that is scattered in, the quality consumption of ethanol water is 90～100 times of yellow particles quality of surperficial coated silica shell; In suspending liquid, add gamma-aminopropyl-triethoxy-silane again, the quality consumption of gamma-aminopropyl-triethoxy-silane is 0.2～0.4 times of yellow particles quality of surperficial coated silica shell, the dilute sulfuric acid adjusting pH that also adds 5mol/L in suspending liquid is 3, at 60～80 ℃ of reaction time 8～12h of temperature, go out particle through centrifuging, particle washed with ethanol with deionized water successively washs, again through temperature 60 ℃ of vacuum drying, obtain having-NH at the silica shell laminar surface
2The yellow electrophoretic particle of group modified shell-shell-core composite structure, the particle diameter of particle are 200～1000nm;
(4) or with ultrasonic being scattered in of yellow particles of the surperficial coated silica layer of step (2) preparation form suspending liquid in the acetonitrile, the quality consumption of acetonitrile is 30～50 times of yellow particles consumption; Under 50～70 ℃ of temperature, it is 3～4% succinic acid acetonitrile solution that acetonitrile is dissolved in succinic acid preparation mass concentration, in the succinic acid acetonitrile solution, add the yellow particles of surperficial coated silica layer and the suspending liquid of acetonitrile, the quality consumption of succinic acid acetonitrile solution is 30～50 times of yellow particles quality of surperficial coated silica shell, keep 70～80 ℃ of reaction time 20～25h of temperature then, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through 60 ℃ of vacuum drying of temperature, obtain having on silica shell laminar surface surface-yellow electrophoretic particle of the group modified shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm.
3. the method for the yellow electrophoretic particle of a shell-shell-core composite structure for preparing the described modification of claim 1 is characterized in that comprising following process:
(1) a kind of among benzidine yellow G, permanent yellow GR and the Hansa yellow 100 or two kinds or three kinds are dispersed in the isopropyl alcohol, the quality consumption of isopropyl alcohol is 20～30 times of yellow uitramarine consumption, and behind soak time 12～36h, centrifuging goes out particle, and wash particle with ethanol, make yellow particles;
(2) yellow particles that step (1) is made adds in the deionized water, the quality consumption of deionized water is 100～110 times of yellow particles consumption, in the emulsion of yellow particles and water, add cetyl trimethyl ammonium bromide again, the quality consumption of cetyl trimethyl ammonium bromide is 0.18～2.20 times of yellow particles consumption, and emulsification jitter time 0.5～1h forms emulsion; With emulsion heating-up temperature to 85～95 ℃, drip mass concentration and be the aqueous solution of 30～40% sodium silicate, the quality consumption of sodium silicate is 4～5 times of yellow particles quality, the reactant liquor of the dilute sulfuric acid of Dropwise 5 mol/L control simultaneously pH is 9～10, the dropping time is 2～3h, keeps 85～95 ℃ of reaction time 5～8h of temperature then; Dilute sulfuric acid conditioned reaction liquid pH with 5mol/L is 3 then, keep 85～95 ℃ of temperature to continue reaction 2～3h, go out particle through centrifuging, particle is washed with ethanol with deionized water successively washed, obtain the yellow particles of surperficial coated silica shell again through 60 ℃ of vacuum drying of temperature;
(3) be to form suspending liquid in 85～90% the ethanol water with the yellow particles of the surperficial coated silica shell of step (2) preparation with the ultrasonic mass concentration that is scattered in, the quality consumption of ethanol water is 90～100 times of yellow particles quality of surperficial coated silica shell; In suspending liquid, add gamma-aminopropyl-triethoxy-silane again, the quality consumption of gamma-aminopropyl-triethoxy-silane is 0.2～0.4 times of yellow particles quality of surperficial coated silica shell, the dilute sulfuric acid adjusting pH that also adds 5mol/L in suspending liquid is 3, at 60～80 ℃ of reaction time 8～12h of temperature, go out particle through centrifuging, particle washed with ethanol with deionized water successively washs, again through temperature 60 ℃ of vacuum drying, obtain having-NH at the silica shell laminar surface
2The yellow electrophoretic particle of group modified shell-shell-core composite structure, the particle diameter of particle are 200～1000nm;
(4) or with ultrasonic being scattered in of yellow particles of the surperficial coated silica layer of step (2) preparation form suspending liquid in the acetonitrile, the quality consumption of acetonitrile is 30～50 times of yellow particles consumption; Under 50～70 ℃ of temperature, it is 3～4% succinic acid acetonitrile solution that acetonitrile is dissolved in succinic acid preparation mass concentration, in the succinic acid acetonitrile solution, add the yellow particles of surperficial coated silica layer and the suspending liquid of acetonitrile, the quality consumption of succinic acid acetonitrile solution is 30～50 times of yellow particles quality of surperficial coated silica shell, keep 70～80 ℃ of reaction time 20～25h of temperature then, go out particle through centrifuging, particle washed with ethanol with deionized water successively wash, again through 60 ℃ of vacuum drying of temperature, obtain having on silica shell laminar surface surface-yellow electrophoretic particle of the group modified shell-shell-core composite structure of COOH, the particle diameter of particle is 200～1000nm.
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| CN102698668A (en) * | 2011-11-08 | 2012-10-03 | 京东方科技集团股份有限公司 | Electronic ink microcapsule and preparation method thereof |
| CN103540162A (en) * | 2012-07-17 | 2014-01-29 | 广州奥翼电子科技有限公司 | Method for preparing electrophoretic particles by using organic pigment |
| CN108059852A (en) * | 2017-09-20 | 2018-05-22 | 广州奥翼电子科技股份有限公司 | A kind of pigment particles and Electronphoretic display unit applied to electrophoresis showed |
| CN111643683A (en) * | 2020-06-17 | 2020-09-11 | 点靓纳谱(上海)生物医药科技有限公司 | Composite Raman probe and preparation method and application thereof |
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Cited By (8)
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| CN102641703A (en) * | 2011-05-27 | 2012-08-22 | 京东方科技集团股份有限公司 | Electronic ink microcapsule and preparation method thereof |
| CN102698668A (en) * | 2011-11-08 | 2012-10-03 | 京东方科技集团股份有限公司 | Electronic ink microcapsule and preparation method thereof |
| CN102698668B (en) * | 2011-11-08 | 2014-11-12 | 京东方科技集团股份有限公司 | Electronic ink microcapsule and preparation method thereof |
| CN103540162A (en) * | 2012-07-17 | 2014-01-29 | 广州奥翼电子科技有限公司 | Method for preparing electrophoretic particles by using organic pigment |
| CN108059852A (en) * | 2017-09-20 | 2018-05-22 | 广州奥翼电子科技股份有限公司 | A kind of pigment particles and Electronphoretic display unit applied to electrophoresis showed |
| CN108059852B (en) * | 2017-09-20 | 2019-12-03 | 广州奥翼电子科技股份有限公司 | A kind of pigment particles and Electronphoretic display unit applied to electrophoresis showed |
| CN111643683A (en) * | 2020-06-17 | 2020-09-11 | 点靓纳谱(上海)生物医药科技有限公司 | Composite Raman probe and preparation method and application thereof |
| CN115160825A (en) * | 2022-08-18 | 2022-10-11 | 亚士创能新材料(滁州)有限公司 | Modified yellow pigment and preparation method and application thereof |
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