CN116496663A - Quick-response electronic ink, preparation method and high-refresh-rate electrophoretic display device - Google Patents
Quick-response electronic ink, preparation method and high-refresh-rate electrophoretic display device Download PDFInfo
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- CN116496663A CN116496663A CN202310599147.6A CN202310599147A CN116496663A CN 116496663 A CN116496663 A CN 116496663A CN 202310599147 A CN202310599147 A CN 202310599147A CN 116496663 A CN116496663 A CN 116496663A
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- electronic ink
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- 230000004044 response Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 131
- 230000002378 acidificating effect Effects 0.000 claims abstract description 56
- 125000000524 functional group Chemical group 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000049 pigment Substances 0.000 claims description 37
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000004185 ester group Chemical group 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 11
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- -1 alkenyl succinimide Chemical compound 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229960002317 succinimide Drugs 0.000 claims description 6
- 239000012463 white pigment Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001962 electrophoresis Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 235000014692 zinc oxide Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000693 micelle Substances 0.000 abstract 1
- 239000002609 medium Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000012454 non-polar solvent Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 150000004028 organic sulfates Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- ZBNRGEMZNWHCGA-PDKVEDEMSA-N [(2r)-2-[(2r,3r,4s)-3,4-bis[[(z)-octadec-9-enoyl]oxy]oxolan-2-yl]-2-hydroxyethyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC ZBNRGEMZNWHCGA-PDKVEDEMSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09D11/52—Electrically conductive inks
-
- 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
- C09D11/03—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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
- G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The application belongs to the technical field of electronic display devices, and particularly relates to fast-response electronic ink, a preparation method and an electrophoretic display device with high refresh rate; according to the electronic ink, the electrophoretic particles in the electronic ink are modified electrophoretic particles connected with acidic and alkaline mixed groups, one functional group connected with the modified electrophoretic particles in the electronic ink promotes the proton transfer process of the other functional group and the reverse micelle to improve the charge capacity of the particles, and the response speed of the electronic ink is improved, so that the technical problem that the response speed of the electronic ink in the prior art is not high enough is solved.
Description
Technical Field
The application belongs to the technical field of electronic display devices, and particularly relates to fast-response electronic ink, a preparation method and an electrophoretic display device with high refresh rate.
Background
Increasing the charge of the electrophoretic particles in the electronic ink can improve the response speed of the electronic ink, and at present, the electrophoretic particles are usually modified by introducing functional groups such as amino groups, carboxyl groups, ester groups and the like to ensure that the electrophoretic particles are positively or negatively charged, and the surface charge of the modified particles obtained by the method is related to the number of the added functional groups and the inherent acid-base property of the functional groups, for example, the more acidic the introduced functional groups (such as the acidity ratio of-COOH functional groups to-CH 2 Stronger), the greater the number of functional groups introduced, the greater the effective acidity of the particle, the greater the negative charge on the particle surface, however, the enhancement of the charge capacity imparted to the particle surface is limited, which is related to the inherent acid-base nature of the introduced functional groups, and it is difficult to further increase the particle surface charge.
Therefore, in the prior art, the surface charge amount of the electrophoretic particle charge amount in the electronic ink is limited, so that the response speed of the electronic ink needs to be improved.
Disclosure of Invention
In view of this, the present application provides fast-response electronic ink, a preparation method thereof and a high-refresh rate electrophoretic display device, which are used for solving the technical problem that the response speed of the electronic ink is not high enough in the prior art.
A first aspect of the present application provides a fast-response electronic ink comprising modified electrophoretic particles, a charge control agent, and an electrophoretic medium;
the surface of the modified electrophoretic particle is simultaneously connected with an acidic group and a basic group;
the introduction density of the acid groups is 1-300 mmol/cm 3 The introduction density of the alkaline groups is 0.5-150 mmol/cm 3 。
Preferably, the acidic groups include acidic groups containing ester groups and/or carboxyl groups, the acidic groups having an incorporated density of 5.96 to 39.19mmol/cm 3 ；
The basic groups comprise amino-containing basic groups, and the introduction density of the basic groups is 3.41-37.49mmol/cm 3 。
The density of the introduced groups is the number of moles of the basic or acidic groups introduced per unit volume of the particle surface.
Preferably, the acidic group and the basic group are connected through chemical bonding, and the basic group is connected through physical adsorption;
the chemically bonding means for attaching the acidic groups includes attaching the acidic groups via a silane coupling agent and/or a polymer monomer.
Preferably, the acidic group and the basic group are connected through chemical bonding, and the acidic group is connected through physical adsorption;
the chemically bonding to the basic group includes bonding the basic group via a silane coupling agent and/or a polymer monomer.
Preferably, the acidic groups include gamma-methacryloxypropyl trimethoxysilane and methacrylate;
the basic group comprises a mono alkenyl succinimide.
Preferably, the basic groups include gamma-aminopropyl triethoxysilane and aminostyrene;
the acidic group comprises polyoxyethylene sorbitan monooleate.
Preferably, the modified electrophoretic particles are modified white pigment particles;
the white pigment particles are modified titanium dioxide, silicon dioxide, zinc white or aluminum oxide particles.
The particle size of the modified white pigment particles is 200-1000 nm.
Preferably, the electrophoretic medium is a non-polar solvent;
the nonpolar solvent is selected from one or more of halohydrocarbon, paraffin, silicone oil, alkane compound, epoxy compound, aromatic hydrocarbon and vinyl ether.
Preferably, the charge control agent is selected from one or more of organic sulfonates, organic sulfates, organic phosphates, polyesters, polyolefins, polyacrylate charge control agents.
The second aspect of the present application provides a method for preparing a fast-responding electronic ink, the method comprising the steps of:
step S1, dispersing pigment particles with hydroxyl groups on the surfaces, a silane coupling agent with acidic functional groups and a silane coupling agent with unsaturated bonds in a first solvent for a coupling reaction to obtain modified pigment particles;
s2, dispersing modified pigment particles, a polymer monomer containing an acidic functional group and an initiator in a second solvent for grafting reaction to obtain acidic modified pigment particles;
step S3, ball milling is carried out on the acid modified pigment particles and the synergist containing the alkaline groups, so as to obtain the electrophoresis particles with the surfaces connected with the acid groups and the alkaline groups;
and S4, preparing the electrophoretic particles, the charge control agent and the electrophoretic medium into electronic ink.
The third aspect of the present application provides a method for preparing an electronic ink with a rapid response, the method comprising the steps of:
step S11, dispersing pigment particles with hydroxyl groups on the surfaces, a silane coupling agent with basic functional groups and a silane coupling agent with unsaturated bonds in a first solvent for a coupling reaction to obtain modified pigment particles;
step S12, dispersing modified pigment particles, a polymer monomer containing an alkaline functional group and an initiator in a second solvent for grafting reaction to obtain alkaline modified pigment particles;
step S13, ball milling is carried out on the alkaline modified pigment particles and the synergist containing the acidic groups, so as to obtain modified electrophoretic particles with the surfaces connected with the acidic groups and the alkaline groups;
step S14, preparing the modified electrophoretic particles, the charge control agent and the electrophoretic medium into electronic ink.
Preferably, in step S1 and step S11, the first solvent is selected from absolute ethanol;
the unsaturated bond-containing silane coupling agent is selected from vinyl trimethoxy silane and vinyl triethoxy silane;
preferably, in the step S1 and the step S11, in the coupling reaction, the mass ratio of the pigment particles having hydroxyl groups on the surface, the first solvent, the silane coupling agent having acidic functional groups, and the silane coupling agent having unsaturated bonds is 1: 20-30: 0.5 to 2: 0.5-2, and the time is 12-36 h.
Preferably, the coupling reaction further comprises adding a surfactant;
the surfactant is selected from sodium dodecyl benzene sulfonate;
the mass ratio of the pigment particles with the surface containing hydroxyl to the surfactant is 1:0.015 to 0.025.
Preferably, in step S2 and step S12, the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide or dicumyl peroxide.
The second solvent is selected from toluene, benzene, xylene, chloroform or tetrachloroethylene.
Preferably, in the step S3 and the step S13, the ball milling container is a ball milling tank, and the ball milling time is 1-8 hours; the ball milling solvent is straight chain, branched chain and cyclic aliphatic hydrocarbon of carbon tetrachloride, n-hexane, nonane, sunflower alkane, synthetic isoparaffin, synthetic paraffin, synthetic cycloparaffin, synthetic alkane or cyclohexane.
Preferably, in step 4 and step S14, the electrophoretic medium comprises a nonpolar solvent.
It should be noted that, in addition to the nonpolar solvent as the dispersion medium, other conventional additives may be added to the electrophoretic medium in the electronic ink as required.
A fourth aspect of the present application provides a high refresh rate electrophoretic display device comprising a microcavity encapsulating the electronic ink described above.
Preferably, the electrophoretic display device may be used as an electronic book, bus stop board, shelf label, or smart wearable application.
It should be noted that, the structure of the electrophoretic display device in the present application is the structure of the conventional electrophoretic display device, and because the microcavity attached to the surface of the electrophoretic display device and playing a display function in the present application is encapsulated with the electronic ink with a fast response speed, the refresh rate of the electrophoretic display device is improved, and the electrophoretic display device with low power consumption and fast refresh display is obtained.
In summary, the application provides the fast-response electronic ink, the preparation method and the high-refresh rate electrophoretic display device, wherein the fast-response electronic ink comprises a dispersion medium and modified electrophoretic particles, and the surfaces of the modified electrophoretic particles are connected with acidic groups and basic groups through charged functional groups of chemically bonded small molecules, so that the particles are endowed with larger charging potential. Meanwhile, the charge control agent of macromolecules in the electronic ink is also introduced to the particle surface by physical adsorption. The meaning of such modification is: the acidic (or alkaline) functional groups can promote the proton transfer process between the alkaline (or acidic) functional groups and the charge control agent in the electrophoretic fluid, so that the effective pH value of the particle surface is improved, and the particles are provided with more charges, namely, the mixed groups are connected to the surface of the electrophoretic particles, so that one functional group promotes the proton transfer process between the other functional group and the charge control agent in the electrophoretic fluid to improve the charge capacity of the particles.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a preparation flow of modified electrophoretic particles in electronic ink provided in embodiment 2 of the present application;
FIG. 2 is a schematic diagram of the electronic ink response test results provided in examples 2 and 4 of the present application;
FIG. 3 is a schematic diagram of the electronic ink response test results provided in examples 3 and 5 of the present application;
in the figure, 11 is pigment particles, 12 is silane-coupled particles containing acidic groups, 13 is particles coated with a polymer containing acidic functional groups, and 14 is particles coated with a synergist containing basic groups.
Detailed Description
The application provides fast-response electronic ink, a preparation method and a high-refresh rate electrophoretic display device, which are used for solving the technical problem that the response speed of the electronic ink is not high enough in the prior art.
The following description of the embodiments of the present application will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
In view of the defects that the effective pH value of electrophoretic particles in the existing electronic ink is low, the surface charge is low, and the response speed of the electronic ink is relatively slow, embodiment 1 of the application provides the electronic ink, wherein the electronic ink comprises an electrophoretic medium, a charge control agent and modified electrophoretic particles, the electrophoretic medium is the electrophoretic medium of the existing electronic ink, the electrophoretic medium comprises a nonpolar solvent, the nonpolar solvent is selected from solvents such as common halogenated hydrocarbon, paraffin, silicone oil, alkane compounds, epoxy compounds, aromatic hydrocarbons, vinyl ethers and the like, the charge control agent is one or more of common charge control agents selected from organic sulfonates, organic sulfates, organic phosphates, organic phosphate esters, polyesters, polyolefin and polyacrylate charge control agents, and the modified electrophoretic particles are electrophoretic particles with surfaces connected with acidic groups and alkaline groups; compared with the conventional electrophoretic ink preparation process, the method has the advantages that in the electrophoretic ink preparation process, the acidic or alkaline charge control agent is dropwise added into the solution, and the charge control agent of macromolecules is introduced to the surface of particles in a physical adsorption mode to enable the particles to be charged, the electrophoretic particles connected with the acidic groups and the alkaline groups are in the electrophoretic liquid, one functional group (acidic) can promote the proton transfer process between the other functional group (alkaline) and the charge control agent in the electrophoretic liquid, so that the electrophoretic particles further have more charges, and in addition, the charge control agent of macromolecules in electronic ink in the electronic ink is also introduced to the surface of the particles in a subsequent physical adsorption mode, so that the modified electrophoretic particles have higher response speed in the electronic ink, and the defect of slower response speed of the electronic ink is overcome.
Preferably, the acidic group comprises an acidic group comprising an ester group and/or a carboxyl group, and the basic group comprises a basic group comprising an amino group; the acid group containing the ester group and/or the carboxyl group comprises a silane coupling agent containing the ester group and/or the carboxyl group and a polymer monomer containing the ester group and/or the carboxyl group; after the silane coupling agent containing ester groups and/or carboxyl groups is chemically bonded on the electrophoretic particles through coupling reaction, polymer monomers containing the ester groups and/or carboxyl groups are grafted on the electrophoretic particles through grafting reaction, and finally synergists such as alkaline groups containing amino groups are physically adsorbed on the electrophoretic particles through ball milling, so that modified electrophoretic particles with the surfaces connected with the acidic groups and the alkaline groups are obtained; in the technical scheme, silane coupling agents such as gamma-methacryloxypropyl trimethoxy silane and the like are preferably connected on the surfaces of the electrophoretic particles through chemical bonding and physical adsorption, and polymer monomers containing groups such as acrylic acid, methacrylic acid, sulfonic acid groups, ether bonds and the like and synergists such as mono alkenyl succinimide (T-151) or sorbitan trioleate (Span 85) and the like; of course, the electrophoretic particles are connected with other silane coupling agents containing acidic or basic groups and polymer monomers through chemical bonding and physical adsorption, and synergists containing acidic or basic groups are all within the protection scope of the patent.
Preferably, the present application also provides an alternative technical solution, wherein the amino-containing basic group comprises an amino-containing silane coupling agent and an amino-containing polymer monomer, and the acidic group comprising an ester group and/or a carboxyl group comprises a synergist comprising an ester group and/or a carboxyl group; in the technical scheme, the surface of the electrophoresis particle is preferably connected with silane coupling agents such as gamma-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane, polymer monomers such as aminostyrene, and synergists such as polyoxyethylene sorbitan monooleate (Span 80) or succinimide (OLOA 11000) through chemical bonding and physical adsorption; of course, the electrophoretic particles are connected with other silane coupling agents containing alkaline groups and polymer monomers and synergists containing acidic groups through chemical bonding and physical adsorption, and the electrophoretic particles are all within the protection scope of the patent.
Preferably, the modified electrophoretic particles are modified with white pigment particles containing a large number of hydroxyl groups on the surface, such as titanium dioxide, silicon dioxide, zinc white, or aluminum oxide, as a matrix.
Example 2
Embodiment 2 of the present application provides a method for preparing the electronic ink described in embodiment 1, where the method includes preparing modified electrophoretic particles and preparing the modified electrophoretic particles, the charge control agent and the electrophoretic medium into the electronic ink, and the process of preparing the modified electrophoretic particles and the electrophoretic medium into the electronic ink is the same as the process of preparing the conventional electrophoretic particles and the electrophoretic medium into the electronic ink, and the electronic ink composition used in the present application includes Isopar-G and modified electrophoretic particles containing 3.0% aot, and the method for preparing the modified electrophoretic particles specifically includes a coupling reaction step, a grafting reaction step and a ball milling reaction step.
The coupling reaction steps include: hydroxyl group-containing pigment particles, such as titanium dioxide pigment particles having a large number of hydroxyl groups on the surface, are dispersed in absolute ethanol, the mass of which is 20 to 30 times the amount of the titanium dioxide pigment particles, an acid group-containing silane coupling agent, such as gamma-methacryloxypropyl trimethoxysilane, is added thereto, the amount of gamma-methacryloxypropyl trimethoxysilane is 0.5 to 2 times the amount of the particles, and vinyl trimethoxysilane having the same mass as gamma-methacryloxypropyl trimethoxysilane is added thereto, a surfactant SDBS is added during stirring, the amount of the surfactant SDBS is 0.015 to 0.025 times the amount of the particles, and after stirring for 12 to 36 hours, the mixture is centrifuged and washed a plurality of times and dried to obtain modified pigment particles.
The grafting reaction steps include: the modified pigment particles are dispersed in toluene which is a low-polarity dispersion solvent and has a mass 5 to 15 times that of the modified pigment particles, a polymer monomer containing an acidic functional group such as a polymer monomer methacrylic acid containing an acidic group such as an ester group or a carboxyl group is added to the solution in an amount of 0.5 to 2 times that of the particles, and a surfactant SDBS is added thereto to raise the temperature to 70 to 110 ℃. And (3) dropwise adding toluene (the dosage of the initiator is 0.05 times of that of the modified pigment particles) serving as a low-polarity solvent containing AIBN after stirring for 15-30 min, stirring the mixture for 5-24 hours by using a stirrer, performing the whole reaction in an inert atmosphere, finally, filtering the reaction mixture after the temperature of a reactant container is reduced to room temperature, washing the reaction mixture with the low-polarity solvent for a plurality of times, and drying to obtain the acid modified pigment particles chemically bonded and connected to the titanium dioxide pigment particles.
The ball milling reaction steps comprise: dispersing acid modified pigment particles in nonpolar solvent carbon tetrachloride in an amount of 1-10 times that of the acid modified pigment particles, placing the mixture containing the acid modified pigment particles in a ball milling tank, adding ball milling beads, additionally introducing a large amount of groups on the surfaces of the acid modified pigment particles by ball milling, ball milling the acid modified pigment particles and a synergist containing alkaline groups such as an amino group-containing alkaline functional group-containing synergist monoalkenyl succinimide together for 1-8 hours to prepare a particle dispersion, so as to generate sufficiently close contact between the synergist and the particles, thereby enabling sufficient amount of the synergist monoalkenyl succinimide to be physically adsorbed on the surfaces of the particles, and then centrifugally drying to obtain chemical bonding and physical adsorption connection of 7.8 millimoles/cubic centimeter (surface of particles per unit volume) of acid groups (-COOH) and 7.5 millimoles/cubic centimeter (surface of particles per unit volume) of alkaline groups (-NH) 2 ) Is a modified electrophoretic particle of (a).
Example 3
Example 3 of the present application provides another method of preparing the electronic ink described in example 1, which differs from example 2 in that the electronic ink uses an electrophoretically-mediated Isopa comprising 3.0% span85r-G, modified electrophoretic particles used in electronic ink are chemically bonded and physically adsorbed to connect 6.8 mmol/cc (surface per unit volume of particles) of acidic groups (-COOH) and 8.1 mmol/cc (surface per unit volume of particles) of basic groups (-NH) 2 )。
Example 4
Example 4 of the present application provides another preparation method of electronic ink, which is different from example 2 in that the ball milling reaction step is not included, the electrophoretic particles are modified through the coupling reaction step and the grafting reaction step, and 9.2 millimoles per cubic centimeter (per volume of particle surface) of acid groups (-COOH) are chemically bonded to the electrophoretic particles.
Example 5
Example 5 of the present application provides another preparation method of electronic ink, which is different from example 3 in that the ball milling reaction step, the coupling reaction step and the grafting reaction step are not included to modify the electrophoretic particles, and the obtained electrophoretic particles are chemically bonded with 8.8 millimoles per cubic centimeter (per volume of particle surface) of acidic groups (-NH) 2 )。
Experimental example 1
Experimental example 1 of the present application was used to test the response speed of the electronic ink provided in examples 2-5, package the electronic ink into the microcavity of the electronic paper electrophoretic display device, and then test the performance of the electronic paper electrophoretic display device packaged with the electronic ink provided in examples 2-5, as shown in Table 1 and FIGS. 2-3.
As can be seen from fig. 2-3, compared with the electronic paper encapsulated with the electronic ink provided in embodiment 4-5, the electronic paper encapsulated with the electronic ink provided in embodiment 2-3 has a faster response speed in white state and a faster response speed in disappearance of white state, which indicates that the electrophoretic particles connected with the acidic and alkaline mixed functional groups have a stronger charge capacity, so that the electronic ink has a faster response and migration rate in the electrophoretic display device, and the refresh rate of the electronic paper encapsulated with the electronic ink provided in embodiment 2-3 is greatly improved, thereby providing the electrophoretic display device with low power consumption and fast refresh display.
TABLE 1
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A fast-response electronic ink comprising modified electrophoretic particles, a charge control agent, and an electrophoretic medium;
the surface of the modified electrophoretic particle is simultaneously connected with an acidic group and a basic group;
the introduction density of the acid groups is 1-300 mmol/cm 3 The introduction density of the alkaline groups is 0.5-150 mmol/cm 3 。
2. The quick response electronic ink according to claim 1, wherein the acidic groups comprise acidic groups containing ester groups and/or carboxyl groups, the acidic groups having an incorporated density of 5.96-39.19 mmol/cm 3 ；
The basic group comprises an amino-containing basic group, and the introduction density of the basic group is 3.41-37.49 mmol/cm 3 。
3. A fast response electronic ink according to claim 2 wherein said acidic groups comprise gamma methacryloxypropyl trimethoxysilane and methacrylate;
the basic group comprises a mono alkenyl succinimide.
4. A fast response electronic ink according to claim 2 wherein said basic groups include gamma-aminopropyl triethoxysilane and aminostyrene;
the acidic group comprises polyoxyethylene sorbitan monooleate.
5. The fast response electronic ink according to claim 1, wherein said modified electrophoretic particles are modified white pigment particles;
the white pigment particles are modified titanium dioxide, silicon dioxide, zinc white or aluminum oxide particles.
6. The quick response electronic ink of claim 1 wherein the linking of the acidic groups to the basic groups is by chemical bonding and by physical adsorption;
the chemically bonding means for attaching the acidic groups includes attaching the acidic groups via a silane coupling agent and/or a polymer monomer.
7. The quick response electronic ink of claim 1 wherein the linking of the acidic groups to the basic groups is by chemical bonding and by physical adsorption;
the chemically bonding to the basic group includes bonding the basic group via a silane coupling agent and/or a polymer monomer.
8. A method of preparing a fast response electronic ink according to any one of claims 1-6, comprising the steps of:
step S1, dispersing pigment particles with hydroxyl groups on the surfaces, a silane coupling agent with acidic functional groups and a silane coupling agent with unsaturated bonds in a first solvent for a coupling reaction to obtain modified pigment particles;
s2, dispersing modified pigment particles, a polymer monomer containing an acidic functional group and an initiator in a second solvent for grafting reaction to obtain acidic modified pigment particles;
step S3, ball milling is carried out on the acid modified pigment particles and the synergist containing the alkaline groups, so as to obtain the electrophoresis particles with the surfaces connected with the acid groups and the alkaline groups;
and S4, preparing the electrophoretic particles, the charge control agent and the electrophoretic medium into electronic ink.
9. A method of preparing a fast response electronic ink according to any one of claims 1-5 or claim 7, comprising the steps of:
step S11, dispersing pigment particles with hydroxyl groups on the surfaces, a silane coupling agent with basic functional groups and a silane coupling agent with unsaturated bonds in a first solvent for a coupling reaction to obtain modified pigment particles;
step S12, dispersing modified pigment particles, a polymer monomer containing an alkaline functional group and an initiator in a second solvent for grafting reaction to obtain alkaline modified pigment particles;
step S13, ball milling is carried out on the alkaline modified pigment particles and the synergist containing the acidic groups, so as to obtain modified electrophoretic particles with the surfaces connected with the acidic groups and the alkaline groups;
step S14, preparing the modified electrophoretic particles, the charge control agent and the electrophoretic medium into electronic ink.
10. An electrophoretic display device with a high refresh rate, comprising microcavities encapsulating the electronic ink according to any one of claims 1 to 7 or the electronic ink prepared by the preparation method according to any one of claims 8 to 9.
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| CN202310599147.6A CN116496663B (en) | 2023-05-25 | Quick-response electronic ink, preparation method and high-refresh-rate electrophoretic display device |
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| CN202310599147.6A CN116496663B (en) | 2023-05-25 | Quick-response electronic ink, preparation method and high-refresh-rate electrophoretic display device |
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