CN114181694A - Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof - Google Patents

Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof Download PDF

Info

Publication number
CN114181694A
CN114181694A CN202111510969.XA CN202111510969A CN114181694A CN 114181694 A CN114181694 A CN 114181694A CN 202111510969 A CN202111510969 A CN 202111510969A CN 114181694 A CN114181694 A CN 114181694A
Authority
CN
China
Prior art keywords
sio
particles
electronic paper
red fluorescent
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111510969.XA
Other languages
Chinese (zh)
Other versions
CN114181694B (en
Inventor
吴明娒
洪俊宇
周磊
陈颖源
陈军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Yat Sen University
Original Assignee
Sun Yat Sen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sun Yat Sen University filed Critical Sun Yat Sen University
Priority to CN202111510969.XA priority Critical patent/CN114181694B/en
Publication of CN114181694A publication Critical patent/CN114181694A/en
Application granted granted Critical
Publication of CN114181694B publication Critical patent/CN114181694B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/77922—Silicates
    • 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
    • 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
    • G02F1/1675—Constructional details
    • G02F2001/1678—Constructional details characterised by the composition or particle type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Luminescent Compositions (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

The invention discloses red fluorescence electrophoresis particles for electronic paper and a preparation method and application thereof, wherein the red fluorescence electrophoresis particles have a core-shell structure, and the core is a hollow Y2‑ xEuxSiO5Wherein x is more than or equal to 0.001<2, the shell is SiO with a surface grafted with a polymer2，Y2‑xEuxSiO5With SiO2In a molar ratio of 1: (0.01-2). The red fluorescence electrophoresis particle of the invention is hollow Y2‑xEuxSiO5As core, the core can emit red fluorescence under ultraviolet excitation, and the core Y2‑xEuxSiO5Is inorganic, and makes the particles have higher chemical stability and good weather resistance, and the surface grafted polymer can be in the presence ofA space barrier is formed in the organic electrophoresis medium, the suspension stability of the particles in the electrophoresis liquid is improved, and the organic electrophoresis medium can be used for preparing colored electronic paper.

Description

Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrophoretic particles, in particular to a red fluorescent electrophoretic particle for electronic paper and a preparation method and application thereof.
Background
The electronic paper is a novel display, and compared with the traditional liquid crystal display, a light-emitting diode display, an organic light-emitting diode display and the like, the electronic paper has the advantages of wide viewing angle, energy conservation, environmental protection, light weight, easiness in carrying, easiness in realizing flexible display and the like, is popular with consumers and has huge market prospect. The current commercialized electronic paper products mainly have black and white displays, and are difficult to meet the needs of people. In order to expand the application field of electronic paper and enhance the reading experience of consumers, colorization of electronic paper has become a research hotspot.
At present, color electronic paper generally adopts a filter scheme or a color multi-particle scheme. The scheme of the optical filter is that a layer of optical filter is covered on the traditional black-and-white electronic paper; and the color multi-particle scheme uses three or more electrophoretic particles to realize a multi-color display. However, the filter may reduce brightness and saturation of the electronic paper, and the multi-particle scheme requires a complicated technique to precisely control movement of various particles of different colors and charges.
Disclosure of Invention
The invention aims to overcome the defect or deficiency that an optical filter or a color multi-particle scheme is needed after the conventional electrophoretic particles and black particles are prepared into an electrophoretic solution, and provides red fluorescent electrophoretic particles for electronic paper.
The invention also aims to provide a preparation method of the red fluorescent electrophoretic particles for the electronic paper.
It is a further object of the present invention to provide the use of said red fluorescent electrophoretic particles.
The above object of the present invention is achieved by the following technical solutions:
the red fluorescence electrophoresis particle for the electronic paper has a core-shell structure, wherein the core is a hollow Y2-xEuxSiO5Wherein x is more than or equal to 0.001<2, the shell is surface graftedSiO of polymer2，Y2-xEuxSiO5With SiO2In a molar ratio of 1: (0.01-2).
The red fluorescence electrophoresis particle of the invention is white and is hollow Y2-xEuxSiO5(wherein 0.001. ltoreq. x<2) As a core, the core can emit red fluorescence under the excitation of ultraviolet rays, and after the core is prepared into an electrophoretic solution with commercial black particles, the electronic paper product can display black and white under a non-excited state and red under an excited state by using a double-particle scheme under the condition that an optical filter is not needed, so that the defects or the defects of the optical filter or a color multi-particle scheme can be overcome. At the same time, core Y2-xEuxSiO5(wherein 0.001. ltoreq. x<2) The polymer grafted on the surface can form a space barrier in the organic electrophoresis medium, and the suspension stability of the particles in an electrophoresis solution is improved.
Preferably, the core is hollow Y2-xEuxSiO5Wherein x is more than or equal to 0.01 and less than or equal to 1. Too low a concentration of Eu will result in lower luminescence intensity, and too high a concentration will result in a decrease in luminescence intensity due to quenching.
The particle size of the electrophoretic particles is 200-400 nm.
The polymer is selected from one or more of polystyrene, polylauryl methacrylate and polymethyl methacrylate.
The silane coupling agent is selected from one or more of KH550, KH560 and KH 570.
The invention also provides a preparation method of the red fluorescent electrophoretic particles for the electronic paper, which comprises the following steps:
s1, adding a mixed solution of yttrium salt and europium salt into a urea aqueous solution, stirring, performing water bath reaction at 60-95 ℃ for 2-6 h, and performing post-treatment to obtain Y2-xEuxOHCO3Particles; the molar ratio of yttrium element in yttrium salt to europium element in europium salt is (2-x): x, wherein 0.001 ≤x＜2；
S2, mixing Y2-xEuxOHCO3Dispersing the particles in an alcohol solution, adding tetraethoxysilane, adding ammonia water to adjust the pH value to be alkaline, stirring for 2-8 h, and performing post-treatment to obtain the surface-coated SiO2Y of (A) is2-xEuxOHCO3Roasting the particles at 800-1100 ℃ for 4-10 h to obtain hollow Y-shaped particles with cores2-xEuxSiO5The shell is SiO2The spherical particles of (1);
s3, mixing Y2-xEuxSiO5@SiO2Dispersing the spherical particles in an alcohol solution, adding ammonia water and a silane coupling agent, reacting for 2-6 h at 30-60 ℃, and performing post-treatment to obtain Y2-xEuxSiO5@SiO2-silane coupling agent particles;
s4, mixing Y2-xEuxSiO5@SiO2Mixing silane coupling agent particles, polymer monomers, an initiator and a solvent, reacting for 8-48 h at the temperature of 60-90 ℃ in an inert atmosphere, and performing post-treatment to obtain the red fluorescence electrophoresis particles.
Preferably, in step S1, the concentration of the urea aqueous solution is 10-40 g/L, and the concentration of the mixed solution of yttrium salt and europium salt is 0.005-2 mol/L.
The alcohol solution is an ethanol or methanol water solution, and the alcohol-water ratio is (5-50): 1.
preferably, in step S2, Y is2-xEuxOHCO3The solid-liquid ratio of the particles to the alcoholic solution is 0.5-10 g/L, and the volume ratio of the ethyl orthosilicate to the alcoholic solution is 40-120 mL/L.
Preferably, in step S3, the volume ratio of the silane coupling agent to the alcohol solution is (1-20): 100.
preferably, in step S3, Y is2-xEuxSiO5@SiO2The solid-to-liquid ratio of the spherical particles to the alcohol solution is 50-300 g/L.
Preferably, in step S4, Y is2-xEuxSiO5@SiO2The solid-liquid ratio of the silane coupling agent particles to the solvent is 50-300 g/L.
Preferably, in step S4, the solid-to-liquid ratio of the polymer monomer to the solvent is 100-600 g/L.
The yttrium salt and the europium salt of the invention are selected from the conventional rare earth salts in the field.
Preferably, the yttrium salt is selected from one or more of yttrium nitrate, yttrium acetate and yttrium chloride.
Preferably, the europium salt is selected from one or more of europium nitrate, europium acetate and europium chloride.
In the invention, the adding speed of the initiator cannot be too high, otherwise, the polymerization reaction is too high, the grafted molecular chain is too short, and the particles are easy to agglomerate.
Preferably, the step S4 is: will Y2-xEuxSiO5@SiO2Mixing silane coupling agent particles, polymer monomers and a solvent, dripping an initiator solution at the temperature of 60-90 ℃ at the speed of 1-10 mL/min under the protection of inert atmosphere, reacting for 8-48 h, and performing post-treatment to obtain the red fluorescence electrophoresis particles.
The initiator is an organic peroxide initiator or an inorganic peroxide initiator;
the organic peroxide initiator is acyl peroxide, hydroperoxide, dialkyl peroxide, ester peroxide, ketone peroxide or dicarbonate peroxide;
the inorganic peroxide initiator is potassium persulfate, sodium persulfate, ammonium persulfate or azo initiator.
Preferably, the initiator is an azo-type initiator, such as azobisisobutyronitrile or azobisisoheptonitrile.
Preferably, the inert atmosphere is a nitrogen atmosphere and/or an argon atmosphere.
The polymer monomer is selected from one or more of styrene, lauryl methacrylate and methyl methacrylate.
The post-treatment of the invention comprises centrifugation and drying in turn. In particular, centrifugation and drying at 80 ℃ for 6 h.
The solvent of the invention is selected from the conventional solvents in the field. Preferably, the solvent is toluene.
An electrophoretic fluid comprises the red fluorescent electrophoretic particles and black particles.
The invention also protects the application of the red fluorescent electrophoretic particles in the preparation of electronic paper.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides red fluorescent electrophoretic particles for electronic paper, which are white in body color and are hollow Y2-xEuxSiO5(wherein 0.001. ltoreq. x<2) As a core, the core can emit red fluorescence under the excitation of ultraviolet rays, and after the core is prepared into an electrophoretic solution with commercial black particles, the electronic paper product can display black and white under a non-excited state and red under an excited state only by using a double-particle scheme under the condition that an optical filter is not needed, so that the defects of the optical filter scheme and the multi-particle scheme are overcome.
2. Core Y of the red fluorescence electrophoresis particle2-xEuxSiO5(wherein 0.001. ltoreq. x<2) The organic dye is inorganic, has high chemical stability, is not influenced by the swelling effect of organic electrophoresis media, has stronger weather resistance than organic dyes, and prolongs the service life of the color electrophoresis particles.
3. The red fluorescence electrophoresis particle has a hollow structure, is low in density, has monodispersity and regular appearance, and is a sphere of 200-400 nm. Meanwhile, the polymer grafted on the surface can form a space barrier in an organic electrophoresis medium, so that the suspension stability of the particles in an electrophoresis solution is improved.
Drawings
FIG. 1 is a TEM image of the red fluorescent electrophoretic particles prepared in example 1.
FIG. 2 is a scanning electron microscope photograph of the red fluorescent electrophoretic particles prepared in example 1.
FIG. 3 is an X-ray diffraction pattern of the red fluorescent electrophoretic particles prepared in example 1.
FIG. 4 is an emission spectrum of the red fluorescent electrophoretic particles prepared in example 1 under the excitation of ultraviolet rays at 393 nm.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.92Eu0.08OHCO3Particles;
s2, mixing 5g Y1.92Eu0.08OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.92Eu0.08OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.92Eu0.08SiO5@SiO2Spherical particles;
s3, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 260mL silane coupling agent KH570, reacting at 50 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.92Eu0.08SiO5@SiO2-KH570 particles;
s4, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L of toluene into KH570 particles, adding 300g of lauryl methacrylate, stirring under nitrogen atmosphere for 1h, heating to 80 deg.C, adding 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution at 5mL/minDropping into the system at the speed of (1), reacting for 40h under the protection of nitrogen, centrifuging and drying at 80 ℃ to obtain the red fluorescence electrophoresis particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.92Eu0.08SiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，Y1.92Eu0.08SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 2
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.92Eu0.08OHCO3Particles;
s2, mixing 5g Y1.92Eu0.08OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.92Eu0.08OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.92Eu0.08SiO5@SiO2Spherical particles;
s3, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 25mL ammonia water with mass fraction of 25% and 250mL silane coupling agent KH560, reacting at 50 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.92Eu0.08SiO5@SiO2-KH560 particles.
S4, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L of toluene into KH560 particles, adding 300g of lauryl methacrylate, stirring under nitrogen atmosphere for 1h, heating to 80 deg.C, mixing150mL of 0.02g/mL azobisisobutyronitrile/toluene solution is dripped into the system at the speed of 5mL/min, reacts for 40 hours under the protection of nitrogen, and is centrifuged and dried at 80 ℃ to obtain red fluorescent electrophoretic particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.92Eu0.08SiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，Y1.92Eu0.08SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 3
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.92Eu0.08OHCO3Particles;
s2, mixing 5g Y1.92Eu0.08OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.92Eu0.08OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.92Eu0.08SiO5@SiO2Spherical particles;
s3, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 200mL KH550 of silane coupling agent, reacting at 40 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.92Eu0.08SiO5@SiO2-KH550 particles.
S4, 150g Y1.92Eu0.08SiO5@SiO2KH550 particles were mixed with 1L of toluene, 200g of styrene were added, and the mixture was stirred under a nitrogen atmosphereStirring for 1h, heating to 85 ℃, dripping 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 5mL/min, reacting for 36h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescent electrophoretic particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.92Eu0.08SiO5The shell is SiO with polystyrene grafted on the surface2，Y1.92Eu0.08SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 4
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.92Eu0.08OHCO3Particles;
s2, mixing 5g Y1.92Eu0.08OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.92Eu0.08OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.92Eu0.08SiO5@SiO2Spherical particles;
s3, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 200mL KH550 of silane coupling agent, reacting at 40 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.92Eu0.08SiO5@SiO2-KH550 particles.
S4, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L toluene into KH550 granules, and adding 300g of formazanStirring methyl methacrylate in nitrogen atmosphere for 1h, heating to 80 ℃, dropping 200mL of 0.02g/mL azodiisobutyronitrile/toluene solution into the system at the speed of 5mL/min, reacting for 40h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescent electrophoretic particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.92Eu0.08SiO5The shell is SiO with the surface grafted with polymethyl methacrylate2，Y1.92Eu0.08SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 5
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.92Eu0.08OHCO3Particles;
s2, mixing 5g Y1.92Eu0.08OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.92Eu0.08OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.92Eu0.08SiO5@SiO2Spherical particles;
s3, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 25mL ammonia water with mass fraction of 25% and 250mL silane coupling agent KH560, reacting at 40 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.92Eu0.08SiO5@SiO2-KH560 particles.
S4, 150g Y1.92Eu0.08SiO5@SiO2Adding 1L of toluene into the-KH 560 particles, adding 300g of methyl methacrylate, stirring for 1h in a nitrogen atmosphere, heating to 80 ℃, dropping 200mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 5mL/min, reacting for 40h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescence electrophoresis particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.92Eu0.08SiO5The shell is SiO with the surface grafted with polymethyl methacrylate2，Y1.92Eu0.08SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 6
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y1.999Eu0.001OHCO3Particles;
s2, mixing 5g Y1.999Eu0.001OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.999Eu0.001OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y1.999Eu0.001SiO5@SiO2Spherical particles;
s3, 150g Y1.999Eu0.001SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 260mL silane coupling agent KH570, reacting at 50 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y1.999Eu0.001SiO5@SiO2-KH570 particles;
s4, mixing150g Y1.999Eu0.001SiO5@SiO2Adding 1L of toluene into the-KH 570 particles, adding 300g of lauryl methacrylate, stirring for 1h in a nitrogen atmosphere, heating to 80 ℃, dropping 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 5mL/min, reacting for 40h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescence electrophoresis particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.999Eu0.001SiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，Y1.999Eu0.001SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 7
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium nitrate and europium nitrate mixed solution, stirring for 30 minutes, reacting in a water bath at 90 ℃ for 3 hours, centrifuging, and drying at 80 ℃ to obtain Y0.02Eu1.98OHCO3Particles;
s2, mixing 5g Y0.02Eu1.98OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring at normal temperature for 6h, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is0.02Eu1.98OHCO3Calcining the particles at 1000 deg.C for 8h to obtain hollow Y0.02Eu1.98SiO5@SiO2Spherical particles;
s3, 150g Y0.02Eu1.98SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 260mL silane coupling agent KH570, reacting at 50 deg.C for 3h, centrifuging, and drying at 80 deg.C to obtain Y0.02Eu1.98SiO5@SiO2-KH570 particles;
s4, 150g Y0.02Eu1.98SiO5@SiO2Adding 1L of toluene into the-KH 570 particles, adding 300g of lauryl methacrylate, stirring for 1h in a nitrogen atmosphere, heating to 80 ℃, dropping 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 5mL/min, reacting for 40h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescence electrophoresis particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y0.02Eu1.98SiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，Y0.02Eu1.98SiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 8
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium acetate and europium acetate mixed solution, wherein the amount ratio of rare earth elements is Y to Eu is 1:1, stirring for 30 minutes, reacting in a water bath at 60 ℃ for 6 hours, centrifuging, and drying at 80 ℃ to obtain YEuOHCO3Particles;
s2, mixing 5g of YEuOHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring for 2h at normal temperature, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2YEuOHCO of3The particles are roasted at 800 ℃ for 10h to obtain hollow YEuSiO5@SiO2Spherical particles;
s3, mixing 150g of YEuSiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 260mL KH570 as silane coupling agent, reacting at 30 deg.C for 6h, centrifuging, and drying at 80 deg.C to obtain YEuSiO5@SiO2-KH570 particles;
s4, mixing 150g of YEuSiO5@SiO2-KH570 particles were added to 1L of toluene,and adding 300g of lauryl methacrylate, stirring for 1h in a nitrogen atmosphere, heating to 60 ℃, dropping 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 1mL/min, reacting for 48h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescent electrophoretic particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow YEuSiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，YEuSiO5With SiO2In a molar ratio of 1: (0.01-2).
Example 9
The embodiment provides a preparation method of red fluorescent electrophoretic particles for electronic paper, which comprises the following steps:
s1, adding 20g of urea and 1L of water into a reactor, stirring and dissolving, adding 100mL of 0.5mol/L yttrium chloride and europium chloride mixed solution, stirring for 30 minutes, reacting in a water bath at 95 ℃ for 2 hours, centrifuging, and drying at 80 ℃ to obtain Y1.99Eu0.01OHCO3Particles;
s2, mixing 5g Y1.99Eu0.01OHCO3Dispersing the particles into 1L ethanol, dropwise adding 80mL ethyl orthosilicate and 100mL ammonia water with the mass fraction of 25%, stirring for 2h at normal temperature, centrifuging, and drying at 80 ℃ for 6h to obtain the surface-coated SiO2Y of (A) is1.99Eu0.01OHCO3Particles, which are calcined at 1100 ℃ for 4h to obtain hollow Y1.99Eu0.01SiO5@SiO2Spherical particles;
s3, 150g Y1.99Eu0.01SiO5@SiO2Adding 1L ethanol water solution (alcohol-water ratio of 25:1) into the particles, stirring for 30 min, adding 20mL ammonia water with mass fraction of 25% and 260mL silane coupling agent KH570, reacting at 60 deg.C for 2h, centrifuging, and drying at 80 deg.C to obtain Y1.99Eu0.01SiO5@SiO2-KH570 particles;
s4, 150g Y1.99Eu0.01SiO5@SiO2-KH570 particles were added to 1L of toluene, followed byAdding 300g of lauryl methacrylate, stirring for 1h in a nitrogen atmosphere, heating to 90 ℃, dropping 150mL of 0.02g/mL azobisisobutyronitrile/toluene solution into the system at the speed of 10mL/min, reacting for 8h under the protection of nitrogen, centrifuging, and drying at 80 ℃ to obtain the red fluorescent electrophoretic particles.
The red fluorescence electrophoresis particle obtained in the embodiment has a core-shell structure, and the core is hollow Y1.99Eu0.01SiO5The shell is SiO with the surface grafted with polylauryl methacrylate2，Y1.99Eu0.01SiO5With SiO2In a molar ratio of 1: (0.01-2).
Comparative example 1
The present comparative example provides a white particle for electrophoretic display, which is prepared by the following method:
s1, respectively adding 100g of titanium dioxide pretreated into hydrophobic titanium dioxide by a silane coupling agent, 80g of lauryl methacrylate and 120g of toluene into a three-necked bottle; transferring the three-necked bottle into an oil bath, and introducing N in the whole process2Protecting, namely heating the temperature to 70 ℃, dissolving 0.7g of azodiisobutyronitrile in 35g of toluene, dropwise adding the azodiisobutyronitrile into a three-necked bottle through a dropwise adding funnel, finishing the reaction after 24 hours, cooling the solution in the reaction bottle to room temperature, performing centrifugal separation, washing for 3 times by using toluene, wherein a lower layer white precipitate is the titanium dioxide coated with the polymer prepared by one-step free radical polymerization, and then transferring the titanium dioxide prepared by the reaction to a vacuum drying oven for drying treatment for 24 hours;
s2, respectively adding 100g of polymer-coated titanium dioxide prepared by one-step free radical polymerization, 50g of sodium dodecyl benzene sulfonate and 120g of toluene into a three-necked bottle. Transferring the three-necked bottle into an oil bath, and introducing N in the whole process2The temperature was raised to 70 ℃ with protection. And after 24h, cooling the solution in the reaction bottle to room temperature, performing centrifugal separation, washing for 3 times by using toluene, wherein the lower white precipitate is white particles for electrophoretic display of the coating polymer and the surfactant prepared by the one-step free radical polymerization reaction and the two-step adsorption modification method. The white particles for electrophoretic display prepared by the reaction are transferred to a vacuum drying oven for drying treatment for 24 h.
The comparative example provides a white particle for electrophoretic display, which is coated with polymer and surfactant, has better suspension stability, but multicolor display can be realized only by covering a filter on the surface of the white particle after the white particle is prepared into electrophoretic solution with black particles, and the defect or the deficiency of the filter or the color multi-particle scheme can not be overcome.
Characterization of
FIG. 1 is a TEM image of the red fluorescent electrophoretic particles prepared in example 1. As can be seen from FIG. 1, the particles have a core-shell hollow structure, the core being a hollow Y2-xEuxSiO5(dark part of spherical particles) wherein 0.001. ltoreq. x<2, the outer layer is SiO2Shell (light part of spherical particle). The transmission electron microscope images of the core-shell structure spherical particles prepared in examples 2 to 9 are substantially the same as those in fig. 1.
FIG. 2 is a scanning electron microscope photograph of the red fluorescent electrophoretic particles prepared in example 1. As can be seen from FIG. 1, the particles are spherical, have good dispersibility and have a particle size distribution of 200 to 400 nm. The scanning electron micrographs of the red fluorescent electrophoretic particles prepared in examples 2 to 9 substantially correspond to those of FIG. 2.
FIG. 3 is an X-ray diffraction pattern of the red fluorescent electrophoretic particles prepared in example 1. As can be seen from FIG. 3, the diffraction peak and Y of the red fluorescence electrophoretic particle2SiO5The standard diffraction peak of Eu is consistent, and the doping of Eu and the modification of silane coupling agent and polymer do not change the crystal structure of the core. The X-ray diffraction patterns of the red fluorescence electrophoretic particles prepared in examples 2 to 9 are substantially the same as those of FIG. 3.
FIG. 4 is an emission spectrum of the red fluorescent electrophoretic particles prepared in example 1 under the excitation of ultraviolet rays at 393 nm. As can be seen from FIG. 4, the red fluorescence electrophoretic particles obtained in example 1 can display red color in the excited state, as indicated by the red light region having an emission peak in the range of 575 to 725 nm. The emission spectra of the red fluorescence electrophoretic particles prepared in examples 2 to 9 under 393nm ultraviolet excitation are substantially the same as those in FIG. 4.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The red fluorescence electrophoresis particle for the electronic paper is characterized by having a core-shell structure, wherein the core is a hollow Y2-xEuxSiO5Wherein x is more than or equal to 0.001<2, the shell is SiO with a surface grafted with a polymer2，Y2-xEuxSiO5With SiO2In a molar ratio of 1: (0.01-2).
2. The red fluorescent electrophoretic particle for electronic paper as claimed in claim 1, wherein the core is hollow Y2-xEuxSiO5Wherein x is more than or equal to 0.01 and less than or equal to 1.
3. The red fluorescent electrophoretic particle for electronic paper according to claim 1, wherein the particle size of the electrophoretic particle is 200 to 400 nm.
4. The red fluorescent electrophoretic particle for electronic paper according to claim 1, wherein the polymer is selected from one or more of polystyrene, polylauryl methacrylate, and polymethyl methacrylate.
5. The method for preparing the red fluorescent electrophoretic particles for electronic paper according to any one of claims 1 to 4, comprising the steps of:
s1, adding an aqueous solution of yttrium salt and europium salt into an aqueous solution of urea, stirring, carrying out water bath reaction at 60-95 ℃ for 2-6 h, and carrying out post-treatment to obtain Y2-xEuxOHCO3Particles;
the molar ratio of yttrium element in the yttrium salt to europium element in the europium salt is (2-x): x, wherein x is more than or equal to 0.001 and less than 2;
s2, mixing Y2-xEuxOHCO3Dispersing in an alcohol solution, adding tetraethoxysilane, adding ammonia water to adjust the pH to be alkaline, stirring for 2-8 h, and performing post-treatment to obtain the surface-coated SiO2Y of (A) is2-xEuxOHCO3Roasting the particles at 800-1100 ℃ for 4-10 h to obtain hollow Y-shaped particles with cores2-xEuxSiO5The shell is SiO2The spherical particles of (1);
s3, mixing Y2-xEuxSiO5@SiO2Dispersing the spherical particles in an alcohol solution, adding ammonia water and a silane coupling agent, reacting for 2-6 h at 30-60 ℃, and performing post-treatment to obtain Y2-xEuxSiO5@SiO2-silane coupling agent particles;
s4, mixing Y2-xEuxSiO5@SiO2Mixing silane coupling agent particles, polymer monomers, an initiator and a solvent, reacting for 8-48 h at the temperature of 60-90 ℃ in an inert atmosphere, and performing post-treatment to obtain the red fluorescence electrophoresis particles.
6. The method for preparing red fluorescent electrophoretic particles for electronic paper according to claim 5, wherein the yttrium salt is selected from one or more of yttrium nitrate, yttrium acetate and yttrium chloride.
7. The method for preparing red fluorescent electrophoretic particles for electronic paper according to claim 5, wherein the europium salt is selected from one or more of europium nitrate, europium acetate, and europium chloride.
8. The method for preparing red fluorescent electrophoretic particles for electronic paper according to claim 5, wherein the step S4 is: will Y2-xEuxSiO5@SiO2Mixing silane coupling agent particles, polymer monomers and a solvent, dripping an initiator solution at the temperature of 60-90 ℃ at the speed of 1-10 mL/min under the protection of inert atmosphere, reacting for 8-48 h, and performing post-treatment to obtain red fluorescent powderAnd (4) electrophoretic particles.
9. An electrophoretic fluid comprising the red fluorescent electrophoretic particles according to any one of claims 1 to 4 and black particles.
10. Use of the red fluorescent electrophoretic particles according to any one of claims 1 to 4 in the preparation of electronic paper.
CN202111510969.XA 2021-12-10 2021-12-10 Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof Active CN114181694B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111510969.XA CN114181694B (en) 2021-12-10 2021-12-10 Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111510969.XA CN114181694B (en) 2021-12-10 2021-12-10 Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114181694A true CN114181694A (en) 2022-03-15
CN114181694B CN114181694B (en) 2023-06-02

Family

ID=80604504

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111510969.XA Active CN114181694B (en) 2021-12-10 2021-12-10 Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114181694B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285955A (en) * 2023-03-22 2023-06-23 成都理工大学 LED fluorescent powder used in damp and hot environment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090108385A (en) * 2008-04-11 2009-10-15 주식회사 엘지화학 Charged particle for image display device and method for manufacturing the same
CN106520111A (en) * 2016-12-09 2017-03-22 广州奥翼电子科技股份有限公司 Color-changing electrophoretic particle and preparation method thereof and electrophoretic display
CN108165271A (en) * 2018-02-27 2018-06-15 南方科技大学 One kind is based on encapsulated electro-phoretic colour quantum dot light electroluminescent material and its luminescent method and application
CN109976063A (en) * 2019-03-15 2019-07-05 广州奥翼电子科技股份有限公司 A kind of electrophoresis showed micro unit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090108385A (en) * 2008-04-11 2009-10-15 주식회사 엘지화학 Charged particle for image display device and method for manufacturing the same
CN106520111A (en) * 2016-12-09 2017-03-22 广州奥翼电子科技股份有限公司 Color-changing electrophoretic particle and preparation method thereof and electrophoretic display
CN108165271A (en) * 2018-02-27 2018-06-15 南方科技大学 One kind is based on encapsulated electro-phoretic colour quantum dot light electroluminescent material and its luminescent method and application
CN109976063A (en) * 2019-03-15 2019-07-05 广州奥翼电子科技股份有限公司 A kind of electrophoresis showed micro unit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIANWEI MENG ET AL.: ""Luminescent Electrophoretic Particles via Miniemulsion Polymerization for Night-Vision Electrophoretic Displays"", ACS APPL. MATER. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285955A (en) * 2023-03-22 2023-06-23 成都理工大学 LED fluorescent powder used in damp and hot environment

Also Published As

Publication number Publication date
CN114181694B (en) 2023-06-02

Similar Documents

Publication Publication Date Title
CN108728077A (en) The preparation method of synthetic silica coated inorganic perovskite quantum dot
EP3064554B1 (en) Colored glossy pigment using vegetable type natural dye and method for preparing same
CN105957944B (en) White light source containing three bandgap photonic crystals and preparation method thereof
CN105700265B (en) Color electrophoretic display with electric field response photonic crystal properties and preparation method thereof and display methods
CN102492428A (en) Uniform fluorescent microball and preparation method
CN103725282B (en) Coated silicate fluorescent powder and film-coating method thereof
CN101575463B (en) Composite electrophoresis particle of silicon dioxide and polymer core-shell structure and preparation method thereof
CN114181694B (en) Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof
CN113548670B (en) Preparation method of inorganic structure color material
CN110607015A (en) Plastic light conversion agricultural film with lasting light conversion effect and preparation method thereof
CN110511758A (en) A kind of CdSe/CdS core-shell nano sheet material and preparation method thereof
CN103540162A (en) Method for preparing electrophoretic particles by using organic pigment
CN109504203B (en) Color-light water-based functional coating suitable for indoor entertainment and preparation method and application thereof
CN100564428C (en) The electrophoresis particle preparation method of composite structure who is used for the core-pigment layer-shell of electric ink
CN113861737B (en) Environment-friendly antibacterial finger painting pigment containing nano-silver modified silicon dioxide colored composite microspheres
CN116751463A (en) Composite pigment coated with nano aluminum hydroxide and preparation method thereof
CN110499158A (en) A kind of rare earth samarium doped tin oxide nano hollow ball sensitized luminescence body, preparation method and application
CN109306199A (en) A kind of open air luminescent coating noctilucence masterbatch and preparation method
Meng et al. Preparation of electrophoretic nanoparticles for electronic paper
CN108864824A (en) Quantum dot fluorescence anti-forgery ink and preparation method thereof
CN112048218A (en) Photo-induced color development anti-counterfeiting water-based ink and preparation method thereof
CN110776905B (en) Quantum dot fluorescent nanosphere based on amphiphilic silicon carrier and preparation method thereof
CN113388290A (en) Water-based nano anti-counterfeiting ink-jet ink and preparation method thereof
CN109608658B (en) Structural color particle and preparation method thereof
CN113214730A (en) Water-based energy-storage luminous paint with fireproof function for tunnel and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant