CN106381140B - Quantum dot composition, quantum dot composite material, preparation method and application - Google Patents
Quantum dot composition, quantum dot composite material, preparation method and application Download PDFInfo
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- CN106381140B CN106381140B CN201610623563.5A CN201610623563A CN106381140B CN 106381140 B CN106381140 B CN 106381140B CN 201610623563 A CN201610623563 A CN 201610623563A CN 106381140 B CN106381140 B CN 106381140B
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Abstract
The present invention provides a kind of quantum dot composition, quantum dot composite material, preparation method and applications.The quantum dot composition includes quantum dot and the macromolecule matrix for disperseing quantum dot, and macromolecule matrix includes acrylate, epoxy acrylate and epoxy resin.Since increased epoxy acrylate has amphipathic, epoxy group end and epoxy resin have good compatibility, and there is good compatibility at acrylate end with acrylic resin, thus bridge connection function is played between acrylate and epoxy resin.The compatibility of acrylate and quantum dot is best, and the outermost that epoxy resin is connected to three kinds of ingredients as hydrophilic system is used for starvation and aqueous vapor.The present invention sets about in terms of macromolecule matrix material composition, solve the problems, such as with the compatibility of quantum dot and starvation and aqueous vapor, improve the luminous efficiency and stability of quantum dot composite material.
Description
Technical field
The present invention relates to quantum dot light emitting Material Fields, compound in particular to a kind of quantum dot composition, quantum dot
Material, preparation method and application.
Background technology
Quantum dot, and can be described as nanocrystalline, it is a kind of nano particle being made of II-VI group or iii-v element.Amount
The grain size of son point is typically in the range of between 1~10nm, and since electrons and holes are by quantum confinement, continuous band structure becomes to have
The discrete energy level structure of molecular characterization can emit fluorescence after being excited.Based on quantum effect, quantum dot is in solar cell, hair
The fields such as optical device, optical bio label are with a wide range of applications.
Quantum dot has exciting light spectrum width and continuously distributed, and emission spectrum is narrow and symmetrical, Color tunable, photochemical stable
Property high, the superior fluorescent characteristic such as fluorescence lifetime length.By the shape, structure and size that control quantum dot, so that it may with easily
Its energy gap width, exciton are adjusted (in semiconductor, if an electronics is gone on from full valence to empty conduction band, in valence
With one hole of interior generation, and an electronics is generated in conduction band, to form an electron-hole pair.Hole is positively charged, electricity
Subband negative electricity, the coulomb adelphotaxy between them can be spatially bound together under certain conditions, such shape
At complex be known as exciton) (bands of a spectrum of organic compound are often because of substituent group for the energy blue shift of the size of binding energy and exciton
Variation and the change of quantity of solvent so that maximum absorption wavelength and intensity is changed.Claim when maximum wavelength is moved to shortwave direction
For blue shift；Blue shift refers to the frequency of the electromagnetic wave that the object of positive observer's movement is scattered on spectrum line to the side at blue end
To movement, it is meant that wavelength reduces.) etc. electronic states.With being gradually reduced for quantum dot size, the light absorption of quantum dot is composed
Existing blue-shifted phenomenon.Therefore, the arbitrarily desired spectrum in visible light region can be obtained, and can pass through by the size of control quantum dot
Half-peak breadth size is controlled, the monochromatic light of pure color is obtained, colour gamut and color saturation can be increased substantially for display field.
Between being typically in the range of 1~10nm due to the grain size of quantum dot, there is very big specific surface area, surface phase atomicity
Increase, the coordination for resulting in surface atom is insufficient, unsaturated bond and dangling bond (i.e. the unpaired electronics of crystalline surface) increase, and makes
These surface atoms have high activity, extremely unstable, it is easy to be combined with other atoms.Therefore, general quantum dot surface needs
Suitable ligand is selected to be coordinated with the metal of quantum dot surface, the type of ligand has certainly the efficiency and stability of quantum dot
Qualitatively influence.With the development and optimization of quantum dot synthetic technology, the efficiency and stability of quantum dot have reached industrialization
Level.But the unique skin effect of quantum dot also determines that its sensibility to aqueous vapor and oxygen, aqueous vapor and oxygen can be broken
The ligand of bad quantum dot surface reduces the efficiency of quantum dot.Quantum dot size is smaller, and specific surface area is bigger, to aqueous vapor and oxygen
Sensibility it is higher.
With the maturation of quanta point material, the demand to quanta point material is increasingly urgent to, especially display field still, amount
Son point material cannot be used alone, it is necessary to be dispersed in macromolecule matrix.In view of the characteristic of quantum dot itself, macromolecule matrix
There must be following characteristic：(1) there is preferable compatibility with quanta point material, quantum dot will not be quenched；(2) there is preferable resistance
Every property, there is preferable barrier property to aqueous vapor and oxygen；It (3) can be by liquid curing at solid-state under the action of light or heat.
Macromolecule matrix about dispersion quantum dot has many reports, can be summarized as following a few classes：(1) to quantum dot surface
It carries out silicone-modified, selects organosilicon material as macromolecule matrix, be mainly used for the encapsulation in situ of LED chip.Organosilicon
Material has extraordinary thermal stability and optical stability, still, due to the high-flexibility of organosilicon material silicon oxygen bond and big
Bond angle, it is poor to the barrier property of aqueous vapor and oxygen.Under conditions of high temperature and blue light illumination, quanta point material be easy by
The destruction of aqueous vapor and oxygen and fail.(2) it is made using porous material absorption quantum dot or by quantum dot epoxy resin cladding
Microballoon.Epoxy resin is poor with the compatibility of quantum dot due to higher polarity, and hair is easy under conditions of high temperature illumination
Huang influences quantum dot luminous efficiency.(3) select acrylate monomer or polyacrylate as macromolecule matrix.Acrylate
There are preferable compatibility, quantum dot that can preferably be dispersed in acrylate with quantum dot.But acrylate is to aqueous vapor and oxygen
The barrier property of gas is poor.(4) phase separation structure is formed, disperses quantum dot using hydrophobic systems (acrylate), outer layer is used
Hydrophilic system (epoxy resin) starvation, is macroscopically forming phase separation structure.Nothing between acrylic resin and epoxy resin
Chemical bond and effect, there are certain defects for long-term chemical durability aspect.
Therefore, it is still necessary to the application of quantum dot in the prior art is improved, to improve the luminous efficiency of quantum dot
And stability.
Invention content
The main purpose of the present invention is to provide a kind of quantum dot composition, quantum dot composite material, preparation method and
Using, with solve the prior art due to aqueous vapor and oxygen barrier property difference or with dispersion quantum dot matrix poor compatibility and lead
The low problem with stability difference of luminous efficiency of the quantum dot light emitting material of cause.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of quantum dot composition, the quantum dot
Composition includes quantum dot and the macromolecule matrix for disperseing quantum dot, and macromolecule matrix includes acrylate, propylene oxide
Acid esters and epoxy resin.
Further, the mass ratio of acrylate, epoxy acrylate and epoxy resin is 5~10：1~5：1~5.
Further, in quantum dot composition further include diluent, preferred diluent is the acrylic monomers of single functionality.
Further, the mass ratio of the quality of the acrylic monomers of single functionality and macromolecule matrix is 1~5：10~20.
Further, further include crosslinking agent in quantum dot composition, preferably crosslinking agent is the propylene that degree of functionality is more than or equal to 2
Acid monomers, more preferably bifunctionality or three-functionality-degree acrylic monomers.
Further, the mass ratio of acrylic monomers of the degree of functionality more than or equal to 2 and macromolecule matrix is 1~3：10~
20。
Further, further include curing agent in quantum dot composition, preferred consolidation agent be radical UV curing agent and sun from
Sub-light curing agent, or be radical UV curing agent and thermal curing agents.
Further, in quantum dot composition further include additive, additive is light diffusion particle and/or antioxidant.
According to another aspect of the present invention, a kind of preparation method of quantum dot composite material, the preparation method are provided
Including：Macromolecule matrix, optional diluent, crosslinking agent, curing agent, quantum dot and optional additive are mixed,
Obtain the first mixture；First mixture is cured, quantum dot composite material is obtained；Wherein, macromolecule matrix includes third
Olefin(e) acid ester, epoxy acrylate and epoxy resin.
Further, the mass ratio of acrylate, epoxy acrylate and epoxy resin is 5~10：1~5：1~5.
Further, diluent is the acrylic monomers of single functionality；It is highly preferred that the acrylic monomers of single functionality with
The mass ratio of macromolecule matrix is 1~5：10~20.
Further, crosslinking agent is the acrylic monomers that degree of functionality is more than or equal to 2；It is preferred that degree of functionality is more than or equal to the third of 2
The mass ratio of acrylic monomer and acrylate is 1~3：10~20.
Further, curing agent includes radical UV curing agent and thermal curing agents or radical UV curing agent and cation
The step of light curing agent, solidification includes：Pair the first mixture carries out photocuring under the action of radical UV curing agent, consolidate
Change semi-finished product；Heat cure or photocuring are carried out to solidification semi-finished product under the action of thermal curing agents or cation photocuring agent, obtained
To quantum dot composite material.
Further, the step of curing agent includes radical UV curing agent and cation photocuring agent, solidification include：Certainly
By curing to the first mixture under being acted on while base light curing agent and cation photocuring agent, quantum dot composite wood is obtained
Material.
Further, additive is light diffusion particle and/or antioxidant.
According to a further aspect of the invention, a kind of quantum dot composite material is provided, which uses
Any of the above-described kind of preparation method is prepared.
According to a further aspect of the invention, a kind of quantum dot composite material is provided, which includes：
Quantum dot and the macromolecule matrix solidfied material being coated on around quantum dot, macromolecule matrix solidfied material have as shown in following formula (I)
Structural unit；
Wherein, R1For
R2For
R3For
The integer that n is >=1.
According to another aspect of the present invention, a kind of quantum dot light emitting device is provided, which includes amount
Son point composite material, quantum dot composite material is above-mentioned quantum dot composite material.
Further, the quantum dot in quantum dot composite material is red quantum dot and green quantum dot.
Further, quantum dot light emitting device is quantum dot film or quantum dot pipe.
It applies the technical scheme of the present invention, in above-mentioned quantum dot composition, selection is widely used as the propylene that adhesive uses
Acid esters and epoxy resin, and the epoxy acrylate that can be combined well with epoxy resin and acrylate is as dispersion quantum
The macromolecule matrix of point.Wherein, the compatibility of acrylate and quantum dot is best, and one end of epoxy acrylate is epoxy group
Group and the other end is acrylate, have amphipathic, epoxy group end and epoxy resin have a good compatibility, and acrylate
There is good compatibility at end with acrylic resin, thus bridge connection function is played between acrylate and epoxy resin.Ring
The outermost that oxygen resin is connected to three kinds of ingredients as hydrophilic system is used for starvation and aqueous vapor.From macromolecule matrix material group
Set about at aspect, solve the problems, such as with the compatibility of quantum dot and starvation and aqueous vapor, improve quantum dot composite wood
The luminous efficiency and stability of material.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows the quantum dot and macromolecule matrix and the microstate schematic diagram of crosslinking agent of the present invention；Acrylic acid
Ester can be realized with quantum dot to dissolve each other well, and epoxy resin need to form bridging knot by epoxy acrylate and acrylate
Structure；Wherein, center circle represents quantum dot；The molecules present acrylate of double bond is carried around the both ends of center circle；There are three tools
The monomer molecule of double bond represents acrylic monomers；One end is the molecules present epoxy acrylate that the double bond other end is stain；Two
End is the molecules present epoxy resin of stain.
Fig. 2 shows the solidification semi-finished product schematic diagram for being quantum dot composite material shown in FIG. 1 after first time cures；
Wherein center circle represents quantum dot；Acrylate is complete by UV photocurings, forms the first annular structure around center circle,
It is denoted as the first shell；One end is the molecules present epoxy acrylate that the double bond other end is stain, and acrylate end is also
It is cured, and one end of the epoxy group of acrylate is still in free state, same both ends are the molecules present epoxy of stain
Resin, also still in free state；And
Fig. 3 shows that Fig. 2 by the microcosmic schematic diagram of quantum dot composite material after the completion of solidification, forms nucleocapsid,
Core is quantum dot, and the first shell is acrylate, and the second shell is epoxy resin, and epoxy acrylate is acted on by chemical bonding
Nucleocapsid is linked together.
In above-mentioned attached drawing, including with lower label：
10, quantum dot；20, acrylate；30, epoxy acrylate；40, epoxy resin；50, acrylic monomers；
60, the first shell；70, the second shell.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As background technology part is previously mentioned, due to the barrier property difference to aqueous vapor and oxygen or the matrix with dispersion quantum dot
Poor compatibility and cause quantum dot light emitting material in the prior art to there is a problem of that luminous efficiency is low and stability difference, in order to change
It is apt to this situation, in a kind of typical embodiment of the present invention, provides a kind of quantum dot composition, the quantum dot composition
Macromolecule matrix including quantum dot and for disperseing quantum dot, the macromolecule matrix include acrylate, epoxy acrylate
And epoxy resin.
In the above-mentioned quantum dot composition of the present invention, selection is widely used as the acrylate and asphalt mixtures modified by epoxy resin that adhesive uses
Fat, and the epoxy acrylate (i.e. epoxy-modified acrylate) that can be combined well with epoxy resin and acrylate are made
To disperse the macromolecule matrix of quantum dot.Wherein, the compatibility of acrylate and quantum dot is best, and the one of epoxy acrylate
End for epoxy group and the other end is acrylate, have amphipathic, epoxy group end and epoxy resin have good compatibility,
And there is good compatibility at acrylate end with acrylic resin, thus bridge company is played between acrylate and epoxy resin
Connect effect.The outermost that epoxy resin is connected to three kinds of ingredients as hydrophilic system is used for starvation and aqueous vapor.From macromolecule
Set about in terms of basis material composition, solves the problems, such as and the compatibility of quantum dot and starvation and aqueous vapor, the amount of improving
The luminous efficiency and stability of son point composite material.
The type of epoxy resin in the above-mentioned macromolecule matrix of the present invention can be the epoxy resin of any kind.More preferably
Bisphenol-A and bisphenol F type epoxy resins, bisphenol A type epoxy resin, that is, diphenol propane glycidol ether, in the epoxy it
Raw material is easy to get, therefore cost is minimum, and yield maximum (75-80% for accounting for about whole epoxy resin total amounts), purposes is most wide.Bisphenol-A
The good manufacturability of type epoxy resin, when solidification, do not generate small molecule volatile matter, and solidfied material has very high bulk strength and bonding
Intensity has good corrosion resistance and electrical property.Bisphenol f type epoxy resin is to reduce bisphenol A type epoxy resin
Viscosity simultaneously has same performance and a kind of neo-epoxy resin for developing, and condensate performance is several with bisphenol A type epoxy resin
It is identical.
The macromolecule matrix of mentioned component can be obtained by the reaction by the epoxy resin and acrylic acid of different ratio.It is following anti-
Formula is answered to show the epoxy resin and acrylic acid product obtained by the reaction (I) of different ratio, (II) and (III).
Wherein, R is
The integer that n is >=1.
Product (I) is acrylate, and the epoxy group on reactant epoxy resin is obtained by acrylic acid is fully open, with
The compatibility of quantum dot is good.Product (II) is that one end is epoxy group, and the other end is epoxy-modified acrylate, has amphiphilic
Property, there is good compatibility at epoxy group end with epoxy resin, and epoxy-modified acrylate has well with acrylate
Compatibility can play bridge connection function between product (I) and product (III).Product (III) is unreacted asphalt mixtures modified by epoxy resin
Fat.
The above-mentioned quantum dot composition of the present invention selects to contain above-mentioned three kinds of ingredients as the polymer-based of dispersion quantum dot
Body, due to the connection between chemical bond occurs that can react to each other between three kinds of ingredients, and according to the difference of three's molecular structure
It the hydrophobic layer that can be formed centered on quantum dot and the amphiphilic layer being arranged on the outside of hydrophobic layer and is connected on the outside of amphiphilic layer
Hydrophilic layer (as shown in Figure 1 to Figure 3).The specific molecular structure for forming three layers can be different according to specific ratio used in three
And it is adjusted.In a kind of preferred embodiment of the present invention, in above-mentioned quantum dot composition, acrylate, epoxy acrylic
The mass ratio of ester and epoxy resin is 5~10：1~5：1~5.By control three mass ratio within the above range, a side
Face can ensure that the compatibility of quantum dot and macromolecule matrix is preferable, on the other hand pass through the epoxy of epoxy acrylate and outer layer
Resin forms chemical crosslinking structure, its barrier property to aqueous vapor and oxygen can be effectively improved, to improve the effect of quantum dot
Rate and stability.
In above-mentioned quantum dot composition, particular/special requirement is had no to the amount ratio of quantum dot and macromolecule matrix, as long as high score
Subbase body can be evenly dispersed to quantum dot progress, and can maintain the luminous efficiency and stability of quantum dot.For example, according to
A certain amount of macromolecule matrix, which is actually needed, to disperse one or a group quantum dot.In a kind of preferred reality of the present invention
It applies in example, the mass ratio of quantum dot and macromolecule matrix is 0.1~1：10~100.Specific ratio need to be according to objective optics parameter
Depending on.
In above-mentioned quantum dot composition, according to actual needs, can will be prepared into it is required a kind of in product process or
Various other auxiliary elements are included, and can not also be included, and are provided separately in specific preparation process.
In another preferred embodiment of the invention, above-mentioned quantum dot composition includes diluent, preferred diluent
For the reactive monomer of single functionality, which is acrylic monomers.Select reactive monomer as diluent herein,
Polymerisation can be participated in, is added in macromolecule matrix as a component, and can effectively reduce the viscosity of system, is conducive to
Machine-shaping.
It is highly preferred that the acrylic monomers of above-mentioned single functionality is selected from methyl acrylate, methyl methacrylate, acrylic acid
Ethyl ester, ethyl methacrylate, n-propyl, n propyl methacrylate, acrylic acid isopropyl ester, methacrylic acid isopropyl
Fat, n-butyl acrylate, n-BMA, isobutyl acrylate, Isobutyl methacrylate, tert-butyl acrylate,
Tert-butyl Methacrylate, Isooctyl acrylate monomer, isooctyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate,
Hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, methacrylate, isobornyl acrylate, first
Base isobornyl acrylate, isodecyl acrylate, lauryl acrylate, lauryl methacrylate, 2- Phenoxyethyl propylene
Acid esters, 2- phenoxyethyl methacrylates, 3,3,5- trimethyl-cyclohexanes acrylate, tetrahydrofuran acrylate, third
One or more of dimethomorph.
In above-mentioned quantum dot composition, according to actual production technique and the specific kind of difference of diluent, used in
The dosage of diluent can be by suitably adjusting to obtain.In another preferred embodiment of the invention, the propylene of single functionality
The mass ratio of acid monomers and macromolecule matrix is 1~5：10~20.The mass ratio of diluent and macromolecule matrix is controlled at this
In range, system viscosity can be efficiently controlled, machine-shaping is conducive to.
In another preferred embodiment of the invention, further includes crosslinking agent in above-mentioned quantum dot composition, be preferably crosslinked
Agent is the acrylic monomers that degree of functionality is more than or equal to 2, the more preferably acrylic monomers of bifunctionality or three-functionality-degree.Herein
Crosslinking agent is internal crosslinker, is entered in macromolecular structure chain in polymerization as a kind of monomer, or be added as a component
Into macromolecule matrix, can storage-stable, only can just crosslink reaction being heated to certain temperature or radiation condition.
It is preferred that acrylic monomers of the above-mentioned degree of functionality more than or equal to 2 be as crosslinking agent, three kinds of active group and macromolecule matrix at
Divide react and form cross-linked structure, cross-linking efficiency is high, and adverse reaction and cohesion does not occur.
It is highly preferred that the acrylic monomers of above-mentioned bifunctionality or three-functionality-degree be selected from 1,6- hexanediyl esters,
Triethylene-glycol dimethylacrylate, Tricyclodecane Dimethanol diacrylate, three (2- ethoxys) isocyanic acids, three propylene
Acid esters, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, 3- ethyoxyls-trimethylolpropane tris acrylic acid
Ester, 9- ethyoxyls-trimethylolpropane trimethacrylate, propoxyl group-trimethylolpropane trimethacrylate and trihydroxy methyl
It is one or more in propane trimethyl acrylic ester.These crosslinking agents are under the premise of ensureing curing rate and the degree of cross linking, tool
There are preferable flexibility and intensity.
In above-mentioned quantum dot composition, according to actual production technique and the specific kind of difference of crosslinking agent, used in
The dosage of crosslinking agent can be by suitably adjusting to obtain.In another preferred embodiment of the invention, degree of functionality is more than or equal to 2
Acrylic monomers and acrylate mass ratio be 1~3：10~20.By the mass ratio control of acrylic monomers and acrylate
System in the range, can realize speed well and the cross-linking effect that cross-linked structure is stablized under the premise of relatively fewer dosage.
It has been observed that according to actual needs, other required one or more auxiliary in product process can will be prepared into
Ingredient is included.Further include curing agent in above-mentioned quantum dot composition in another preferred embodiment of the invention, it is excellent
It is radical UV curing agent, cation photocuring agent and thermal curing agents to select curing agent.
The specific type of radical UV curing agent in above preferred embodiment includes but are not limited to 1- hydroxy-cyclohexyls
Phenyl ketone (photoinitiator 184), 2- methyl-1s-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone (photoinitiator 907), 2- hydroxyls
Base-aminomethyl phenyl propane -1- ketone (photoinitiator 1173), 2,4,6- trimethylbenzoy-dipheny phosphine oxide (photoinitiators
TPO), bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (photoinitiator 819) of phenyl, 2- phenyl benzyl -2- dimethyl amines -1-
[4- morpholine benzyls phenyl]-butanone (photoinitiator 369), α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone (photoinitiator 651), hexichol
Any one or a few in ketone (photoinitiator b P) and methyl benzoylformate (photoinitiator MBF).Cationic photopolymerization is solid
The specific type of agent includes but are not limited to 4,4'- dimethyl diphenyl salt compounded of iodine hexafluorophosphate, bis- (4- 2-methyl-2-phenylpropanes bases)
Iodine hexafluorophosphate, bis- (4- 2-methyl-2-phenylpropanes base) iodine fluoroform sulphonates, cyclopropyl diphenyl sulphur tetrafluoroborate, diphenyl
Iodine hexafluorophosphate, diphenyl iodine arsenate, diphenyl iodine trifluoro-methanyl sulfonate, triphenyl sulphur tetrafluoroborate,
Any one or a few in triphenyl phosphonium bromide sulfonium and tri-p-tolylsulfonium hexafluorophosphate.The specific type packet of thermal curing agents
Include but lose be limited to ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-phenylene diamine (MPD), two amido diphenyl sulfones,
Hydroxyethyl ethylenediamine, benzophenone tetracarboxylic dianhydride, tetrabydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride,
Any one or a few in benzene tetracarboxylic acid acid anhydride, 2-methylimidazole and 2- ethyl imidazol(e)s.These curing agent have applicability wide,
The advantages that curing rate is fast, and curing efficiency is high, being used in combination has certain synergistic effect, obtains solidfied material of good performance.
In actual production, according to the difference of the performance requirement for the luminescent device to be prepared, above-mentioned quantum dot composition
In can also include improving or the ingredient comprising its performance, to further increase the luminous efficiency of quantum dot in luminescent device
And stability of photoluminescence.Further include additive in above-mentioned quantum dot composition, this adds in another preferred embodiment of the invention
It is light diffusion particle and/or antioxidant to add agent.Light diffusion particle selects conventional photodiffusion material, includes in the present invention
But it is not limited only to TiO2、Zr2O3、ZnO、Al2O3、BaSO4、CaCO3、SiO2And any one or a few in organic silicon.It is anti-
Oxygen agent includes but are not limited to 4- hydroxy-dodecanoic acids anilid, N, double -3 (3, the 5- di-t-butyl -4- hydroxyls of six methines of N'-
Base phenyl) propionamide, 4,4-, bis- t-octyl diphenylamines, 2,6-di-tert-butyl p-cresol (BHT), β (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid octadecyl (antioxidant 1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(antioxidant 1010), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), bis- (2,4- DI-tert-butylphenol compounds) seasons penta
Any one in tetrol diphosphites (antioxidant 626) and the double octadecyl esters (antioxidant 618) of pentaerythrite diphosphorous acid
Or it is several.Light diffusion particle can effectively improve the luminous efficiency of quantum dot, and antioxidant helps to extend quantum dot composite material
Stability.On the one hand, the light diffusion particle of mentioned kind has preferable light diffusion effect, can effectively improve quantum dot effect
Rate, and cost is relatively low, preferably dissolves each other with polymer-based physical efficiency.On the other hand, the antioxidant of mentioned kind has preferable anti-
Oxygen effect, phenomena such as xanthochromia and the degradation of macromolecule matrix can be effectively inhibited.Moreover, Hinered phenols and phosphorous acid esters antioxygen
Agent is used in compounding the synergistic effect that can reach certain, has more good antioxidant effect.
In another typical embodiment of the invention, a kind of preparation method of quantum dot composite material is provided, it should
Preparation method includes：Macromolecule matrix, optional diluent, crosslinking agent, curing agent, quantum dot and optional additive are mixed
Conjunction obtains the first mixture；First mixture is cured, quantum dot composite material is obtained；Wherein, macromolecule matrix includes
Acrylate, epoxy acrylate and epoxy resin.
The preparation method of above-mentioned quantum dot composite material, by combining isolation performance of the epoxy resin to aqueous vapor and oxygen
It is good, and the advantage that the compatibility of acrylic resin and quantum dot is good, use epoxy resin, epoxy acrylate and acrylate
Macromolecule matrix of the hybrid systems as quantum dot, successfully solved by the crosslinking of crosslinking agent and the solidification of curing agent
With the compatibility of quantum dot and barrier sex chromosome mosaicism, and the presence of additive also contributes to improve the starting efficiency and length of quantum dot
Phase stability.
In above-mentioned preparation method, the molar ratio of acrylate, epoxy acrylate and epoxy resin can be according to reality
The difference needed is rationally adjusted.In a kind of preferred embodiment of the present invention, acrylate, epoxy acrylate and ring
The ratio of oxygen resin is 5~10：1~5：1~5, three be used in the proportional region on the one hand can ensure quantum dot with
The compatibility of macromolecule matrix is preferable, on the other hand forms chemical crosslinking knot by the epoxy resin of epoxy acrylate and outer layer
Structure can effectively improve its barrier property to aqueous vapor and oxygen, to improve the efficiency and stability of quantum dot.
Crosslinking agent used in above-mentioned preparation method is the crosslinking agent of routine, and dosage can be according to specific crosslinking agent kind
The difference of class and it is different.In a kind of preferred embodiment of the present invention, above-mentioned crosslinking agent is the acrylic acid that degree of functionality is more than or equal to 2
Monomer；It is preferred that the mass ratio of acrylic monomers of the degree of functionality more than or equal to 2 and acrylate is 1~3：10~20.Degree of functionality is big
Have curing rate fast and the advantages such as degree of cross linking height in the acrylic monomers equal to 2.And the acrylic acid by degree of functionality more than or equal to 2
The mass ratio of monomer and acrylate is controlled 1~3：In the range of 10~20, ensureing that curing rate is fast and the degree of cross linking is high
Under the premise of, balance the flexibility demand of solidfied material.
In the above preparation method, the molar ratio of quantum dot and macromolecule matrix can be according to the luminous product to be prepared
Requirement to luminescent properties reasonably selects.Quantum dot can be single quantum dot, or numerous quantum dots.
In a kind of preferred embodiment of the present invention, the molar ratio of above-mentioned quantum dot and macromolecule matrix is 0.1~1：10~100.It will amount
Son point and the molar ratio of macromolecule matrix control within the above range, can substantially meet current luminous product and be wanted to luminescent properties
It asks.
Particular/special requirement is had no to the specific type of used curing agent in above-mentioned preparation method, as long as can be formed by curing
Quantum dot composite material.In a kind of preferred embodiment of the present invention, above-mentioned curing agent include radical UV curing agent and
The step of thermal curing agents, above-mentioned solidification includes：Pair the first mixture carries out photocuring under the action of radical UV curing agent, obtains
To solidification semi-finished product；Heat cure is carried out to solidification semi-finished product under the action of thermal curing agents, obtains quantum dot composite material.
Above preferred embodiment by using radical UV curing agent and thermal curing agents to contain quantum dot and crosslinking agent with
And the first mixture of additive carries out step curing, obtains quantum dot composite material.Above-mentioned radical UV curing agent is selected from 1-
Hydroxycyclohexylphenylketone (photoinitiator 184), 2- methyl-1s-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone are (light-initiated
Agent 907), 2- hydroxy-methyl phenyl-propane -1- ketone (photoinitiator 1173), 2,4,6- trimethylbenzoy-diphenies oxidation
Bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (photoinitiator 819) of phosphine (photoinitiator TPO), phenyl, 2- phenyl benzyls -2- two
Methyl amine -1- [4- morpholine benzyls phenyl]-butanone (photoinitiator 369), α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone (photoinitiator
651), any one or a few in benzophenone (photoinitiator b P) and methyl benzoylformate (photoinitiator MBF).Heat
Curing agent is selected from ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-phenylene diamine (MPD), two amido diphenyl sulfones, hydroxyl
Ethylethylenediamine, benzophenone tetracarboxylic dianhydride, tetrabydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, equal benzene
Any one or a few in tetracarboxylic acid anhydride, 2-methylimidazole and 2- ethyl imidazol(e)s.Work of the esters of acrylic acid in light curing agent
Semi-solid preparation product are formed with lower cross-linking reaction, then, cures after being carried out to epoxy resin by thermal curing agents, system can be effectively improved
The degree of cross linking.Different curing agent, which are used in compounding, can realize curing rate soon and curing efficiency height and condensate performance is excellent consolidates
Change effect.
The specific preparation method of above-mentioned quantum dot composite material is as shown in Figure 1, Figure 2 and Figure 3.Fig. 1 show acrylate
20, the admixture of epoxy acrylate 30, epoxy resin 40 and quantum dot 10 is (while containing including crosslinking agent acrylic monomers
50).According to the priority of compatibility, quantum dot 10 is preferentially dispersed in acrylate 20, and with 10 compatibility of quantum dot compared with
The epoxy resin 40 of difference is then ostracised in outermost layer, and the nucleocapsid of microphase-separated is formed, and epoxy acrylate 30 plays bridge
Beam effect connects acrylate 20 and epoxy resin 40.Under the irradiation of UV light, the acrylic acid of acrylate 20 and polyfunctionality
Monomer 50 crosslinks reaction under the action of radical UV curing agent, and one end of epoxy acrylate 30 may participate in reaction, shape
At the first shell 60 around quantum dot 10, and other end epoxy group can not be reacted with free epoxy resin 40, such as Fig. 2 institutes
Show.After UV cures, quantum dot 10 is covered by acrylate 20.Thermal curing agents in system under heating conditions may be used
Cross-linking reaction further is carried out to remaining epoxy resin 40, forms internal layer acrylate cladding (the first shell 60), outer layer ring
The multi-layer core-shell structure of oxygen resin cladding, i.e. the second shell 70, forms the first shell 60 and the second shell 70 surrounds centronucleus amount
Son point 10 forms multi-layer core-shell structure, as shown in Figure 3.
In another preferred embodiment of the invention, above-mentioned curing agent includes that radical UV curing agent and cationic photopolymerization are solid
The step of agent, above-mentioned solidification includes：It is mixed to first under being acted on while radical UV curing agent and cation photocuring agent
It closes object to be cured, obtains quantum dot composite material.The preferred embodiment uses free radical and cation photocuring agent, by same
When pair the first mixture carry out a UV irradiations solidification process can be completed, obtain quantum dot composite material.
In above-mentioned curing schedule, the solidification of epoxy resin is to realize photocuring by cation photocuring agent.In acrylic acid
It is added radical UV curing agent and cation photocuring agent in ester, epoxy acrylate and epoxy resin, when solidification selects 365nm
UV lamp (and/or 450nm blue-ray lights are simultaneously) is irradiated, and can ensure that the free radical of acrylic acid causes (365nm) and epoxy group in this way
The cation of group causes (ultraviolet 365nm and blue light 450nm can) and is carried out at the same time.Moreover, because free radical velocity of initiation ratio
Cationic curing is faster, and the state initially formed is also shown in FIG. 2, and after curing after the cation of certain time,
End-state is consistent with Fig. 3 that heat cure is formed.The advantages of radical UV curing is quick solidifying, the disadvantage is that cubical contraction is big；
And the advantages of cation photocuring, is that cubical contraction is small, the disadvantage is that slow curing (all slower than heat cure, radical UV curing), but
Above-mentioned curing not only takes full advantage of its advantage, but also has adapted to successively cured demand, same time using its disadvantage
Irradiation time is saved.
In a kind of more specifical embodiment, in the different solidification process of above two, the light source of UV irradiations is 365nm
LED cold light sources or it is metal halogen lamp source centered on 365nm or mercury lamp light source or is centered on 450nm
Visible light source.
In another typical embodiment of the invention, a kind of quantum dot composite material is additionally provided, the quantum dot is multiple
Condensation material is prepared using any of the above-described kind of preparation method.Had using the quantum dot composite material that the above method is prepared
Compatibility and barrier property are superior, and luminous efficiency is high, the good advantageous effect of stability of photoluminescence.
In another typical embodiment of the invention, a kind of quantum dot composite material is additionally provided, the quantum dot is multiple
Condensation material includes：Quantum dot and the macromolecule matrix solidfied material being coated on around quantum dot, macromolecule matrix solidfied material have such as
Lower formula (I) structural unit is as follows：
Wherein, wherein R1For
R2For
R3For
, n be >=1 integer.
Structural unit in above-mentioned quantum dot composite material refers to constituting macromolecular chain and determining macromolecular structure with certain
The atom combination that mode connects.Constitute above structure unit raw material be respectively：Acrylate, structural formula areEpoxy acrylate, structural formula areAsphalt mixtures modified by epoxy resin
Fat, structural formula areWherein, R1、R2And R3Substituent group it is same as described above, and will not be described here in detail.
Acrylate end-allyl group active group containing there are two, can be with an end-allyl group activity on epoxy acrylate
Group reacts, and also itself polymerisation can occur；Epoxy resin end ring oxygen activity group containing there are two, can be with epoxy acrylate
On an end ring oxygen activity group reaction, also can itself occur polymerisation；Pass through acrylate, epoxy acrylate and ring
Chemical reaction between oxygen resin forms space net structure.Multiple "-" of above structure cell end represent double bond or epoxy
Key open after half of chemical bond, the structure list that arbitrary half of chemical bond in each above structure unit can be adjacent thereto
Arbitrary half of chemical bond in member is attached to form complete chemical bond.Every half of chemical bond is arbitrary with another structural unit
Half of chemistry key connection, just forms the macromolecule matrix solidfied material of reticular structure in this way.The macromolecule matrix of reticular structure is solid
Compound surrounds the above-mentioned quantum dot composite material that central quantum dot just forms the application.Such quantum dot composite material,
Center is high to the compatibility of quantum dot, and outer layer is higher to the barrier property of aqueous vapor and oxygen, and passes through amphiphilic between outer layer and internal layer
The chemical bonds of property, so as to form with stable luminescent property and the higher quantum dot composite material of luminous efficiency.It is above-mentioned
Quantum dot can be a quantum dot or a group quantum dot.
In another typical embodiment of the invention, a kind of quantum dot light emitting device, quantum dot hair are additionally provided
Optical device includes quantum dot composite material, and quantum dot composite material is above-mentioned quantum dot composite material.Including above-mentioned quantum dot is multiple
The quantum dot light emitting device of condensation material has the advantages that luminous efficiency is high and stability is good.
In quantum dot composite material contained by above-mentioned quantum dot light emitting device, the specific luminescent color of quantum dot can basis
Practical luminescent device is reasonably selected.In a kind of preferred embodiment of the present invention, quantum dot be red quantum dot and
Green quantum dot.Red quantum dot and green quantum dot can be used in display field, red under the irradiation of blue led backlight
Blue light can be absorbed with green quantum dot and converts thereof into red light and green light, and RGB is formed with unabsorbed blue light
White light field.Due to the half-peak width of red and green quantum dot, compared with traditional liquid crystal display, quantum dot shows that colour gamut is high,
Color saturation is high.
Above-mentioned quantum dot light emitting device can be quantum dot film or quantum dot pipe according to actual needs.Quantum dot composition exists
Film-forming can form quantum dot film on carrier.In concrete application environment, the upper layer of quantum dot film or lower layer can be with
There are the Obstruct membrane or protective film that polymer film is formed, or there can also be other among quantum dot film and polymer film
Layer, for example obstruct the metal oxide layer of water oxygen.Quantum dot composition cures in the cavity of pipeline forms quantum dot pipe,
Quantum dot pipe is that quantum dot composition is placed into solidification in tubular container then to seal, and the light for display backlight system is converted
Device.
Advantageous effect to further illustrate the present invention below in conjunction with specific embodiments.
Embodiment 1
Using acrylate, epoxy acrylate and epoxy resin as macromolecule matrix, by macromolecule matrix, dilution
Agent, crosslinking agent, curing agent, additive and quantum dot are mixed to get the first mixture；First mixture is cured to obtain quantum
Point composite material, each specific reactant of step is raw materials used to be shown in Table 1, and when specific reaction condition is shown in Table the dosage between each raw material
2。
Embodiment 2---10
Embodiment 2 to embodiment 10 uses step same as Example 1, using preparation parameter shown in Tables 1 and 2 and
It is prepared by condition.
Comparative example 1
Using polyacrylate as macromolecule matrix, other parameters condition is shown in Tables 1 and 2.
Comparative example 2
Using bisphenol A epoxide resin as macromolecule matrix, other parameters condition is shown in Tables 1 and 2.
Comparative example 3
Using the mixture of acrylate and epoxy resin as macromolecule matrix, other parameters condition is shown in Tables 1 and 2.
Table 1：Each raw materials used type of embodiment and comparative example
Table 2：The preparation condition of each embodiment and comparative example
Detection：
The performance of quantum dot composite material prepared by the various embodiments described above and comparative example is detected, specific detection side
Method is as follows, and testing result is shown in Table 3.
The detection method of quantum dot light emitting efficiency is：Using 450nm blue LED lamps as backlight spectra, integrating sphere is utilized
Blue backlight spectrum and the spectrum through quantum dot composite material are tested respectively, and calculating quantum dot using the integral area of spectrogram sends out
Light efficiency.
Quantum dot light emitting efficiency=(red quantum dot absorbs peak area+green quantum dot and absorbs peak area)/(Blue backlight
Peak area-is through the unabsorbed blue peak area of quantum dot composite material) * 100%.
The detection method of stability of photoluminescence is：The test method of stability of photoluminescence is mainly included in high temperature blue light illumination (70
DEG C, 0.5W/cm2), under the aging conditions such as high temperature and humidity (65 DEG C/95%RH) and high-temperature storage (85 DEG C), detection quantum dot is compound
The efficiency change and invalid edges size of material.
Table 3：
Note：The above efficiency is relative efficiency, the efficiency of comparative example 1 is set to 100%, other efficiency correspond in proportion.
Table 4：
Note：The above invalid edges are after making quantum dot film, by determining the size of edge invalid edges, quantum dot under microscope
The size of film is 6cm*6cm.
From above-mentioned table 3 and table 4 as can be seen that in the macromolecule matrix for preparing quanta point material, acrylate ratio is higher,
Start efficiency is higher, and aging attenuation amplitude is bigger, and black surround is bigger；Conversely, epoxy resin ratio is higher, start efficiency is lower, always
Change attenuation amplitude is smaller, and black surround is smaller.Compared with comparative example 1, initial light emission efficiency differs not embodiment 1-10 with comparative example 1
Greatly, but luminous efficiency attenuation amplitude (passes through formula：Attenuation amplitude=(aging behind efficiency-starting efficiency)/starting efficiency x
100% is calculated) it is substantially reduced compared with comparative example 1, stability of photoluminescence greatly enhances.Embodiment 1-10 is compared with comparative example 2, just
It originates light efficiency and is far above comparative example 2, and luminous efficiency attenuation amplitude is not much different with comparative example 2.It is real compared with comparative example 3
Apply a 1-10 and use the amphiphilic compound containing epoxy acrylate, in a manner of being keyed by chemistry by acrylate and
The macromolecule matrix that epoxy resin is formed by connecting surrounds the luminescent material that quantum dot is formed, with the acrylate using physical blending
With epoxy resin and the quanta point material that is formed is compared, not only there is higher luminous efficiency, and luminous efficiency after aging
Attenuation amplitude it is small, the size of invalid edges is also relatively small, and the stability of luminous efficiency is stronger.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：The present invention's
Quantum dot composition selection is widely used as the acrylate and epoxy resin that adhesive uses, and can well with epoxy resin
Macromolecule matrix of the epoxy acrylate combined with acrylate as dispersion quantum dot.Wherein, acrylate and quantum dot
Compatibility it is best, and one end of epoxy acrylate is epoxy group and the other end is acrylate, have amphipathic, epoxy
Group end and epoxy resin have a good compatibility, and acrylate end and acrylic resin have a good compatibility, thus
Bridge connection function is played between acrylate and epoxy resin.Epoxy resin is connected to three kinds of ingredients most as hydrophilic system
Outside is used for starvation and aqueous vapor.The present invention sets about in terms of macromolecule matrix material composition, solves the phase with quantum dot
The problem of capacitive and starvation and aqueous vapor, improves the luminous efficiency and stability of quantum dot composite material.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (29)
1. a kind of quantum dot composition, which is characterized in that the quantum dot composition includes quantum dot and for disperseing the amount
The macromolecule matrix of son point, the macromolecule matrix includes acrylate, epoxy acrylate and epoxy resin.
2. quantum dot composition according to claim 1, which is characterized in that the acrylate, epoxy acrylate with
And the mass ratio of epoxy resin is 5~10：1~5：1~5.
3. quantum dot composition according to claim 1, which is characterized in that further include dilution in the quantum dot composition
Agent.
4. quantum dot composition according to claim 3, which is characterized in that the diluent is the acrylic acid of single functionality
Monomer.
5. quantum dot composition according to claim 4, which is characterized in that the matter of the acrylic monomers of the single functionality
The mass ratio of amount and the macromolecule matrix is 1~5：10~20.
6. quantum dot composition according to claim 1, which is characterized in that further include crosslinking in the quantum dot composition
Agent.
7. quantum dot composition according to claim 6, which is characterized in that the crosslinking agent is that degree of functionality is more than or equal to 2
Acrylic monomers.
8. quantum dot composition according to claim 6, which is characterized in that the crosslinking agent is bifunctionality or trifunctional
Spend acrylic monomers.
9. quantum dot composition according to claim 7, which is characterized in that the degree of functionality is more than or equal to 2 acrylic acid
The mass ratio of monomer and the macromolecule matrix is 1~3：10~20.
10. quantum dot composition according to claim 1, which is characterized in that further include solid in the quantum dot composition
Agent.
11. quantum dot composition according to claim 10, which is characterized in that the curing agent is radical UV curing agent
With cation photocuring agent, or be radical UV curing agent and thermal curing agents.
12. quantum dot composition according to claim 1, which is characterized in that further include adding in the quantum dot composition
It is light diffusion particle and/or antioxidant to add agent, the additive.
13. a kind of preparation method of quantum dot composite material, which is characterized in that the preparation method includes：
Macromolecule matrix, crosslinking agent, curing agent and quantum dot are mixed, the first mixture is obtained；
First mixture is cured, the quantum dot composite material is obtained；
Wherein, the macromolecule matrix includes acrylate, epoxy acrylate and epoxy resin.
14. preparation method according to claim 13, which is characterized in that by the macromolecule matrix, diluent, the friendship
Connection agent, the curing agent and the quantum dot are mixed, and first mixture is obtained.
15. preparation method according to claim 13, which is characterized in that by the macromolecule matrix, the crosslinking agent, institute
It states curing agent, the quantum dot and additive to be mixed, obtains first mixture.
16. preparation method according to claim 13, which is characterized in that by the macromolecule matrix, diluent, the friendship
Connection agent, the curing agent, the quantum dot and additive are mixed, and first mixture is obtained.
17. preparation method according to claim 13, which is characterized in that the acrylate, epoxy acrylate and
The mass ratio of epoxy resin is 5~10：1~5：1~5.
18. the preparation method according to claim 14 or 16, which is characterized in that the diluent is the propylene of single functionality
Acid monomers.
19. preparation method according to claim 18, which is characterized in that the acrylic monomers of the single functionality with it is described
The mass ratio of macromolecule matrix is 1~5：10~20.
20. preparation method according to claim 13, which is characterized in that the crosslinking agent is degree of functionality more than or equal to 2
Acrylic monomers.
21. preparation method according to claim 20, which is characterized in that the degree of functionality is more than or equal to 2 acrylic acid list
The mass ratio of body and the acrylate is 1~3：10~20.
22. preparation method according to claim 13, which is characterized in that the curing agent include radical UV curing agent and
The step of thermal curing agents or radical UV curing agent and cation photocuring agent, the solidification includes：
Photocuring is carried out to first mixture under the action of radical UV curing agent, obtains solidification semi-finished product；
Heat cure or light are carried out to the solidification semi-finished product under the action of thermal curing agents or the cation photocuring agent
Solidification, obtains the quantum dot composite material.
23. preparation method according to claim 13, which is characterized in that the curing agent include radical UV curing agent and
The step of cation photocuring agent, the solidification includes：
First mixture is carried out under being acted on while the radical UV curing agent and the cation photocuring agent
Solidification, obtains the quantum dot composite material.
24. preparation method according to claim 15 or 16, which is characterized in that the additive be light diffusion particle and/
Or antioxidant.
25. a kind of quantum dot composite material, which is characterized in that the quantum dot composite material, which uses in claim 13 to 24, appoints
Preparation method described in one is prepared.
26. a kind of quantum dot composite material, which is characterized in that the quantum dot composite material includes：Quantum dot and it is coated on institute
The macromolecule matrix solidfied material around quantum dot is stated, the macromolecule matrix solidfied material has the structure list as shown in following formula (I)
Member；
Wherein, R1For
R2For
R3For
The integer that n is >=1.
27. a kind of quantum dot light emitting device, including quantum dot composite material, which is characterized in that the quantum dot composite material is
Quantum dot composite material described in claim 26.
28. quantum dot light emitting device according to claim 27, which is characterized in that the amount in the quantum dot composite material
Son point is red quantum dot and green quantum dot.
29. quantum dot light emitting device according to claim 27, which is characterized in that the quantum dot light emitting device is quantum
Point film or quantum dot pipe.
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| CN111384269A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423275B (en) | 2017-08-29 | 2020-03-31 | 纳晶科技股份有限公司 | Quantum dot composition, quantum dot luminescent material, preparation method thereof and luminescent device containing quantum dot luminescent material |
| US20200326597A1 (en) * | 2017-10-17 | 2020-10-15 | Kateeva, Inc. | Ink compositions with high quantum dot concentrations for display devices |
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| CN108389943B (en) * | 2018-02-27 | 2019-07-26 | 苏州星烁纳米科技有限公司 | Light emitting diode with quantum dots and preparation method thereof |
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| CN111378444A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot film and preparation method thereof |
| CN110591608B (en) * | 2019-09-26 | 2021-04-23 | 厦门玻彩新材料有限公司 | Thermosetting quantum dot glue, quantum dot film and preparation method thereof |
| CN111808601A (en) * | 2020-06-05 | 2020-10-23 | 苏州星烁纳米科技有限公司 | Quantum dot composition and display device |
| WO2022257701A1 (en) * | 2021-06-11 | 2022-12-15 | 纳晶科技股份有限公司 | Composite material and preparation method therefor, and optical conversion device |
| CN115651639B (en) * | 2022-12-27 | 2023-03-21 | 北京北达聚邦科技有限公司 | Quantum dot, quantum dot and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937158A (en) * | 2014-03-24 | 2014-07-23 | 北京化工大学 | Quantum dot with high transparency and high fluorescence efficiency/epoxy resin nano composite material, preparation and applications thereof |
| CN104090413A (en) * | 2014-06-20 | 2014-10-08 | 京东方科技集团股份有限公司 | Displaying base plate, manufacture method thereof and display device |
| EP3032923A1 (en) * | 2014-12-08 | 2016-06-15 | LG Electronics Inc. | Method for preparing light conversion composite, light conversion film, backlight unit and display device having the same |
| CN105694590A (en) * | 2016-01-19 | 2016-06-22 | 纳晶科技股份有限公司 | Quantum dot ink, light-emitting film and electroluminescent device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102149938B1 (en) * | 2013-08-08 | 2020-09-01 | 삼성전자주식회사 | Methods of grinding semiconductor nanocrystal polymer composite particles |
-
2016
- 2016-08-02 CN CN201610623563.5A patent/CN106381140B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937158A (en) * | 2014-03-24 | 2014-07-23 | 北京化工大学 | Quantum dot with high transparency and high fluorescence efficiency/epoxy resin nano composite material, preparation and applications thereof |
| CN104090413A (en) * | 2014-06-20 | 2014-10-08 | 京东方科技集团股份有限公司 | Displaying base plate, manufacture method thereof and display device |
| EP3032923A1 (en) * | 2014-12-08 | 2016-06-15 | LG Electronics Inc. | Method for preparing light conversion composite, light conversion film, backlight unit and display device having the same |
| CN105694590A (en) * | 2016-01-19 | 2016-06-22 | 纳晶科技股份有限公司 | Quantum dot ink, light-emitting film and electroluminescent device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384269A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111384269B (en) * | 2018-12-29 | 2021-08-03 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
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