CN106188429A - Quantum dot composition, quantum dot composite material, its preparation method and application - Google Patents
Quantum dot composition, quantum dot composite material, its preparation method and application Download PDFInfo
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- CN106188429A CN106188429A CN201610632828.8A CN201610632828A CN106188429A CN 106188429 A CN106188429 A CN 106188429A CN 201610632828 A CN201610632828 A CN 201610632828A CN 106188429 A CN106188429 A CN 106188429A
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- quantum dot
- agent
- composite material
- epoxy
- macromolecule matrix
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- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention provides a kind of quantum dot composition, quantum dot composite material, its preparation method and application.Wherein, quantum dot composition includes quantum dot and macromolecule matrix, and macromolecule matrix includes Epoxy Phenolic Acrylates block copolymer.Above-mentioned quantum dot composition comprises the Epoxy Phenolic Acrylates block copolymer macromolecule matrix as dispersion quantum dot by selection, owing to Epoxy Phenolic Acrylates block copolymer combines, acrylate is good with the quantum dot compatibility and epoxy resin is to oxygen and the advantage of aqueous vapor good barrier property, and epoxy block is linked by chemical bond and effect with arylate blocks, there is extraordinary chemical stability.The application sets about in terms of macromolecule matrix material composition, the problem solving the compatibility with quantum dot and starvation and aqueous vapor, improves luminous efficiency and the stability of quantum dot composite material.
Description
Technical field
The present invention relates to quantum dot composite material field, be combined in particular to a kind of quantum dot composition, quantum dot
Material, its preparation method and application.
Background technology
Quantum dot, can be described as again nanocrystalline, is a kind of nano-particle elementary composition by II-VI group or iii-v.Amount
The particle diameter of son point is typically in the range of between 1～10nm, and owing to electronics and hole are by quantum confinement, continuous print band structure becomes and has
The discrete energy levels structure of molecular characterization, can launch fluorescence after being excited.Based on quantum effect, quantum dot at solaode, send out
The fields such as optical device and optical bio labelling are with a wide range of applications.
Quantum dot has exciting light spectrum width and continuous distribution, and emission spectrum is narrow and symmetrical, Color tunable, photochemical stable
Property high, the superior fluorescent characteristic such as fluorescence lifetime length.By controlling the shape of quantum dot, structure and size, it is possible to easily
Regulate its energy gap width, exciton (in quasiconductor, if an electronics goes, then at valency to empty conduction band from full valence
Produce a hole in band, and in conduction band, produce an electronics, thus form an electron-hole pair.Hole band positive electricity, electricity
Subband negative electricity, the coulomb adelphotaxy between them can the most spatially be bound together, such shape
The complex become is referred to 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
Change with quantity of solvent makes maximum absorption wavelength and absorption intensity change.It is referred to as when maximum wavelength moves to shortwave direction
Blue shift；Blue shift refers to the frequency of the electromagnetic wave that the object that a forward observer moves scattered direction to blue end on spectral line
Mobile, it is meant that wavelength reduces.With particle size reduction and color moves to blue light direction) etc. electronic state.Therefore, can lead to
Cross the size controlling quantum dot, obtain the color that visible region is arbitrarily wanted, and can obtain by controlling the size of half-peak breadth
The monochromatic light of pure color, is used for showing that field can increase substantially colour gamut and color saturation.
Owing to the particle diameter of quantum dot is typically in the range of between 1～10nm, there is the biggest specific surface area, surface phase atomic number
Increase, the coordination that result in surface atom is not enough, 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 atom.Therefore, general quantum dot surface needs
Selecting suitable part to carry out the metal-complexing with quantum dot surface, efficiency and the stability of quantum dot are had certainly by the kind of part
Affect qualitatively.Along with development and the optimization of quantum dot synthetic technology, the efficiency of quantum dot and stability have all reached industrialization
Level.But, the skin effect of quantum dot uniqueness also determines it and can break aqueous vapor and the sensitivity of oxygen, aqueous vapor and oxygen
The part of bad quantum dot surface, reduces the efficiency of quantum dot.Quantum dot size is the least, and specific surface area is the biggest, to aqueous vapor and oxygen
Sensitivity the highest.
Along with the maturation of quanta point material, the application of quanta point material is increasingly wider, especially in display field.But, amount
Son point material can not be used alone, it is necessary to is dispersed in macromolecule matrix.In view of the characteristic of quantum dot itself, macromolecule matrix
Must have characteristics that (1) and quanta point material have the preferable compatibility, can well keep the luminous efficiency of quantum dot
(2) aqueous vapor and oxygen had preferable barrier；(3) solid-state can be become by liquid curing under the effect of light or heat.
Macromolecule matrix about dispersion quantum dot has a lot of report, can be summarized as following a few class: (1) is to quantum dot surface
Carry out silicone-modified, select organosilicon material as macromolecule matrix, be mainly used in the original position encapsulation of LED chip.Organosilicon
Material has extraordinary heat stability and optical stability, but, owing to the high-flexibility of organosilicon material siliconoxygen bond is with big
Bond angle, it is the most poor to the barrier of aqueous vapor and oxygen.Under conditions of high temperature and blue light illumination, quanta point material is easily subject to
Aqueous vapor and the destruction of oxygen and lost efficacy.(2) utilize porous material absorption quantum dot or quantum dot epoxy resin cladding is made
Microsphere.Epoxy resin is due to higher polarity, and the compatibility with quantum dot is poor, and easily sends out under conditions of high temperature illumination
Huang, affects quantum dot luminous efficiency.(3) select acrylate monomer or polyacrylate as macromolecule matrix.Acrylate
Having the preferable compatibility with quantum dot, quantum dot can preferably be dispersed in acrylate.But, acrylate is to aqueous vapor and oxygen
The barrier of gas is poor.(4) forming phase separation structure, utilize hydrophobic systems (acrylate) to disperse quantum dot, 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 is certain defect in long-term chemical durability aspect.
Therefore, it is still necessary to the application to quantum dot of the prior art improves, to improve the luminous efficiency of quantum dot
And stability.
Summary of the invention
Present invention is primarily targeted at a kind of quantum dot composition of offer, quantum dot composite material, its preparation method and
Application, with solve prior art due to the barrier of aqueous vapor and oxygen difference or with the dispersion matrix poor compatibility of quantum dot and lead
The problem that the luminous efficiency of quantum dot composite material that causes is low.
To achieve these goals, according to an aspect of the invention, it is provided a kind of quantum dot composition, quantum dot group
Compound includes quantum dot and macromolecule matrix, and macromolecule matrix includes epoxy novolac-acrylate block copolymer.
Further, epoxy novolac-acrylate block copolymer is that the epoxy novolac-acrylate of following structural formula is embedding
Duan Gongju
Thing: wherein, x, y are integer, and x >=1, y >=1, and 3≤x+y≤7.
Further, quantum dot composition also including, cross-linking agent, preferably cross-linking agent are double/three-functionality-degree acrylic monomers
And/or double/three-functionality-degree epoxy monomer；The most double/three-functionality-degree acrylic monomers and/or double/three-functionality-degree epoxy monomer
It is 1～3:10～20 with the mass ratio of epoxy novolac-acrylate block copolymer.
Further, also including firming agent in quantum dot composition, preferred consolidation agent is radical UV curing agent and thermosetting
Agent, or be radical UV curing agent and cation photocuring agent.
Further, quantum dot composition also includes additive, and preferable additives is light diffusion particle and/or antioxidant.
According to a further aspect in the invention, it is provided that the preparation method of a kind of quantum dot composite material, preparation method includes:
Macromolecule matrix, cross-linking agent, firming agent quantum dot and optional additive are mixed to get the first mixture；To the first mixing
Thing solidifies, and obtains quantum dot composite material；Wherein, macromolecule matrix includes epoxy novolac-acrylate block copolymer.
Further, the structural formula of epoxy novolac-acrylate block copolymer is:Its
In, x, y are integer, and x >=1, y >=1, and 3≤x+y≤7.
Further, cross-linking agent is bifunctionality acrylic monomers, three-functionality-degree acrylic monomers, bifunctionality epoxy list
Body and/or three-functionality-degree epoxy monomer；More preferably cross-linking agent is 1 with the mass ratio of epoxy novolac-acrylate block copolymer
～3:10～20.
Further, firming agent is radical UV curing agent and thermal curing agents, and the step of preferred consolidation includes: use freely
Base light curing agent carries out photocuring to the first mixture, obtains solidifying semi-finished product；Use thermal curing agents that solidification semi-finished product are carried out
Heat cure, obtains quantum dot composite material.
Further, firming agent is radical UV curing agent and cation photocuring agent, and the step of solidification includes: in freedom
Under effect, the first mixture is solidified while base light curing agent and cation photocuring agent, obtain quantum dot composite wood
Material.
Further, additive is light diffusion particle and/or antioxidant.
According to an aspect of the present invention, it is provided that a kind of quantum dot composite material, quantum dot composite material uses above-mentioned
A kind of preparation method is prepared from.
According to a further aspect in the invention, it is provided that a kind of quantum dot composite material, quantum dot composite material includes quantum
Point and the macromolecule matrix solidfied material being coated on around quantum dot, macromolecule matrix solidfied material is that epoxy novolac-acrylate is embedding
Cross-linking products between section copolymer, cross-linking products has a construction unit as shown in following formula (I):
To achieve these goals, according to a further aspect of the invention, it is provided that a kind of quantum dot light emitting device, including
Quantum dot 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 point and/or green quantum dot.
Further, quantum dot light emitting device is quantum dot film or quantum dot pipe.
Application technical scheme, it is embedding that above-mentioned quantum dot composition comprises epoxy novolac-acrylate by selection
Section copolymer is as the macromolecule matrix of dispersion quantum dot, owing to epoxy novolac-acrylate block copolymer combines propylene
Acid esters and the quantum dot compatibility are good and epoxy resin is to oxygen and the advantage of aqueous vapor good barrier property, and epoxy block and acrylic acid
Ester block, by chemical bond and effect link, has extraordinary chemical stability.The application forms from macromolecule matrix material
Aspect is set about, the problem solving the compatibility with quantum dot and starvation and aqueous vapor, improves quantum dot composite material
Luminous efficiency and stability.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c) show according to forming lamellar phase in a kind of preferred embodiment of the present invention
The microcosmic chain form schematic diagram of the epoxy novolac-acrylate block copolymer separated: before Fig. 1 (a) solidification；Fig. 1 (b) photocuring
After；After Fig. 1 (c) heat or photocuring；
Fig. 2 (a), Fig. 2 (b) and Fig. 2 (c) show according to forming spherical phase in a kind of preferred embodiment of the present invention
The microcosmic chain form schematic diagram of the epoxy novolac-acrylate block copolymer separated: wherein, before Fig. 2 (a) solidification；Fig. 2 (b)
After photocuring；After Fig. 2 (c) heat or photocuring；
Above-mentioned accompanying drawing 1 (a) is in accompanying drawing 2 (b), and single pore represents green quantum dot, and the biggest stain represents
Red quantum point, the molecules present novolac epoxy resin block of band pore, the generation of band double bond on linear segment on linear segment
Table arylate blocks, the monomer molecule of three double bonds represents acrylic monomers, and the monomer molecule of three pores represents epoxy
Monomer, the reference that above-claimed cpd is corresponding is respectively as follows:
10, green quantum dot；20, red quantum point；30, novolac epoxy resin block；40, arylate blocks；50, third
Acrylic monomer；60, epoxy monomer；80, arylate blocks cured layer；90, novolac epoxy resin block cured layer；100, first
Shell；110, the second shell.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combination mutually.The present invention is described in detail below in conjunction with embodiment.
In the application, epoxy novolac-acrylate block copolymer refers to what novolac epoxy resin and acrylate were formed
Block copolymer.
As background section is previously mentioned, due to the barrier difference of aqueous vapor and oxygen or the matrix with dispersion quantum dot
Poor compatibility and cause quantum dot light emitting material of the prior art to exist luminous efficiency is low and the problem of poor stability, in order to change
This situation kind, in a kind of typical embodiment of the present invention, it is provided that a kind of quantum dot composition, this quantum dot composition
Including quantum dot and macromolecule matrix, macromolecule matrix includes epoxy novolac-acrylate block copolymer.
Above-mentioned quantum dot composition comprises epoxy novolac-acrylate block copolymer as dispersion quantum dot by selection
Macromolecule matrix, due to epoxy novolac-acrylate block copolymer combine acrylate and the quantum dot compatibility good with
And epoxy resin is to oxygen and the advantage of aqueous vapor good barrier property, and epoxy block passes through chemical bond and effect with arylate blocks
Link, has extraordinary chemical stability, thus sets about in terms of macromolecule matrix material composition, solve and quantum dot
The compatibility and starvation and the problem of aqueous vapor, improve luminous efficiency and the stability of quantum dot composite material.
In above-mentioned quantum dot composition, epoxy novolac-acrylate block copolymer is novolac epoxy resin and acrylic acid
What reaction was formed not only contains epoxide group but also contain the block copolymer of acrylic acid groups.Its reaction scheme is as follows:
Wherein, n=x+y, x, y are integer, and x >=1, y >=1, and 3≤n=x+y≤7.
Adjust above-mentioned novolac epoxy resin and acrylic acid ratio, the block copolymer of available heterogeneity.At this
In bright a kind of preferred embodiment, above-mentioned novolac epoxy resin-acrylic block copolymers is the epoxy novolac of following structural formula
Resin-propylene acid block copolymer:Wherein, x >=1,
Y >=1, and 3≤x+y≤7.Big I according to x and y forms different phase separation structures.When x Yu y approximately equal, phenolic aldehyde ring
Oxygen-acrylate block copolymer forms stratiform phase separation structure, novolac epoxy resin block and arylate blocks rule
It is arranged in layer structure.As shown in Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c), novolac epoxy resin block 30 is arranged in side, propylene
Acid esters block 40 is arranged in opposite side.And work as x=1, during y=5, epoxy novolac-acrylate block copolymer is then formed spherical
Phase separation structure.Such as Fig. 2 (a) to Fig. 2 (c), arylate blocks 40 is shorter due to segment, during the formation that flocks together is spherical
The heart, novolac epoxy resin block 30 is then arranged in outside, forms arylate blocks 40 and surrounds shape.Quantum dot (includes green
Color quantum dot 10 and red quantum point 20) due to the compatibility with arylate blocks 40 preferably, preferentially it is dispersed in acrylate
In block 40.
In above-mentioned quantum dot composition, the amount ratio of quantum dot Yu macromolecule matrix be there is no particular/special requirement, if high score
Quantum dot can be carried out dispersed by subbase body, and can maintain luminous efficiency and the stability of quantum dot.Such as, according to
It is actually needed a certain amount of macromolecule matrix can one or a group quantum dot be disperseed.A kind of the most real in the present invention
Executing in example, quantum dot is 0.1～1:10～100 with the mass ratio of macromolecule matrix.Concrete ratio need to be according to objective optics parameter
Depending on.
In above-mentioned quantum dot composition, according to actual needs, can be prepared as in product process required one or
Other auxiliary elements multiple are included, it is also possible to be not included in interior and be provided separately in concrete preparation process.At this
In bright another kind of preferred embodiment, above-mentioned quantum dot composition also including, cross-linking agent, preferably cross-linking agent are that degree of functionality is more than
The acrylic monomers of the acrylic monomers equal to 2 or epoxy monomer, more preferably bifunctionality or three-functionality-degree and/or difunctionality
Degree or the epoxy monomer of three-functionality-degree.
Cross-linking agent herein is internal crosslinker, enters in macromolecular structure chain when polymerization as a kind of monomer, or makees
It is that a component joins in macromolecule matrix, it is possible to storage-stable, is only being heated to uniform temperature or radiation condition
Reaction can be crosslinked.Preferably the acrylic monomers of three-functionality-degree and epoxy monomer are as cross-linking agent, its active group respectively with
Arylate blocks and novolac epoxy resin block reaction form cross-linked structure, and cross-linking efficiency is high, and do not occur adverse reaction and
Cohesion.
It is highly preferred that the acrylic monomers of above-mentioned bifunctionality or three-functionality-degree is selected from 1,6-hexanediyl ester,
Triethylene-glycol dimethylacrylate, Tricyclodecane Dimethanol diacrylate, three (2-ethoxy) Carbimide. three propylene
Acid esters, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, 3-ethyoxyl-trimethylolpropane tris acrylic acid
Ester, 9-ethyoxyl-trimethylolpropane trimethacrylate, propoxyl group-trimethylolpropane trimethacrylate and trihydroxy methyl
One or more in propane trimethyl acrylic ester.The epoxy monomer of above-mentioned bifunctionality or three-functionality-degree is selected from ethylene glycol bisthioglycolate
Glycidyl ether, 1,6-hexanediol diglycidyl ether, BDDE, trimethylolpropane tris shrink sweet
One or more in oil ether and triglycidyl isocyanurate.These cross-linking agent are ensureing curing rate and the degree of cross linking
Under premise, there is preferable pliability and intensity.
In above-mentioned quantum dot composition, according to the specific kind of difference of actual production technique and cross-linking agent, it is used
The consumption of cross-linking agent can obtain by suitably adjusting.In another kind preferred embodiment of the present invention, bifunctionality or three officials
The epoxy monomer of the acrylic monomers of energy degree and/or bifunctionality or three-functionality-degree and epoxy novolac-acrylic ester block
The mass ratio of thing is 1～3:10～20.Mass ratio is controlled within the range, it is possible to realize on the premise of relatively fewer consumption
Speed well and the stable cross-linking effect of cross-linked structure.
It has been observed that according to actual needs, other auxiliary of required one or more will can be prepared as in product process
Composition is included.In another preferred embodiment of the present invention, above-mentioned quantum dot composition also includes firming agent, excellent
Selecting firming agent is radical UV curing agent and thermal curing agents, or radical UV curing agent and cation curing agent.Free radical light
Firming agent more preferably UV free radical curing agent, cation curing agent more preferably cation photocuring agent.
The concrete kind of the radical UV curing agent in above preferred embodiment includes but are not limited to 1-hydroxy-cyclohexyl
Phenyl ketone (light trigger 184), 2-methyl isophthalic acid-[4-methyl mercapto phenyl]-2-morpholinyl-1-acetone (light trigger 907), 2-hydroxyl
Base-aminomethyl phenyl propane-1-ketone (light trigger 1173), 2,4,6-trimethylbenzoy-dipheny phosphine oxide (light triggers
TPO), phenyl double (2,4,6-trimethylbenzoyl) phosphine oxide (light trigger 819), 2-phenyl benzyl-2-dimethyl amine-1-
[4-morpholine benzyl phenyl]-butanone (light trigger 369), α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone (light trigger 651), hexichol
Any one or a few in ketone (photoinitiator b P) and methyl benzoylformate (light trigger MBF).Cationic photopolymerization is solid
The concrete kind of agent includes but are not limited to 4,4'-dimethyl diphenyl iodine salt hexafluorophosphate, double (4-2-methyl-2-phenylpropane bases)
Iodine hexafluorophosphate, double (4-2-methyl-2-phenylpropane base) iodine fluoroform sulphonate, cyclopropyl diphenyl sulfur tetrafluoroborate, diphenyl
Iodine hexafluorophosphate, diphenyl iodine arsenate, diphenyl iodine trifluoro-methanyl sulfonate, triphenyl sulfur tetrafluoroborate,
Any one or a few in triphenyl phosphonium bromide sulfonium and three p-methylphenyl sulfonium hexafluorophosphates.The concrete kind bag of thermal curing agents
Include but lose be limited to ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-diaminobenzene., two amido sulfobenzide .s,
Hydroxyethylethylene diamine, Benzophenone carboxylic acid dianhydride, tetrabydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, all
Any one or a few in benzene tetracarboxylic acid acid anhydride, 2-methylimidazole and 2-ethyl imidazol(e).It is wide that these firming agent have the suitability,
Curing rate is fast, and curing efficiency advantages of higher, compound use has certain cooperative effect, obtains solidfied material of good performance.
In actual production, according to the difference of the performance requirement of the luminescent device to be prepared, above-mentioned quantum dot composition
In can also include the composition that improves or comprise its performance, to improve the luminous efficiency of quantum dot in luminescent device further
And stability of photoluminescence.In another kind preferred embodiment of the present invention, also including additive in above-mentioned quantum dot composition, this adds
Adding agent is light diffusion particle and/or antioxidant.
In above preferred embodiment, light diffusion particle selects conventional photodiffusion material, include in the present invention but
It is not limited only to TiO2、Zr2O3、ZnO、Al2O3、BaSO4、CaCO3、SiO2And any one or a few in silicone.Antioxygen
Agent includes but are not limited to 4-hydroxy-dodecanoic acid anilid, N, N'-six double 3 (3,5-di-t-butyl-4-hydroxyls of methine
Phenyl) propionic acid amide., 4,4-bis-t-octyl diphenylamines, 2,6 ditertiary butyl p cresol (BHT), β (3,5-di-t-butyl-4-hydroxyls
Phenyl) propanoic acid octadecyl (antioxidant 1076), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester
(antioxidant 1010), three [2.4-di-tert-butyl-phenyl] phosphite ester (irgasfos 168), double (2,4-DI-tert-butylphenol compounds) season penta
Any one in the double octadecyl ester (antioxidant 618) of tetrol diphosphites (antioxidant 626) and tetramethylolmethane diphosphorous acid
Or it is several.Light diffusion particle can be effectively improved the luminous efficiency of quantum dot, and antioxidant contributes to extending 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 ability.On the other hand, the antioxidant of mentioned kind has the most anti-
Oxygen effect, the phenomenon such as xanthochromia and the degraded that can effectively suppress macromolecule matrix.And, Hinered phenols and phosphorous acid esters antioxygen
Agent compounds and uses the cooperative effect that can reach certain, has better antioxidant effect.
In the another kind of typical embodiment of the present invention, it is provided that the preparation method of a kind of quantum dot composite material, should
Preparation method includes: macromolecule matrix, cross-linking agent, firming agent, quantum dot and optional additive are mixed, and obtains the
One mixture；First mixture is solidified, obtains quantum dot composite material；Wherein, macromolecule matrix include epoxy novolac-
Acrylate block copolymer.
The preparation method of above-mentioned quantum dot composite material, has epoxy resin concurrently to aqueous vapor and the insulating of oxygen by employing
Can be good, and the epoxy novolac-acrylate block copolymer of the good advantage of the compatibility of acrylate and quantum dot is as amount
The macromolecule matrix of son point, the solidification caused by crosslinking and the firming agent of cross-linking agent successfully solves the phase with quantum dot
Capacitive and barrier problem, and the existence of additive also contributes to improve efficiency and the long-time stability of quantum dot.
In above-mentioned preparation method, in epoxy novolac-acrylate block copolymer, the ratio of two blocks can be according to reality
The difference that border needs carries out Reasonable adjustment.Size according to x and y adjusts can form different phase separation structures.When x Yu y approximates
Time equal, epoxy novolac-acrylate block copolymer forms stratiform phase separation structure, novolac epoxy resin block and acrylic acid
What ester block was regular is arranged in layer structure.As shown in Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c), novolac epoxy resin block 30 arranges
In side, arylate blocks 40 is arranged in opposite side, and arylate blocks 40 first forms acrylic acid under the effect of photocuring
Ester block cured layer 80；Then novolac epoxy resin block 30 forms novolac epoxy resin under the effect of heat cure or photocuring
Block cured layer 90.And work as x=1, during y=5, epoxy novolac-acrylate block copolymer then forms spherical phase separation structure.
As shown in Fig. 2 (a), Fig. 2 (b) and Fig. 2 (c), arylate blocks 40 is shorter due to segment, during the formation that flocks together is spherical
The heart, novolac epoxy resin block 30 is then arranged in outside, forms arylate blocks 40 and surrounds shape.Quantum dot (includes green
Color quantum dot 10 and red quantum point 20) due to the compatibility with arylate blocks 40 preferably, preferentially it is dispersed in acrylate
In block 40.After radical UV curing, arylate blocks 40 first solidify to form around green quantum dot 10 and amount of red
First shell 100 of son point 20, then under the effect of heat cure or photocuring, novolac epoxy resin block 30 solidify to form
The periphery of the first shell 100, forms the second shell 110.
In above-mentioned preparation method, the mass ratio of quantum dot and macromolecule matrix can be according to the luminous product to be prepared
Requirement to luminescent properties rationally selects.Quantum dot can be single quantum dot, it is also possible to for numerous quantum dots.?
In one preferred embodiment of the present invention, above-mentioned quantum dot is 0.1～1:10～100 with the mass ratio of macromolecule matrix.Will amount
Son point controls within the above range with the mass ratio of macromolecule matrix, can substantially meet current luminous product and want luminescent properties
Ask.
Cross-linking agent used in above-mentioned preparation method is conventional cross-linking agent, and its consumption can be according to concrete cross-linking agent kind
The difference of class and different.In one preferred embodiment of the present invention, above-mentioned cross-linking agent is the acrylic acid that degree of functionality is more than or equal to 2
Monomer and epoxy monomer；More preferably cross-linking agent is three-functionality-degree acrylic monomers and epoxy monomer；More preferably three-functionality-degree propylene
The mass ratio of acid monomers and epoxy monomer and epoxy novolac-acrylate block copolymer is 1～3:10～20.Degree of functionality is more than
Acrylic monomers equal to 2 and epoxy monomer have that curing rate is fast and the advantage such as degree of cross linking height.And by bifunctionality or three officials
The mass ratio of energy degree acrylic monomers and epoxy monomer and epoxy novolac-acrylate block copolymer control 1～3:10～
In the range of 20, ensureing that curing rate is fast and on the premise of degree of cross linking height, balancing the pliability demand of solidfied material.
In above-mentioned preparation method, the concrete kind to the firming agent used there is no particular/special requirement, as long as can solidify to form
Quantum dot composite material.In one preferred embodiment of the present invention, above-mentioned firming agent include radical UV curing agent and
Thermal curing agents, the step of above-mentioned solidification includes: carries out photocuring to first under the effect of radical UV curing agent, is solidified
Semi-finished product；Under the effect of thermal curing agents, solidification semi-finished product are carried out heat cure, obtain quantum dot composite material.
Above preferred embodiment by use radical UV curing agent and thermal curing agents to containing quantum dot and cross-linking agent with
And the first mixture of additive carries out step curing, obtain quantum dot composite material.Above-mentioned radical UV curing agent is selected from 1-
Hydroxycyclohexylphenylketone (light trigger 184), 2-methyl isophthalic acid-[4-methyl mercapto phenyl]-2-morpholinyl-1-acetone is (light-initiated
Agent 907), 2-hydroxy-methyl phenyl-propane-1-ketone (light trigger 1173), 2,4,6-trimethylbenzoy-dipheny oxidation
Phosphine (light trigger TPO), phenyl double (2,4,6-trimethylbenzoyl) phosphine oxide (light trigger 819), 2-phenyl benzyl-2-two
Methyl amine-1-[4-morpholine benzyl phenyl]-butanone (light trigger 369), α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone (light trigger
651), any one or a few in benzophenone (photoinitiator b P) and methyl benzoylformate (light trigger MBF).Heat
Firming agent is selected from ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-diaminobenzene., two amido sulfobenzide .s, hydroxyl
Ethylethylenediamine, Benzophenone carboxylic acid 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).Esters of acrylic acid is at the work of light curing agent
Form semi-solid preparation product with lower cross-linking reaction, then, solidify after epoxy resin being carried out by thermal curing agents, system can be effectively improved
The degree of cross linking.Different firming agent compound use can realize that curing rate is fast and curing efficiency height and excellent the consolidating of condensate performance
Change effect.
The solidification process of above-mentioned quantum dot composite material such as Fig. 1 (a)-Fig. 1 (b)-Fig. 1 (c) and Fig. 2 (a)-Fig. 2 (b)-Fig. 2
Shown in (c).Wherein, Fig. 1 (a) to Fig. 1 (c) respectively illustrates epoxy novolac-acrylate block copolymer and forms lamellar phase and divide
The microcosmic chain form schematic diagram of (c) after (b) and heat or photocuring after (a), photocuring before solidification when structure.
As shown in Fig. 1 (a), before solidification, novolac epoxy resin block 30 is arranged in side, and arylate blocks 40 is arranged in
Opposite side；Under the effect of photocuring, as shown in Fig. 1 (b), using acrylic monomers 50 as cross-linking agent, arylate blocks 40
First it solidify to form arylate blocks cured layer 80；Then as shown in Fig. 1 (c), using epoxy monomer 60 as cross-linking agent, phenol
Formaldehyde epoxy resin block 30 forms novolac epoxy resin block cured layer 90 under the effect of heat cure or photocuring.And work as x=
When 1, y=5, epoxy novolac-acrylate block copolymer then forms spherical phase separation structure.As shown in Fig. 2 (a), acrylic acid
Ester block 40 is shorter due to segment, and flock together the spherical center of formation, and novolac epoxy resin block 30 is then arranged in outside,
Arylate blocks 40 is formed and surrounds shape.Quantum dot (include green quantum dot 10 and red quantum point 20) due to acrylic acid
The compatibility of ester block 40 is preferable, is preferentially dispersed in arylate blocks 40.After radical UV curing, as shown in Fig. 2 (b),
Arylate blocks 40, using acrylic monomers 50 as cross-linking agent, first solidify to form around green quantum dot 10 and amount of red
First shell 100 of son point 20, then under the effect of heat cure or photocuring, as shown in Fig. 2 (c), novolac epoxy resin is embedding
Section 30, using epoxy monomer 60 as cross-linking agent, solidify to form the periphery at the first shell 100, forms the second shell 110.
In another kind preferred embodiment of the present invention, above-mentioned firming agent includes that radical UV curing agent and cationic photopolymerization are solid
Agent, the step of above-mentioned solidification includes: mix first under effect while radical UV curing agent and cation photocuring agent
Compound solidifies, and obtains quantum dot composite material.The preferred embodiment uses free radical and cation photocuring agent, by same
Time the first mixture carried out UV irradiate and can complete solidification process, obtain quantum dot composite material.
In above-mentioned curing schedule, the solidification of novolac epoxy resin block 30 is to realize light admittedly by cation photocuring agent
Change.In epoxy novolac-acrylate block copolymer, add radical UV curing agent and cation photocuring agent, select during solidification
Select 365nm UV lamp (with 450nm blue-ray light simultaneously) to irradiate, so can ensure that acrylic acid free radical causes (365nm) and ring
The cation of oxygen groups causes (ultraviolet 365nm and blue light 450nm can) to carry out simultaneously.It is additionally, since free radical and causes speed
Spending more faster than cationic curing, the state initially formed is equally as shown in Fig. 1 (b) and Fig. 2 (b), and only double bond is partial cross-linked,
Epoxide group is still in free state；And after the cation of certain time after solidification, end-state and heat cure are formed
Fig. 1 (c) is consistent with Fig. 2 (c), and epoxide group successfully cross-links.The advantage of radical UV curing is quick solidifying, and shortcoming is volume contraction
Rate is big；And the advantage of cation photocuring to be cubical contraction little, shortcoming is that solidification is slow (than heat cure, radical UV curing the most all
Slowly), but above-mentioned curing not only takes full advantage of its advantage, but also utilizes its shortcoming to adapt to the demand of successively solidification,
Save irradiation time simultaneously.
In a kind of more specific embodiment, in the solidification process that above two is different, the light source that UV irradiates is 365nm
LED cold light source or the metal halogen lamp source centered by 365nm or mercury lamp light source or centered by 450nm
Visible light source.
In another typical embodiment of the present invention, additionally providing a kind of quantum dot composite material, this quantum dot is multiple
Condensation material uses any of the above-described kind of preparation method to be prepared from.The quantum dot composite material using said method to be prepared from has
The compatibility and barrier property are superior, and luminous efficiency is high, the beneficial effect that stability of photoluminescence is good.
In another typical embodiment of the present invention, additionally providing a kind of quantum dot composite material, this quantum dot is multiple
Condensation material includes quantum dot and the macromolecule matrix solidfied material being coated on around quantum dot, and this macromolecule matrix solidfied material is phenolic aldehyde
Cross-linking products between epoxy-acrylic ester block copolymer, this cross-linking products has a construction unit as shown in following formula (I):
The quantum dot composite material with said structure unit can be embedding according to novolac epoxy resin block and acrylate
The length of section can form different phase separation structures.When novolac epoxy resin block and arylate blocks approximately equal, phenol
Aldehyde epoxy-acrylic ester block copolymer cambium layer shape phase separation structure, as shown in Fig. 1 (a) to Fig. 1 (c), novolac epoxy resin
Block 30 and arylate blocks 40 rule be arranged in layer structure, novolac epoxy resin block 30 is arranged in side, propylene
Acid esters block 40 is arranged in opposite side, forms novolac epoxy resin block cured layer 90 respectively and arylate blocks is solid after solidification
Change layer 80.And when arylate blocks 40 is much smaller than novolac epoxy resin block 30, epoxy novolac-acrylic ester block
Thing then forms spherical phase separation structure, and as shown in Fig. 2 (a) to Fig. 2 (c), arylate blocks 40 is shorter due to segment, is gathered in
Forming spherical center together, novolac epoxy resin block 30 is then arranged in outside, forms arylate blocks 40 and surrounds shape.
Quantum dot is preferable due to the compatibility with arylate blocks 40, is preferentially dispersed in arylate blocks 40.Acrylate is embedding
Section 40 is solidificated in internal layer and is formed around green quantum dot 10 and the first shell 100 of red quantum point 20, and novolac epoxy resin is embedding
Section 30 then solidify to form around green quantum dot 10 and the second shell 110 of red quantum point 20 at outer layer, thus is formed with amount
Nucleocapsid structure centered by son point.
Construction unit in above-mentioned quantum dot composite material refers to constitute macromolecular chain and determine that macromolecular structure is with necessarily
The atom combination that mode couples together.Multiple "-" of said structure cell end represent double bond or epoxy bond open after half
Chemical bond, any half in the construction unit that any half chemical bond in each said structure unit can be adjacent
Chemical bond is attached forming complete chemical bond.Every half chemical bond is bonded with any half chemistry of another construction unit
Connect, the most just define cancellated macromolecule matrix solidfied material.Cancellated macromolecule matrix solidfied material surrounds central authorities
Quantum dot just define above-mentioned quantum dot composite material.
In another typical embodiment of the present invention, additionally providing a kind of quantum dot light emitting device, this quantum dot is sent out
Optical device includes quantum dot composite material, and quantum dot composite material is above-mentioned quantum dot composite material.Comprise above-mentioned quantum dot multiple
The quantum dot light emitting device of condensation material has luminous efficiency height and the advantage of good stability.
In quantum dot composite material contained by above-mentioned quantum dot light emitting device, the concrete glow color of quantum dot can basis
Actual luminescent device needs rationally to select.In one preferred embodiment of the present invention, quantum dot be red quantum point and
Green quantum dot.Red quantum point and green quantum dot can be used in display field, under the irradiation of blue led backlight, red
Blue light can be absorbed with green quantum dot and convert thereof into redness and green light, white with unabsorbed blue light formation RGB
Light field.Due to the half-peak width of red and green quantum dot, compared with traditional liquid crystal display, quantum dot display colour gamut is high, face
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
On carrier, film-forming can form quantum dot film.In concrete applied environment, upper strata or the lower floor of quantum dot film are all right
There are Obstruct membrane or protecting film that polymer film formed, or can also have other in the middle of quantum dot film with polymer film
Layer.Quantum dot composition solidifies i.e. formation quantum dot pipe in the cavity of pipeline, and quantum dot pipe is to be placed by quantum dot composition
Solidify in tubular container and then seal, for the light-switching device of display backlight system.
Further illustrate beneficial effects of the present invention below in conjunction with specific embodiments.
Embodiment 1
Use epoxy novolac-acrylate block copolymer as macromolecule matrix, by macromolecule matrix, cross-linking agent and
Firming agent, obtains the first mixture；Being solidified by first mixture, obtain quantum dot composite material, each step is specifically reacted
Thing is raw materials used is shown in Table 1, and the when concrete reaction condition of the consumption between each raw material is shown in Table 2.
Embodiment 2
Embodiment 2 use epoxy novolac-acrylate block copolymer as macromolecule matrix, by macromolecule matrix, friendship
Connection agent, firming agent and additive, obtain the first mixture；This first mixture is solidified, obtains quantum dot composite wood
Material, the concrete reactant of each step is raw materials used is shown in Table 1, and the when concrete reaction condition of the consumption between each raw material is shown in Table 2.
Embodiment 3-10
Embodiment 3-10 uses the step identical with embodiment 1 or 2, uses the preparation parameter shown in Tables 1 and 2 and condition
It is prepared.
Comparative example 1
Using polyacrylate as macromolecule matrix, other Parameter Conditions are shown in Tables 1 and 2.
Comparative example 2
Using bisphenol A epoxide resin as macromolecule matrix, other Parameter Conditions are shown in Tables 1 and 2.
Comparative example 3
Using the mixture of acrylate and epoxy resin as macromolecule matrix, other Parameter Conditions are shown in Tables 1 and 2.
Table 1: each embodiment and the raw materials used kind of comparative example
Table 2: each embodiment and the preparation condition of comparative example
Detection: the performance of the quantum dot composite material prepared by the various embodiments described above and comparative example is detected, detection
The results are shown in Table 3 and table 4.
The detection method of quantum dot light emitting efficiency is: utilizes 450nm blue led lamp as backlight spectra, utilizes integrating sphere
Test Blue backlight spectrum and the spectrum through quantum dot composite material respectively, utilizes the integral area of spectrogram to calculate quantum dot and sends out
Light efficiency.
Quantum dot light emitting efficiency=(red quantum point absworption peak area+green quantum dot peak absorption area)/(Blue backlight
Peak area-through the unabsorbed blue peak area of quantum dot composite material) * 100%.
The method of testing of stability of photoluminescence specifically include that high temperature blue light illumination (70 DEG C, 0.5W/cm2), hot and humid
(65 DEG C/95%RH), under the aging condition such as high-temperature storage (85 DEG C), the efficiency change of detection quantum dot composite material and invalid edges
Size.
Table 3:
Note: above efficiency is relative efficiency, and the efficiency of comparative example 1 is set to 100%, and other efficiency are the most corresponding.
Table 4:
Note: after above invalid edges is for making quantum dot film, by determining the size of edge invalid edges, quantum dot under microscope
The size of film is 6cm*6cm.
From table 3 and table 4 it can be seen that arylate blocks is the most, start efficiency is the highest, and aging attenuation amplitude is the biggest, black
Bian Yue great；Otherwise, epoxy block is the most, and start efficiency is the lowest, and aging attenuation amplitude is the least, and black surround is the least.Embodiment 1-10 with
Comparative example 1 is compared, and initial light emission efficiency is more or less the same with comparative example 1, but luminous efficiency attenuation amplitude (passes through formula: decay width
Degree=(aging behind efficiency-starting efficiency)/starting efficiency x 100% calculates) relatively comparative example 1 is substantially reduced, stable luminescence
Property is greatly enhanced.Embodiment 1-10 is compared with comparative example 2, and initial light emission efficiency is far above comparative example 2, and luminous efficiency decay width
Degree is more or less the same with comparative example 2.Compared with comparative example 3, embodiment 1-10 uses containing novolac epoxy resin block and acrylic acid
The block copolymer of ester block, the macromolecule matrix formed by the way of with chemical bond connection is around sending out that quantum dot is formed
Luminescent material, compared with the quanta point material formed with using the acrylate of physical blending and epoxy resin, it not only has relatively
High luminous efficiency, and the attenuation amplitude of aging rear luminous efficiency is little, and the size of invalid edges is the most relatively small, luminous efficiency
Stability is higher.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect: by selecting
Comprise novolac epoxy resin-acrylic block copolymers as dispersion quantum dot macromolecule matrix, due to novolac epoxy resin-
Acrylic block copolymers combines acrylate and the quantum dot compatibility is good and epoxy resin is to oxygen and aqueous vapor barrier
Good advantage, has amphipathic, thus sets about in terms of macromolecule matrix material composition, solve the compatibility with quantum dot with
And starvation and the problem of aqueous vapor, improve luminous efficiency and the stability of quantum dot composite material.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (16)
1. a quantum dot composition, it is characterised in that described quantum dot composition includes quantum dot and macromolecule matrix, described
Macromolecule matrix includes epoxy novolac-acrylate block copolymer.
Quantum dot composition the most according to claim 1, it is characterised in that described epoxy novolac-arylate blocks is common
Polymers is the epoxy novolac-acrylate block copolymer of following structural formula:
Wherein, x, y are integer, and x >=1, y >=1, and 3≤x+y≤7.
Quantum dot composition the most according to claim 1, it is characterised in that also include crosslinking in described quantum dot composition
Agent, the most described cross-linking agent is double/three-functionality-degree acrylic monomers and/or double/three-functionality-degree epoxy monomer；More preferably described
Double/three-functionality-degree acrylic monomers and/or double/three-functionality-degree epoxy monomer and described epoxy novolac-acrylic ester block
The mass ratio of thing is 1～3:10～20.
Quantum dot composition the most according to claim 1, it is characterised in that also include solidification in described quantum dot composition
Agent, the most described firming agent is radical UV curing agent and thermal curing agents, or is that radical UV curing agent and cationic photopolymerization are solid
Agent.
Quantum dot composition the most according to claim 1, it is characterised in that described quantum dot composition also includes adding
Agent, the most described additive is light diffusion particle and/or antioxidant.
6. the preparation method of a quantum dot composite material, it is characterised in that described preparation method includes:
Macromolecule matrix, cross-linking agent, firming agent, quantum dot and optional additive are mixed to get the first mixture；
Described first mixture is solidified, obtains described quantum dot composite material；
Wherein, described macromolecule matrix includes epoxy novolac-acrylate block copolymer.
Preparation method the most according to claim 6, it is characterised in that described epoxy novolac-acrylate block copolymer
Structural formula be:Wherein, x, y are integer,
And x >=1, y >=1, and 3≤x+y≤7.
Preparation method the most according to claim 6, it is characterised in that described cross-linking agent be bifunctionality acrylic monomers,
Three-functionality-degree acrylic monomers, bifunctionality epoxy monomer and/or three-functionality-degree epoxy monomer；The most described cross-linking agent and institute
The mass ratio stating epoxy novolac-acrylate block copolymer is 1～3:10～20.
Preparation method the most according to claim 6, it is characterised in that described firming agent is radical UV curing agent and thermosetting
Agent, the step of the most described solidification includes:
Use described radical UV curing agent that described first mixture is carried out photocuring, obtain solidifying semi-finished product；
Use thermal curing agents that described solidification semi-finished product are carried out heat cure, obtain described quantum dot composite material.
Preparation method the most according to claim 6, it is characterised in that described firming agent is radical UV curing agent and sun
Ionic light firming agent, the step of described solidification includes:
Under effect, described first mixture is solidified while radical UV curing agent and cation photocuring agent, obtain
Described quantum dot composite material.
11. preparation methoies according to claim 6, it is characterised in that described additive is light diffusion particle and/or antioxygen
Agent.
12. 1 kinds of quantum dot composite materials, it is characterised in that described quantum dot composite material uses in claim 6 to 11 appoints
One described preparation method is prepared from.
13. 1 kinds of quantum dot composite materials, it is characterised in that described quantum dot composite material includes quantum dot and is coated on described
Macromolecule matrix solidfied material around quantum dot, described macromolecule matrix solidfied material is epoxy novolac-acrylic ester block
Cross-linking products between thing, described cross-linking products has a construction unit as shown in following formula (I):
14. 1 kinds of quantum dot light emitting devices, including quantum dot composite material, it is characterised in that described quantum dot composite material is
Quantum dot composite material described in claim 13.
15. quantum dot light emitting devices according to claim 14, it is characterised in that the amount in described quantum dot composite material
Son point is red quantum point and/or green quantum dot.
16. quantum dot light emitting devices according to claim 14, it is characterised in that described quantum dot light emitting device is quantum
Point film or quantum dot pipe.
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| CN111512452B (en) * | 2017-10-17 | 2023-11-21 | 科迪华公司 | Ink composition with high quantum dot concentration for display device |
| CN112375497A (en) * | 2020-11-16 | 2021-02-19 | 京东方科技集团股份有限公司 | Light-emitting film, light-emitting device, manufacturing method of light-emitting device and display substrate |
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