CN109439067A - Quantum dot ink and quantum stippling film - Google Patents

Quantum dot ink and quantum stippling film Download PDF

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Publication number
CN109439067A
CN109439067A CN201811202426.XA CN201811202426A CN109439067A CN 109439067 A CN109439067 A CN 109439067A CN 201811202426 A CN201811202426 A CN 201811202426A CN 109439067 A CN109439067 A CN 109439067A
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quantum dot
ester
quantum
cyclohexyl
dot ink
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CN109439067B (en
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王思元
王允军
邓德晖
李鑫
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Suzhou Xingshuo Nanotech Co Ltd
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Suzhou Xingshuo Nanotech Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/36Inkjet printing inks based on non-aqueous solvents

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

This application discloses a kind of quantum dot ink and quantum stippling films.Wherein, quantum dot ink includes quantum dot and the esters solvent with cyclic structure, and the quantum dot accounts for 10wt%~45wt% of the quantum dot ink.The quantum dot ink of the application uses the esters with cyclic structure as solvent, improves the dispersion stabilization of quantum dot in the ink.Process is smooth when carrying out inkjet printing using the ink, not blocking sprayer, and obtained quantum stippling film planarization is good, film forming uniformly, emitting brightness with higher.

Description

Quantum dot ink and quantum stippling film
Technical field
The application belongs to quantum dot light emitting technical field more particularly to a kind of quantum dot ink and quantum stippling film.
Background technique
Quanta point material has many advantages, such as that excitation purity is high, luminescent color is high with size adjustable, phototransformation efficiency.Use quantum Point is used as the light conversion material of the color film (color filter) of LCD (Liquid crystal display, liquid crystal display) When, it is remarkably improved the colour gamut of display and the utilization efficiency to backlight.Currently, the preparation of quantum stippling film (QDCF) is mainly sharp With quantum dot photoresist, but this method is more demanding to the heat-resisting of quanta point material itself, acid-proof alkaline, the solidification of photoresist Process can generate adverse effect to the luminous efficiency of quantum dot itself, and the mode of photoetching can consume a large amount of quantum dot, make At waste of material, higher cost.
To solve the above problems, quantum dot can be dispersed to be configured to quantum dot ink in a solvent, pass through inkjet printing Mode prepares quantum stippling film.But in the prior art, being used to prepare the ink of quantum stippling film, often film forming is poor, printing It is not smooth, it is easy blocking sprayer.
Summary of the invention
In view of the above technical problems, the application provides a kind of quantum dot ink and quantum stippling film.
According to a first aspect of the present application, a kind of quantum dot ink is provided, including quantum dot and with the ester of cyclic structure Class solvent, the quantum dot account for 10wt%~45wt% of the quantum dot ink.
Further, the esters solvent includes at least one high boiling ester and a kind of low-boiling ester, the two boiling point At least differ 20 DEG C.
Further, normal atmosphere is depressed, and the higher boiling is 230~320 DEG C, and the low boiling point is 150~220 DEG C.
Further, the cyclic structure is alicyclic structure.
Further, the esters solvent is selected from cyclohexyl formate, cyclohexyl acetate, methyl cyclohexanol acetate, propionic acid ring Own ester, cyclohexyl butyrate, pentanoic acid cyclohexyl ester, caproic acid cyclohexyl, verdox, cyclohexyl acrylate, benzoic acid At least one of cyclohexyl, cyclohexyl methacrylate.
Further, the cyclic structure is caged scaffold.
Further, the esters solvent is selected from isobornyl acrylate, isobornyl methacrylate, isobomyl At least one of ester, isobutyric acid Isobornyl.
Further, with the surfactant of 1wt%~10wt% in the quantum dot ink.
Further, the surfactant is alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty acid Polyoxyethylene ester, fatty acid methyl ester ethoxylate, the ethylene oxide adduct of polypropylene glycol, polyoxyethylated ionic table Face activating agent, sorbitan ester, sucrose fatty ester, alkylolamides type surfactant, non-ion fluorin carbon surface active At least one of agent, Pluronic F68.
According to further aspect of the application, a kind of quantum stippling film is provided, the quantum stippling film is by above-mentioned quantum Point ink printed preparation.
The utility model has the advantages that the quantum dot ink of the application uses the esters with cyclic structure as solvent, can be prepared into To high concentration and the good quantum dot ink of stability.Comprising the esters that at least two boiling points are different in ink, in inkjet printing, During ink droplet is dry, the ester of low boiling point can preferential volatilization, and the high ester of boiling point volatilizees after the meeting, to realize the gradient of solvent Volatilization can effectively inhibit the phenomenon that the quantum dot in ink droplet is easy to reduce bad caused by coffee ring effect to marginal deposit It influences.Process is smooth when carrying out inkjet printing using the ink, not blocking sprayer, and obtained quantum stippling film planarization is good, film forming Uniformly, optical property is excellent.
Specific embodiment
Below in conjunction with the application embodiment, technical solutions in the embodiments of the present application is described in detail.It answers It is noted that described embodiment is only a part of embodiment of the application, rather than whole embodiments.
This application provides a kind of quantum dot inks, including quantum dot and with the esters solvent of cyclic structure, quantum dot Account for 10wt%~45wt% of quantum dot ink.
In the prior art, quantum dot is often dispersed in the less short chain alkanes of carbon atom number, such as pentane, hexane, still Viscosity is lower at room temperature for these short chain alkanes, and evaporation rate is fast, and when carrying out inkjet printing, ink droplet rate of drying is too fast, It is easy to cause spray nozzle clogging.In addition, when preparing quantum stippling film, high concentration more demanding to the concentration of quantum dot in ink Quantum dot be often not easy stable dispersion in short chain alkanes solvent.
Since in esters solvent compound, compared with common group, the steric hindrance of cyclic structure is bigger, so that ester The polarity of class solvent is very weak, the inventors of the present application found that the quantum dot of high concentration such as 10wt%~45wt% exists Also it is able to maintain good dispersion stabilization in esters solvent with cyclic structure, places also not occur reuniting or sink for a long time and gather The phenomenon that.When carrying out inkjet printing using the ink, since quantum dot is not easy to reunite, so that print procedure is smooth, do not block up Nozzle is filled in, obtained quantum stippling film planarization is good, and film forming is uniform, emitting brightness with higher.
Quantum dot can be selected from IIB-VIA compounds of group, IIIA-VA compounds of group, IB-IIIA-VIA compounds of group and calcium At least one of titanium ore.Specifically can for CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、 CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、MgZnSe、MgZnS、HgZnTeS、CdZnSeS、 CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTe、GaN、GaP、 GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、 AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、 GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、 InAlNAs、InAlNSb、InAlPAs、InAlPSb、CsPbX3(X=Cl, Br, I) or CH3NH3PbX3(X=Cl, Br, I) amount Sub-, but not limited to this.
In one preferred embodiment, esters solvent includes that at least one high boiling ester and one kind are low-boiling Ester, the two boiling point at least differ 20 DEG C.For example, normal atmosphere is depressed, higher boiling is 230~320 DEG C, and low boiling point is 150~220 ℃.When using solvent of the esters solvent of two kinds of different boilings as quantum dot ink, in inkjet printing, ink droplet is dry In the process, the ester of low boiling point can preferential volatilization, and the high ester of boiling point volatilizees after the meeting, to realize the gradient volatilization of solvent, favorably In inhibiting the phenomenon that the quantum dot in ink droplet is easy to reduce adverse effect caused by coffee ring effect, put down to marginal deposit Whole uniform quantum dot film.
In one preferred embodiment, the mass ratio of high boiling ester and low boiling ester is (0.25~4): 1.Specifically may be used Think 0.25:1,0.5:1,1:1,2:1,3:1,4:1.
In a specific embodiment, cyclic structure is alicyclic structure.Esters solvent containing alicyclic structure includes But it is not limited to cyclohexyl formate, cyclohexyl acetate, methyl cyclohexanol acetate, cyclohexyl propionate, cyclohexyl butyrate, valeric acid ring Own ester, caproic acid cyclohexyl, verdox, cyclohexyl acrylate, benzoate ester, methacrylic acid hexamethylene Ester, butyl cyclohexyl phthalate, dicyclohexyl phthalate, 1- chloroethene butylcyclohexyl carbonic ester, p-methyl benzenesulfonic acid ring Own ester, to t-butyl cyclohexyl methacrylate, methyl acetate cyclohexyl, acetic acid -3- t-butyl cyclohexyl methacrylate, vertenex, 1- Ethylacrylic acid cyclohexyl, 2- monoxone cyclohexyl, chloro-carbonic acid are to t-butyl cyclohexyl methacrylate, cyclohexanecarboxylic acid cyclohexyl, 2- methyl-prop Sour cyclohexyl, 3,3,5- trimethylace tonitric cyclohexyl.
In a specific embodiment, cyclic structure is caged scaffold.Esters solvent containing caged scaffold includes But be not limited to isobornyl acrylate, isobornyl methacrylate, isobornyl acetate, isobutyric acid Isobornyl etc..
It in a specific embodiment, also include the surfactant of 1wt%~10wt% in quantum dot ink.Table Face activating agent can be non-ionic, anionic, cationic or amphoteric surfactant.Preferably, surfactant is It is non-ionic, including but not limited to alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, Fatty acid methyl ester ethoxylate, polyoxyethylated ionic surfactant, loses the ethylene oxide adduct of polypropylene glycol Water sorbitol ester, sucrose fatty ester, alkylolamides type surfactant, non-ion fluorin carbon surface active agent, polyoxyethylene- At least one of poiyoxypropylene copolymer.
The viscosity and surface tension of ink system is not only adjusted in the use of above-mentioned surfactant, makes it have preferable Levelability, to meet the requirement of inkjet printing, additionally it is possible to effectively facilitate dispersion stabilization of the quantum dot in ink system, in turn Raising is printed as film property, obtains the quantum dot film of even uniform.
In the application one typical embodiment, a kind of quantum stippling film is disclosed, is passed through by above-mentioned quantum dot ink Inkjet printing preparation.Ink utilizes esters mixed solvent and surfactant with cyclic structure, improves point of quantum dot Stability is dissipated, and makes ink that there is viscosity appropriate and surface tension.Process smoothness when inkjet printing is carried out, does not block spray Mouth, obtained quantum stippling film planarization is good, and film forming is uniform, blue light absorption rate and emitting brightness with higher.
Hereinafter, embodiment is described in more detail referring to embodiment.However, they are exemplary implementation of the invention Mode, and the invention is not limited thereto.
Embodiment 1
The present embodiment provides a kind of quantum dot inks, comprising: the feux rouges CdSeS quantum dot of 30wt%, the acetic acid of 30wt% Cyclohexyl (boiling point is 173.5 DEG C), the cyclohexyl methacrylate (boiling point is 210 DEG C) of 35wt%, 5wt% polyoxyethylene 16 Alkyl ether.Above-mentioned quantum dot ink is stirred each component and can be prepared by simple and mechanical.
Above-mentioned ink, which can be placed, still keeps stable for 90 days, is not in reunion or deposited phenomenon.Utilize above-mentioned quantum dot ink Water carries out inkjet printing, and process is smooth, and film forming uniformly, obtains smooth quantum stippling film.
The luminescent properties of the quantum stippling film are tested, the initial emitting brightness of used blue light backlight 1000cd/m2, the blue light absorption rate of quantum stippling film, emitting brightness, outer quantum yield (EQE) the results are shown in Table 1.
Embodiment 2
The present embodiment provides a kind of quantum dot inks, comprising: the feux rouges InP/ZnS quantum dot of 35wt%, the vinegar of 28wt% Acid methyl cyclohexyl (boiling point is 182 DEG C), the isobornyl acetate (boiling point is 220 DEG C) of 33wt%, the polyoxyethylene of 4wt% loses Water sorbitol olein.Above-mentioned quantum dot ink is stirred each component and can be prepared by simple and mechanical.
Above-mentioned ink, which can be placed, still keeps stable for 90 days, is not in reunion or deposited phenomenon.Utilize above-mentioned quantum dot ink Water carries out inkjet printing, and process is smooth, and film forming uniformly, obtains smooth quantum stippling film.
The luminescent properties of the quantum stippling film are tested, the initial emitting brightness of used blue light backlight 1000cd/m2, the blue light absorption rate of quantum stippling film, emitting brightness, outer quantum yield (EQE) the results are shown in Table 1.
Embodiment 3
The present embodiment provides a kind of quantum dot inks, comprising: the green light CdSe/CdS/ZnS quantum dot of 39wt%, 30wt% Cyclohexyl acrylate (boiling point be 182 DEG C), the 3 of 25wt%, 3,5- trimethylace tonitric cyclohexyls (boiling point is 211 DEG C), 6wt% Polyoxyethylenepropylene stearate.Above-mentioned quantum dot ink is stirred each component and can be prepared by simple and mechanical It arrives.
Above-mentioned ink, which can be placed, still keeps stable for 90 days, is not in reunion or deposited phenomenon.Utilize above-mentioned quantum dot ink Water carries out inkjet printing, and process is smooth, and film forming uniformly, obtains smooth quantum stippling film.
The luminescent properties of the quantum stippling film are tested, the initial emitting brightness of used blue light backlight 1000cd/m2, the blue light absorption rate of quantum stippling film, emitting brightness, outer quantum yield (EQE) the results are shown in Table 1.
Embodiment 4
The present embodiment provides a kind of quantum dot inks, comprising: the green light InP quantum dot of 32wt%, the butyric acid ring of 30wt% Own ester (boiling point is 202 DEG C), the isobornyl acrylate (boiling point is 244 DEG C) of 33wt%, the polyoxyethylenepropylene of 5wt% is stearic Acid esters.Above-mentioned quantum dot ink is stirred each component and can be prepared by simple and mechanical.
Above-mentioned ink, which can be placed, still keeps stable for 90 days, is not in reunion or deposited phenomenon.Utilize above-mentioned quantum dot ink Water carries out inkjet printing, and process is smooth, and film forming uniformly, obtains smooth quantum stippling film.
The luminescent properties of the quantum stippling film are tested, the initial emitting brightness of used blue light backlight 1000cd/m2, the blue light absorption rate of quantum stippling film, emitting brightness, outer quantum yield (EQE) the results are shown in Table 1.
In embodiment 1 to embodiment 4, the printing of quantum dot ink uses FUJIFILM DMP-3000 ink-jet printer.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Blue light absorption rate (%) 82 65 80 62
Emitting brightness (cd/m2) 900 894 3980 3465
EQE (%) 25.8 17.9 20.2 21.3
As shown in Table 1, the color film that in the application prepared by quantum dot ink to the absorptivity of blue light up to 82%, emitting brightness Up to 3980cd/m2, external quantum efficiency EQE is up to 25.8%, shows good optical property.
Although inventor has done more detailed elaboration to the technical solution of the application and has enumerated, it should be understood that for For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious , cannot all be detached from the essence of the application spirit, the term occurred in the application be used for elaboration to technical scheme and Understand, the limitation to the application can not be constituted.

Claims (10)

1. a kind of quantum dot ink, which is characterized in that including quantum dot and with the esters solvent of cyclic structure, the quantum dot Account for 10wt%~45wt% of the quantum dot ink.
2. quantum dot ink according to claim 1, which is characterized in that the esters solvent includes at least one higher boiling Ester and a kind of low-boiling ester, the two boiling point at least differ 20 DEG C.
3. quantum dot ink according to claim 2, which is characterized in that normal atmosphere pressure, the higher boiling be 230~ 320 DEG C, the low boiling point is 150~220 DEG C.
4. quantum dot ink according to any one of claims 1 to 3, which is characterized in that the cyclic structure is alicyclic ring knot Structure.
5. quantum dot ink according to claim 4, which is characterized in that the esters solvent is selected from cyclohexyl formate, second Sour cyclohexyl, methyl cyclohexanol acetate, cyclohexyl propionate, cyclohexyl butyrate, pentanoic acid cyclohexyl ester, caproic acid cyclohexyl, acetic acid uncle neighbour At least one of butylcyclohexyl ester, cyclohexyl acrylate, benzoate ester, cyclohexyl methacrylate.
6. quantum dot ink according to any one of claims 1 to 3, which is characterized in that the cyclic structure is bridged ring knot Structure.
7. quantum dot ink according to claim 6, which is characterized in that the esters solvent is selected from isobomyl acrylate At least one of ester, isobornyl methacrylate, isobornyl acetate, isobutyric acid Isobornyl.
8. quantum dot ink according to claim 1, which is characterized in that in the quantum dot ink have 1wt%~ The surfactant of 10wt%.
9. quantum dot ink according to claim 8, which is characterized in that the surfactant is alkylphenol-polyethenoxy Ether, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, fatty acid methyl ester ethoxylate, polypropylene glycol epoxy Ethane additive product, polyoxyethylated ionic surfactant, sorbitan ester, sucrose fatty ester, alkylolamides At least one of type surfactant, non-ion fluorin carbon surface active agent, Pluronic F68.
10. a kind of quantum stippling film, which is characterized in that the quantum stippling film is by any quantum dot of claim 1~9 Ink printed preparation.
CN201811202426.XA 2018-10-16 2018-10-16 Quantum dot ink and quantum dot color film Active CN109439067B (en)

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