CN109439067B - Quantum dot ink and quantum dot color film - Google Patents
Quantum dot ink and quantum dot color film Download PDFInfo
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- CN109439067B CN109439067B CN201811202426.XA CN201811202426A CN109439067B CN 109439067 B CN109439067 B CN 109439067B CN 201811202426 A CN201811202426 A CN 201811202426A CN 109439067 B CN109439067 B CN 109439067B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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Abstract
The application discloses quantum dot ink and a quantum dot color film. The quantum dot ink comprises quantum dots and an ester solvent with a cyclic structure, wherein the quantum dots account for 10-45 wt% of the quantum dot ink. The quantum dot ink uses the ester with the cyclic structure as a solvent, and improves the dispersion stability of the quantum dots in the ink. The process is smooth when the ink is used for ink-jet printing, the spray head is not blocked, and the obtained quantum dot color film has good smoothness, uniform film formation and higher brightness.
Description
Technical Field
The application belongs to the technical field of quantum dot luminescence, and particularly relates to quantum dot ink and a quantum dot color film.
Background
The quantum dot material has the advantages of high color purity, adjustable luminescent color along with size, high light conversion efficiency and the like. When the quantum dots are used as the light conversion material of a color film (color filter) of an LCD (Liquid crystal display), the color gamut of the display and the utilization efficiency of backlight can be obviously improved. At present, quantum dot photoresist is mainly used for preparing a Quantum Dot Color Film (QDCF), but the method has high requirements on heat resistance and acid and alkali resistance of a quantum dot material, the curing process of the photoresist can generate adverse effects on the luminous efficiency of the quantum dot, and a large amount of quantum dots can be consumed in a photoetching mode, so that material waste is caused, and the cost is high.
In order to solve the problems, quantum dots can be dispersed in a solvent to prepare quantum dot ink, and a quantum dot color film is prepared in an ink-jet printing mode. However, in the prior art, the ink used for preparing the quantum dot color film is often poor in film forming property, unsmooth in printing and easy to block a nozzle.
Disclosure of Invention
In view of the above technical problems, the present application provides a quantum dot ink and a quantum dot color film.
According to a first aspect of the present application, there is provided a quantum dot ink, including a quantum dot and an ester solvent having a cyclic structure, wherein the quantum dot accounts for 10 wt% to 45 wt% of the quantum dot ink.
Further, the ester solvent comprises at least one high boiling ester and one low boiling ester, which have boiling points that differ by at least 20 ℃.
Further, under the standard atmospheric pressure, the high boiling point is 230-320 ℃, and the low boiling point is 150-220 ℃.
Further, the cyclic structure is an alicyclic structure.
Further, the ester solvent is at least one selected from cyclohexyl formate, cyclohexyl acetate, methylcyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, cyclohexyl valerate, cyclohexyl hexanoate, o-tert-butylcyclohexyl acetate, cyclohexyl acrylate, cyclohexyl benzoate and cyclohexyl methacrylate.
Further, the ring structure is a bridged ring structure.
Further, the ester solvent is at least one selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, isobornyl acetate, and isobornyl isobutyrate.
Further, the quantum dot ink has 1 wt% to 10 wt% of a surfactant.
The surfactant is at least one of alkylphenol ethoxylates, high-carbon fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, fatty acid methyl ester ethoxylates, ethylene oxide adducts of polypropylene glycol, polyoxyethylated ionic surfactants, sorbitan esters, sucrose fatty acid esters, alkylolamide surfactants, nonionic fluorocarbon surfactants and polyoxyethylene-polyoxypropylene copolymers.
According to another aspect of the application, a quantum dot color film is provided, and the quantum dot color film is prepared by printing the quantum dot ink.
Has the advantages that: the quantum dot ink uses the ester with the cyclic structure as a solvent, and the quantum dot ink with high concentration and good stability can be prepared. The ink contains at least two esters with different boiling points, and when the ink is used for ink-jet printing, the ester with the low boiling point can be preferentially volatilized in the drying process of the ink drop, and the ester with the high boiling point can be volatilized later, so that the gradient volatilization of a solvent is realized, the phenomenon that quantum dots in the ink drop are easily deposited to the edge can be effectively inhibited, and the adverse effect caused by the coffee ring effect is reduced. The process is smooth when the ink is used for ink-jet printing, the spray head is not blocked, and the obtained quantum dot color film has good smoothness, uniform film formation and excellent optical property.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments.
The application provides quantum dot ink which comprises quantum dots and an ester solvent with an annular structure, wherein the quantum dots account for 10 wt% -45 wt% of the quantum dot ink.
In the prior art, quantum dots are often dispersed in short-chain alkanes with fewer carbon atoms, such as pentane and hexane, but the short-chain alkanes have low viscosity and high volatilization speed at room temperature, and the ink drop drying speed is too high when ink-jet printing is carried out, so that nozzles are easily blocked. In addition, when a quantum dot color film is prepared, the requirement on the concentration of quantum dots in the ink is high, and the quantum dots with high concentration are not easy to stably disperse in a short-chain alkane solvent.
In the ester solvent compound, the steric hindrance of the cyclic structure is larger than that of a common group, so that the polarity of the ester solvent is very weak, and the inventor of the application finds that quantum dots with high mass concentration such as 10 wt% -45 wt% can maintain good dispersion stability in the ester solvent with the cyclic structure, and the phenomenon of agglomeration or settlement does not occur after long-time storage. When the ink is used for ink-jet printing, the quantum dots are not easy to agglomerate, so that the printing process is smooth, the nozzle is not blocked, the obtained quantum dot color film is good in smoothness, uniform in film forming and high in brightness.
The quantum dots may be selected from at least one of group IIB-VIA compounds, group IIIA-VA compounds, group IB-IIIA-VIA compounds, and perovskites. Specific examples thereof include 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, ZnSeS, CdZnSeTe, CdZnSnZnSTe, CdHgSeS, CdHgSeTe, Cd, HgZnS, HgZnSe, HgZnS, HgZnSeS, HgZnSe, 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) quantum dots, but are not limited thereto.
In a preferred embodiment, the ester solvent comprises at least one high boiling ester and one low boiling ester, the boiling points of which differ by at least 20 ℃. For example, the high boiling point is 230 to 320 ℃ and the low boiling point is 150 to 220 ℃ under the standard atmospheric pressure. When two ester solvents with different boiling points are used as solvents of the quantum dot ink, in the ink-jet printing process, the ester with the low boiling point can be preferentially volatilized, and the ester with the high boiling point can be volatilized later, so that the gradient volatilization of the solvent is realized, the phenomenon that the quantum dots in the ink drops are easily deposited to the edge is favorably inhibited, the adverse effect caused by the coffee ring effect is reduced, and the smooth and uniform quantum dot film is obtained.
In a preferred embodiment, the mass ratio of the high-boiling ester to the low-boiling ester is (0.25 to 4): 1. specifically, the ratio may be 0.25:1, 0.5:1, 1:1, 2:1, 3:1 or 4: 1.
In a specific embodiment, the cyclic structure is an alicyclic structure. Ester solvents containing an alicyclic structure include, but are not limited to, cyclohexyl formate, cyclohexyl acetate, methylcyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, cyclohexyl valerate, cyclohexyl hexanoate, o-t-butylcyclohexyl acetate, cyclohexyl acrylate, cyclohexyl benzoate, cyclohexyl methacrylate, butylcyclohexyl phthalate, dicyclohexyl phthalate, 1-chloroethylcyclohexyl carbonate, cyclohexyl p-toluenesulfonate, p-t-butylcyclohexyl, methylcyclohexyl acetate, 3-t-butylcyclohexyl acetate, p-t-butylcyclohexyl acetate, cyclohexyl 1-ethacrylate, cyclohexyl 2-chloroacetate, p-t-butylcyclohexyl chloroformate, cyclohexyl formate, cyclohexyl 2-methylpropionate, cyclohexyl 3,3, 5-trimethylacetate.
In a specific embodiment, the cyclic structure is a bridged ring structure. The ester solvent having a bridged ring structure includes, but is not limited to, isobornyl acrylate, isobornyl methacrylate, isobornyl acetate, isobornyl isobutyrate, and the like.
In a specific embodiment, the quantum dot ink further comprises 1 wt% to 10 wt% of a surfactant. The surfactant may be a nonionic, anionic, cationic or amphoteric surfactant. Preferably, the surfactant is nonionic, including but not limited to at least one of alkylphenol ethoxylates, high-carbon fatty alcohol ethoxylates, fatty acid polyoxyethylene esters, fatty acid methyl ester ethoxylates, ethylene oxide adducts of polypropylene glycol, polyoxyethylated ionic surfactants, sorbitan esters, sucrose fatty acid esters, alkylolamide type surfactants, nonionic fluorocarbon surfactants, polyoxyethylene-polyoxypropylene copolymers.
The use of the surfactant can adjust the viscosity and surface tension of an ink system, so that the ink system has good leveling property, the requirement of ink-jet printing is met, the dispersion stability of quantum dots in the ink system can be effectively promoted, the printing film-forming property is improved, and a smooth and uniform quantum dot film is obtained.
In an exemplary embodiment of the present application, a quantum dot color film is disclosed, which is prepared by inkjet printing the quantum dot ink. The ink utilizes the ester mixed solvent with a cyclic structure and the surfactant, improves the dispersion stability of the quantum dots, and enables the ink to have proper viscosity and surface tension. The process is smooth when the ink-jet printing is carried out, the nozzle is not blocked, the obtained quantum dot color film has good smoothness and uniform film formation, and has higher blue light absorption rate and light-emitting brightness.
Hereinafter, embodiments are described in more detail with reference to examples. However, they are exemplary embodiments of the present invention, and the present invention is not limited thereto.
Example 1
The present embodiment provides a quantum dot ink, including: 30 wt% of red light CdSeS quantum dots, 30 wt% of cyclohexyl acetate (the boiling point is 173.5 ℃), 35 wt% of cyclohexyl methacrylate (the boiling point is 210 ℃) and 5 wt% of polyoxyethylene cetyl ether. The quantum dot ink can be prepared by simply mechanically stirring and mixing the components.
The ink can be kept stable after being placed for 90 days, and agglomeration or precipitation can not occur. The quantum dot ink is used for ink-jet printing, the process is smooth, the film is formed uniformly, and a smooth quantum dot color film is obtained.
Testing the luminous performance of the quantum dot color film, wherein the initial light-emitting brightness of the adopted blue light backlight source is 1000cd/m2The results of blue light absorption, luminance, and external quantum yield (EQE) of the quantum dot color films are shown in table 1.
Example 2
The present embodiment provides a quantum dot ink, including: 35 wt% of red InP/ZnS quantum dots, 28 wt% of methylcyclohexyl acetate (boiling point 182 ℃), 33 wt% of isobornyl acetate (boiling point 220 ℃), and 4 wt% of polyoxyethylene sorbitan trioleate. The quantum dot ink can be prepared by simply mechanically stirring and mixing the components.
The ink can be kept stable after being placed for 90 days, and agglomeration or precipitation can not occur. The quantum dot ink is used for ink-jet printing, the process is smooth, the film is formed uniformly, and a smooth quantum dot color film is obtained.
Testing the luminous performance of the quantum dot color film, wherein the initial light-emitting brightness of the adopted blue light backlight source is 1000cd/m2The results of blue light absorption, luminance, and external quantum yield (EQE) of the quantum dot color films are shown in table 1.
Example 3
The present embodiment provides a quantum dot ink, including: 39 wt% of green CdSe/CdS/ZnS quantum dots, 30 wt% of cyclohexyl acrylate (boiling point 182 ℃), 25 wt% of cyclohexyl 3,3, 5-trimethylacetate (boiling point 211 ℃), and 6 wt% of polyoxyethylene propylene stearate. The quantum dot ink can be prepared by simply mechanically stirring and mixing the components.
The ink can be kept stable after being placed for 90 days, and agglomeration or precipitation can not occur. The quantum dot ink is used for ink-jet printing, the process is smooth, the film is formed uniformly, and a smooth quantum dot color film is obtained.
Testing the luminous performance of the quantum dot color film, wherein the initial light-emitting brightness of the adopted blue light backlight source is 1000cd/m2The results of blue light absorption, luminance, and external quantum yield (EQE) of the quantum dot color films are shown in table 1.
Example 4
The present embodiment provides a quantum dot ink, including: 32 weight percent of green InP quantum dots, 30 weight percent of cyclohexyl butyrate (boiling point of 202 ℃), 33 weight percent of isobornyl acrylate (boiling point of 244 ℃) and 5 weight percent of polyoxyethylene propylene stearate. The quantum dot ink can be prepared by simply mechanically stirring and mixing the components.
The ink can be kept stable after being placed for 90 days, and agglomeration or precipitation can not occur. The quantum dot ink is used for ink-jet printing, the process is smooth, the film is formed uniformly, and a smooth quantum dot color film is obtained.
Testing the luminous performance of the quantum dot color film, wherein the initial light-emitting brightness of the adopted blue light backlight source is 1000cd/m2The results of blue light absorption, luminance, and external quantum yield (EQE) of the quantum dot color films are shown in table 1.
In examples 1 to 4, the quantum dot ink was printed using a FUJIFILM DMP-3000 inkjet printer.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Blue light absorption (%) | 82 | 65 | 80 | 62 |
| Luminance of light emission (cd/m)2) | 900 | 894 | 3980 | 3465 |
| EQE(％) | 25.8 | 17.9 | 20.2 | 21.3 |
As can be seen from Table 1, the absorption rate of the color film prepared by the quantum dot ink in the application to blue light can reach 82%, and the maximum brightness of the emergent light is 3980cd/m2The external quantum efficiency EQE was up to 25.8%, all exhibiting good optical performance.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.
Claims (7)
1. The quantum dot ink is characterized by comprising quantum dots and an ester solvent with a cyclic structure, wherein the quantum dots account for 30-45 wt% of the quantum dot ink;
wherein the ester solvent with the cyclic structure is at least two ester solvents with alicyclic structures, or at least one ester solvent with an alicyclic structure and at least one ester solvent with a bridged ring structure;
the ester solvent comprises at least one high boiling point ester and one low boiling point ester, and the boiling points of the two esters are different by at least 20 ℃.
2. The quantum dot ink according to claim 1, wherein the high boiling point is 230 to 320 ℃ and the low boiling point is 150 to 220 ℃ under normal atmospheric pressure.
3. The quantum dot ink according to claim 1, wherein the ester solvent having an alicyclic structure is at least one selected from the group consisting of cyclohexyl formate, cyclohexyl acetate, methylcyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, cyclohexyl valerate, cyclohexyl hexanoate, o-tert-butylcyclohexyl acetate, cyclohexyl acrylate, cyclohexyl benzoate, and cyclohexyl methacrylate.
4. The quantum dot ink according to claim 1, wherein the ester solvent having a bridged ring structure is at least one selected from isobornyl acrylate, isobornyl methacrylate, isobornyl acetate, and isobornyl isobutyrate.
5. The quantum dot ink of claim 1, wherein the quantum dot ink has 1 wt% to 10 wt% of a surfactant.
6. The quantum dot ink according to claim 5, wherein the surfactant is at least one of alkylphenol ethoxylates, high-carbon fatty alcohol ethoxylates, fatty acid polyoxyethylene esters, fatty acid methyl ester ethoxylates, ethylene oxide adducts of polypropylene glycol, polyoxyethylated ionic surfactants, sorbitan esters, sucrose fatty acid esters, alkylolamide surfactants, nonionic fluorocarbon surfactants, and polyoxyethylene-polyoxypropylene copolymers.
7. A quantum dot color film, wherein the quantum dot color film is prepared by printing the quantum dot ink according to any one of claims 1 to 6.
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| 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 |
| CN112099266B (en) * | 2020-09-18 | 2023-01-17 | 苏州星烁纳米科技有限公司 | Color film, preparation method thereof, processing device and display device |
| CN112646417A (en) * | 2020-12-21 | 2021-04-13 | 广东聚华印刷显示技术有限公司 | Quantum dot ink, preparation method of quantum dot light-emitting diode and display device |
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