Quantum dot composition, resin composition using the same, and wavelength conversion material

Abstract

To provide a quantum dot composition in which deterioration in fluorescent emission efficiency is suppressed, a resin composition using the same, and a wavelength conversion material.SOLUTION: A quantum dot composition contains a quantum dot emitting fluorescent light by excitation light, in which the quantum dot is composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell which do not contain Cd or Pb, and the surface of the quantum dot is modified with a phosphonic acid derivative.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a quantum dot composition, a resin composition using the same, and a wavelength converting material. [Background technology]

[0002] Quantum dots, which are semiconductor particles with nano-sized particle diameters, have discrete energy levels of the semiconductor nanoparticles due to the fact that excitons generated by light absorption are confined in nano-sized spaces, and the band gap depends on the particle diameter. For this reason, quantum dots have a high efficiency of fluorescence emission and a sharp emission spectrum. In addition, because the band gap changes depending on the particle diameter, quantum dots have the characteristic of being able to control the emission wavelength, and are expected to be used as wavelength conversion materials for solid-state lighting and displays (Patent Document 1).

[0003] Quantum dots that exhibit excellent fluorescence emission properties include those containing Cd and Pb. However, because Cd and Pb are highly toxic to the human body and the environment, restrictions on their use are being considered around the world, including the European Union's RoHS Directive. For this reason, quantum dots that do not contain these toxic elements are being considered.

[0004] In addition, a method has been proposed for implementing quantum dots as a wavelength conversion material, in which quantum dots are dispersed in a resin material, and a resin composition containing the quantum dots is laminated with a transparent film to incorporate it into a backlight unit as a wavelength conversion film (Patent Document 2).

[0005] However, quantum dots are easily destabilized because their particle size is as small as nanometers, their specific surface area is large, their surface energy is high, and they are surface active. This makes them susceptible to surface defects due to dangling bonds on the quantum dot surface and oxidation reactions, which cause deterioration of the fluorescent emission characteristics. Currently available quantum dots have such stability problems, and are known to cause deterioration of their emission characteristics due to heat, humidity, photoexcitation, etc.

[0006] To prevent this deterioration, organic ligands called ligands are attached to the quantum dot surface after synthesis. The coordination of these ligands improves dispersibility in solvents and resins, and also suppresses deterioration of the fluorescence emission efficiency by passivating defects.

[0007] However, if an appropriate ligand is not selected for the quantum dot surface, the ligand may be detached from the quantum dot surface due to external influences such as heat or light irradiation, resulting in a deterioration in the fluorescence emission efficiency.

[0008] Changes in the fluorescence emission efficiency of quantum dots over time can lead to defects such as uneven color and emission, and missing dots when used in displays, so the stability of quantum dots is an important issue.

[0009] To address these problems, methods being considered include coating the surface of the quantum dots with a polymer or an inorganic oxide (Patent Document 3) and improving the stability of the quantum dots by using a gas barrier film with low oxygen and moisture permeability (Patent Document 4).

[0010] However, in the process of coating the surface of the quantum dots to improve the stability, the fluorescence efficiency of the quantum dots cannot be maintained, and the characteristics deteriorate. In addition, the stabilization by the barrier film also has the problem of deterioration due to the diffusion of oxygen and water vapor from the film edge. Furthermore, for mobile applications such as tablets and smartphones, the wavelength conversion film needs to be made thinner, but the barrier film is generally about 20 to 200 μm thick, and since it must be at least 40 μm thick to protect both sides of the film, there is a limit to how thin the wavelength conversion film can be made.

[0011] Furthermore, a method has been proposed in which quantum dots are used as color filters, rather than as wavelength conversion films, to directly convert blue excitation light into green and red light (Patent Document 5). When quantum dots are used as color filters, barrier films, etc. cannot be used as in the above-mentioned wavelength conversion films, and deterioration of the fluorescence emission efficiency of the quantum dots due to hardening of the quantum dot composition, subsequent manufacturing processes, and long-term use becomes an important issue. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] JP 2012-022028 A [Patent Document 2] Special Publication No. 2013-544018 [Patent Document 3] International Publication No. 2011 / 081037 [Patent Document 4] Patent No. 5900720 [Patent Document 5] JP 2018-109141 A Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, an object of the present invention is to provide a quantum dot composition in which deterioration of the fluorescence emission efficiency is suppressed, a resin composition using the same, and a wavelength converting material. [Means for solving the problem]

[0014] In order to solve the above problems, the present invention provides a quantum dot composition comprising quantum dots that emit fluorescence when excited by excitation light, the quantum dots comprising a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, and the surfaces of the quantum dots are modified with a phosphonic acid derivative.

[0015] Such a quantum dot composition is composed of quantum dots with low toxicity, and the deterioration of the fluorescence emission efficiency is suppressed.

[0016] In this case, it is preferable that the quantum dot is composed of the semiconductor nanoparticle core and one or more semiconductor nanoparticle shells covering the semiconductor nanoparticle core.

[0017] With such a quantum dot composition, the deterioration of the fluorescence emission efficiency is further suppressed.

[0018] At this time, the semiconductor nanoparticle core is ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AgGaS 2 , AgInS 2 , AgGaSe 2 , AgInSe 2 , CuGaS 2 , CuGaSe 2 , CuInS 2 , CuInSe 2 , ZnSiP 2 , and ZnGeP 2 It is preferable that the compound is selected from the group consisting of the following compounds as a single crystal, a plurality of crystals or a mixed crystal:

[0019] Such a quantum dot composition is preferable in terms of fluorescence emission characteristics and stability.

[0020] In this case, it is preferable that the semiconductor nanoparticle shell is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single crystal, multiple crystals, or mixed crystals.

[0021] Such a quantum dot composition is preferable from the viewpoints of improving the fluorescence emission efficiency and stability.

[0022] In this case, the phosphonic acid derivative is preferably represented by the following formula (I). [ka] (In formula (I), R 1 is a monovalent organic group having one or more carbon atoms.

[0023] Such a quantum dot composition suppresses deterioration of the fluorescence emission efficiency and improves stability.

[0024] In this case, the phosphonic acid derivative is 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, hexylphosphonic acid, 4 -Phosphonobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (aminomethyl)phosphonic acid, (2-phenylethyl)phosphonic acid, ethylphosphonic acid, butylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, (2-chloroethyl)phosphonic acid, 4-methoxy Phenylphosphonic acid, hexadecylphosphonic acid, (4-hydroxybenzyl)phosphonic acid, phenylphosphonic acid, (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid, tetradecylphosphonic acid, (1-aminoethyl)phosphonic acid, undecylphosphonic acid, heptylphosphonic acid, 10-carboxydecylphosphonic acid, 11-aminoundecylphosphonic acid hydrobromide, 11-hydroxyundecylphosphonic acid, 1H,1 It is preferable that the phosphonic acid is one or more selected from H,2H,2H-perfluoro-n-hexylphosphonic acid, 1H,1H,2H,2H-perfluorooctylphosphonic acid, 1H,1H,2H,2H-perfluoro-n-decylphosphonic acid, 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid, 12-mercaptodecylphosphonic acid, and [11-(acryloyloxy)undecyl]phosphonic acid.

[0025] Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.

[0026] In this case, the phosphonic acid derivative is preferably represented by the following formula (II): [ka] (In formula (II), R 2 is a divalent organic group having one or more carbon atoms.

[0027] Such a quantum dot composition suppresses deterioration of the fluorescence emission efficiency and improves stability.

[0028] In this case, the phosphonic acid derivative is preferably one or more selected from m-xylylenediphosphonic acid, o-xylylenediphosphonic acid, methylenediphosphonic acid, 4-phosphonobenzoic acid, alendronic acid, 1,4-butylenediphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylenediphosphonic acid, zoledronic acid, 1,3-propylenediphosphonic acid, 1,5-pentylenediphosphonic acid, 1,4-phenylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,6-hexylenediphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid.

[0029] Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.

[0030] In this case, the phosphonic acid derivative is preferably represented by the following formula (III). [ka] (In formula (III), R 3 is a trivalent organic group having one or more carbon atoms.

[0031] Such a quantum dot composition suppresses deterioration of the fluorescence emission efficiency and improves stability.

[0032] In this case, the phosphonic acid derivative is preferably nitrilotris(methylene phosphonic acid).

[0033] Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.

[0034] In this case, the phosphonic acid derivative is preferably represented by the following formula (IV). [ka] (In formula (IV), R 4 is a divalent organic group having one or more carbon atoms.

[0035] Such a quantum dot composition suppresses deterioration of the fluorescence emission efficiency and improves stability.

[0036] In this case, the phosphonic acid derivative is preferably N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).

[0037] Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.

[0038] At this time, the R 1 , R 2 , R 3 , and R 4 preferably contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[0039] Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.

[0040] The present invention also provides a resin composition in which the quantum dot composition is dispersed in a resin.

[0041] Such a resin composition is one in which the deterioration of the fluorescent light emission efficiency is suppressed.

[0042] In this case, the resin is preferably at least one selected from the group consisting of epoxy resins, acrylic resins, fluorine resins, silicone resins, carbonate resins, and glass.

[0043] Such resins can be used in the resin composition of the present invention.

[0044] The present invention also provides a wavelength converting material using a cured product of the above resin composition.

[0045] Such a wavelength conversion material suppresses deterioration of the fluorescence emission efficiency and improves reliability. Effect of the Invention

[0046] As described above, according to the present invention, there are provided a quantum dot composition in which deterioration of the fluorescence emission efficiency is suppressed, a resin composition using the same, and a wavelength converting material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] As described above, there is a problem in producing a quantum dot composition in which the deterioration of the fluorescence emission efficiency is suppressed by using quantum dots with low toxicity.

[0048] The present inventors have conducted extensive research into the above-mentioned problems, and as a result have found that a quantum dot composition that contains quantum dots that emit fluorescence when excited by excitation light, the quantum dots being composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, and the surfaces of the quantum dots being modified with a phosphonic acid derivative, can suppress deterioration of the fluorescence emission efficiency, and have completed the present invention.

[0049] That is, the present invention relates to a quantum dot composition comprising quantum dots that emit fluorescence when exposed to excitation light, the quantum dots comprising a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, and the surfaces of the quantum dots are modified with a phosphonic acid derivative.

[0050] Hereinafter, embodiments of the present invention will be described. However, in the present invention, the composition, type, and production method of the quantum dots and phosphonic acid derivatives are not limited to the following embodiments.

[0051] [Quantum dots] The structure of the quantum dot in the present invention is not particularly limited as long as it is composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell. Such quantum dots have excellent fluorescent emission properties and stability. In semiconductor nanoparticles with a core / shell structure in which a nano-sized semiconductor particle is used as the core and a semiconductor particle having a larger band gap and lower lattice mismatch than the core is used as the shell, the excitons generated in the shell are confined inside the core particle, improving the fluorescent emission efficiency, and further improving the stability since the core surface is covered with the shell.

[0052] In addition, it is preferable that the quantum dots are composed of the semiconductor nanoparticle core and one or more semiconductor nanoparticle shells covering the semiconductor nanoparticle core. With such a quantum dot composition, the deterioration of the fluorescence emission efficiency is further suppressed.

[0053] The material for the semiconductor nanoparticle core of the core / shell semiconductor nanoparticle is not particularly limited as long as it does not contain the elements Cd or Pb from the viewpoint of toxicity, and may be, for example, a compound selected from the group consisting of II-VI group compounds, III-V group compounds, I-III-VI group compounds, II-IV-V group compounds, and alloys or mixed crystals thereof. Specifically, ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AgGaS 2 , AgInS 2 , AgGaSe 2 , AgInSe 2 , CuGaS 2 , CuGaSe 2 , CuInS 2 , CuInSe 2 , ZnSiP 2 , and ZnGeP 2Among these materials, ZnSe, ZnTe, and InP are particularly preferred in terms of their fluorescent emission characteristics and stability.

[0054] The material of the semiconductor nanoparticle shell is not particularly limited as long as it does not contain elements such as Cd and Pb from the viewpoint of toxicity, but it is preferable that the material has a large band gap and low lattice mismatch with the core material, and can be selected from the group consisting of alloys and mixed crystals of II-VI and III-V compounds. Specific shell materials can be selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single element, multiple elements, or mixed crystals. Of these materials, ZnSe and ZnS are particularly preferable from the viewpoints of improving the fluorescence emission efficiency and stability.

[0055] There are various methods for producing semiconductor nanoparticles, such as a liquid phase method and a gas phase method, but the present invention is not particularly limited to these. From the viewpoint of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained by a hot soap method or a hot injection method, in which a precursor species is reacted at high temperature in a nonpolar solvent with a high boiling point.

[0056] In order to reduce surface defects during and after synthesis, the quantum dots preferably have organic ligands, called ligands, coordinated to their surfaces.

[0057] The ligand preferably contains an aliphatic hydrocarbon from the viewpoint of suppressing the aggregation of quantum dots. Examples of such ligands include oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, octanoic acid, oleylamine, stearyl (octadecyl)amine, dodecyl (lauryl)amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanethiol, trioctylphosphine, trioctylphosphine oxide, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, and tributylphosphine oxide, and the like, which may be used alone or in combination.

[0058] Furthermore, the quantum dot surface may have a coating layer of polymer or inorganic molecules, and the structure is not limited. When the coating layer is present, the thickness of the coating layer can be appropriately selected according to the purpose. The thickness of the coating layer is not particularly limited, but if the particle diameter of the quantum dot is 100 nm or less, the decrease in dispersibility can be more suppressed, and as a result, the decrease in light transmittance and aggregation can be more suppressed, so that the thickness is preferably about 100 nm or less.

[0059] Examples of the coating layer include polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polysilsesquioxane, poly(methyl methacrylate), polyacrylonitrile, and polyethylene glycol, and inorganic molecules such as silica, alumina, titania, zirconia, zinc oxide, gallium oxide, silicon nitride, and gallium nitride.

[0060] [Phosphonic acid derivatives] The surface modifier of quantum dots useful in the present disclosure is a phosphonic acid derivative, and the quantum dot composition in this document is composed of the quantum dots and the phosphonic acid derivative that modifies the surface of the quantum dots.

[0061] In this paper, "modification" refers to the state in which the quantum dot surface is contacted with the phosphonic acid derivative and adheres to the surface. The adhesion of the phosphonic acid derivative to the quantum dot surface by "modification" includes partial and full adhesion, and indicates a state in which the phosphonic acid derivative is adhered to at least a part of the surface.

[0062] The term "adhesion" as used above may refer to either physical adsorption or chemical bonding, and may broadly refer to, for example, covalent bonding, ionic bonding, or hydrogen bonding, or may refer to a combination of these.

[0063] In addition, in one example, the quantum dot composition may be in a state in which the organic ligand attached to the quantum dot surface during synthesis and the phosphonic acid derivative coexist.

[0064] The type of phosphonic acid derivative is not particularly limited, but it is desirable for the derivative to have one or more groups for adhering to the quantum dot surface, as well as one or more groups that affect compatibility with solvents or resins or the stability of the quantum dots.

[0065] The chemical structure of the phosphonic acid derivative is not particularly limited, but for example, the structure of this compound is preferably one represented by the following formulae (I), (II), (III), and (IV).

[0066] [ka] (In formula (I), R 1 is a monovalent organic group having one or more carbon atoms.

[0067] [ka] (In formula (II), R 2 is a divalent organic group having one or more carbon atoms.

[0068] [ka] (In formula (III), R 3is a trivalent organic group having one or more carbon atoms.

[0069] [ka] (In formula (IV), R 4 is a divalent organic group having one or more carbon atoms.

[0070] In certain embodiments of compounds of Formulae (I)-(IV), R 1 ~R 4 preferably contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[0071] Specific examples of the compound represented by formula (I) include 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, hexylphosphonic acid, 4-phosphonobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (aminomethyl)phosphonic acid, (2-phenylethyl)phosphonic acid, ethylphosphonic acid, butylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, (2-chloroethyl)phosphonic acid, Acid, 4-methoxyphenylphosphonic acid, hexadecylphosphonic acid, (4-hydroxybenzyl)phosphonic acid, phenylphosphonic acid, (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid, tetradecylphosphonic acid, (1-aminoethyl)phosphonic acid, undecylphosphonic acid, heptylphosphonic acid, 10-carboxydecylphosphonic acid, 11-aminoundecylphosphonic acid hydrobromide, 11-hydroxyundecylphosphonic acid hydrobromide, decylphosphonic acid, 1H,1H,2H,2H-perfluoro-n-hexylphosphonic acid, 1H,1H,2H,2H-perfluorooctylphosphonic acid, 1H,1H,2H,2H-perfluoro-n-decylphosphonic acid, 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid, 12-mercaptodecylphosphonic acid, and [11-(acryloyloxy)undecyl]phosphonic acid.

[0072] Specific examples of the compound represented by formula (II) include m-xylylenediphosphonic acid, o-xylylenediphosphonic acid, methylenediphosphonic acid, 4-phosphonobenzoic acid, alendronic acid, 1,4-butylenediphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylenediphosphonic acid, zoledronic acid, 1,3-propylenediphosphonic acid, 1,5-pentylenediphosphonic acid, 1,4-phenylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,6-hexylenediphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid.

[0073] A specific example of the compound represented by formula (III) is nitrilotris(methylene phosphonic acid).

[0074] A specific example of the compound represented by formula (IV) is N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).

[0075] The above phosphonic acid derivatives can be used alone or in combination of two or more.

[0076] The heating temperature when modifying the quantum dot surface with the phosphonic acid derivative is not particularly limited, but in order to perform the modification efficiently, the heating temperature is preferably in the range of 50 to 300° C., and more preferably in the range of 80 to 240° C. Within such a range, the quantum dot surface can be modified more efficiently.

[0077] The amount of the phosphonic acid derivative added as the surface modifier is not particularly limited as long as the phosphonic acid derivative modifies the quantum dot surface. However, from the viewpoints that, for example, if the concentration of the surface modifier is high, the quantum dots may aggregate with each other or the phosphonic acid derivative may precipitate, and if the concentration is low, the effect of modifying the quantum dot surface may be insufficient, the weight of the surface modifier added is preferably in the range of 0.01 to 30 wt %, and more preferably in the range of 0.1 to 15 wt %, based on the solid weight of the quantum dots.

[0078] [Quantum dot composition] In the quantum dot composition in which the quantum dot surface is modified with the above-mentioned phosphonic acid derivative, the defects on the quantum dot surface are passivated, so that the deterioration of the fluorescence emission efficiency is suppressed and the stability is improved.

[0079] [Resin composition] In addition, the quantum dot composition can be used as a resin composition dispersed in a resin. The resin material is not particularly limited, but is preferably one in which the quantum dot composition does not aggregate or the fluorescence emission efficiency does not deteriorate, and examples thereof include at least one selected from epoxy resins, acrylic resins, fluorine resins, silicone resins, carbonate resins, and glass.

[0080] In order to increase the efficiency of fluorescent light emission, it is preferable that these resin compositions have high transmittance, and it is particularly preferable that the transmittance be 80% or more.

[0081] In addition, the concentration of quantum dots contained in the resin composition is not particularly limited, and can be appropriately adjusted according to the film thickness, the luminous efficiency of the quantum dots, and the characteristics of the intended wavelength converting material.

[0082] The resin composition may contain substances other than the quantum dot composition, may contain fine particles such as silica, zirconia, alumina, titania, etc. as light scatterers, and may contain inorganic phosphors or organic phosphors. Examples of inorganic phosphors include YAG, LSN, LYSN, CASN, SCASN, KSF, CSO, β-SIALON, GYAG, LuAG, and SBCA, and examples of organic phosphors include perylene derivatives, anthraquinone derivatives, anthracene derivatives, phthalocyanine derivatives, cyanine derivatives, dioxazine derivatives, benzoxazinone derivatives, coumarin derivatives, quinophthalone derivatives, benzoxazole derivatives, and pyrarizone derivatives.

[0083] [Wavelength conversion materials] The present invention also provides a wavelength converting material using a cured product of the above-mentioned resin composition. The wavelength converting material may be used as it is or may be processed. One form of the wavelength converting material is a wavelength conversion film in which the quantum dot composition is dispersed in the resin by processing it into a sheet and then curing it.

[0084] The method for producing the wavelength converting material is not particularly limited. For example, a resin composition in which a quantum dot composition is dispersed in a resin can be applied to a transparent film such as PET or polyimide, cured, and laminated to obtain the wavelength converting material.

[0085] The transparent film can be coated with the resin layer by spraying, inkjet, or other spraying methods, spin coating, bar coater, or doctor blade methods. The thickness of the resin layer and the transparent film is not particularly limited and can be appropriately selected depending on the application. Such a wavelength conversion material suppresses the deterioration of the fluorescence emission efficiency and improves reliability. EXAMPLES

[0086] The present invention will be specifically described below using Production Examples, Examples, and Comparative Examples, but the present invention is not limited to these.

[0087] (Evaluation of luminescence properties) In the manufacturing examples, examples, and comparative examples, the fluorescence emission properties of the quantum dots, quantum dot compositions, and wavelength conversion materials were evaluated by measuring the fluorescence emission efficiency (internal quantum efficiency) at an excitation wavelength of 450 nm using a quantum efficiency measurement system (QE-2100) manufactured by Otsuka Electronics Co., Ltd.

[0088] (Quantum dot manufacturing) (Production Example 1) In the flask, 0.070g (0.24mmol) of indium acetate, 0.256g (0.72mmol) of palmitic acid, and 4.0mL of 1-octadecene were added, and the mixture was heated and stirred at 100°C under reduced pressure, and degassed for 1 hour while dissolving. After cooling the flask to room temperature, nitrogen was purged, and 0.50mL (0.17mmol) of 10vol% (tris)trimethylsilylphosphine / octadecene solution was added to the flask. The flask was heated to 300°C and stirred for 20 minutes to synthesize InP semiconductor core particles. Next, the flask was cooled to 200°C, and 4.0mL (1.2mmol) of 0.30M zinc stearate / octadecene solution was added and stirred for 30 minutes. Furthermore, 0.60mL (0.90mmol) of 1.5M selenium / trioctylphosphine solution was added to the flask and stirred for 30 minutes. Next, after cooling the flask to room temperature, 0.22 g (1.1 mmol) of zinc acetate was added, and the mixture was heated and stirred at 100 °C under reduced pressure, and degassed for 1 hour while dissolving. After purging the flask with nitrogen, it was heated to 230 °C, and 0.48 mL (2.0 mmol) of 1-dodecanethiol was added and stirred for 30 minutes. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate quantum dots consisting of InP as a core, ZnSe as a shell, and ZnS as a shell, and the supernatant was removed. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene or octadecene to prepare an InP / ZnSe / ZnS dispersion. The resulting InP / ZnSe / ZnS toluene dispersion had a fluorescent emission wavelength peak of 534 nm and an internal quantum efficiency of 76%. In addition, the InP / ZnSe / ZnS toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured. The internal quantum efficiency was then found to be 62%.

[0089] (Production Example 2) 0.033g (0.20mmol) of silver acetate (I), 0.058g (0.20mmol) of indium acetate, 0.65mL (2.7mmol) of 1-dodecanethiol and 4.0mL of oleylamine were added to the flask, and the mixture was heated and stirred at 100°C under reduced pressure for 1 hour. Nitrogen was then purged into the flask, and the mixture was heated to 200°C and held for 20 minutes. The flask was then heated to 230°C, and a 1.25M sulfur / trioctylphosphine solution was prepared, 1.0mL was added to the reaction solution, and the mixture was stirred for 1 hour. Finally, 0.066g (0.36mmol) of zinc acetate, 0.24mL (0.76mmol) of oleic acid and 0.15mL of oleylamine were added to the flask, and the mixture was heated and stirred at 230°C for 1 hour. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dots and remove the supernatant. Toluene was further added to disperse the mixture, ethanol was added again, the mixture was centrifuged, the supernatant was removed, and the mixture was redispersed in toluene or octadecene to obtain AgInS 2 A AgInS / ZnS dispersion was prepared. 2 The fluorescence emission wavelength peak of the AgInS / ZnS toluene dispersion was 597 nm, and the internal quantum efficiency was 56%. 2 The / ZnS toluene dispersion was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) in an air atmosphere for 12 hours, and the fluorescence emission efficiency was measured. The internal quantum efficiency was found to be 38%.

[0090] (Surface modification with phosphonic acid derivatives) Example 1 In a nitrogen atmosphere, 10 g of the 1.0 wt% InP / ZnSe / ZnS octadecene dispersion obtained in Production Example 1 and 31 mg of hexadecylphosphonic acid were added to a three-neck flask. Next, the flask was heated and stirred at 120°C under reduced pressure, and degassed for 30 minutes while dissolving. Nitrogen was purged into the flask, and the mixture was heated to 230°C and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with hexadecylphosphonic acid. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the obtained quantum dot composition was 74%. A toluene dispersion of the quantum dot composition was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an atmospheric environment, and the fluorescence emission efficiency was measured. The internal quantum efficiency was then found to be 71%.

[0091] Example 2 In a nitrogen atmosphere, 10 g of the 1.0 wt% InP / ZnSe / ZnS octadecene dispersion obtained in Production Example 1 and 27 mg of 10-carboxydecylphosphonic acid were added to a three-neck flask. Next, the flask was heated and stirred at 120°C under reduced pressure, and degassed for 30 minutes while dissolving. Nitrogen was purged into the flask, and the mixture was heated to 230°C and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with 10-carboxydecylphosphonic acid. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the obtained quantum dot composition was 72%. A toluene dispersion of the quantum dot composition was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an atmospheric environment, and the fluorescence emission efficiency was measured. The internal quantum efficiency was then found to be 70%.

[0092] Example 3 In a nitrogen atmosphere, 10 g of the 1.0 wt% InP / ZnSe / ZnS octadecene dispersion obtained in Production Example 1, 31 mg of hexadecylphosphonic acid, and 22 mg of (4-bromobutyl)phosphonic acid were added to a three-neck flask. Next, the flask was heated and stirred at 120°C under reduced pressure, and degassed for 30 minutes while dissolving. Nitrogen was purged into the flask, and the mixture was heated to 230°C and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with hexadecylphosphonic acid and (4-bromobutyl)phosphonic acid. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the resulting quantum dot composition was 76%. A toluene dispersion of the quantum dot composition was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an atmospheric environment, and the fluorescence emission efficiency was measured. The internal quantum efficiency was then found to be 74%.

[0093] Example 4 In a nitrogen atmosphere, 10 g of the 1.0 wt% InP / ZnSe / ZnS octadecene dispersion obtained in Production Example 1 and 43 mg of 1H,1H,2H,2H-perfluorooctylphosphonic acid were added to a three-neck flask. Next, the flask was heated and stirred at 120°C under reduced pressure, and degassed for 30 minutes while dissolving. Nitrogen was purged into the flask, and the mixture was heated to 230°C and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with 1H,1H,2H,2H-perfluorooctylphosphonic acid. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the obtained quantum dot composition was 71%. A toluene dispersion of the quantum dot composition was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an atmospheric environment, and then the fluorescence emission efficiency was measured. The internal quantum efficiency was found to be 68%.

[0094] Example 5 In a nitrogen atmosphere, the 1.0 wt% AgInS obtained in Production Example 2 was placed in a three-neck flask. 210g of ZnS / Octadecene dispersion and 31mg of hexadecylphosphonic acid were added. Next, the flask was heated and stirred at 120°C under reduced pressure, and degassed for 30 minutes while dissolving. Nitrogen was purged into the flask, heated to 230°C, and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with hexadecylphosphonic acid. The obtained solution was cooled to room temperature, ethanol was added, and centrifuged to precipitate the quantum dot composition and remove the supernatant. Further, toluene was added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the obtained quantum dot composition was 56%. The toluene dispersion of the quantum dot composition was irradiated with blue light of 450nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Co., Ltd.) for 12 hours under atmospheric atmosphere, and then the fluorescence emission efficiency was measured. As a result, the internal quantum efficiency was 48%.

[0095] Example 6 In a nitrogen atmosphere, the 1.0 wt% AgInS obtained in Production Example 2 was placed in a three-neck flask. 2 10 g of ZnS octadecene dispersion and 43 mg of 1H,1H,2H,2H-perfluorooctylphosphonic acid were added. The flask was then heated and stirred under reduced pressure at 120°C, and degassed for 30 minutes while dissolving. The flask was purged with nitrogen, heated to 230°C, and stirred for 30 minutes to obtain a quantum dot composition in which the quantum dot surface was modified with 1H,1H,2H,2H-perfluorooctylphosphonic acid. The resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was further added to the precipitate to disperse it, ethanol was added again, centrifuged, the supernatant was removed, and the mixture was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition. The internal quantum efficiency of the resulting quantum dot composition was 50%. A toluene dispersion of the quantum dot composition was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an atmospheric environment, and the fluorescence emission efficiency was measured. The internal quantum efficiency was then found to be 44%.

[0096] When comparing the internal quantum yield values ​​after blue light irradiation between the quantum dot toluene dispersion of Production Example 1 and the toluene dispersion of the quantum dot composition of Examples 1 to 4, and between the quantum dot toluene dispersion of Production Example 2 and the toluene dispersion of the quantum dot composition of Examples 5 and 6, it was shown that the quantum dot compositions of Examples 1 to 4 and Examples 5 and 6 retain higher internal quantum yield values. From this result, it was confirmed that the quantum dot surface was modified with a phosphonic acid derivative, thereby suppressing the decrease in internal quantum yield due to light irradiation and improving photostability.

[0097] (Preparation of resin composition and wavelength converting material) Example 7 A wavelength converting material was produced using the quantum dot composition obtained in Example 1. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. After that, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was produced. The thickness of the obtained wavelength converting material was 96 μm. The internal quantum efficiency of the obtained wavelength converting material was 43%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 41%.

[0098] Example 8 A wavelength converting material was prepared using the quantum dot composition obtained in Example 2. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. After that, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was prepared. The thickness of the obtained wavelength converting material was 92 μm. The internal quantum efficiency of the obtained wavelength converting material was 42%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 40%.

[0099] Example 9 A wavelength converting material was prepared using the quantum dot composition obtained in Example 3. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. After that, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was prepared. The thickness of the obtained wavelength converting material was 95 μm. The internal quantum efficiency of the obtained wavelength converting material was 45%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 43%.

[0100] Example 10 A wavelength converting material was prepared using the quantum dot composition obtained in Example 4. 2.5 g of a 20 wt% toluene solution of the quantum dot composition was mixed with 5.0 g of a 40% xylene solution of a fluoroethylene-vinyl ether copolymer (LUMIFLON LF200 manufactured by AGC), which is a fluorine-containing resin, and the solvent was removed under reduced pressure while being stirred and heated at 60°C. The mixture was then vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. A PET film was then laminated onto the resin composition layer. The film was heated at 80°C for 2 hours and at 100°C for 2 hours to harden the resin composition layer, thereby preparing a wavelength converting material. The thickness of the obtained wavelength converting material was 96 μm. The internal quantum efficiency of the obtained wavelength converting material was 38%. The obtained wavelength converting material was treated at 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 37%.

[0101] Example 11 A wavelength converting material was prepared using the quantum dot composition obtained in Example 5. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. After that, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was prepared. The thickness of the obtained wavelength converting material was 98 μm. The internal quantum efficiency of the obtained wavelength converting material was 29%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 27%.

[0102] Example 12 A wavelength converting material was prepared using the quantum dot composition obtained in Example 6. 2.5 g of a 20 wt% toluene solution of the quantum dot composition was mixed with 5.0 g of a 40% xylene solution of a fluoroethylene-vinyl ether copolymer (LUMIFLON LF200 manufactured by AGC), which is a fluorine-containing resin, and the solvent was removed under reduced pressure while being heated at 60°C while stirring. The mixture was then vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. A PET film was then laminated onto the resin composition layer. The film was heated at 80°C for 2 hours and at 100°C for 2 hours to harden the resin composition layer, thereby preparing a wavelength converting material. The thickness of the obtained wavelength converting material was 96 μm. The internal quantum efficiency of the obtained wavelength converting material was 24%. The obtained wavelength converting material was treated at 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 22%.

[0103] Comparative Example 1 A wavelength converting material was produced using the quantum dots obtained in Production Example 1. 2.5 g of a 20 wt % toluene solution of the quantum dots was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. Thereafter, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was produced. The thickness of the obtained wavelength converting material was 96 μm. The internal quantum efficiency of the obtained wavelength converting material was 37%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 19%.

[0104] Comparative Example 2 A wavelength converting material was produced using the quantum dots obtained in Production Example 1. 2.5 g of a 20 wt% toluene solution of the quantum dots was mixed with 5.0 g of a 40% xylene solution of a fluoroethylene-vinyl ether copolymer (LUMIFLON LF200 manufactured by AGC), which is a fluorine-containing resin, and the solvent was removed under reduced pressure while being stirred and heated at 60°C. The mixture was then vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. A PET film was then laminated onto the resin composition layer. The film was heated at 80°C for 2 hours and at 100°C for 2 hours to harden the resin composition layer, and a wavelength converting material was produced. The thickness of the obtained wavelength converting material was 98 μm. The internal quantum efficiency of the obtained wavelength converting material was 26%. The obtained wavelength converting material was treated at 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 7%.

[0105] Comparative Example 3 A wavelength converting material was produced using the quantum dots obtained in Production Example 2. 2.5 g of a 20 wt % toluene solution of the quantum dots was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C. Thereafter, the mixture was vacuum degassed and applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm, and a resin composition layer was formed by a bar coater. Furthermore, a PET film was laminated on the resin composition layer. This film was heated at 60°C for 2 hours and at 150°C for 4 hours to harden the resin composition layer, and a wavelength converting material was produced. The thickness of the obtained wavelength converting material was 98 μm. The internal quantum efficiency of the obtained wavelength converting material was 26%. The obtained wavelength converting material was treated under conditions of 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, and the internal quantum efficiency was 12%.

[0106] Comparative Example 4 A wavelength converting material was produced using the quantum dots obtained in Production Example 2. 2.5 g of a 20 wt% toluene solution of the quantum dots was mixed with 5.0 g of a 40% xylene solution of a fluororesin, fluoroethylene-vinyl ether copolymer (LUMIFLON LF200 manufactured by AGC), and the solvent was removed under reduced pressure while stirring and heating at 60°C. The mixture was then vacuum degassed and applied onto a polyethylene terephthalate (PET) film with a thickness of 50 μm, and a resin composition layer was formed using a bar coater. A PET film was then laminated onto the resin composition layer. This film was heated at 80°C for 2 hours and at 100°C for 2 hours to harden the resin composition layer, and a wavelength converting material was produced. The thickness of the obtained wavelength converting material was 97 μm. The internal quantum efficiency of the obtained wavelength converting material was 14%. The obtained wavelength converting material was treated at 85°C and 85% RH for 500 hours, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 4%.

[0107] The internal quantum efficiency of the wavelength converting materials of Comparative Example 1 and Examples 7 to 9, the wavelength converting materials of Comparative Example 2 and Example 10, the wavelength converting materials of Comparative Example 3 and Example 11, and the wavelength converting materials of Comparative Example 4 and Example 12 after treatment for 500 hours under conditions of 85°C and 85% RH was compared. As a result, it was confirmed that the wavelength converting materials using the quantum dot composition of the present invention modified with a phosphonic acid derivative showed higher internal quantum efficiency values ​​than the wavelength converting materials using quantum dots not modified with a phosphonic acid derivative.

[0108] As described above, it was confirmed that the quantum dot composition produced in the present invention suppresses the deterioration of the fluorescence emission efficiency due to light irradiation and has improved stability. Furthermore, it was confirmed that the resin composition using this quantum dot composition and the wavelength converting material obtained by curing the same suppress the deterioration of the fluorescence emission efficiency under high temperature and high humidity conditions and are highly reliable.

[0109] The present specification includes the following aspects. [1]: A quantum dot composition comprising quantum dots that emit fluorescence when exposed to excitation light, the quantum dots comprising a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, and the surfaces of the quantum dots are modified with a phosphonic acid derivative. [2]: The quantum dot composition according to [1] above, characterized in that the quantum dots are composed of the semiconductor nanoparticle core and a single or multiple semiconductor nanoparticle shells covering the semiconductor nanoparticle core. [3]: The semiconductor nanoparticle core is ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AgGaS 2 , AgInS 2 , AgGaSe 2 , AgInSe 2 , CuGaS 2 , CuGaSe 2 , CuInS 2 , CuInSe 2 , ZnSiP 2 , and ZnGeP 2 The quantum dot composition according to the above [1] or [2], characterized in that the quantum dot composition is selected from the following as a single crystal, a plurality of crystals, or a mixed crystal: [4]: The quantum dot composition according to any one of [1] to [3] above, characterized in that the semiconductor nanoparticle shell is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single crystal, multiple crystals, or mixed crystals. [5]: The quantum dot composition according to any one of [1] to [4] above, wherein the phosphonic acid derivative is represented by the following formula (I): [ka] (In formula (I), R 1 is a monovalent organic group having one or more carbon atoms. [6]: The phosphonic acid derivative is 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, hexylphosphonic acid, 4-phospho nobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (aminomethyl)phosphonic acid, (2-phenylethyl)phosphonic acid, ethylphosphonic acid, butylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, (2-chloroethyl)phosphonic acid, 4-methoxyphenylphosphonic acid Acid, hexadecylphosphonic acid, (4-hydroxybenzyl)phosphonic acid, phenylphosphonic acid, (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid, tetradecylphosphonic acid, (1-aminoethyl)phosphonic acid, undecylphosphonic acid, heptylphosphonic acid, 10-carboxydecylphosphonic acid, 11-aminoundecylphosphonic acid hydrobromide, 11-hydroxyundecylphosphonic acid, 1H,1H,2H,2H-perfluoro 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid, 12-mercaptodecylphosphonic acid, and [11-(acryloyloxy)undecyl]phosphonic acid. [7]: The quantum dot composition according to any one of [1] to [4] above, wherein the phosphonic acid derivative is represented by the following formula (II): [ka] (In formula (II), R 2 is a divalent organic group having one or more carbon atoms. [8]: The quantum dot composition according to [7] above, characterized in that the phosphonic acid derivative is one or more selected from m-xylylenediphosphonic acid, o-xylylenediphosphonic acid, methylenediphosphonic acid, 4-phosphonobenzoic acid, alendronic acid, 1,4-butylenediphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylenediphosphonic acid, zoledronic acid, 1,3-propylenediphosphonic acid, 1,5-pentylenediphosphonic acid, 1,4-phenylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,6-hexylenediphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid. [9]: The quantum dot composition according to any one of [1] to [4] above, wherein the phosphonic acid derivative is represented by the following formula (III): [ka] (In formula (III), R 3 is a trivalent organic group having one or more carbon atoms.

[10] : The quantum dot composition according to [9] above, wherein the phosphonic acid derivative is nitrilotris(methylene phosphonic acid).

[11] : The quantum dot composition according to any one of [1] to [4] above, wherein the phosphonic acid derivative is represented by the following formula (IV): [ka] (In formula (IV), R 4 is a divalent organic group having one or more carbon atoms.

[12] : The quantum dot composition according to

[11] above, wherein the phosphonic acid derivative is N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).

[13] : The above R 1The quantum dot composition according to [5] above, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[14] : The above R 2 The quantum dot composition according to [7] above, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[15] : The above R 3 The quantum dot composition according to [9] above, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[16] : The above R 4 The quantum dot composition according to

[11] above, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

[17] : A resin composition comprising any one of the quantum dot compositions described above in [1] to

[16] dispersed in a resin.

[18] : The resin composition according to

[17] , characterized in that the resin is at least one selected from the group consisting of epoxy resins, acrylic resins, fluorine-based resins, silicone resins, carbonate resins, and glass.

[19] A wavelength converting material, characterized in that it uses a cured product of the resin composition according to

[17] or

[18] above.

[0110] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A quantum dot composition comprising quantum dots that emit fluorescence when excited by excitation light, the quantum dots comprising a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, and the surface of the quantum dots is modified with a phosphonic acid derivative.

2. 2. The quantum dot composition according to claim 1, wherein the quantum dot comprises the semiconductor nanoparticle core and one or more semiconductor nanoparticle shells surrounding the semiconductor nanoparticle core.

3. The semiconductor nanoparticle core is ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AgGaS ２ , AgInS ２ , AgGaSe ２ , AgInSe ２ , CuGaS ２ , CuGaSe ２ , CuInS ２ , CuInSe ２ , ZnSiP ２ , and ZnGeP ２ 2. The quantum dot composition according to claim 1, characterized in that the quantum dot composition is selected from the group consisting of a single crystal, a plurality of crystals, or a mixed crystal.

4. 2. The quantum dot composition of claim 1, wherein the semiconductor nanoparticle shell is selected from the group consisting of ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single crystal, multiple crystals, or mixed crystals.

5. 2. The quantum dot composition according to claim 1, wherein the phosphonic acid derivative is represented by the following formula (I): 【Chemistry 1】 (In formula (I), R １ is a monovalent organic group having one or more carbon atoms.

6. The phosphonic acid derivatives include 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, hexylphosphonic acid, and 4-phosphonobutyric acid. , propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (aminomethyl)phosphonic acid, (2-phenylethyl)phosphonic acid, ethylphosphonic acid, butylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, (2-chloroethyl)phosphonic acid, 4-methoxyphenylphosphonic acid, he xadecylphosphonic acid, (4-hydroxybenzyl)phosphonic acid, phenylphosphonic acid, (1H,1H,2H,2H-heptadecafluorodecyl)phosphonic acid, tetradecylphosphonic acid, (1-aminoethyl)phosphonic acid, undecylphosphonic acid, heptylphosphonic acid, 10-carboxydecylphosphonic acid, 11-aminoundecylphosphonic acid hydrobromide, 11-hydroxyundecylphosphonic acid, 1H,1H,2H,2H-perfluoro 6. The quantum dot composition according to claim 5, which is one or more selected from the group consisting of 11-(1-(2-(2-methoxyethoxy)ethoxy)ethoxy)undecylphosphonic acid, 12-mercaptodecylphosphonic acid, and [11-(acryloyloxy)undecyl]phosphonic acid.

7. The quantum dot composition according to claim 1, characterized in that the phosphonic acid derivative is represented by the following formula (II): 【Chemistry 2】 (In formula (II), R ２ is a divalent organic group having one or more carbon atoms.

8. The quantum dot composition according to claim 7, characterized in that the phosphonic acid derivative is one or more selected from m-xylylene diphosphonic acid, o-xylylene diphosphonic acid, methylene diphosphonic acid, 4-phosphonobenzoic acid, alendronic acid, 1,4-butylene diphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylene diphosphonic acid, zoledronic acid, 1,3-propylene diphosphonic acid, 1,5-pentylene diphosphonic acid, 1,4-phenylene diphosphonic acid, 1,2-ethylene diphosphonic acid, 1,6-hexylene diphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid.

9. The quantum dot composition according to claim 1, characterized in that the phosphonic acid derivative is represented by the following formula (III): 【Chemistry 3】 (In formula (III), R ３ is a trivalent organic group having one or more carbon atoms.

10. 10. The quantum dot composition of claim 9, wherein the phosphonic acid derivative is nitrilotris(methylene phosphonic acid).

11. 2. The quantum dot composition according to claim 1, wherein the phosphonic acid derivative is represented by the following formula (IV): 【Chemistry 4】 (In formula (IV), R ４ is a divalent organic group having one or more carbon atoms.

12. 12. The quantum dot composition of claim 11, wherein the phosphonic acid derivative is N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).

13. The R １ The quantum dot composition according to claim 5, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

14. The R ２ The quantum dot composition according to claim 7, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

15. The R ３ The quantum dot composition according to claim 9, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

16. The R ４ The quantum dot composition according to claim 11, characterized in that it contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.

17. A resin composition comprising the quantum dot composition according to any one of claims 1 to 16 dispersed in a resin.

18. 18. The resin composition according to claim 17, wherein the resin is at least one selected from the group consisting of epoxy resins, acrylic resins, fluorine resins, silicone resins, carbonate resins, and glass.

19. A wavelength converting material using a cured product of the resin composition according to claim 17.