JP6966358B2 - Quantum dots with organic ligands and their uses - Google Patents

Description

The present invention relates to a quantum dot having an organic ligand and its use, and more particularly, as an organic ligand, a malonic acid derivative, a thiothiol compound, a thiocarboxylic acid compound, and a compound containing an ester group and a thiol group. The present invention relates to a quantum dot having one or more of them and having excellent oxidation stability and its use.

Quantum dots are semiconductor nanocrystals having a size of nanometers, and have a characteristic that the energy band gap (Bandgap, Eg) changes depending on the size and shape. Such quantum dots can adjust the emission wavelength only by adjusting the size of the quantum dots by the quantum confinement effect, and can exhibit excellent color purity and high PL (photoluminescence) efficiency. , Not only in displays, but also in fields such as lighting sources, solar cells, semiconductor lasers / photoluminescences, and bioimaging.

Quantum dots are mainly manufactured by a wet chemical process in that quantum dots having excellent optical properties can be mass-produced. The wet chemical process is a method of putting a precursor substance in an organic solvent to grow particles. When quantum dots are manufactured by such a wet chemical process, an organic ligand is used to prevent the aggregation of the quantum dots and to control the particle size of the quantum dots to the nano level. Oleic acid is generally used as such an organic ligand [see Korean Registered Patent No. 10-1,447,238].

However, such quantum dots are easily oxidized by oxygen in the air. Therefore, it is desired to develop a quantum dot having excellent oxidative stability.

One object of the present invention is to provide quantum dots having excellent oxidative stability.

Another object of the present invention is to provide a quantum dot film containing the quantum dots.

Another object of the present invention is to provide a self-luminous photosensitive resin composition containing the quantum dots.

A further object of the present invention is to provide a color filter using the self-luminous photosensitive resin composition.

A further object of the present invention is to provide a quantum dot light emitting diode (QLED) containing the quantum dots.

On the other hand, the present invention comprises quantum dots having a ligand layer on the surface, wherein the ligand layer contains one or more of the compounds represented by the following chemical formulas 1 to 4. offer.

In the above formula,
X ¹ is a hydrogen or an alkyl group of _{C 1 to} C _{3 and}
R ¹ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ² and Y ¹ are independently hydrogen or alkyl groups of _{C 1 to} C _{3, respectively.}
R ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
n is an integer of 0 to 1 and is
X ³ is an alkylene group of _{C 1 to} C _{3 and is an alkylene group.}
R ³ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ⁴ is an alkylene group of _{C 1 to} C _{5 and is an alkylene group.}
Y ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22.}

On the other hand, the present invention provides a quantum dot film containing the quantum dots.

On the other hand, the present invention provides a self-luminous photosensitive resin composition containing the quantum dots.

On the other hand, the present invention provides a color filter using the self-luminous photosensitive resin composition.

On the other hand, the present invention provides a quantum dot light emitting diode including the quantum dots.

Since the quantum dots according to the present invention have excellent oxidative stability, they can be effectively applied to various applications such as quantum dot films, color filters, and quantum dot light emitting diodes.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention is a quantum dot having a ligand layer on its surface, wherein the ligand layer is a malonic acid derivative represented by the following chemical formula 1 and a thiothiol compound represented by the chemical formula 2. The present invention relates to a thiocarboxylic acid compound represented by the chemical formula 3 and a quantum dot containing one or more of the ester group and the thiol group-containing compound represented by the chemical formula 4.

In the above formula,
X ¹ is a hydrogen or an alkyl group of _{C 1 to} C _{3 and}
R ¹ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ² and Y ¹ are independently hydrogen or alkyl groups of _{C 1 to} C _{3, respectively.}
R ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
n is an integer of 0 to 1 and is
X ³ is an alkylene group of _{C 1 to} C _{3 and is an alkylene group.}
R ³ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ⁴ is an alkylene group of _{C 1 to} C _{5 and is an alkylene group.}
Y ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22.}

As used herein, _{the alkyl groups C 1 to} C ₃ mean linear or branched hydrocarbons consisting of 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl and i-propyl. Etc., but are not limited to these.

As used herein, _{the alkyl group C 4 to} C ₂₂ means a linear or branched hydrocarbon consisting of 4 to 22 carbon atoms, for example, n-butyl, i-butyl, t-butyl. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eikosanyl, docosanyl and the like, but are not limited thereto.

As used herein, _{the alkenyl group C 4 to} C ₂₂ means a linear or branched unsaturated hydrocarbon consisting of 4 to 22 carbon atoms with one or more carbon-carbon double bonds. For example, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undosenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadesenyl, eicosenyl, docosenyl, etc. is not it.

As used herein, _{the alkylene group C 1 to} C ₃ means a linear or branched divalent hydrocarbon consisting of 1 to 3 carbon atoms, for example, methylene, ethylene, n-propylene, i. -Includes, but is not limited to, propylene and the like.

_{The alkylene group C 1 to} C ₅ used in the present specification means a linear or branched divalent hydrocarbon consisting of 1 to 5 carbon atoms, and for example, methylene, ethylene, propylene, butylene and the like. Included, but not limited to.

In one embodiment of the present invention, the compound represented by Formula 1 is ^{X 1} is hydrogen or _methyl, ^{R 1} is an alkenyl group of alkyl or _C 16 _{-C 20} in C 16 _{-C 20} It may be a compound.

In one embodiment of the present invention, the compound represented by Formula 1, ^{X 1} is _hydrogen, ^{R 1} is a compound which is an alkenyl group having an alkyl group or a _C 16 _{-C 20} in C 16 _{-C 20} It may be there.

In one embodiment of the present invention, the compound represented by the chemical formula 1 may be a compound represented by any one of the following chemical formulas 5 to 7.

In one embodiment of the present invention, the malonic acid derivative represented by the chemical formula 1 is an organic ligand and can perform a role of coordinating and bonding to the surface of the quantum dots to stabilize the quantum dots. ..

Since the malonic acid derivative represented by the chemical formula 1 is a strong acid having a divalent acid and a pKa of 3 or less, it binds to quantum dots as compared with oleic acid having a pKa of 4.25 and a monovalent acid. Excellent in power.

Further, in the malonic acid derivative represented by the chemical formula 1, when X ¹ is hydrogen, both an acid functional group and a hydroxy group can be present due to keto-enol taturism. It can form stronger coordination bonds with the metal elements that make up the quantum dots.

In one embodiment of the present invention, in the compound represented by the chemical formula 2, X ² and Y ¹ are independently hydrogen, methyl or isopropyl, and R ² is an alkyl group of _{C 16 to} C _20. Alternatively, it may be a compound which is an alkenyl group of _{C 16 to} C _{20 and n is an integer of 0 to 1.}

In one embodiment of the present invention, the compound represented by Formula 2, ^{X 2} and ^{Y 1} are _hydrogen, ^{R 2} is an alkenyl group of alkyl or _C 16 _{-C 20} in C 16 _{-C 20} Yes, n may be a compound that is an integer of 0 to 1.

In one embodiment of the present invention, the compound represented by the chemical formula 2 may be a compound represented by any one of the following chemical formulas 8 to 12.

In one embodiment of the present invention, the thiothiol compound represented by the chemical formula 2 is an organic ligand and can perform a role of coordinating and bonding to the surface of the quantum dots to stabilize the quantum dots.

The thiothiol compound represented by the chemical formula 2 is a polar functional group, and by having both a thiol and a mercapto (sulfur) group, it is superior in binding force to quantum dots as compared with oleic acid.

Further, the thiothiol compound represented by the chemical formula 2 ^{constitutes a quantum dot because when X 2} and Y ¹ are hydrogen, it can be bonded to the quantum dot at a closer distance because the steric hindrance is small. It can form stronger coordination bonds with metal elements.

In one embodiment of the present invention, the compound represented by the chemical formula 3 may be a compound represented by any one of the following chemical formulas 13 to 16.

In the above formula,
R ³ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22.}

In one embodiment of the present invention, the compound represented by Formula 3 may be a compound ^{wherein R 3} is an alkenyl group having an alkyl group or a _C 10 _{-C 14} in _C 10 _{-C 14.}

In one embodiment of the present invention, the compound represented by the chemical formula 3 may be a compound represented by any one of the following chemical formulas 17 to 20.

In one embodiment of the present invention, the thiocarboxylic acid compound represented by the chemical formula 3 is an organic ligand and can perform a role of coordinating and bonding to the surface of the quantum dots to stabilize the quantum dots. ..

The thiocarboxylic acid compound represented by the chemical formula 3 is a polar functional group, and by having both a carboxylic acid and a mercapto (sulfur) group, it is superior in binding force to quantum dots as compared with oleic acid.

Further, thiocarboxylic acid compound represented by the chemical formula 3, for better when X ³ is a straight chain structure is non-polar compared with the case having a branched structure, be advantageous to these sequences preferable.

In one embodiment of the present invention, the compound represented by Formula 4, ^{Y 2} may be a compound which is alkenyl alkyl or _C 16 _{-C 20} in _C 16 _{-C 20.}

In one embodiment of the present invention, the compound represented by the chemical formula 4 may be a compound represented by any one of the following chemical formulas 21 to 27.

In one embodiment of the present invention, the compound containing the ester group and the thiol group represented by the chemical formula 4 is an organic ligand, and the ester group “= o” and the thiol group “= o” on the surface of the quantum dot. "S" can be double-coordinated and coupled to perform the role of stabilizing quantum dots.

The compound containing an ester group and a thiol group represented by the chemical formula 4 is a polar functional group, and by having both a thiol and an ester group, it is superior in binding force to quantum dots as compared with oleic acid. There is.

Further, the compound containing the ester group and the thiol group represented by the chemical formula 4 can be bonded to the quantum dots at a closer distance because the steric hindrance is small when ^{X 4 has a linear structure.} Therefore, a stronger coordination bond can be formed with the metal element constituting the quantum dot.

One or more of the compounds represented by the chemical formulas 1 to 4 may cover the surface of 5% or more of the total surface area of the quantum dots.

At this time, the content of one or more of the compounds represented by the chemical formulas 1 to 4 may be 0.1 to 10 mol with respect to 1 mol of the quantum dots.

The ligand layer containing one or more of the compounds represented by the chemical formulas 1 to 4 may have a thickness of 0.1 nm to 2 nm, for example, a thickness of 0.5 nm to 1.5 nm.

In one embodiment of the invention, the quantum dots may refer to nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When such nanoparticles exhibit semiconductor characteristics, they are called quantum dots. When the quantum dot receives energy from the outside and becomes a floating state, the quantum dot emits energy corresponding to the energy band gap corresponding to the quantum dot itself.

The quantum dots are not particularly limited as long as they are quantum dot particles that can emit light by stimulation with light or electricity. For example, it may be selected from the group consisting of II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; Group IV elements or compounds containing them; and combinations thereof. May be used alone or in combination of two or more.

Specifically, the II-VI group semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnS, a compound selected from these three elements; It may be selected from the group consisting of four element compounds selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, but is limited thereto. It's not a thing.

The group III-V semiconductor compound is a two-element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A three-element compound selected from the group consisting of GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof; and GaAlNP, GaAlNAs, GaAlNSb, It may be selected from the group consisting of four element compounds selected from the group consisting of GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. However, it is not limited to these.

The IV-VI group semiconductor compound is a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, A three-element compound selected from the group consisting of SnPbSe, SnPbTe, and a mixture thereof; and one or more selected from a group consisting of a four-element compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and a mixture thereof. However, the present invention is not limited to these.

The Group IV element or a compound containing the same is an element selected from the group consisting of Si, Ge and a mixture thereof; and a group consisting of a two-element compound selected from the group consisting of SiC, SiGe and a mixture thereof. It may be selected, but is not limited to these.

The quantum dots may have a homogeneous single structure; a dual structure such as a core-shell, gradient structure, etc.; or a mixed structure thereof. Preferably, the quantum dots may have a core-shell structure that includes a core and a shell covering the core.

Specifically, in the core-shell dual structure, the substance forming each core and shell may be composed of the above-mentioned different semiconductor compounds. For example, the cores include InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, ZnSeTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgS, HgS. Containing one or more of GaAs, InGaN, InAs, and ZnO, the shell comprises ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP. , InGaN, InZnSCdSe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

The quantum dots may be synthesized by a wet chemical process.

The wet chemical step is a method of adding a precursor substance to an organic solvent to grow particles. As the crystal grows, the organic solvent naturally coordinates on the surface of the quantum dot crystal and acts as a dispersant to regulate the crystal growth, as in organic metal chemical vapor deposition processes and molecular beam epitaxy. It is preferable to produce the quantum dots by using the wet chemical step because the growth of nanoparticles can be controlled through a step that is easier and cheaper than the vapor deposition method.

When producing quantum dots by a wet chemical process, an organic ligand is used to prevent the aggregation of the quantum dots and to control the particle size of the quantum dots to the nano level. Generally, oleic acid may be used as such an organic ligand.

In one embodiment of the present invention, the oleic acid used in the process of producing the quantum dots is exchanged by one or more of the compounds represented by the chemical formulas 1 to 4 by a ligand exchange method.

The ligand exchange is one of the organic ligands to be exchanged with the original organic ligand, that is, the dispersion liquid containing the quantum dots having oleic acid, that is, the compounds represented by the chemical formulas 1 to 4. The above is added, and the mixture is stirred at room temperature to 200 ° C. for 30 minutes to 3 hours to obtain quantum dots to which one or more of the compounds represented by the chemical formulas 1 to 4 are bonded. good. If necessary, a process of separating and purifying the quantum dots to which one or more of the compounds represented by the chemical formulas 1 to 4 are bonded may be further performed.

As described above, the quantum dots according to the embodiment of the present invention can be produced by the organic ligand exchange method under a simple stirring treatment at room temperature, and therefore have an advantage that they can be mass-produced.

Further, the quantum dots according to the embodiment of the present invention can maintain a quantum efficiency of 80% or more with respect to the initial quantum efficiency even after 10 days, and can be stably stored for a long period of time. It can be commercialized for various purposes.

<Quantum dot film>
One embodiment of the present invention relates to a quantum dot film containing the above-mentioned quantum dots.

The quantum dot film includes a polymer resin and a quantum dot dispersion layer containing the above-mentioned quantum dots dispersed in the polymer resin.

Examples of the polymer resin include epoxy, epoxy acrylate, lauryl acrylate, norbornene, polyethylene, polystyrene, ethylene-styrene copolymer, acrylate containing bisphenol A and bisphenol A derivative, and acrylate containing fluorene derivative. Isobornyl acrylates, polyphenylalkylsiloxanes, polydiphenylsiloxanes, polydialkylsiloxanes, silsesquioxane, fluorinated silicones, and vinyl and hydride-substituted silicones may be used, these polymeric resins alone or Two or more kinds may be mixed and used.

The quantum dot film may further include a barrier layer on at least one side of the quantum dot dispersion layer.

The barrier layer may have an oxygen permeability of 0.001 ^{cm 3} / m ^{2 · bar or less and a water permeability of 0.001 g / m 2} · day or less, for example, polyester, polycarbonate, polyolefin, etc. It may contain a cyclic olefin polymer or a polyimide.

The thickness of the quantum dot dispersion layer may be 10 μm to 100 μm, and the thickness of the barrier layer may be 50 μm to 70 μm.

<Self-luminous photosensitive resin composition>
One embodiment of the present invention relates to a self-luminous photosensitive resin composition containing the above-mentioned quantum dots.

The self-luminous photosensitive resin composition contains quantum dots, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

The content of the quantum dots in the self-luminous photosensitive resin composition is not particularly limited, and is, for example, 3 to 80% by weight, for example, 5 to 70% by weight based on 100% by weight of the total solid content of the self-luminous photosensitive resin composition. It may be% by weight.

The alkali-soluble resin can make the non-exposed portion of the pattern produced by the self-luminous photosensitive resin composition alkaline-soluble so that it can be removed, and can fulfill the role of leaving the exposed region. Further, when the self-luminous photosensitive resin composition contains the alkali-soluble resin, the quantum dots can be uniformly dispersed in the composition, and the quantum dots are protected during the process to maintain the brightness. Can perform the role of

As the alkali-soluble resin, one having an acid value of 50 to 200 (KOHmg / g) may be selected and used. The "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer and is involved in solubility. If the acid value of the alkali-soluble resin is less than the above range, it may be difficult to secure a sufficient development speed, and if it exceeds the above range, the adhesion to the substrate is reduced and the pattern is likely to be short-circuited. , There may be a problem that the storage stability of the entire composition is lowered and the viscosity is increased.

The weight average molecular weight of the alkali-soluble resin may be 3,000 to 30,000, preferably 5,000 to 20,000, and the molecular weight distribution is 1.5 to 6.0, preferably 1.5 to 6.0. It may be 1.8 to 4.0.

The alkali-soluble resin may be a polymer of a carboxyl group-containing unsaturated monomer, a copolymer with a monomer having an unsaturated bond capable of copolymerizing the polymer, or a combination thereof.

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Specifically, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated dicarboxylic acid may be an acid anhydride, and specific examples thereof include maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride. The unsaturated dicarboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester thereof, for example, monosuccinic acid (2-acryloyloxyethyl), monosuccinic acid (2-methacryloyloxyethyl). , Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. The unsaturated dicarboxylic acid may be a mono (meth) acrylate of a dicarboxypolymer having both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers may be used alone or in combination of two or more.

The monomers that can be copolymerized with the carboxyl group-containing unsaturated monomer include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, and unsaturated carboxylic acid glycidyl ester compounds. Carvone vinyl ester compounds, unsaturated ether compounds, vinyl cyanide compounds, unsaturated amide compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, giant monomers having a monoacryloyl group or a monomethacrylloyl group at the end of the molecular chain. , Bulky monomers, and combinations thereof may be one selected from the group.

More specifically, the copolymerizable monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-. Methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Aromatic vinyl compounds such as inden; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-Butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl Methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, Methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornylacrylle Acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- Unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate , 2-Aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate and the like unsaturated Carboxylaminoalkyl ester compounds; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ethyl Unsaturated ether compounds such as ethers and allylglycidyl ethers; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylicamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide , N-2-Acrylate methacrylicamide and other unsaturated amide compounds; Maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other unsaturatedimide compounds; 1,3-butadiene, isoprene, chloroprene and other aliphatic compounds. Conjugated diene compound; and a giant single having a monoacryloyl group or a monomethacrylloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane. Quantitative; Examples thereof include bulky monomers having a norbornyl skeleton whose specific dielectric constant value can be lowered, a monomer having an adamantan skeleton, and a monomer having a rosin skeleton.

The alkali-soluble resin is 5 to 80% by weight, specifically 10 to 70% by weight, more specifically 15 to 60% by weight, based on 100% by weight of the total solid content of the self-luminous photosensitive resin composition. May be included in.

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers. ..

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Can be mentioned.

The type of the bifunctional monomer is not particularly limited, and is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di ( Examples thereof include meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The types of other polyfunctional monomers are not particularly limited, and are, for example, trimethylol propanetri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, and the like. Penta-erythritol tri (meth) acrylate, penta-erythritol tetra (meth) acrylate, dipenta-erythritol tri (meth) acrylate, dipenta-erythritol penta (meth) acrylate, ethoxylated dipenta-erythritol hexa (meth) acrylate, propoxylated di Examples thereof include pentaerythritol hexa (meth) acrylate and dipentaerytritor hexa (meth) acrylate. Of these, polyfunctional monomers having two or more functions are preferably used.

The photopolymerizable compound is 5 to 70% by weight, specifically 10 to 60% by weight, more specifically 15 to 50% by weight, based on 100% by weight of the total solid content of the self-luminous photosensitive resin composition. May be included in.

The type of the photopolymerization initiator may be used without particular limitation as long as it can polymerize the photopolymerizable compound. In particular, the photopolymerization initiator is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound, and thioxanthone from the viewpoints of polymerization characteristics, starting efficiency, absorption wavelength, availability, price, and the like. It is preferable to use one or more compounds selected from the group consisting of system compounds.

Specific examples of the acetphenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxy). Ethoxy) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4-) Examples thereof include methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxy). Carbonyl) Benzophenone, 2,4,6-trimethylbenzophenone and the like can be mentioned.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6. -(4-methoxynabutyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-Triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3). -Dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5, Examples thereof include a 5'-tetraphenyl-1,2'-biimidazole or a biimidazole compound in which the phenyl group at the 4,4', 5,5'position is replaced with a carboalkoxy group. Of these, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole is preferably used.

Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, and commercially available products include Irgacure OXE 01 and OXE 02 manufactured by BASF. It is a typical one.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

The photopolymerization initiator is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the total solid content of the self-luminous photosensitive resin composition. May be included in% by weight.

The photopolymerization initiator may further contain a photopolymerization initiator in order to improve the sensitivity of the self-luminous photosensitive resin composition according to the present invention. When the photopolymerization initiation assisting agent is contained, there is an advantage that the sensitivity is further increased and the productivity is improved.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used, but are limited thereto. It's not a thing.

The self-luminous photosensitive resin composition may further contain a solvent, and the solvent is not particularly limited and may be an organic solvent usually used in the art.

For example, examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol. Diethylene glycol dialkyl ethers such as dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. , Alkylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, methethylene; methylethylketone, acetone, methylamylketone, methylisobutylketone , Cyclohexanone, cyclopentanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and other alcohols; ethyl 3-ethoxypropionate, 3-methoxypropionate and other esters; γ -Cyclic esters such as butyrolactone; and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the self-luminous photosensitive resin composition is 20 to 90% by weight, preferably 25 to 85% by weight, more preferably 25% by weight, based on 100% by weight of the whole self-luminous photosensitive resin composition. It may be contained in an amount of 30 to 80% by weight.

The self-luminous photosensitive resin composition according to the present invention may further contain additives such as an adhesion promoter, a surfactant, an antioxidant, an ultraviolet absorber, and an antiaggregating agent.

The additive is 0.05 to 10% by weight, specifically 0.1 to 10% by weight, more specifically 0.1, based on 100% by weight of the whole self-luminous photosensitive resin composition. It may be used in an amount of ~ 5% by weight, but is not limited thereto.

One embodiment of the present invention relates to a color filter using the self-luminous photosensitive resin composition described above.

Since the color filter according to the present invention contains a cured product of the self-luminous photosensitive resin composition containing the quantum dots according to the present invention, there is an advantage that the quantum dots are excellent in oxidation stability and light emission characteristics.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the color filter itself, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the polymer substrate may be polyethersulfone (PES), polycarbonate (PC) or the like. It's okay.

The pattern layer is a layer containing the self-luminous photosensitive resin composition according to the present invention, and is a layer formed by applying the self-luminous photosensitive resin composition and exposing, developing, and thermosetting the self-luminous photosensitive resin composition in a predetermined pattern. May be. The pattern layer may be formed by a method generally known in the art.

The color filter including the substrate and the pattern layer as described above may further include, but is not limited to, a partition wall or a black matrix formed between the patterns.
Further, a protective film formed on the upper part of the pattern layer of the color filter may be further included.

The color filter may include one or more selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter is one or more selected from the group consisting of a red pattern layer containing red quantum dots, a green pattern layer containing green quantum dots, and a blue pattern layer containing blue quantum dots according to the present invention. May include. The red pattern layer, the green pattern layer, and the blue pattern layer can emit red light, green light, and blue light, respectively, when irradiated with light, and at this time, the emitted light of the light source is not particularly limited. A light source that emits blue light may be used because of its excellent color reproducibility.

The color filter may include only a pattern layer having two hues of a red pattern layer, a green pattern layer, and a blue pattern layer, but is not limited thereto. When the color filter includes only two types of hue pattern layers, the pattern layer may further include a transparent pattern layer that does not contain the quantum dot particles.

When the color filter includes only the pattern layer of the two types of hues, a light source that emits light having a wavelength other than the above two types of hues may be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source that emits blue light may be used. In this case, the red quantum dots emit red light and the green quantum dots emit green light. The transparent pattern layer may be colored blue by allowing blue light from the light source to pass through.

One embodiment of the present invention relates to an image display device provided with the above-mentioned color filter.

The color filter according to the present invention can be applied not only to a normal liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

<Quantum dot light emitting diode>
One embodiment of the present invention relates to a quantum dot light emitting diode (QLED) including the above-mentioned quantum dots.
The quantum dot emission diode is an electroluminescence (EL) type element in which quantum dots are electrically excited to emit light.

In the quantum dot light emitting diode, electrons and holes injected from both electrodes form excitons in the quantum dot light emitting layer, and emit light by radiative recombination of excitons. Since this has the same operating principle as an organic light-emitting diode (OLED), only the light emitting layer is organic in a multilayer element structure using the electron / hole injection layer and transport layer of an ordinary OLED as it is. It may be configured by using quantum dots instead of the light emitting material.

Further, the quantum dots according to the embodiment of the present invention can be applied not only as the above-mentioned display but also as a material for a light source for lighting, a solar cell, a semiconductor laser / optical amplifier, bioimaging and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. It should be noted that these examples, comparative examples and experimental examples are merely for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

Synthesis Example 1: Synthesis of quantum dots of InP core alone 0.05839 g of indium acetate, 0.12019 g of oleic acid and 10 mL of 1-octadecene (ODE) were placed in a three-necked flask (3-neck flask). The flask was subjected to a degassing process at 110 ° C. under 100 mTorr for 30 minutes with stirring, and then heated at a temperature of 270 ° C. under an inert gas until the solution became transparent.

0.025054 g of tris (trimethylsilyl) phosphine was prepared as a phosphorus (P) precursor, placed in 0.5 mL of 1-octadecene and 0.5 mL of tri-n-octylphosphine and stirred, and this was stirred under an inert gas, 270. It was quickly poured into the flask heated at ° C. After reacting for 1 hour, the reaction was terminated by cooling quickly. Then, when the temperature of the flask reached 100 ° C., 10 mL of toluene was injected and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using the precipitation and redispersion method. The purified InP core nanoparticles were dispersed in 1-octadecene and then stored.

Synthesis Example 2: Synthesis of InP / ZnS core-shell quantum dots 3.669 g of zinc acetate, 20 mL of oleic acid and 20 mL of 1-octadecene are placed in a three-necked flask and degassed at 110 ° C. under 100 mTorr for 30 minutes with stirring. After going through the degassing) process, the solution was heated at a temperature of 270 ° C. under an inert gas until the solution became transparent, and then cooled to 60 ° C. to obtain a clear precursor solution in the form of zinc oleate.

Put 0.6412 g of sulfur and 10 mL of tri-n-octylphosphine in a three-necked flask, heat at a temperature of 80 ° C. with stirring in an inert gas atmosphere until the solution becomes transparent, and then cool to room temperature. TOP: S-form S precursor solution was obtained.

In another three-necked flask, put the nanoparticle solution of InP core prepared in advance in Synthesis Example 1, adjust the temperature of the flask to 300 ° C., and then quickly add 0.6 mL of the zinc precursor solution prepared in advance with a syringe. Infused. Then, 0.3 mL of the S precursor solution prepared in advance was injected into the flask at a rate of 2 mL / hr with a syringe pump. After the injection was completed, the reaction was further advanced for 3 hours and cooled quickly to terminate the reaction. When the temperature of the flask reached 100 ° C., 10 mL of toluene was injected and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using the precipitation and redispersion method. The purified InP / ZnS core-shell structure nanoparticles were dispersed in 1-octadecene and then stored.

Example 1-1: Production of quantum dots of InP core alone having a ligand represented by Chemical Formula 5 1 g of quantum dots of InP core alone of Synthesis Example 1 in which oleic acid is bonded to the surface is dispersed in 10 ml of toluene. 0.5 g of a novel ligand for a malonic acid derivative represented by Chemical Formula 5 was added to the prepared solution, and the mixture was stirred for 30 minutes or more. In this process, the novel ligand represented by Chemical Formula 5 replaced the oleic acid on the surface of the quantum dot of the core alone. Next, 10 ml of ethanol was added to a mixed solution containing a quantum dot-new ligand bond and an unreacted ligand to aggregate the quantum dot-new ligand bond. Quantum dot-new ligand conjugates aggregated by centrifugation (8000 rpm, 30 minutes) were separated from oleic acid and unreacted ligands that had fallen from the quantum dots. The quantum dot-novel ligand bond was then dispersed in toluene at a concentration of 0.1 g / ml.

Example 1-2: Production of InP / ZnS core-shell quantum dots having a ligand represented by the chemical formula 5 1 g of InP / ZnS quantum dots of Synthesis Example 2 in which oleic acid is bonded to the surface is added to 10 ml of toluene. 0.5 g of the new ligand of the malonic acid derivative represented by the chemical formula 5 was added to the dispersed solution, and the mixture was stirred for 30 minutes or more. In this process, a novel ligand replaced the oleic acid on the surface of the quantum dots. Next, 10 ml of ethanol was added to a mixed solution containing a quantum dot-new ligand bond and an unreacted ligand to aggregate the quantum dot-new ligand bond. Quantum dot-new ligand conjugates aggregated by centrifugation (8000 rpm, 30 minutes) were separated from oleic acid and unreacted ligands that had fallen from the quantum dots. The quantum dot-novel ligand bond was then dispersed in toluene at a concentration of 0.1 g / ml.

Example 2-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 6 A ligand represented by the chemical formula 6 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 2-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 6 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 6 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 3-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 7 A ligand represented by the chemical formula 7 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 3-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 7 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 7 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 4-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 8 A ligand represented by the chemical formula 8 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 4-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 8 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 8 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 5-1: Manufacture of a quantum dot of an InP core alone having a ligand represented by the chemical formula 9 A ligand represented by the chemical formula 9 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 5-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 9 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 9 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 6-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 12 A ligand represented by the chemical formula 12 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 6-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 12 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 12 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 7-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 17 A ligand represented by the chemical formula 17 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 7-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 17 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 17 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 8-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 18 Using a ligand represented by the chemical formula 18 instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 8-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 18 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 18 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 9-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 19 A ligand represented by the chemical formula 19 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 9-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 19 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 19 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 10-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 21 Using a ligand represented by the chemical formula 21 instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 10-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 21 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 21 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 11-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 22 A ligand represented by the chemical formula 22 is used instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 11-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 22 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 22 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Example 12-1: Production of quantum dots of an InP core alone having a ligand represented by the chemical formula 27 Using a ligand represented by the chemical formula 27 instead of the ligand represented by the chemical formula 5. Except for the above, the same procedure as in Example 1-1 was carried out.

Example 12-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula 27 Instead of the ligand represented by the chemical formula 5, a ligand represented by the chemical formula 27 is used. It was carried out in the same manner as in Example 1-2 except that it was used.

Comparative Example 1-1: Preparation of Quantum Dot of InP Core alone Not Performed by Ligand Exchange Reaction 0.1 g / ml of quantum dot of InP core alone of Synthesis Example 1 in which oleic acid is bonded to the surface is 0.1 g / ml in toluene. Was dispersed at the concentration of.

Comparative Example 1-2: Preparation of InP / ZnS core-shell quantum dots not subjected to ligand exchange reaction 0.1 g / g of InP / ZnS quantum dots of Synthesis Example 2 in which oleic acid is bonded to the surface is added to toluene. Dispersed at a concentration of ml.

Comparative Example 2-1: Manufacture of a quantum dot of an InP core alone having a ligand represented by the chemical formula a Instead of the ligand represented by the chemical formula 5, a ligand represented by the following chemical formula a was used. It was carried out in the same manner as in Example 1-1 except that it was used.

Comparative Example 2-2: Production of InP / ZnS core-shell quantum dot having a ligand represented by the chemical formula a A ligand represented by the chemical formula a is used instead of the ligand represented by the chemical formula 5. It was carried out in the same manner as in Example 1-2 except that it was used.

Experimental Example 1:
(1) Maximum absorption wavelength (λmax)
The maximum absorption wavelength (λmax) at the initial stage of manufacturing the quantum dot dispersions of Examples 1-1 to 12-1 and Comparative Examples 1-1 and 2-1 and the maximum absorption wavelength (λmax) after being left at room temperature for 4 days are set to UV. -Measured using a Visible spectrophotometer.

When the surface of the quantum dots is oxidized, the size of the quantum dots decreases and the maximum absorption wavelength (λmax) decreases. Therefore, the amount of decrease in the maximum absorption wavelength (λmax) is measured to confirm the oxidation stability. be able to. That is, the oxidative stability can be confirmed by measuring Δλmax.

The measurement results are shown in Table 1 below.

As shown in Table 1, the quantum dots of Examples 1-1 to 12-1 having one or more organic ligands among the compounds represented by the chemical formulas 1 to 4 according to the present invention are compared. It was confirmed that the oxidation stability was superior to that of the quantum dots of Examples 1-1 and 2-1.

(2) Quantum efficiency The quantum efficiency (QY%) at the initial stage of manufacturing the quantum dot dispersions of Examples 1-2 to 12-2 and Comparative Examples 1-2 and 2-2 and the quantum efficiency after being left at room temperature for 10 days (2). QY%) was measured using a PL spectrophotometer and a UV-Vis spectrophotometer.

When the surface of the quantum dot is oxidized, the quantum efficiency decreases, so that the amount of decrease in the quantum efficiency can be measured to confirm the oxidation stability. That is, the oxidative stability can be confirmed by measuring ΔQY%.

As shown in Table 2, the quantum dots of Examples 1-2 to 12-2 having one or more organic ligands among the compounds represented by the chemical formulas 1 to 4 according to the present invention are compared. It was confirmed that the decrease in quantum efficiency was suppressed as compared with the quantum dots of Examples 1-2 and 2-2. Therefore, the quantum dots of Examples 1-2-12-2 having one or more organic ligands among the compounds represented by the chemical formulas 1 to 4 according to the present invention are Comparative Examples 1-2 and 2-. It was confirmed that the oxidation stability was superior to that of the quantum dot No. 2.

In particular, the quantum dots of Examples 1-2 to 12-2 having one or more organic ligands among the compounds represented by the chemical formulas 1 to 4 according to the present invention have initial quantum efficiencies even after 10 days. While the quantum efficiency of 80% or more is maintained, the quantum dot of Comparative Example 1-2 having an oleic acid ligand greatly reduces the quantum efficiency to the level of 35% with respect to the initial quantum efficiency. However, the quantum dots of Comparative Example 2-2 having a ligand having a thiol group at the terminal also show a quantum efficiency of 65% level with respect to the initial quantum efficiency, and are inferior in the effect of suppressing the decrease in quantum efficiency. I was able to confirm.

Although the specific parts of the present invention have been described in detail above, such a specific description is merely a suitable embodiment for a person having ordinary knowledge in the technical field to which the present invention belongs. It is clear that the scope of the invention is not limited. A person having ordinary knowledge in the technical field to which the present invention belongs will be able to carry out various applications and modifications within the scope of the present invention based on the above contents.

Therefore, it can be said that the substantial scope of the present invention is defined by the claims and their equivalents.

Claims (17)

Quantum dots with a ligand layer on the surface,
Quantum dots in which the ligand layer contains one or more of the compounds represented by the following chemical formulas 1 to 4:

In the above formula,
X ¹ is a hydrogen or an alkyl group of _{C 1 to} C _{3 and}
R ¹ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ² and Y ¹ are independently hydrogen or alkyl groups of _{C 1 to} C _{3, respectively.}
R ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
n is an integer of 0 to 1 and is
X ³ is an alkylene group of _{C 1 to} C _{3 and is an alkylene group.}
R ³ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22,}
X ⁴ is an alkylene group of _{C 1 to} C _{5 and is an alkylene group.}
Y ² _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22.} The compound represented by Formula 1 is ^{X 1} is hydrogen or methyl, quantum dot of claim 1 ^{R 1} is an alkenyl group of alkyl or _C 16 _{-C 20} in _C 16 _{-C 20.} X ¹ is hydrogen, quantum dot of claim 2 ^{R 1} is an alkenyl group of alkyl or _C 16 _{-C 20} in _C 16 _{-C 20.} The quantum dot according to claim 1, wherein the compound represented by the chemical formula 1 is a compound represented by any one of the following chemical formulas 5 to 7.

The compound represented by Formula 2, ^{X 2} and ^{Y 1} are each independently hydrogen, methyl or _isopropyl, ^{R 2} is alkenyl alkyl or _C 16 _{-C 20} in C 16 _{-C 20} The quantum dot according to claim 1, wherein n is an integer of 0 to 1. X ² and ^{Y 1} is hydrogen, ^{R 2} _is an alkenyl group of alkyl or _C 16 _{-C 20} in C 16 _{-C 20,} n is as defined in claim 5 is an integer from 0 to 1 Quantum dots. The quantum dot according to claim 1, wherein the compound represented by the chemical formula 2 is a compound represented by any one of the following chemical formulas 8 to 12.

The quantum dot according to claim 1, wherein the compound represented by the chemical formula 3 is a compound represented by any one of the following chemical formulas 13 to 16.

In the above formula,
R ³ _is an alkenyl group of alkyl or _C 4 _{-C 22} in C 4 _{-C 22.} R ³ _is, quantum dot of claim 8 alkenyl group of the alkyl group or _C 10 _{-C 14} in C 10 _{-C 14.} The quantum dot according to claim 1, wherein the compound represented by the chemical formula 3 is a compound represented by any one of the following chemical formulas 17 to 20.

The compound represented by Formula 4, the quantum dot according to claim 1 ^{Y 2} is an alkenyl group of alkyl or _C 16 _{-C 20} in _C 16 _{-C 20.} The quantum dot according to claim 1, wherein the compound represented by the chemical formula 4 is a compound represented by any one of the following chemical formulas 21 to 27.

The quantum dots have a core-shell structure that includes a core and a shell that covers the core.
The cores are InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaN. Contains one or more of InAs and ZnO
The shell is one of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TIO, SrSe, and HgSe. The quantum dot according to claim 1, which comprises a species or more. A quantum dot film containing the quantum dots according to any one of claims 1 to 13. A self-luminous photosensitive resin composition containing the quantum dots according to any one of claims 1 to 13. A color filter using the self-luminous photosensitive resin composition according to claim 15. A quantum dot light emitting diode (QLED) containing the quantum dots according to any one of claims 1 to 13.