KR20220134942A - Quantum dots, curable composition comprising the same, and curable pattern and image display formed from the composition - Google Patents

Abstract

Quantum dot particles of embodiments of the present invention include a ligand having a thiol group, an ester group, and a hydrofluorocarbon or a fluorocarbon group. As the quantum dot particles include the ligand, a curable composition having excellent stability and optical properties can be provided. In addition, a curing pattern having excellent light efficiency and durability and an image display device including the same may be provided.

Description

QUANTUM DOTS, CURABLE COMPOSITION COMPRISING THE SAME, AND CURABLE PATTERN AND IMAGE DISPLAY FORMED FROM THE COMPOSITION

The present invention relates to quantum dot particles, a curable composition comprising the same, and a cured pattern and an image display device formed therefrom. More specifically, it relates to quantum dot particles including a ligand, a curable composition including the same, and a cured pattern and an image display device formed therefrom.

A color filter is a thin film type optical component that extracts red, green, blue, and three colors from white light and functions as a fine pixel unit. The size of one pixel is tens to hundreds of micrometers. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a plurality of colors (typically, red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order have a structure in which they are sequentially stacked. In general, color filters can be manufactured by coating three or more kinds of colors on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, etc. Recently, a pigment dispersion method using a pigment dispersion type photosensitive resin is mainly used. have.

According to the pigment dispersion method, which is one of the methods for implementing a color filter, first, a photosensitive resin composition including a colorant, alkali-soluble resin, photopolymerization monomer, photoinitiator, epoxy resin, solvent, and other additives is formed on a transparent substrate provided with a black matrix. coated on the substrate. Thereafter, after exposing the pattern to be formed, the non-exposed portion is removed with a solvent and a series of steps of thermosetting are repeated to form a colored thin film.

However, the color reproduction is implemented by the light irradiated from the light source passing through the color filter. In this process, part of the light is absorbed by the color filter, so that the light efficiency may be reduced. In addition, perfect color reproducibility may not be secured due to the characteristics of the pigment as a color filter.

Korean Patent Application Laid-Open No. 10-2012-112188 discloses an example of a red coloring composition for a color filter and a color filter.

Korean Patent Publication No. 10-2012-112188

One object of the present invention is to provide quantum dot particles having excellent optical properties and reliability, and a curable composition comprising the same.

One object of the present invention is to provide a cured pattern and an image display device formed from the curable composition.

1. Quantum dot particles comprising a fluorine-based ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group.

2. The quantum dot particle of the above 1, wherein the fluorohydrocarbon group or the fluorocarbon group is located at the terminal of the fluorine-based ligand, and has 1 to 10 carbon atoms.

3. The quantum dot particle according to the above 1, wherein the fluorine-based ligand comprises a compound represented by the following Chemical Formula 1:

[Formula 1]

(In Formula 1, R ₁ is a methylene group or an ethylene group, R ₂ is a hydrogen atom or a fluorine atom, m is 1 or 2, and n is an integer of 1 to 10).

4. The quantum dot particle of the above 1, wherein the fluorine-based ligand includes at least one selected from the group consisting of compounds represented by the following formulas (1) to (64).

5. The quantum dot particle according to the above 1, further comprising a non-fluorine-based ligand.

6. The quantum dot particle of the above 5, wherein the non-fluorine-based ligand includes at least one of an ether group, a cyclic ether group, and an ester group.

7. The quantum dot particle according to the above 6, wherein the non-fluorine-based ligand comprises a compound represented by the following Chemical Formula 3 or Chemical Formula 4:

[Formula 3]

(In Formula 3, R ₃ is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including an ester group, L is a thiol group or a carboxyl group, and x is an integer of 0 to 10)

[Formula 4]

(In Formula 4, R ₄ is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ₅ is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ₆ is a substitutable aliphatic having 1 to 10 carbon atoms. a hydrocarbon group or a substitutable aromatic hydrocarbon group having 6 to 12 carbon atoms, L is a thiol group or a carboxyl group, and y is an integer of 0 to 10).

8. The quantum dot particle according to the above 5, wherein the mass ratio of the fluorine-based ligand and the non-fluorine-based ligand included in the quantum dot particle is 5:95 to 95:5.

9. The quantum dot according to 1 above, wherein the quantum dot particles include at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, or a compound containing the same. particle.

10. The quantum dot particle according to 1 above, wherein the quantum dot particle includes a core and a shell covering the core.

11. The quantum dot particle according to 10 above, wherein the core includes indium (In) or phosphorus (P), and the shell includes zinc (Zn), selenium (Se) or sulfur (S).

12. The method of 11 above, wherein the shell includes a first shell layer covering the core and a second shell layer covering the first shell layer, wherein the core includes InP or InZnP, and the first shell layer includes ZnSe or ZnSeS. Including, wherein the second shell layer comprises ZnS, quantum dot particles.

13. A curable composition comprising quantum dot particles containing a thiol group, an ester group, and a ligand having a fluorohydrocarbon group or a fluorocarbon group.

14. The curable composition of 13 above, further comprising at least one of a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.

15. A cured pattern formed from the curable composition according to 13 above.

16. An image display device comprising the curing pattern according to 15 above.

Quantum dot particles according to embodiments of the present invention may be provided with a curable composition having excellent optical properties by including a ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group.

In addition, the quantum dot particles according to exemplary embodiments include a ligand having a fluorohydrocarbon group or a fluorocarbon group at the terminal, and thus may have excellent chemical resistance and heat resistance even under severe conditions.

In addition, by using the curable composition according to the exemplary embodiments, it is possible to provide a cured pattern having excellent light efficiency and durability, and an image display device including the same.

According to embodiments of the present invention, quantum dot particles including a ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group are provided. As the quantum dot particle includes a ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group, it may have excellent solubility in a solvent, and excellent reliability in severe conditions (high temperature/humidity) can be provided.

In addition, a curable composition including the quantum dot particles, a cured pattern formed from the curable composition, and an image display device including the cured pattern are provided. Since the cured pattern and the image display device include the quantum dot particles, light efficiency, color reproducibility, and durability may be excellent.

Hereinafter, quantum dot particles according to embodiments of the present invention will be described in detail. When there is an isomer of the compound or resin represented by the formula used in the present application, the compound or resin represented by the formula means the representative formula including the isomer.

Hereinafter, embodiments of the present invention will be described in detail.

<Quantum Dot Particles>

Quantum dot particles according to embodiments of the present invention may include a ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group. For example, the ligand may be a quantum dot particle disposed on the surface or the surface of which is modified with the ligand.

Quantum dots may refer to nano-sized semiconductor materials. Specifically, atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots.

When the quantum dot particle receives energy from the outside and reaches an excited state, it emits energy (eg, light) according to the energy band gap of its own quantum dot. Specifically, quantum dot particles are capable of photoluminescence that emits light by irradiation or electroluminescence that emits light by application of current, and are light emitting materials in various fields such as display devices, energy devices, or bioluminescent devices. can be applied as

For example, quantum dot particles may be used in LCD (Liquid Crystal Diodes)-based displays using light emitting devices or QLED (Quantum Dot Light Emitting Diodes) based displays using electroluminescent devices.

The curable composition and the cured pattern according to the exemplary embodiments may emit light by themselves, for example, by light irradiated from a light source by including such quantum dot particles.

The quantum dot particles may control the energy band gap of the quantum dot by controlling the size and/or composition of the nanocrystal. For example, as the size of the quantum dot particle decreases, it may have a wide energy bandgap and the emission wavelength may decrease. Accordingly, quantum dot particles emitting light of a desired wavelength can be realized by controlling the particle size and/or composition of the quantum dot particles.

For example, the quantum dot particles may include blue quantum dots emitting blue light, green quantum dots emitting green light, or red quantum dots emitting red light. For example, in the case of the green quantum dots or red quantum dots, blue light may be irradiated and light-converted into green light or red light.

In addition, in the case of a general image display device including a color filter, part of the light may be absorbed by the color filter while the irradiated white light passes through the color filter to realize color. Accordingly, light efficiency may be reduced in the process of passing through the color filter.

In the case of including a color filter made of a curable composition including quantum dot particles according to exemplary embodiments, since the color filter emits light by itself by the light irradiated from the light source, superior light efficiency may be realized.

According to example embodiments, the quantum dot particles may include a material that emits light when stimulated by light. For example, it may include a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element or a compound including the same, and mixtures thereof. These may be used alone or in combination of two or more.

The group II-VI compound may be a binary compound selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, and mixtures thereof; ternary compounds selected from CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

The group III-V compound may include a binary compound selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; a ternary compound selected from GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and quaternary compounds selected from GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

The group IV-VI compound is a binary compound selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and a quaternary compound selected from SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

The group IV element or a compound containing the same may include an elemental compound selected from Si, Ge, and mixtures thereof; and a binary compound selected from SiC, SiGe, and mixtures thereof.

According to exemplary embodiments, the quantum dot particle may have a homogeneous single structure, a core-shell structure, a gradient structure, or a mixture thereof.

In some embodiments, the quantum dot particle may have a core-shell structure including a core and a shell covering the core. The core may be a portion that substantially emits light. The shell may serve to improve the stability and efficiency of the quantum dot particles by preventing oxidation of the core and reducing the surface trap energy level.

The material constituting each core and the shell may be made of the different compounds described above. For example, the core may be GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InNP, InZnP, InNAs, InNSb, InPAs, InPSb GaInPAs, GaInPSb, InAlNP, InAlNAs, It may include one or more materials selected from the group consisting of InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The shell may include one or more materials selected from the group consisting of ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, ZnSe, ZnS, ZnSeS, and mixtures thereof. Preferably, the core may include In and P, and the shell may include Zn, Se and/or S.

In some embodiments, the shell may have a multi-layered shell structure including one or more shell layers. For example, the quantum dot particles may include a core, a first shell layer covering the core, and a second shell layer covering the first shell layer.

In some embodiments, adjacent core and shell layers in the multilayer shell structure may have different compositions. For example, the core may include InP and/or InZnP, the first shell layer may include ZnSe and/or ZnSeS, and the second shell layer may include ZnS.

In some embodiments, the quantum dot particles may be non-cadmium-based quantum dots that do not substantially contain cadmium (Cd). Accordingly, it is possible to prevent environmental or human harm caused by cadmium.

A ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group may be disposed on the surface of the quantum dot particle. For example, the quantum dot particles may be surface-modified by the fluorine-based ligand.

In some embodiments, the fluorine-based ligand may be a substituted or unsubstituted hydrocarbon having a thiol group and a fluorohydrocarbon group or a fluorocarbon group at both ends and an ester group in the main chain.

As the ligand includes a thiol group having strong binding affinity with the quantum dot particle at one end, the passivation property for the quantum dot particle may be improved. For example, a thiol group may be chemically bonded to the surface of the quantum dot particle. For example, the thiol group of the fluorine-based ligand may form a coordination bond with Zn included in the shell of the quantum dot particle.

In addition, as the ligand includes an ester group in the main chain, dispersibility in a polar organic solvent may be improved, for example, compatibility in a display process may be improved.

For example, in the case of a ligand generally used for quantum dots, it is composed of an aliphatic cahin having a high carbon content, so the quantum dot particles are mainly soluble in non-polar solvents, and dispersibility in polar organic solvents or water it was fever Accordingly, for example, compatibility in a display process was poor and sufficient light efficiency was not provided.

Quantum dot particles according to exemplary embodiments may have improved solubility and dispersibility in polar solvents and water as a ligand including an ester group having a polarity is disposed on the surface. For example, aggregation of quantum dot particles in a polar solvent may be suppressed and uniformly distributed in the solvent. Accordingly, quantum efficiency of the quantum dot particles may be excellent, and color reproducibility and viewing angle may be improved.

In addition, the ligand may include a fluorohydrocarbon group or a fluorocarbon group and may have excellent shielding properties against moisture and/or oxygen, and thus the light conversion rate of the quantum dot particles may be improved.

For example, the photoconversion function of quantum dot particles may be rapidly deteriorated with the lapse of time or progress of a process due to damage caused by oxygen, moisture, heat, or the like. For example, the core and/or shell of the quantum dot particles may be oxidized by chemical/mechanical impact, or may be damaged such as cracks or cracks, thereby reducing quantum efficiency.

Quantum dot particles according to exemplary embodiments may have excellent stability in harsh conditions because the surface may be stably passivated by a fluorohydrocarbon group or a fluorocarbon group having excellent mechanical/chemical properties. Accordingly, it is possible to prevent a decrease in optical efficiency due to oxidation and damage of the quantum dot particles, and a color filter having excellent reliability and optical properties can be provided even under severe conditions such as long-term storage or heat and exposure processes.

The fluorohydrocarbon group may refer to an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom and includes at least one hydrogen atom. The fluorocarbon group may mean an aliphatic hydrocarbon group in which all hydrogen atoms are substituted with fluorine atoms.

For example, the fluorohydrocarbon group may be -(CF ₂ )nCHF ₂ . For example, the fluorocarbon group may be -(CF ₂ )nCF ₃ .

In some embodiments, the fluorine-based ligand may include a fluorohydrocarbon group having 1 to 10 carbon atoms or a fluorocarbon group having 1 to 10 carbon atoms. While maintaining the dispersibility of the quantum dot particles in the solvent within the carbon number range, moisture resistance and heat resistance may be excellent.

In some embodiments, the fluorine-based ligand may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ may be a methylene group or an ethylene group, and R ₂ may be a hydrogen atom or a fluorine atom. m may be 1 or 2, and n may be an integer from 1 to 10.

As shown in Formula 1, dispersibility in a polar solvent and/or water may be improved as the fluorine-based ligand includes an ester group in the main chain. In addition, by including a fluorohydrocarbon group or a fluorocarbon group at the end, it is possible to easily block the penetration of moisture and oxygen into the quantum dot particles, and it is possible to alleviate mechanical/physical impact. Therefore, by preventing oxidation/damage of quantum dot particles, quantum efficiency can be maintained excellently even during long-term storage or processing.

In some embodiments, the fluorine-based ligand may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas (1) to (64).

(1)

(One)

(2)

(2)

(3)

(3)

(4)

(4)

(5)

(5)

(6)

(6)

(7)

(7)

(8)

(8)

(9)

(9)

(10)

(10)

(11)

(11)

(12)

(12)

(13)

(13)

(14)

(14)

(15)

(15)

(16)

(16)

(17)

(17)

(18)

(18)

(19)

(19)

(20)

(20)

(21)

(21)

(22)

(22)

(23)

(23)

(24)

(24)

(25)

(25)

(26)

(26)

(27)

(27)

(28)

(28)

(29)

(29)

(30)

(30)

(31)

(31)

(32)

(32)

(33)

(33)

(34)

(34)

(35)

(35)

(36)

(36)

(37)

(37)

(38)

(38)

(39)

(39)

(40)

(40)

(41)

(41)

(42)

(42)

(43)

(43)

(44)

(44)

(45)

(45)

(46)

(46)

(47)

(47)

(48)

(48)

(49)

(49)

(50)

(50)

(51)

(51)

(52)

(52)

(53)

(53)

(54)

(54)

(55)

(55)

(56)

(56)

(57)

(57)

(58)

(58)

(59)

(59)

(60)

(60)

(61)

(61)

(62)

(62)

(63)

(63)

(64)

(64)

According to exemplary embodiments, the quantum dot particles may further include a non-fluorine-based ligand. For example, the quantum dot particle may be a quantum dot particle in which a fluorine-based ligand and a non-fluorine-based ligand are disposed on the surface, or the surface is modified with a fluorine-based ligand and a non-fluorine-based ligand.

The non-fluorine-based ligand may serve to supplement the solubility of the quantum dot particles in a polar solvent. For example, the non-fluorine-based ligand may have a polar functional group in its molecular structure to ensure excellent dispersibility in a polar solvent.

In some embodiments, the non-fluorine-based ligand may include at least one of an ether group, a cyclic ether group, and an ester group. Accordingly, the solubility and dispersibility of the quantum dot particles in a polar solvent or water may be improved.

For example, the non-fluorine-based ligand may include compounds represented by Chemical Formulas 3 and 4 below.

[Formula 3]

In Formula 3, R ₃ may be a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including an ester group, L may be a thiol group or a carboxyl group, and x may be an integer of 0 to 10.

[Formula 4]

In Formula 4, R ₄ may be a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ₅ may be a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ₆ is a substitutable carbon number of 1 to 10 It may be a monovalent aliphatic hydrocarbon group or a substitutable aromatic hydrocarbon group having 6 to 12 carbon atoms, and y may be an integer of 0 to 10.

The monovalent or divalent aliphatic hydrocarbon group may be a straight chain, branched chain or cyclic hydrocarbon group.

For example, the monovalent aliphatic hydrocarbon group may be an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or a cycloalkynyl group. For example, the divalent aliphatic hydrocarbon may be an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, or a cycloalkynylene group.

The aromatic hydrocarbon group may be an aryl group, an arylalkyl group, or an alkylaryl group. For example, it may be a benzyl group or a phenyl group.

The "substitutable" means that at least one of the hydrogen atoms of the hydrocarbon group is a halogen atom, a hetero atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a carboxyl group, an amino group, a cyano group, a nitro group, a thiol group It means to be substituted with at least one selected from the group consisting of a group.

A thiol group or a carboxyl group of the compound represented by Chemical Formulas 3 and 4 may be chemically bonded to the surface of the quantum dot particle. For example, the thiol group or the carboxyl group may form a coordination bond with Zn of the quantum dot particle shell.

As the quantum dot particles contain both the fluorine-based ligand and the non-fluorine-based ligand, it is possible to prevent oxidation of the quantum dot particles while stably maintaining solubility and dispersibility in a polar organic solvent. Accordingly, chemical resistance, moisture resistance, and optical properties of the cured pattern may be improved.

In some embodiments, the mass ratio of the fluorine-based ligand and the non-fluorine-based ligand included in the quantum dot particle may be about 5:95 to about 95:5. Within the above range, the dispersibility of the quantum dot particles in the solvent may be excellent, and storage stability and reliability may be improved. Preferably, the mass ratio of the fluorine-based ligand and the non-fluorine-based ligand may be about 20:80 to 80:20.

In some embodiments, the content of the fluorine-based ligand or, when a non-fluorine-based ligand is further included, the total content of the fluorine-based ligand and the non-fluorine-based ligand is based on the total weight of the quantum dot particles (eg, core and shell) excluding the ligand. It may be included in an amount of about 30 to 200% by weight. If the content is less than about 30% by weight, the quantum dot particles may not be sufficiently passivated by the ligand. When the content is more than 200% by weight, the degree of curing and light efficiency of the curing pattern may decrease as the ligand is excessively disposed on the surface of the quantum dot particle. Preferably, when the fluorine-based ligand or non-fluorine-based ligand is further included, the total content of the fluorine-based ligand and the non-fluorine-based ligand is about 50 to 150 weight based on the total weight of the quantum dot particles (eg, core and shell) excluding the ligand. % may be included.

According to exemplary embodiments, the average particle diameter of the quantum dot particles may be about 5 to 12 nm. In some embodiments, when the quantum dot particle has a core-shell structure, the average particle diameter of the core may be about 2.5 to 5 nm, and the thickness of the shell may be about 2.5 to 7 nm. When the average particle diameter and thickness are within the above ranges, dispersibility of quantum dot particles is improved, and a desired color can be efficiently implemented by light irradiation.

In some embodiments, the quantum dot particles are synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process. can The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal is grown, the organic solvent is coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Accordingly, it is possible to control the crystal growth through an easier and cheaper process than a vapor deposition method such as an organometallic chemical vapor deposition process or a molecular beam epitaxy process.

<Curable composition>

The curable composition according to embodiments of the present invention may include quantum dot particles according to exemplary embodiments, and may further include a binder resin, a solvent, a polymerizable compound, a polymerization initiator, and other additives.

As the quantum dot particles include a ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group, a curable composition having excellent long-term storage stability and reliability while maintaining compatibility and dispersibility in a solvent can be provided.

In some embodiments, the content of the quantum dot particles may be about 1 to 30% by weight of the total weight of the solid content of the curable composition. When the content of the quantum dot particles is less than 1% by weight, the luminous efficiency by the quantum dot particles may be reduced. When the content of the quantum dot particles is more than 30% by weight, it may be difficult to form a cured pattern because the content of the other composition is relatively insufficient. Preferably, the quantum dot particles may be included in an amount of about 3 to 20% by weight based on the total weight of the solid content of the curable composition.

binder resin

The binder resin may include a thermosetting resin or an alkali-soluble resin. The binder resin may be a component that imparts solubility to alkali development used in a developing process when forming a pattern.

In some embodiments, the binder resin may include an acrylic resin, a cardo-based resin, or an epoxy resin. These may be used alone or in combination of two or more. Preferably, it may be an acrylic resin and/or a cardo-based resin.

For example, the acrylic resin is polybenzyl methacrylate, meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2- hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like.

For example, the epoxy resin may include a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a phenol novolac-type epoxy resin, a cyclic aliphatic epoxy resin, and an aliphatic polyglycidyl ether.

For example, the cardo-based resin may be a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, phenol anhydride compounds such as rylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methyl pyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

The binder resin may have reactivity to light or heat and improve dispersibility of quantum dot particles. It can also act as a binder resin for quantum dots, and can be used as a support for a cured pattern.

In some embodiments, the binder resin may be included in an amount of about 5 to 80% by weight based on the total weight of the solid content of the curable composition. Within the above range, the solubility in the developer is sufficient, so that the pattern formation may be easy. Further, film reduction in the pixel portion of the exposed portion during development can be prevented, thereby reducing the omission of the non-pixel portion. Preferably, it may be included in an amount of about 10 to 70% by weight based on the total weight of the solid content of the curable composition.

menstruum

In some embodiments, the curable composition may include a solvent. The solvent sufficiently dissolves the above-described quantum dot particles and the binder resin, and may include an organic solvent that does not cause precipitation of components of the composition.

When the curable composition contains quantum dot particles, it is difficult to use a polar organic solvent, such as propylene glycol monomethyl ether acetate, ethylene diglycol methyl ethyl ether, which is generally used in the manufacturing process of a color filter or an image display device. .

However, as described above, in the curable composition according to the exemplary embodiments, as a fluorine-based ligand and/or a non-fluorine-based ligand having an ester group is disposed on the surface of the quantum dot, it is possible to use a polar organic solvent and improve light efficiency. have.

Examples of the solvent include ethylene glycol monoalkyl ethers; diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; butyldiol monoalkyl ethers; butanediol monoalkyl ether acetates; butanediol monoalkyl ether propionates; dipropylene glycol dimethyl ether, dipropylene glycol dialkyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; alcohols such as methanol and ethanol; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; cyclic ethers such as tetrahydrofuran and pyran; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned. These may be used alone or in combination of two or more. Preferably, the solvent may include propylene glycol monomethyl ether (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA).

The solvent may be included in the remaining amount excluding the components of the above-described composition, for example, the remaining amount excluding the quantum dot particles, or the quantum dot particles, binder resin and other additive components may be included in the remaining amount.

In some embodiments, the solvent may be included in an amount of about 40 to 95% by weight, preferably about 45 to 85% by weight of the total weight of the curable composition in consideration of the coatability and dryness of the composition. In the above range, the coating properties and drying properties of the composition can be improved, and a coating can be easily formed through a coating method using a spin coater, a slit and spin coater, a slit coater, a die coater, a curtain flow coater, an inkjet, etc. .

polymeric compound

In some embodiments, the curable composition may include a polymerizable compound. The polymerizable compound is a compound that can be polymerized or crosslinked by the action of a polymerization initiator, which will be described later, and can increase the crosslinking density during the manufacturing process and enhance the mechanical properties of the curing pattern.

The polymerizable compound may be used without particular limitation as long as it is used in the art, and may include, for example, a monofunctional monomer, a difunctional monomer, or a trifunctional or more polyfunctional monomer. These may be used alone or in combination of two or more.

The monofunctional monomer may be nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like. .

The bifunctional monomer is 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A (acryloyloxyethyl) ether, 3-methylpentanediol di(meth)acrylate, and the like.

The polyfunctional monomer is trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

In some embodiments, the content of the polymerizable compound may be about 30 to 85% by weight, preferably about 40 to 80% by weight, based on the total weight of the solid content of the curable composition. When the polymerizable compound is included in the above content range, the durability of the photocurable film may be improved, and the resolution of the composition may be improved during the developing process.

polymerization initiator

In some embodiments, the curable composition may include a polymerization initiator.

The polymerization initiator may be used without particular limitation as long as it can induce a crosslinking reaction or a polymerization reaction of the polymerizable compound by, for example, an exposure process. For example, as the polymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a benzoin-based compound, a triazine-based compound, a biimidazole-based compound, a thioxanthone-based compound, an oxime ester-based compound, etc. may be used, preferably An oxime ester-based compound may be used.

The oxime ester compound is o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione-1-(4-phenylthio)phenyl-2-(o-benzoyl) oxime), ethanone, -1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), and the like, and are commercially available products such as CGI-124 ( Ciba Geigisa), CGI-224 (Chiba Geigisa), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adecas), NCI-831 (Adecas), etc. can These may be used alone or in combination of two or more.

In some embodiments, a polymerization initiation aid may be additionally used to improve the sensitivity of the curable composition. Examples of the polymerization initiation aid include an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

In some embodiments, the polymerization initiator may be included in an amount of about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight, based on the total weight of the solid content of the curable composition. In the above range, it is possible to improve the efficiency and resolution of the exposure process without compromising the durability of the curable composition.

other additives

The curable composition according to the exemplary embodiments may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, UV absorbers, aggregation inhibitors, and chain transfer agents, if necessary.

In addition, the quantum dot particles according to the exemplary embodiments may include other organic or inorganic ligands on the surface in a range that does not impair the properties of the ligands according to the exemplary embodiments. The organic or inorganic ligand may form a coordination bond on the surface of the quantum dot particle, and may improve dispersibility and light emission characteristics of the quantum dot particle.

For example, the organic ligand is trioctylphosphine, trioctylphosphine oxide, oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid, tetradecylphosphine phonic acid, octylphosphinic acid, and the like. The inorganic ligand may include an inorganic material such as halogen, metal halide, chalcogen, metal chalcogenide, metal hydroxide, and SCN-. These may be used alone or in combination of two or more.

<Cured pattern and image display device>

The present invention provides a cured pattern prepared from a curable composition according to exemplary embodiments and an image display device including the cured pattern. For example, the cured pattern may be used as a color filter of an image display device as will be described later.

In forming the curing pattern, the photosensitive film may be formed by applying the curable composition according to the exemplary embodiments on the substrate. Examples of the coating method include inkjet printing, spin coating, cast coating method, roll coating method, slit and spin coating, or slit coating method. After forming the photoresist, a pre-baking process may be performed to remove volatile components such as a solvent.

Thereafter, an exposure process may be performed to form a photocurable film. In order to form a target pattern, ultraviolet rays may be irradiated through a predetermined type of exposure mask. Curing may be performed on the portion irradiated with the ultraviolet rays. As the ultraviolet rays, g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm), etc. may be used.

After the exposure process, a developing process may be performed to form a cured pattern. For example, a cured pattern may be formed by removing the unexposed portion using an alkaline developer. Alternatively, a cured pattern may be formed by removing the exposed portion using an alkaline developer. Examples of the developing step include a liquid addition method, a dipping method, and a spray method. A post baking process may be further performed after the exposure process or the developing process.

In example embodiments, the cured pattern may be used in a color filter. The color filter including the cured pattern may be applied to various image display devices such as an electroluminescence display, a plasma display, and a field emission display, as well as a general liquid crystal display.

The color filter may include a substrate and a cured pattern layer formed on the substrate. For example, the substrate may be the color filter itself, or it may be a portion where the color filter is positioned on a display device or the like. The substrate may be glass, silicon, silicon oxide, or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

When the color filter is applied to an image display device, the quantum dot particles included in the color filter emit light by themselves by the light of the light source, and thus light efficiency may be excellent. In addition, as light having a color is emitted, color reproducibility may be excellent, and since light is emitted in all directions by the quantum dot particles, a viewing angle may be improved.

In some embodiments, the color filter may include a transparent pattern layer, a green pattern layer that converts incident blue light into green light, or a red pattern layer that converts incident blue light into red light. The green pattern layer may include green quantum dots that emit green light when irradiated with blue light, and the red pattern layer may include red quantum dots that emit red light when irradiated with blue light.

In some embodiments, the image display device may include a color filter including a transparent pattern layer, a green pattern layer, and a red pattern layer. In this case, a light source emitting blue light may be used as the light source of the image display device.

As described above, as the curable composition contains a fluorohydrocarbon group or a fluorine-based ligand having a fluorocarbon group, it prevents damage to the quantum dot particles by oxygen, moisture, or heat even under severe conditions such as a thermal process or a furnace process, thereby preventing photoconversion function can be kept excellent. Therefore, since the color filter including the curing pattern can be efficiently converted while minimizing the loss of irradiated light, excellent light efficiency can be realized.

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid understanding of the present invention, but these are merely illustrative of the present invention and do not limit the appended claims, the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope, and it is natural that such variations and modifications fall within the scope of the appended claims.

Synthesis Example: Quantum Dot Particles

Synthesis Example 1: A-1

From a solution in which InP/ZnSe/ZnS core-shell structured quantum dot particles are dispersed (quantum dot solid content 30%), centrifugation is performed twice using acetone and ethanol, and then vacuum-dried to obtain a quantum dot particle powder. After that, 30 g of the quantum dot particles are completely dissolved using 100 g of toluene, and 30 g of the compound of Formula 2-1 is added thereto. Thereafter, the reaction was carried out for 15 hours while maintaining 50° C. under a nitrogen atmosphere to prepare quantum dot particles including a ligand on the surface.

[Formula 2-1]

Synthesis Example 2: A-2

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 2-2 was used instead of the compound represented by the formula 2-1.

[Formula 2-2]

Synthesis Example 3: A-3

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 2-3 was used instead of the compound represented by the formula 2-1.

[Formula 2-3]

Synthesis Example 4: A-4

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 2-4 was used instead of the compound represented by the formula 2-1.

[Formula 2-4]

Synthesis Example 5: A-5

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 2-5 was used instead of the compound represented by the formula 2-1.

[Formula 2-5]

Synthesis Example 6: A-6

A ligand was included on the surface in the same manner as in Synthesis Example 1, except that 15 g of the compound represented by Formula 2-3 and 15 g of the compound represented by Formula 5 were used instead of the compound represented by Formula 2-1. Quantum dot particles were prepared.

[Formula 2-3]

[Formula 5]

Synthesis Example 7: A-7

A ligand was included on the surface in the same manner as in Synthesis Example 1, except that 15 g of a compound represented by Formula 2-5 and 15 g of a compound represented by Formula 6 were used instead of the compound represented by Formula 2-1. Quantum dot particles were prepared.

[Formula 2-5]

[Formula 6]

Synthesis Example 8: A-8

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 5 was used instead of the compound represented by the formula 2-1.

[Formula 5]

Synthesis Example 9: A-9

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 6 was used instead of the compound represented by the formula 2-1.

[Formula 6]

Synthesis Example 10: A-10

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 7 was used instead of the compound represented by the formula 2-1.

[Formula 7]

Synthesis Example 11: A-11

Quantum dot particles including a ligand on the surface were prepared in the same manner as in Synthesis Example 1, except that the compound represented by the following formula 8 was used instead of the compound represented by the formula 2-1.

[Formula 8]

Examples and Comparative Examples

(1) Preparation of curable composition

A curable composition was prepared by mixing the components shown in Table 1 below in the corresponding content (% by weight).

division
(weight%) quantum dot particles binder resin polymeric compound polymerization initiator menstruum Example 1 15
(A-1) 10 1.6 0.1 73.3 Example 2 15
(A-2) 10 1.6 0.1 73.3 Example 3 15
(A-3) 10 1.6 0.1 73.3 Example 4 15
(A-4) 10 1.6 0.1 73.3 Example 5 15
(A-5) 10 1.6 0.1 73.3 Example 6 15
(A-6) 10 1.6 0.1 73.3 Example 7 15
(A-7) 10 1.6 0.1 73.3 Comparative Example 1 15
(A-8) 10 1.6 0.1 73.3 Comparative Example 2 15
(A-9) 10 1.6 0.1 73.3 Comparative Example 3 15
(A-10) 10 1.6 0.1 73.3 Comparative Example 4 15
(A-11) 10 1.6 0.1 73.3

Specific ingredient names listed in Table 1 are as follows.

Quantum dot particle (A)

1) A-1: quantum dot particles prepared in Synthesis Example 1

2) A-2: quantum dot particles prepared in Synthesis Example 2

3) A-3: quantum dot particles prepared in Synthesis Example 3

4) A-4: quantum dot particles prepared in Synthesis Example 4

5) A-5: quantum dot particles prepared in Synthesis Example 5

6) A-6: quantum dot particles prepared in Synthesis Example 6

7) A-7: quantum dot particles prepared in Synthesis Example 7

8) A-8: quantum dot particles prepared in Synthesis Example 8

9) A-9: quantum dot particles prepared in Synthesis Example 9

10) A-10: quantum dot particles prepared in Synthesis Example 10

11) A-11: quantum dot particles prepared in Synthesis Example 11

Binder resin (B)

Acrylic 　 binder 　 resin (SPCY-1L, Showa Polymers Co., Ltd.)

polymerizable compound (C)

Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

polymerization initiator (D)

Irgaqure-907 (manufactured by BASF)

Solvent (E)

Propylene glycol monomethyl ether acetate (PGMEA)

(2) Manufacture of curli filter

After coating the curable compositions according to Examples and Comparative Examples on a glass substrate by spin coating, it was placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. A test photomask having a square transmission pattern of 20 mm X 20 mm and a line/space pattern of 1 to 100 μm was placed on the thin film, and ultraviolet rays were irradiated with an interval of 100 μm from the test photomask. The ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 200 mJ/cm ² in an atmospheric atmosphere using an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio Denki Co., Ltd.). Thereafter, the thin film was developed by immersing it in an aqueous KOH solution of pH 10.5 for 80 seconds.

Thereafter, the color filter was washed with distilled water, dried by blowing nitrogen gas, and heated in an oven at 150° C. for 10 minutes to prepare a color filter. The pattern thickness of the manufactured color filter was 3.0 μm.

Experimental example

(1) storage stability evaluation

The curable compositions according to Examples and Comparative Examples were left at room temperature, and the viscosity over time was measured using a viscometer (manufactured by Brookfield). There is little change in viscosity with time, and the lower the viscosity, the better the storage stability. The evaluation results are shown in Table 2 below.

(2) Light efficiency and durability evaluation

Light efficiency was calculated by measuring the degree of conversion to green light by irradiating blue light to the manufactured color filter. Light efficiency was measured using QE-2000 (manufactured by Otsuka Corporation), and when blue light of 450 nm was applied to the color filter, all green light emitted in all directions was absorbed and calculated as an integral value. The light efficiency was calculated as a percentage of the increase in the peak converted to green light compared to the decrease in the blue light absorption peak.

In addition, after the color filter was left in the blue light source at room temperature for 7 days, the light efficiency was measured and the amount of decrease was calculated. Since the light efficiency is reduced due to the oxidation of the quantum dot particles, durability can be confirmed by measuring the light efficiency after standing. Durability was expressed as a percentage of the ratio of the light efficiency after standing to the initial light efficiency. It means that it is excellent in oxidation stability, so that durability is high.

The evaluation results are also described in Table 2 below.

(3) Heat resistance evaluation

Blue light was irradiated to the prepared color filter, and light efficiency was measured in the same manner as for light durability. Thereafter, the measured color filter was additionally heat-treated on a hot plate at 230° C. for 30 minutes, and then the light efficiency was measured again in the same manner to evaluate the heat resistance. When the quantum dot particles are damaged by heat, the light efficiency is reduced. Therefore, heat resistance can be confirmed by measuring the rate of decrease in light efficiency after heat treatment.

The heat resistance was expressed as the ratio of the light efficiency after the heat treatment to the initial light efficiency as a percentage.

The evaluation results are shown in Table 2 below.

division
storage stability
(viscosity, cP) light efficiency
(%) durability
(%) heat resistance
(%) Early 2 weeks 4 weeks Early 7 days
after neglect after heat treatment Example 1 10.1 10.6 11.1 83 74 73 84.1 87.9 Example 2 10.5 10.9 11.3 81 71 70 87.6 86.4 Example 3 11.1 11.4 11.7 80 71 71 88.8 88.8 Example 4 11.3 11.6 11.9 79 73 72 92.4 91.1 Example 5 11.1 11.6 11.8 81 74 73 91.3 90.1 Example 6 9.2 9.6 10.2 75 62 62 82.6 82.7 Example 7 9.7 10.0 10.8 77 65 62 84.4 80.5 Comparative Example 1 10.3 11.2 12.1 78 47 48 60.3 61.5 Comparative Example 2 11.4 12.1 12.8 72 40 39 55.5 54.1 Comparative Example 3 11.2 11.8 12.5 68 38 41 55.9 60.3 Comparative Example 4 14.8 15.3 15.9 56 33 34 59.4 61.0

Referring to Table 2, it can be seen that, in the case of the color filter manufactured using the curable composition according to the exemplary embodiments, the change in viscosity over time is small. In addition, it can be confirmed that the initial light conversion rate is high, and durability is excellent as the oxidation of the quantum dot particles is prevented. In addition, it can be confirmed that the decrease in the light conversion rate due to heat treatment is low as it has high mechanical/chemical stability.

On the other hand, it can be confirmed that Comparative Examples 1 to 4 did not include a fluorohydrocarbon group or a fluorocarbon group, and thus the storage stability and change in viscosity with time were deteriorated. Therefore, it can be seen that the initial light conversion rate was low, and the light conversion rate significantly decreased with the passage of time and heat treatment.

Claims (16)

Quantum dot particles comprising a fluorine-based ligand having a thiol group, an ester group, and a fluorohydrocarbon group or a fluorocarbon group.
The quantum dot particle according to claim 1, wherein the fluorohydrocarbon group or the fluorocarbon group is located at the terminal of the fluorine-based ligand, and has 1 to 10 carbon atoms.
The quantum dot particle according to claim 1, wherein the fluorine-based ligand comprises a compound represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1,
R ₁ is a methylene group or an ethylene group, R ₂ is a hydrogen atom or a fluorine atom, m is 1 or 2, and n is an integer from 1 to 10).
The quantum dot particle according to claim 1, wherein the fluorine-based ligand comprises at least one selected from the group consisting of compounds represented by the following formulas (1) to (64):

(One)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

(12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28)

(29)

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

(39)

(40)

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

(59)

(60)

(61)

(62)

(63)

(64).
The quantum dot particle of claim 1, further comprising a non-fluorine-based ligand.
The quantum dot particle according to claim 5, wherein the non-fluorine-based ligand includes at least one of an ether group, a cyclic ether group, and an ester group.
The quantum dot particle according to claim 6, wherein the non-fluorine-based ligand comprises a compound represented by the following Chemical Formula 3 or Chemical Formula 4:
[Formula 3]

(In Formula 3,
R ₃ is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including an ester group, L is a thiol group or a carboxyl group, and x is an integer of 0 to 10)
[Formula 4]

(In Formula 4,
R ₄ is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ₅ is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ₆ is a substitutable aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substitutable carbon number an aromatic hydrocarbon group of 6 to 12, L is a thiol group or a carboxyl group, and y is an integer of 0 to 10).
The method according to claim 5, wherein the mass ratio of the fluorine-based ligand and the non-fluorine-based ligand included in the quantum dot particles is 5:95 to 95:5, quantum dot particles.
The quantum dot particle of claim 1, wherein the quantum dot particle comprises at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, or a compound containing the same.
The quantum dot particle of claim 1 , wherein the quantum dot particle comprises a core and a shell covering the core.
The quantum dot particle of claim 10 , wherein the core comprises indium (In) or phosphorus (P), and the shell comprises zinc (Zn), selenium (Se) or sulfur (S).
The method according to claim 11, wherein the shell comprises a first shell layer covering the core and a second shell layer covering the first shell layer,
The core includes InP or InZnP, the first shell layer includes ZnSe or ZnSeS, and the second shell layer includes ZnS.
A curable composition comprising quantum dot particles containing a thiol group, an ester group, and a ligand having a fluorohydrocarbon group or a fluorocarbon group.
The curable composition of claim 13, further comprising at least one of a binder resin, a polymerizable compound, a polymerization initiator, and a solvent.
A cured pattern formed from the curable composition of claim 13 .
Including the curing pattern according to claim 15, an image display device.