Curable composition, cured layer using the same and display device

Abstract

A curable composition, a cured layer manufactured using the curable composition, and a display device including the cured layer are provided. The curable composition includes (A) a quantum dot comprising a functional group represented by Chemical Formula 1; and (B) a polymerizable compound. In Chemical Formula 1, each substituent is the same as defined in the specific embodiments.

Description

[Technical Field]

[0001] Exemplary embodiments of this disclosure relate to a curable composition, a cured layer using said composition, and a display device including said cured layer. [Cross-Reference to Related Applications]

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0083882, filed on June 26, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. [Previous Technology]

[0003] Description of related technologies

[0004] Regarding general quantum dots, due to their hydrophobic surface properties, the solvents in which quantum dots are dispersed are limited, making it difficult to introduce them into polar systems (such as adhesives or curable monomers).

[0005] For example, even for quantum dot ink compositions that are currently under active research, the polarity is relatively low in the initial steps, and they can be dispersed in solvents used in curable compositions with high hydrophobicity. Therefore, since it is difficult to include 20% by weight or more of quantum dots by total composition, it is difficult or impossible to increase the light efficiency of the ink to a level exceeding the set or a certain level. Even if additional quantum dots are added and dispersed to increase light efficiency, the viscosity exceeds the range that allows for ink-jetting, and therefore the processability may be unsatisfactory.

[0006] To achieve a viscosity range suitable for ink spraying, a method of reducing the ink solids content by dissolving approximately 50% by weight or more of a solvent based on the total composition also provides somewhat satisfactory results in terms of viscosity. While this can be considered a satisfactory result in terms of viscosity, nozzle drying and clogging due to solvent evaporation during ink spraying, as well as the reduction in single-film thickness over time after ink spraying, can become more severe and difficult to control thickness deviations after curing. Therefore, it is difficult to apply the above to actual processes.

[0007] Therefore, solvent-free curable compositions (i.e., quantum dot ink compositions) have been developed. However, problems arise due to excessive polymerizable compounds, such as nozzle drying clogging and poor spraying caused by volatility, and reduced single-film thickness due to the volatilization of the ink composition sprayed into the pattern partition wall pixel. In particular, the difficulty in improving the optical properties of solvent-free curable compositions is the biggest problem.

[0008] In fact, neither solvent-type curable components nor solvent-free curable components have shown satisfactory levels of lightfastness reliability. [Summary of the Invention]

[0009] Some exemplary embodiments An exemplary embodiment provides a curable composition having high stability of quantum dots, excellent dispersibility of quantum dots, and therefore excellent reliability and optical properties such as heat resistance and light resistance.

[0010] Some exemplary embodiments provide a cured layer manufactured using a curable composition.

[0011] Some exemplary embodiments provide a display device including a cured layer.

[0012] Some exemplary embodiments provide curable compositions, including (A) quantum dots comprising functional groups represented by chemical formula 1; and (B) polymerizable compounds.

[0013] [Chemical Formula 1]

[0014]

[0015] In chemical formula 1,

[0016] X is a sulfur atom or an oxygen atom.

[0017] R1 is a monovalent functional group that includes a reactive group and a C3 to C20 cycloalkane ring.

[0018] L1 and L2 are each independently substituted or unsubstituted C1 to C20 alkyl groups, and

[0019] n is an integer between 2 and 10.

[0020] The reactive group may include carbon-carbon double bonds, epoxy groups, or combinations thereof.

[0021] R1 can be represented by any one of the chemical formulas R-1 to R-3.

[0022] [Chemical Formula R-1]

[0023]

[0024] [Chemical Formula R-2]

[0025]

[0026] [Chemical Formula R-3]

[0027]

[0028] In chemical formulas R-1 to R-3,

[0029] R2 is a substituted or unsubstituted vinyl group, a substituted or unsubstituted epoxy group, or a C1 to C20 alkyl group substituted with an epoxy group and / or a vinyl group.

[0030] L3 and L4 are each independently a substituted or unsubstituted C1 to C10 alkyl group, and

[0031] m is 0 or 1.

[0032] The functional group represented by chemical formula 1 can be any one selected from chemical formula 1-1 to chemical formula 1-4.

[0033] [Chemical Formula 1-1]

[0034]

[0035] [Chemical Formula 1-2]

[0036]

[0037] [Chemical Formula 1-3]

[0038]

[0039] [Chemical Formula 1-4]

[0040]

[0041] In chemical formulas 1-1 to 1-4,

[0042] n is an integer between 2 and 10.

[0043] The functional group represented by chemical formula 1 can be derived from the compound represented by chemical formula 2.

[0044] [Chemical Formula 2]

[0045]

[0046] In chemical formula 2,

[0047] X is a sulfur atom or an oxygen atom.

[0048] R1 is a monovalent functional group that includes a reactive group and a C3 to C20 cycloalkane ring.

[0049] L1 and L2 are each independently a substituted or unsubstituted C1 to C20 alkyl group, and

[0050] n is an integer between 2 and 10.

[0051] In chemical formula 2, the definitions of reactive groups, X, R1, L1, L2 and n are as described above.

[0052] The compound represented by chemical formula 2 may be a compound represented by any one of chemical formulas 2-1 to 2-4.

[0053] [Chemical Formula 2-1]

[0054]

[0055] [Chemical Formula 2-2]

[0056]

[0057] [Chemical Formula 2-3]

[0058]

[0059] [Chemical Formula 2-4]

[0060]

[0061] In chemical formulas 2-1 to 2-4,

[0062] n is an integer between 2 and 10.

[0063] The curable composition may be a solvent-free curable composition.

[0064] The solvent-free curable composition may include 5% to 60% by weight of quantum dots and 40% to 95% by weight of polymerizable compounds, based on the total amount of solvent-free curable composition.

[0065] The curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0066] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0067] The curable composition may further include malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorinated surfactants, or combinations thereof.

[0068] Quantum dots may include cadmium-free light-emitting materials.

[0069] Quantum dots may have a core / shell structure of InP / ZnS or a core / first shell / second shell structure of InP / ZnSe / ZnS.

[0070] A quantum dot may include: a core comprising Ag, In, Ga and S; and a shell comprising at least two selected from Ag, Ga, Zn and S.

[0071] The curable component may further include a solvent.

[0072] The curable components may include 1% to 40% by weight of quantum dots; 1% to 20% by weight of polymerizable compounds; and 40% to 80% by weight of solvents, based on the total amount of curable components.

[0073] Some exemplary embodiments provide a cured layer manufactured using a curable composition.

[0074] Some exemplary embodiments provide a display device including a cured layer.

[0075] Other exemplary embodiments are included in the following detailed description.

[0076] By using a quantum dot surface-modifying material with an unprecedented composition to surface-modify the quantum dots in a curable composition containing quantum dots, the reliability and optical properties of the curable composition containing quantum dots can be improved.

Implementation Method

[0078] Exemplary embodiments of the present disclosure are described in more detail below. However, these exemplary embodiments are illustrative, and the present disclosure is not limited thereto.

[0079] As used herein, unless otherwise specifically defined, "alkyl group" refers to C1 to C20 alkyl, "alkenyl group" refers to C2 to C20 alkenyl, "cycloalkenyl group" refers to C3 to C20 cycloalkenyl, "heterocycloalkenyl group" refers to C3 to C20 heterocycloalkenyl (or C1 to C20 heterocycloalkenyl), "aryl group" refers to C6 to C20 aryl, "arylalkyl group" refers to C6 to C20 arylalkyl (or C7 to C20 arylalkyl), "alkylene group" refers to C1 to C20 arylalkyl, "arylene group" refers to C6 to C20 arylene, and "alkylarylene group" refers to C6 to C20 arylene. "group" refers to C6 to C20 alkylaryl (or C7 to C20 alkylaryl), "heteroarylene group" refers to C3 to C20 heteroaryl (or C1 to C20 heteroaryl), and "alkoxylene group" refers to C1 to C20 alkoxy.

[0080] As used herein, unless otherwise specifically defined, "substituted" means by replacing at least one hydrogen atom with a substituent selected from the following: a halogen atom (F, Cl, Br or I), hydroxyl, hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, imino, azido, amido, hydrazyl, hydrazinyl, carbonyl, aminomethyl, thiol, ester, ether, carboxyl or a salt thereof. The substituent selected from the following groups—sulfonic acid group or its salt, phosphoric acid group or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocyclic alkyl group, C2 to C20 heterocyclic alkenyl group, C2 to C20 heterocyclic alkynyl group, C3 to C20 heteroaryl group, or combinations thereof—replaces at least one hydrogen atom.

[0081] As used herein, unless otherwise specifically defined, "hetero" means a chemical formula that includes at least one heteroatom of N, O, S and P.

[0082] As used herein, unless otherwise specifically defined, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid".

[0083] As used herein, the term “combination” means a mixture and / or copolymerization unless otherwise specified (e.g., when) a specific definition is not provided.

[0084] As used herein, if (for example, when) no other definition is provided, or if (for example, when) a chemical bond is not drawn where it should be in the chemical formula, then a hydrogen bond is formed at that position.

[0085] In exemplary embodiments, as used herein, unless otherwise defined, "*" refers to a connection point with the same atom or chemical formula or a different atom or chemical formula.

[0086] Curable compositions containing quantum dots according to exemplary embodiments of the present disclosure may use surface-modifying materials with novel structures to surface-modify quantum dots, achieving high heat / light resistance compared to other curable compositions containing quantum dots.

[0087] In accordance with recent trends in the display field, where light sources have been replaced from organic light-emitting diodes (OLEDs) to micro light-emitting diodes (LEDs), the light resistance of films installed inside displays has become more important than ever. Therefore, the light resistance of cured layers formed by curing curable components containing quantum dots has also become crucial for improvement. However, using quantum dot surface modifiers alone cannot guarantee excellent film light resistance and is insufficient for use in micro LED light sources.

[0088] Generally, to improve the curing speed of a molecular dot-curable composition, it is necessary to use additional highly sensitive initiators and / or multifunctional monomers. While the aforementioned prior art, by selecting specific groups or configurations, may improve one of the properties of the molecular dot-curable composition, such as dispersibility, heat resistance, or curing speed, it will reduce other properties besides the improved one. Regarding the properties of molecular dot-curable compositions, no technology has yet been found that can maintain low viscosity and achieve high lightfastness.

[0089] For example, existing technologies to date include encapsulating the surface of quantum dots with polymers or organic materials such as siloxanes (or TEOS (tetraethoxysilane)) containing heat-resistant functional groups, or encapsulating the surface of quantum dots with aluminum, titanium, or their oxides. Recently, attempts have been made to simultaneously increase brightness and durability by doping small amounts of transition metals (Cu, Mn, etc.) during quantum dot synthesis.

[0090] However, the above methods are still in academic research and far from being practically applied to displays. Generally speaking, for displays using quantum dots, efforts are made to increase the intensity of the light source to improve brightness. However, if (for example, when) brightness is improved by increasing the intensity of the light source, the stability of the quantum dot particles will decrease, which inevitably leads to technical challenges in improving panel reliability.

[0091] Therefore, the inventors of this disclosure have conducted repeated studies and completed curable compositions with excellent heat / light resistance reliability by increasing the dispersibility of quantum dots. For example, curable compositions according to some exemplary embodiments include (A) quantum dots comprising functional groups represented by chemical formula 1; and (B) polymerizable compounds.

[0092] [Chemical Formula 1]

[0093]

[0094] In chemical formula 1,

[0095] X is a sulfur atom or an oxygen atom.

[0096] R1 is a monovalent functional group including a reactive group and a C3 to C20 cycloalkane ring.

[0097] L1 and L2 are each independently a substituted or unsubstituted C1 to C20 alkyl group, and

[0098] n is an integer between 2 and 10.

[0099] For example, in chemical formula 1, n can be an integer from 2 to 8.

[0100] For example, reactive groups may include carbon-carbon double bonds, epoxy groups, or combinations thereof.

[0101] Hereinafter, each component constituting a curable composition according to some exemplary embodiments will be further described.

[0102] Quantum dots

[0103] As organic material ligands, the most effective ligands for passivating quantum dot surfaces are considered to be ligands with thiol groups. Among them, carboxylic acid-type ligands have relatively weak interactions with quantum dot surfaces, while phosphoric acid-type ligands have sufficient quantum dot dispersibility but have the problem of reduced efficiency (causing color changes).

[0104] As display technology has evolved from LCD to OLED, NED and more recently micro LED, which gradually increases the intensity of blue light, the durability of quantum dots (e.g., heat resistance and light resistance) also needs to be significantly improved compared to the current level.

[0105] Therefore, this disclosure uses thiol-based ligands, which include a large cycloalkyl group (including a fused ring group) having a carbon-carbon double bond and / or an epoxy group at the end as a reactive group, and having a high binding energy with the quantum dot surface for effective passivation of the quantum dot surface, while (e.g., simultaneously) controlling the structure such that the linking group between the thiol group and the cycloalkyl group is suitably or necessary to be composed of a highly polar oxyalkylene group, so as to obtain a quantum dot-containing curable composition with excellent heat / light resistance reliability, which maintains its initial luminous efficiency even when (e.g., when) exposed to strong blue light such as micro LEDs for a long time, and if (e.g., when) the quantum dot-containing curable composition modified with the above-mentioned ligand surface is mounted on a display panel in a single film state. Highly polar oxoalkyl groups can improve the dispersibility of quantum dots, and under this premise, reactive groups attached to the terminal macrocycloalkyl groups (including fused cycloalkyl groups) can improve lightfastness. If, for example, other linking groups such as ester groups are included in addition to oxoalkyl groups, not only the dispersibility of quantum dots may deteriorate, but also the heat resistance, lightfastness, and optical properties may deteriorate.

[0106] For example, in chemical formula 1, R1 can be represented by any one of chemical formulas R-1 to R-3.

[0107] [Chemical Formula R-1]

[0108]

[0109] [Chemical Formula R-2]

[0110]

[0111] [Chemical Formula R-3]

[0112]

[0113] In chemical formulas R-1 to R-3,

[0114] R2 is a substituted or unsubstituted vinyl group, a substituted or unsubstituted epoxy group, or a C1 to C20 alkyl group substituted with an epoxy group and / or a vinyl group.

[0115] L3 and L4 are each independently a substituted or unsubstituted C1 to C10 alkyl group, and

[0116] m is 0 or 1.

[0117] Because the larger the cycloalkane ring of R¹, the better it can protect the quantum dot from external light, it is advantageous for R¹ to exist in the form of a fused ring including a cycloalkane ring. Therefore, in chemical formulas R-1 and R-2, m can be 1. In exemplary embodiments, this can also be advantageous in terms of improved reliability.

[0118] For example, the functional group represented by chemical formula 1 may be represented by any one of chemical formulas 1-1 to 1-4, but is not necessarily limited to this.

[0119] [Chemical Formula 1-1]

[0120]

[0121] [Chemical Formula 1-2]

[0122]

[0123] [Chemical Formula 1-3]

[0124]

[0125] [Chemical Formula 1-4]

[0126]

[0127] In chemical formulas 1-1 to 1-4,

[0128] n is an integer from 2 to 10, for example, an integer from 2 to 8.

[0129] In an exemplary embodiment, the functional group represented by chemical formula 1 may be derived from (e.g., formed by) a compound represented by chemical formula 2.

[0130] [Chemical Formula 2]

[0131]

[0132] In chemical formula 2,

[0133] X is a sulfur atom or an oxygen atom.

[0134] R1 is a monovalent functional group that includes a reactive group and a C3 to C20 cycloalkane ring.

[0135] L1 and L2 are each independently a substituted or unsubstituted C1 to C20 alkyl group, and

[0136] n is an integer from 2 to 10, for example, an integer from 2 to 8.

[0137] For example, a curable composition according to some exemplary embodiments includes (A) quantum dots surface-modified with a surface-modifying material; and (B) a polymerizable compound, wherein the surface-modifying material may include a compound represented by chemical formula 2.

[0138] R1 can be defined as described above. In an exemplary embodiment, the reactive group, R1, L1, L2 and n in Formula 2 can also be defined as described above.

[0139] For example, a compound represented by chemical formula 2 may be represented by any one of chemical formulas 2-1 to 2-4, but is not necessarily limited to this.

[0140] [Chemical Formula 2-1]

[0141]

[0142] [Chemical Formula 2-2]

[0143]

[0144] [Chemical Formula 2-3]

[0145]

[0146] [Chemical Formula 2-4]

[0147]

[0148] In chemical formulas 2-1 to 2-4,

[0149] n is an integer from 2 to 10, for example, an integer from 2 to 8.

[0150] If, for example, quantum dots that have been surface-modified with a surface-modifying material are added to a polymerizable compound further described herein and stirred, a very transparent dispersion can be obtained, which is a criterion for confirming that the surface modification of the quantum dots is very good.

[0151] For example, quantum dots can have a maximum fluorescence emission wavelength between 500 nanometers and 680 nanometers.

[0152] For example, if (e.g., when) the curable composition according to some exemplary embodiments is a solvent-free curable composition, it may include an amount of quantum dots from 5 wt% to 60 wt%, such as 10 wt% to 60 wt%, such as 20 wt% to 60 wt%, or such as 30 wt% to 50 wt%. If (e.g., when) quantum dots within the above range are included, high light retention rate and light efficiency can be achieved even after curing.

[0153] For example, if (e.g., when) the curable composition according to some exemplary embodiments is a curable composition comprising a solvent, the total amount of the curable composition may include quantum dots in amounts ranging from 1% to 40% by weight, or for example, from 3% to 30% by weight. If (e.g., when) quantum dots within the above range are included, the light conversion efficiency is improved and the patterning and developing properties are not compromised, thus achieving excellent processability.

[0154] To date, curable components (inks) including quantum dots have been developed specifically for use with thiol adhesives or monomers that are well compatible with quantum dots, and some are even being commercialized.

[0155] For example, a quantum dot absorbs light in the wavelength region of 360 nm to 780 nm, or for example, in the wavelength region of 400 nm to 780 nm, and emits fluorescence in the wavelength region of 500 nm to 700 nm, or for example, in the wavelength region of 500 nm to 580 nm, or in the wavelength region of 600 nm to 680 nm. In an exemplary embodiment, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λem) at 500 nm to 680 nm.

[0156] Quantum dots can each independently have a full width at half maximum (FWHM) of 20 nanometers to 100 nanometers, for example, 20 nanometers to 50 nanometers. If (for example, when) quantum dots have a full width at half maximum (FWHM) within the above range, if (for example, when) they are used as color materials in color filters, color reproducibility is increased due to high color purity.

[0157] Quantum dots can be organic materials, inorganic materials, or mixtures of organic and inorganic materials, each independently.

[0158] Quantum dots may each be composed independently of a core and a shell surrounding (e.g., around) the core, and the core and shell may each have the following structures: cores of Group II to Group IV, Group III to Group V and the like, core / shell, core / first shell / second shell, alloy, alloy / shell, etc., but not limited thereto.

[0159] For example, the core may include at least one material selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not limited thereto. The shell surrounding (e.g., around) the core may include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.

[0160] In some exemplary embodiments, due to the increasing global concern for the environment and the strengthened management of toxic materials, environmentally friendly cadmium-free luminescent materials (InP / ZnS, InP / ZnSe / ZnS, etc.) with extremely low quantum efficiency (quantum yield) are used instead of luminescent materials with cadmium-based cores, but this is not necessarily limited to these. In exemplary embodiments, the term "cadmium-free" means substantially free of or completely free of cadmium, where "substantially free of" means that the referenced component, if present, exists only as an incidental impurity.

[0161] In some exemplary embodiments, the quantum dot may be a core comprising Ag, In, Ga, and S; and a shell comprising at least two (or at least three) selected from Ag, Ga, Zn, and S. In this case, the quantum dot may have one or more ligands. For example, the quantum dot may include, but is not necessarily limited to, a first ligand comprising a halide, a second ligand comprising an alkyl and / or alkoxyamine group, or a combination thereof, but is not necessarily limited to these.

[0162] In an exemplary embodiment of the core / shell structured quantum dot, the entire size (average particle size) including the shell may be 1 nanometer to 15 nanometers, or for example 5 nanometers to 15 nanometers.

[0163] For example, quantum dots may independently include red quantum dots, green quantum dots, or combinations thereof. Red quantum dots may independently have an average particle size of 10 nanometers to 15 nanometers. Green quantum dots may independently have an average particle size of 5 nanometers to 8 nanometers.

[0164] In exemplary embodiments, for the dispersion stability of quantum dots, the curable composition according to some exemplary embodiments may further include a dispersant. The dispersant helps to provide uniform (e.g., substantially uniform) dispersion of light conversion materials such as quantum dots in the curable composition and may include nonionic, anionic, and / or cationic dispersants. For example, the dispersant may be polyalkyl glycols and / or their esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonates, sulfonates, carboxylates, carboxylates, alkyl amide alkylene oxide addition products, alkylamines, etc., and may be used alone or in mixtures of two or more. The dispersant may be used in amounts from 0.1% by weight to 100% by weight, for example, from 10% by weight to 20% by weight, based on the solids content of the light conversion material such as quantum dots.

[0165] Polymerizable compounds

[0166] A curable composition according to some exemplary embodiments may include a polymerizable compound, and the polymerizable compound may have a carbon-carbon double bond at its end.

[0167] The total amount of the solvent-free curable composition may include 40% to 95% by weight, for example, 50% to 90% by weight, of a polymerizable compound having carbon-carbon double bonds at the ends. If (for example, when) a polymerizable compound having carbon-carbon double bonds at the ends within the above range is included, a solvent-free curable composition having a viscosity suitable for jetting inks can be prepared, and the quantum dots in the prepared solvent-free curable composition can have improved dispersibility, thereby improving optical properties. For example, the polymerizable compound having carbon-carbon double bonds at the ends may have a molecular weight of 170 g / mol to 1,000 g / mol. If (for example, when) a polymerizable compound having carbon-carbon double bonds at the ends has a molecular weight within the above range, it may be beneficial or advantageous for jetting inks because it does not increase the viscosity of the composition without impairing the optical properties of the quantum dots.

[0168] For example, a polymerizable compound having a carbon-carbon double bond at the end can be represented by chemical formula 3, but is not necessarily limited to this.

[0169] [Chemical Formula 3]

[0170]

[0171] In chemical formula 3,

[0172] R6 and R7 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0173] L8 and L10 are each independently a single-bonded or substituted or unsubstituted C1 to C10 alkyl group.

[0174] L9 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group or ether group (*-O-*).

[0175] For example, a polymerizable compound having a carbon-carbon double bond at the end may be represented by chemical formula 3-1, chemical formula 3-2 or chemical formula 3-3, but is not necessarily limited to these.

[0176] [Chemical Formula 3-1]

[0177]

[0178] [Chemical Formula 3-2]

[0179]

[0180] [Chemical Formula 3-3]

[0181]

[0182] For example, in addition to the compounds represented by chemical formula 3-1, chemical formula 3-2 or chemical formula 3-3, polymerizable compounds having carbon-carbon double bonds at the ends may further include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanedioldiacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, and bisphenol A diacrylate. diacrylate), trimethylolpropanetriacrylate, novolac epoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanedioldimethacrylate, 1,6-hexanedioldimethacrylate, or combinations thereof.

[0183] In an exemplary embodiment, the monomer, along with the monomer having a carbon-carbon double bond at the end, may further include any monomer commonly used in suitable thermosetting or photocurable compositions. For example, the monomer may further include oxetane-based compounds, such as bis[1-ethyl (3-oxetanyl)]methyl ether.

[0184] In an exemplary embodiment, if (for example, when) the curable composition includes a solvent, the amount of polymerizable compound may include 1% to 20% by weight, 1% to 15% by weight, or, for example, 5% to 15% by weight, based on the total amount of the curable composition. If (for example, when) the polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved, and suitable or sufficient curing occurs after exposure during the patterning process, thus improving reliability, and also improving the heat resistance, light resistance, chemical resistance, resolution, and adhesion of the pattern.

[0185] In an exemplary embodiment, if (for example, when) the curable composition includes a solvent, the polymerizable compound may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenic unsaturated double bond.

[0186] Because the polymerizable compound has olefinic unsaturated double bonds, it undergoes suitable or sufficient polymerization after exposure in the patterning process, thereby forming a pattern with excellent heat resistance, light resistance and chemical resistance.

[0187] Examples of polymerizable compounds used in solvent-based curable compositions may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neoopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate Epoxy(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, trimethylol propane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolacepoxy(meth)acrylate, etc.

[0188] Examples of commercially available polymerizable compounds are as follows. Examples of monofunctional esters of (meth)acrylic acid may include Aronix M-101®, M-111®, and M-114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S® and TC-120S® from Nihon Kayaku Co., Ltd.; and V-158® and V-2311® from Osaka Yuki Chemical Industry Co., Ltd. Examples of difunctional esters of (meth)acrylic acid include Aronix M-210®, M-240®, and M-6200® from Toa Synthetic Chemical Industries, Ltd.; KAYARAD HDDA®, HX-220®, and R-604® from Nippon Kayaku Co., Ltd.; and V-260®, V-312®, and V-335 HP® from Osaka Organic Chemical Industries, Ltd. Examples of trifunctional esters of (meth)acrylic acid may include Aronix M-309®, DONG M-400®, DONG M-405®, DONG M-450®, DONG M-7100®, DONG M-8030®, and DONG M-8060® from Toa Synthetic Chemicals, Inc.; KAYARAD TMPTA®, DONG DPCA-20®, DONG-30®, DONG-60®, and DONG-120® from Nippon Kayaku Co., Ltd.; and V-295®, DONG-300®, DONG-360®, DONG-GPT®, DONG-3PA®, and DONG-400® from Osaka Yuki Kayaku Industry Co., Ltd. These products may be used alone or in combination of two or more.

[0189] Polymerizable compounds can also be used by treating them with acid anhydrides to provide better developability.

[0190] Light diffusing agent

[0191] The curable composition according to some exemplary embodiments may further include a light diffusing agent.

[0192] For example, light diffusing agents may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0193] The light diffusing agent can reflect light that has not been absorbed in the aforementioned quantum dots and allow the quantum dots to reabsorb the reflected light. For example, the light diffusing agent can increase the amount of light absorbed by the quantum dots and increase the light conversion efficiency of the curable composition.

[0194] The light diffusing agent may have an average particle size (D50) of 150 nm to 250 nm, or for example, 180 nm to 230 nm. If (for example, when) the average particle size of the light diffusing agent is within the above range, it may have better light diffusion effect and improve light conversion efficiency.

[0195] The curable composition may include 1% to 20% by weight, for example 2% to 15% by weight, or for example 2% to 10% by weight of a light diffusing agent, based on the total amount of the curable composition. If less than 1% by weight of a light diffusing agent is included, it is difficult to expect an improvement in light conversion efficiency due to the use of the light diffusing agent, based on the total amount of the curable composition; however, if more than 20% by weight of a light diffusing agent is included, there is a possibility that quantum dots may be deposited.

[0196] The curable composition according to some exemplary embodiments may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0197] The photopolymerization initiator can be any initiator commonly used in photosensitive resin compositions, such as acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, aminoketone-based compounds, etc., but is not necessarily limited to these.

[0198] Examples of acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-butyltrichloroacetophenone, and p-butyldichloroacetophenone. Acetofenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0199] Examples of benzophenone-based compounds include benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0200] Examples of thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0201] Examples of benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, etc.

[0202] Examples of triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine (2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthyl)-s-triazine, and 2-(naphthyl)-s-triazine. Phenol-1-yl)-4,6-bis(trichloromethyl)-s-triazine (2-(naphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine (2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine), 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine (2-4-bis(trichloromethyl)-6-piperonyl-s-triazine), 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0203] Examples of oxime-based compounds include O-acyloxime-based compounds. Compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octandione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Examples of O-oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, and 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate. Physyl(phenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate, etc.

[0204] Examples of aminoketone-based compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc.

[0205] In addition to the other compounds disclosed herein, photopolymerization initiators may further include thiozolium compounds, diketone compounds, sulfonium borate-based compounds, diazo compounds, imidazole compounds, biimidazole compounds, etc.

[0206] The photopolymerization initiator can be used with a photosensitizer that can initiate a chemical reaction by absorbing light and becoming excited and then transferring its energy.

[0207] Examples of photosensitizers may include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc.

[0208] Examples of thermal polymerization initiators may be peroxides, such as benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydrogen peroxide (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azo-bis(isobutyronitrile), t-butyl perbenzoate. perbenzoate, for example 2,2'-azobis-2-methylpropinonitrile, but not necessarily limited thereto, and any suitable alternative commonly used by one of ordinary skill in the art may be used.

[0209] Based on the total amount of the curable component, it may include an amount from 0.01 wt% to 10 wt%, or for example, from 2 wt% to 8 wt% of a polymerization initiator. If a polymerization initiator within the above range is included (for example, when) it is included, it is possible to obtain excellent reliability due to proper or sufficient curing during exposure and / or thermal curing, and to prevent or reduce the degradation of transmittance due to non-reactive initiators, thereby preventing or reducing the degradation of the optical properties of the quantum dots.

[0210] Adhesive resin

[0211] The curable composition according to some exemplary embodiments may further include binder resin.

[0212] Adhesive resins may include acrylic resins, cardo-based resins, epoxy resins, or combinations thereof.

[0213] The acrylic resin may be a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer that can be copolymerized therewith, and may be a resin comprising at least one acrylic repeating unit.

[0214] Examples of acrylic resins may be polybenzylmethacrylate, (meth)acrylic acid / benzylmethacrylate copolymer, (meth)acrylic acid / benzylmethacrylate / styrene copolymer, (meth)acrylic acid / benzylmethacrylate / 2-hydroxyethylmethacrylate copolymer, (meth)acrylic acid / benzylmethacrylate / styrene / 2-hydroxyethylmethacrylate copolymer, etc., but are not limited thereto, and may be used alone or as a mixture of two or more.

[0215] The weight average molecular weight of the acrylic resin can be from 5,000 g / mole to 15,000 g / mole. If (for example, when) the acrylic resin has a weight average molecular weight within the above range, it improves the close contact properties with the substrate, physical and chemical properties, and the viscosity is suitable or appropriate.

[0216] The acid value of the acrylic resin can be from 80 mg KOH / g to 130 mg KOH / g. If (for example, when) the acrylic resin has an acid value within the above range, excellent pixel resolution can be obtained.

[0217] Fluorene resins may be any suitable one used in curable resin (or photosensitive resin) compositions, such as one suggested in Korean Patent Publication No. 10-2018-0067243, the contents of which are incorporated herein by reference and may be used, but are not limited thereto.

[0218] Fluorene resins can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds, such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds, such as benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; diols, such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohols, such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent-based compounds, such as propylene glycol methylethylacetate and N-methylpyrrolidone; phosphorus compounds, such as triphenylphosphine.And amine or ammonium salt compounds, such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and / or benzyl triethylammonium chloride.

[0219] The weight average molecular weight of the fluorene resin can be from 500 g / mole to 50,000 g / mole, for example from 1,000 g / mole to 30,000 g / mole. If (for example, when) the weight average molecular weight of the fluorene resin is within the above range, a suitable or satisfactory pattern can be formed without residue during the manufacture of the cured layer and without loss of film thickness during the development of the curable composition.

[0220] If (for example, when) the adhesive resin is a fluorene resin, the curable components thereof, such as photosensitive resin components, have excellent developability and photosensitivity during photocuring, and therefore have fine pattern-forming capability.

[0221] The epoxy resin may be a thermally polymerizable monomer and / or a thermally polymerizable oligomer, and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0222] Epoxy resin may further include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin, and / or aliphatic polyglycidyl ether, but is not limited thereto.

[0223] As commercially available products of the compound, bisphenyl epoxy resin may be YX4000, YX4000H, YL6121H, YL6640 and / or YL6677 of Yuka Shell Epoxy Co., Ltd.; cresol novolac epoxy resin may be EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and / or EOCN-1027 and / or EPIKOTE 180S75 of Nippon Kayaku Co., Ltd.; bisphenol A epoxy resin may be EPIKOTE of Yuka Shell Epoxy Co., Ltd. 1001, 1002, 1003, 1004, 1007, 1009, 1010 and / or 828; bisphenol F epoxy resin may be EPIKOTE 807 and / or 834 from Yuxiang Shell Epoxy Limited; phenol novolac epoxy resin may be EPIKOTE 152, 154 and / or 157H65 from Yuxiang Shell Epoxy Limited and / or EPPN 201, 202 from Nippon Chemical Co., Ltd.; cyclic aliphatic epoxy resin may be from Ciba-Geigy AG. CY175, CY177 and / or CY179 of Union Carbide Corporation (UCC), ERL-4234, ERL-4299, ERL-4221 and / or ERL-4206 of Showa Denko KK, Showdyne 509 of Showa Denko KK, Araldite CY-182, CY-192 and / or CY-184 of Ciba Geggi, and Dainippon Ink & Chemicals Inc.EPICLON 200 and / or 400 from Shell Epoxy Co., Ltd., EPIKOTE 871 and / or 872 and / or EP1032H60 from Shell Epoxy Co., Ltd., and ED-5661 and / or ED-5662 from Celanese Coating Corporation; aliphatic polyglycidyl ether can be EPIKOTE 190P and / or 191P from Shell Epoxy Co., Ltd., EPOLITE 100MF from Kyoeisha Yushi Kagaku Kogyo Co., Ltd., and EPIOL TMP from Nihon Yushi KK, etc.

[0224] For example, based on the total amount of the curable composition, if (e.g., when) the curable composition according to some exemplary embodiments is a solvent-free curable composition, it may include 0.5% to 10% by weight, for example, 1% to 5% by weight, of an amount of adhesive resin. In exemplary embodiments, the heat resistance and chemical resistance of the solvent-free curable composition, as well as the storage stability of the composition, may be improved.

[0225] For example, based on the total amount of the curable composition, if (e.g., when) the curable composition according to some exemplary embodiments is a curable composition including a solvent, it may include 1% to 30% by weight, or for example 3% to 20% by weight, an amount of adhesive resin. In exemplary embodiments, this can improve patterning properties, heat resistance, and chemical resistance.

[0226] Other additives

[0227] To improve the stability and dispersibility of quantum dots, the curable composition according to some exemplary embodiments may further include polymerization inhibitors.

[0228] Polymerization inhibitors may include, but are not limited to, hydroquinone-based compounds, catechol-based compounds, or combinations thereof. If (for example, when) the curable composition according to some exemplary embodiments further includes hydroquinone-based compounds, catechol-based compounds, or combinations thereof, room temperature cross-linking may be prevented or reduced during exposure after coating the curable composition.

[0229] For example, hydroquinone compounds, catechol compounds or combinations thereof may be hydroquinone, methyl hydroquinone, methoxy hydroquinone, tributyl hydroquinone, 2,5-di-tributyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tributylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum or combinations thereof, but are not necessarily limited thereto.

[0230] Hydroquinone-based compounds, catechol compounds, or combinations thereof may be used in a dispersed form. Based on the total amount of the curable component, it may include an amount from 0.001% to 3% by weight, or, for example, 0.01% to 2% by weight of a polymerization inhibitor in dispersed form. If (e.g., when) a polymerization inhibitor within the above range is included, the passage of time at room temperature can be addressed or stabilized, and simultaneously (e.g., concurrently) sensitivity deterioration and surface delamination phenomenon can be prevented or reduced.

[0231] In exemplary embodiments, the curable composition according to some exemplary embodiments may further include malonic acid, 3-amino-1,2-propanediol, silane-based coupling agent, leveling agent, fluorine-based surfactant, or combinations thereof to improve heat resistance and reliability.

[0232] For example, the curable composition according to the exemplary embodiment may further include a silane coupling agent having reactive substituents such as vinyl, carboxyl, methacryloxy, isocyanate, epoxy, etc., in order to improve the tight contact properties with the substrate.

[0233] Examples of silane coupling agents may be trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in mixtures of two or more.

[0234] A silane coupling agent comprising 0.01 to 10 parts by weight may be used per 100 parts by weight of curable composition. When a silane coupling agent within the above range is included (for example, when) it can improve tight contact properties, storage capacity, etc.

[0235] In an exemplary embodiment, the curable component may further include surfactants, such as fluorinated surfactants, as needed, to improve coating properties and inhibit or reduce spot formation, for example, to improve leveling performance.

[0236] Fluorinated surfactants may have a low weight-average molecular weight of 4,000 g / mol to 10,000 g / mol, or, for example, 6,000 g / mol to 10,000 g / mol. In an exemplary embodiment, the fluorinated surfactant may have a surface tension of 18 mN / m to 23 mN / m (measured in a 0.1% solution of polyethylene glycol monomethyl ether acetate (PGMEA)). Leveling performance may be further improved if (for example, when) the fluorinated surfactant has a weight-average molecular weight and surface tension within the above range, and excellent properties may be provided if (for example, when) it is applied as a high-speed slit coating, because fewer film defects are generated by preventing or reducing spot formation and suppressing or reducing vapor generation during high-speed coating.

[0237] Examples of fluorinated surfactants include: BM-1000® and / or BM-1100® from BM Chemie Inc.; MEGAFACE F 142D®, F 172®, F 173® and / or F 183® from Dainippon Ink Kagaku Kogyo Co., Ltd.; FL U ORAD FC-135®, FL U ORAD FC-170C®, FL U ORAD FC-430® and / or FL U ORAD FC-431® from Sumitomo 3M Co., Ltd.; and SURFLON S-112®, SURFLON S-113®, SURFLON S-131®, and SURFLON S-131® from ASAHI Glass Co., Ltd. S-141® and / or SURFLON S-145®; and / or SH-28PA®, SH-190®, SH-193®, SZ-6032® and / or SF-8428® from Toray Silicone Co., Ltd.; and F-482, F-484, F-478, F-554 from DIC Co., Ltd.

[0238] In exemplary embodiments, in addition to fluorinated surfactants, the curable composition according to some exemplary embodiments may also include silicone-based surfactants. Examples of silicone-based surfactants may be, but are not limited to, TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba Silicon Co., Ltd.

[0239] Based on 100 parts by weight of the curable composition, it may include 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, of a surfactant. If (for example, when) a surfactant within the above range is included, fewer foreign matter is generated in the sprayed composition.

[0240] In an exemplary embodiment, unless the properties deteriorate, the curable composition according to some exemplary embodiments may further include other additives, such as antioxidants, stabilizers, etc., in a set or predetermined amount.

[0241] solvent

[0242] The curable composition according to some exemplary embodiments may further include a solvent.

[0243] Solvents may include, for example, alcohols, such as methanol, ethanol, etc.; glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; cellosol acetates, such as methyl cellosol acetate, ethyl cellosol acetate, diethyl cellosol acetate, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, methyl n-acetone, etc. Butanone, methyl pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters, such as methyl lactate, ethyl lactate, etc.; alkyl glycolic acid esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkyl acetate alkoxylates, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionic acid esters, such as methyl 3-hydroxypropionic acid, ethyl 3-hydroxypropionic acid, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, 3-ethoxy... Ethyl propionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-hydroxypropionate, etc. 2-Hydroxy-2-methylethyl ester, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, etc.; and / or keto esters, such as ethyl pyruvate, etc., and in exemplary embodiments, may be N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetoacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., but not limited thereto.

[0244] For example, the solvent may suitably or ideally be a glycol ether, such as ethylene glycol monoethylether, ethylene diglycolmethylethylether, etc.; ethylene glycol alkylether acetates, such as ethyl cellosolve acetate, etc.; esters, such as 2-hydroxyethyl propionate, etc.; carbitol, such as diethylene glycol monomethylether, etc.; propylene glycol alkylether acetates, such as propylene glycol monomethylether acetate, propylene glycol propylether acetate, etc.; alcohols, such as ethanol, cyclohexyl acetate, or combinations thereof.

[0245] For example, the solvent may be a high-boiling-point polar solvent, including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, cyclohexyl acetate, or combinations thereof.

[0246] The solvent may be included in an amount of 40% to 80% by weight, or for example, 45% to 80% by weight, based on the total amount of the curable component. If (for example, when) the solvent is within the above range, the solvent-based curable component has a suitable or appropriate viscosity, and therefore may have excellent coating characteristics if (for example, when) it is applied over a large area by spin coating and / or slot coating.

[0247] Some exemplary embodiments provide a cured layer manufactured using the aforementioned curable composition, a color filter including the cured layer, and a display device including the color filter. For example, the display device may include a miniature LED light source.

[0248] An exemplary embodiment of a method for manufacturing a cured layer includes applying a curable composition and a solvent-based curable composition onto a substrate to form a pattern using an ink-jet spraying method (S1); and curing the pattern (S2).

[0249] (S1) Pattern Formation

[0250] The curable composition can be suitably or desirablely coated on a substrate in an inkjet spraying method to a size of 0.5 micrometers to 20 micrometers. The inkjet spraying method can form a pattern by spraying a single color according to each nozzle and thus repeating the spraying multiple times according to the desired number of colors, but the pattern can be formed by simultaneously (e.g., concurrently) spraying the desired number of colors through each inkjet nozzle to reduce the process.

[0251] (S2) Curing

[0252] The obtained pattern is cured to obtain pixels. In an exemplary embodiment, the curing method may be a thermosetting process and / or a photocuring process. The thermosetting process may be performed at 100 degrees Celsius or higher, suitably or desirablely in the range of 100 degrees Celsius to 300 degrees Celsius, and for example in the range of 160 degrees Celsius to 250 degrees Celsius. The photocuring process may include irradiation with actinic rays, such as UV rays of 190 nanometers to 450 nanometers or, for example, 200 nanometers to 400 nanometers. As the light source used in the irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, i-rays, KrF, ArF, I-ArF, EUV, X-rays, and / or electron beams may be used according to exemplary embodiments.

[0253] An exemplary embodiment of the method for manufacturing a cured layer may include manufacturing the cured layer using the aforementioned curable composition by a photolithography method.

[0254] (1) Coating and film formation

[0255] Using spin and / or slit coating, roller coating, screen printing, applicator method, etc., the aforementioned curable composition is coated onto a pre-treated substrate to a suitable or desired thickness, for example, from 2 micrometers to 10 micrometers. Then, the coated substrate is heated at a temperature of 70 to 90 degrees Celsius for 1 to 10 minutes to remove the solvent and form a film.

[0256] (2) Exposure

[0257] After placing a dome having a set or predetermined shape, the resulting film is irradiated with UV rays, such as 190 nm to 450 nm, or photochemical rays, such as 200 nm to 400 nm, to form a suitable or desired pattern. As the light source used in the irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, i-rays, KrF, ArF, I-ArF, EUV, X-rays, and / or electron beams may be used according to exemplary embodiments.

[0258] In an exemplary embodiment of the exposure process, if (e.g., when) a high-pressure mercury lamp is used, a light dose of, for example, 500 mJ / cm² or less (with a 365 nm sensor) is used. However, the light dose may be appropriately varied depending on the type (or variety) of each component of the curable composition, their combination ratio, and the dry film thickness.

[0259] (3)Development

[0260] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unwanted or undesirable portions other than the exposed portions, thereby forming an image pattern. In an exemplary embodiment, if (for example, when) an alkaline developing solution is used for development, the non-exposed areas are dissolved, and an image color filter pattern is formed.

[0261] (4) Post-processing

[0262] The developed image pattern can be heated again and / or irradiated by photochemical rays to cure it, so as to achieve excellent qualities such as heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, and storage stability.

[0263] The subject matter of this disclosure is illustrated in more detail below with reference to examples. However, these examples should not in any way be construed as limiting the scope of this disclosure.

[0264] (Synthesis of surface-modifying materials)

[0265] Synthesis Example 1-1

[0266] 120 g of 5-vinyl-2-norbornene, 78.1 g of 2-mercaptoethanol, 0.3 g of AIBN, and 150 g of methanol were added to a round-bottom flask, heated to 60°C, and reacted for 6 hours. The methanol was then removed using a reduced-pressure condenser. The resulting compound was transferred to a high-pressure reactor, and 0.1 g of NaOH (KOH) was added to the compound, with the internal temperature increased to 80°C. 176 g of ethylene oxide was slowly added and allowed to react while controlling the internal pressure. The resulting compound was placed in a two-neck round-bottom flask and dissolved completely in THF (THF). At an internal temperature of 0°C, 44 g of NaOH and 100 mL of water were added and dissolved completely until a clear solution was obtained. A solution of 210 g of para-toluene sulfonyl chloride dissolved in 300 mL of THF was slowly injected at 0°C. The injection was carried out over 2 hours, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess methylene chloride was added, followed by stirring, and then a saturated solution of NaHCO3 was added, followed by extraction, titration, and removal of water. After solvent removal, the mixture was dried in a drying oven for 24 hours. The resulting dried material was placed in a double-necked round-bottom flask and thoroughly stirred in 500 mL of ethanol. Subsequently, 91.2 g of thiourea was added and dispersed, and then refluxed at 80°C for 12 hours. Then, an aqueous solution of 60 g of NaOH dissolved in 200 mL of water was injected, and after an additional 5 hours of reaction, excess methylene chloride was added to dilute it. Hydrochloric acid solution was added, and extraction, titration, removal of water, and solvent removal were carried out sequentially. The compound represented by chemical formula A-1 was obtained by drying in a vacuum oven for 24 hours.

[0267] [Chemical Formula A-1]

[0268]

[0269] Synthesis Example 2-1

[0270] 150.22 g of hydroxydicyclopentadiene and 0.1 g of KOH were placed in a high-pressure reactor, and the internal temperature was raised to 80°C. HDCP-4 was synthesized by slowly adding 176 g while controlling the internal pressure. 326.22 g of HDCP-4 was added to a double-necked round-bottom flask and dissolved completely in 800 mL of THF. At an internal temperature of 0°C, 44 g of NaOH and 100 mL of water were added and dissolved completely until a clear solution was obtained. A solution of 210 g of p-toluenesulfonyl chloride dissolved in 300 mL of THF was slowly injected at 0°C. The injection was carried out for 2 hours, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and the mixture was stirred. A saturated solution of NaHCO3 was then added, followed by extraction, titration, and removal of water. After solvent removal, the mixture was dried in a drying oven for 24 hours. 481.2 g of the obtained dried material was placed in a double-necked round-bottom flask and thoroughly stirred in 500 mL of ethanol. Then, 91.2 g of thiourea was added and dispersed, followed by reflux at 80°C for 12 hours. Next, an aqueous solution of 60 g of NaOH dissolved in 200 mL of water was injected, and after another 5 hours of reaction, excess dichloromethane was added to dilute it. Hydrochloric acid solution was added, and extraction, titration, removal of water, and removal of solvent were performed sequentially. The compound represented by chemical formula B-1 was obtained by drying in a vacuum oven for 24 hours.

[0271] [Chemical Formula B-1]

[0272]

[0273] Synthesis Example 3-1

[0274] After adding 108 g of 4-vinyl-1-cyclohexane, 78.1 g of 2-mercaptoethanol, 0.3 g of AIBN, and 150 g of methanol, the temperature was raised to 60°C, and the methanol was removed using a reduced pressure concentrator after 6 hours of reaction. The obtained compound was transferred to a high-pressure reactor, and 0.1 g of KOH was added to the compound obtained above, while the internal temperature was raised to 80°C. 176 g of KOH was slowly added and the reaction was carried out while controlling the internal pressure. The obtained compound was placed in a double-necked round-bottom flask and dissolved thoroughly in THF. At 0°C, 44 g of NaOH and 100 mL of water were added and dissolved thoroughly until a clear solution was obtained. A solution of 210 g of p-toluenesulfonyl chloride dissolved in 300 mL of THF was slowly injected at 0°C. Here, the injection was performed for 2 hours, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and stirred, followed by the addition of a saturated solution of NaHCO3, then extraction, titration, and removal of water. After solvent removal, the mixture was dried in a dry oven for 24 hours. 510 g of the dried material was placed in a double-necked round-bottom flask and thoroughly stirred in 500 mL of ethanol. Subsequently, 91.2 g of thiourea was added and dispersed, then refluxed at 80°C for 12 hours. Then, an aqueous solution obtained by dissolving 60 g of NaOH in 200 mL of water was injected, with additional stirring for 5 hours, followed by the addition of excess dichloromethane and stirring, and then the addition of an aqueous hydrochloric acid solution, followed by extraction, titration, removal of water, and removal of solvent in sequence. The compound represented by chemical formula C-1 was obtained by drying in a vacuum oven for 24 hours.

[0275] [Chemical Formula C-1]

[0276]

[0277] Synthesis Example 4-1

[0278] 124 g of 5-norbornen-2-methanol and 0.1 g of KOH were placed in a high-pressure reactor, and the internal temperature was raised to 80°C. NBM-4 was synthesized by slowly adding 176 g of KOH while controlling the internal pressure. 300 g of NBM-4 was added to a double-necked round-bottom flask and dissolved thoroughly in 800 mL of THF. At 0°C, 44 g of NaOH and 100 mL of water were added and dissolved thoroughly until a clear solution was obtained. A solution of 210 g of p-toluenesulfonyl chloride dissolved in 300 mL of THF was slowly injected at 0°C. The injection was carried out for 2 hours, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and stirred, and a saturated solution of NaHCO3 was added, followed by extraction, titration, and removal of water. After solvent removal, the material was dried in a drying oven for 24 hours. 481.2 g of the obtained dried material was placed in a double-necked round-bottom flask and thoroughly stirred in 500 mL of ethanol. Subsequently, 91.2 g of thiourea was added and dispersed, followed by reflux at 80°C for 12 hours. Then, an aqueous solution obtained by dissolving 60 g of NaOH in 200 mL of water was injected, and the mixture was stirred for another 5 hours. Excess dichloromethane was added and stirred, followed by the addition of an aqueous hydrochloric acid solution. Extraction, titration, removal of water, and solvent removal were then performed sequentially. The compound represented by chemical formula D-1 was obtained by drying in a vacuum oven for 24 hours.

[0279] [Chemical Formula D-1]

[0280]

[0281] Comparative Synthesis Example 1

[0282] 100 g of polyethylene glycol ether (Hannong Chemicals Inc.) was placed in a two-necked round-bottom flask and dissolved thoroughly in 300 mL of THF. At 0°C, 15.4 g of NaOH and 100 mL of water were added and dissolved thoroughly until a clear solution was obtained. A solution of 73 g of p-toluenesulfonyl chloride dissolved in 100 mL of THF was slowly injected at 0°C. The injection was carried out for 1 hour, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and stirring continued, followed by the addition of a saturated solution of NaHCO3, followed by extraction, titration, and removal of water. After solvent removal, the product was dried in a drying oven for 24 hours. 50 g of the dried product was added to a two-necked round-bottom flask and stirred thoroughly in 300 mL of ethanol. Subsequently, 27 g of thiourea was added and dispersed, followed by reflux at 80°C for 12 hours. Then, an aqueous solution obtained by dissolving 4.4 g of NaOH in 20 mL of water was injected, and the mixture was stirred for another 5 hours. Excess dichloromethane was added and stirred, followed by the addition of an aqueous hydrochloric acid solution. Extraction, titration, removal of water, and solvent removal were then performed sequentially. The compound represented by the chemical formula W was obtained by drying in a vacuum oven for 24 hours.

[0283] [Chemical Formula W]

[0284]

[0285] Comparative Synthesis Example 2

[0286] 100 g of polyethylene glycol phenyl ether (Hannong Chemicals Inc., Ph-4) was added to a two-necked round-bottom flask and completely dissolved in 300 mL of THF. At 0°C, 15.4 g of NaOH and 100 mL of water were added and dissolved thoroughly until a clear solution was obtained. A solution of 73 g of p-toluenesulfonyl chloride dissolved in 100 mL of THF was slowly injected at 0°C. The injection was carried out for 1 hour, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and stirring continued, followed by the addition of a saturated solution of NaHCO3, followed by extraction, titration, and removal of water. After solvent removal, the product was dried in a drying oven for 24 hours. 50 g of the dried product was added to a two-necked round-bottom flask and stirred thoroughly in 300 mL of ethanol. Subsequently, 27 g of thiourea was added and dispersed, followed by reflux at 80°C for 12 hours. Then, an aqueous solution obtained by dissolving 4.4 g of NaOH in 20 mL of water was injected, and the mixture was stirred for another 5 hours. Excess dichloromethane was added and stirred, followed by the addition of an aqueous hydrochloric acid solution. Extraction, titration, removal of water, and solvent removal were then performed sequentially. The compound represented by chemical formula X was obtained by drying in a vacuum oven for 24 hours.

[0287] [Chemical Formula X]

[0288]

[0289] Comparative Synthesis Example 3

[0290] 102 g of tetrahydrofurfuryl alcohol and 0.1 g of KOH were placed in a high-pressure reactor and the internal temperature was raised to 80°C. THF-4 was synthesized by slowly adding 176 g while controlling the internal pressure. 278 g of THF-4 was added to a double-necked round-bottom flask and dissolved thoroughly in 300 mL of THF. At an internal temperature of 0°C, 15.4 g of NaOH and 100 mL of water were added and dissolved thoroughly until a clear solution was obtained. A solution of 73 g of p-toluenesulfonyl chloride dissolved in 100 mL of THF was slowly injected at 0°C. The injection was carried out for 1 hour, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and stirred, followed by the addition of a saturated solution of NaHCO3, followed by extraction, titration, and removal of water. After solvent removal, the mixture was dried in a drying oven for 24 hours. 50 g of the dried product was added to a double-necked round-bottom flask and stirred thoroughly in 300 mL of ethanol. Then, 27 g of thiourea was added and dispersed, followed by reflux at 80°C for 12 hours. Next, an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water was injected, and after another 5 hours of reaction, excess dichloromethane was added to dilute it. Hydrochloric acid solution was added, and extraction, titration, removal of water, and solvent removal were performed sequentially. The compound represented by chemical formula Y was obtained by drying in a vacuum oven for 24 hours.

[0291] [Chemical Formula Y]

[0292]

[0293] Comparative Synthesis Example 4

[0294] 150.22 g of hydroxydicyclopentadiene and 0.1 g of KOH were placed in a high-pressure reactor and the internal temperature was raised to 80°C. HDCP-4 was synthesized by slowly adding 176 g while controlling the internal pressure. The obtained compound was placed in a double-necked round-bottom flask, and 800 g of cyclohexane, 15 g of sulfuric acid, 120 g of thioglycolic acid, and 0.1 g of MHQ were added. The temperature was raised to 70°C and the reaction was carried out for 12 hours, while the generated H2O was removed. When no more H2O was generated, the mixture was cooled to room temperature, washed twice with distilled water, neutralized once with NaOH aqueous solution, and washed twice with distilled water in sequence. The solvent was then removed by drying under reduced pressure to finally obtain the compound represented by chemical formula Z.

[0295] [Chemical Formula Z]

[0296]

[0297] Preparation of quantum dots

[0298] Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 5

[0299] A magnetic rod was placed in a three-necked round-bottom flask and a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical; quantum dot solid content (26 wt%)) was added. The green quantum dots had substituted oleic acid on their surface. Here, surface-modifying materials according to Synthetic Examples 1-1 to 4-1 and Comparative Synthetic Examples 1 to 4 were added and stirred at 80°C in a nitrogen atmosphere. After the reaction was complete, the result was cooled to room temperature (23°C) and the quantum dot reaction solution was added to cyclohexane to obtain a precipitate. The precipitate was separated from cyclohexane by centrifugation and dried thoroughly in a vacuum oven for one day to obtain surface-modified green quantum dots. The quantum dots of Comparative Preparation Example 1 were unmodified quantum dots, that is, quantum dots with oleic acid substitution on the surface (e.g., unreacted oleic acid substitution on the surface).

[0300] Preparation of solvent-free curable compositions

[0301] Curable compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were prepared according to the following individual components.

[0302] (A) Quantum dots

[0303] (A-1) Green quantum dots with surface modified by a compound of chemical formula A-1 (Preparation Example 1)

[0304] (A-2) Green quantum dots with surface modified by a compound of chemical formula B-1 (Preparation Example 2)

[0305] (A-3) Green quantum dots with surface modified by a compound of chemical formula C-1 (Preparation Example 3)

[0306] (A-4) Green quantum dots with surface modified by the compound of the above chemical formula D-1 (Preparation Example 4)

[0307] (A-5) Green quantum dots without surface modification (Comparative preparation example 1)

[0308] (A-6) Green quantum dots with surface modified by a compound of chemical formula W (Comparative preparation example 2)

[0309] (A-7) Green quantum dots with surface modified by a compound of chemical formula X (Comparative preparation example 3)

[0310] (A-8) Green quantum dots with surface modified by a compound of chemical formula Y (Comparative preparation example 4)

[0311] (A-9) Green quantum dots with surface modified by a compound of chemical formula Z (Comparative preparation example 5)

[0312] (B) Polymerizable compounds

[0313] The compound represented by chemical formula 3-2 (M200, Miwon Chemical Co., Ltd.)

[0314] [Chemical Formula 3-2]

[0315]

[0316] ( C ) Photopolymerization initiator

[0317] TPO-L (Poliniton Company)

[0318] ( D ) Light diffusing agent

[0319] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solids content 50 wt%) Iridos Co., Ltd.

[0320] Examples 1 to 4 and Comparative Examples 1 to 5

[0321] Surface-modified green quantum dots were mixed with a polymerizable compound and stirred for 12 hours. A polymerization inhibitor was added, followed by stirring for 5 minutes. A photopolymerization initiator was then added, followed by a light diffusing agent.

[0322] Taking Example 1 as an example, 41 grams of surface-modified green quantum dots were mixed with 41 grams of a compound represented by chemical formula 3-2 as a polymerizable compound and stirred to prepare a green quantum dot dispersion. 11 grams of another curable monomer represented by chemical formula 3-2 were added to it and stirred for 5 minutes. Subsequently, 3 grams of photopolymerization initiator and 3 grams of light diffusing agent were added to it and stirred to prepare a curable composition (ink).

[0323] Specific components are shown in Table 1 (unit: weight %) and Table 2 (unit: weight %).

[0324] [Table 1] Example 1 Example 2 Example 3 Example 4 quantum dots (A-1) 41 - - - (A-2) - 41 - - (A-3) - - 41 - (A-4) - - - 41 Polymerizable compounds (for dispersion) 41 41 41 41 polymerizable compounds 11 11 11 11 Photopolymerization initiator 3 3 3 3 Light diffusing agent 4 4 4 4

[0325] [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 quantum dots (A-5) 41 - - - - (A-6) - 41 - - - (A-7) - - 41 - - (A-8) - - - 41 - (A-9) - - - - 41 Polymerizable compounds (for dispersion) 41 41 41 41 41 polymerizable compounds 11 11 11 11 11 Photopolymerization initiator 3 3 3 3 3 Light diffusing agent 4 4 4 4 4

[0326] Preparation of solvent-based curable compositions

[0327] Curable compositions according to Examples 5 to 8 and Comparative Examples 6 to 10 were prepared based on the following individual components.

[0328] (A) Quantum dots

[0329] (A-1) Green quantum dots with surface modified by a compound of chemical formula A-1 (Preparation Example 1)

[0330] (A-2) Green quantum dots with surface modified by a compound of chemical formula B-1 (Preparation Example 2)

[0331] (A-3) Green quantum dots with surface modified by a compound of chemical formula C-1 (Preparation Example 3)

[0332] (A-4) Green quantum dots with surface modified by a compound of chemical formula D-1 (Preparation Example 4)

[0333] (A-5) Green quantum dots without surface modification (Comparative preparation example 1)

[0334] (A-6) Green quantum dots with surface modified by a compound of chemical formula W (Comparative preparation example 2)

[0335] (A-7) Green quantum dots with surface modified by a compound of chemical formula X (Comparative preparation example 3)

[0336] (A-8) Green quantum dots with surface modified by a compound of chemical formula Y (Comparative preparation example 4)

[0337] (A-9) Green quantum dots with surface modified by a compound of chemical formula Z (Comparative preparation example 5)

[0338] ( B ) Polymerizable compounds

[0339] Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)

[0340] (C) Photopolymerization initiator

[0341] Oxime initiator (PBG-305, Tronyl)

[0342] ( D ) Light diffusing agent

[0343] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solids content 50 wt%) Iridos Co., Ltd.

[0344] ( E ) Adhesive resin

[0345] TA-001 (Tacoma)

[0346] ( F ) Solvent

[0347] (F-1) Cyclohexyl acetate (Sigma-Aldrich)

[0348] (F-2) Propylene glycol monomethyl ether acetate (PGMEA) (Sigma-Aldrich)

[0349] Examples 5 to 8 and Comparative Examples 6 to 10

[0350] The following components were used to prepare the various photosensitive resin compositions of Examples 5 to 8 and Comparative Examples 6 to 10 having the compositions (unit: weight %) shown in Tables 3 and 4.

[0351] A photopolymerization initiator was dissolved in solvent (F-2) and stirred thoroughly at room temperature for 2 hours. Subsequently, a polymerizable compound, an adhesive resin, and a light diffusing agent were added to the solution, and the mixture was stirred thoroughly for 15 minutes, followed by stirring again at room temperature for 1 hour. On the other hand, quantum dots and a dispersant were added to solvent (F-1) and stirred at room temperature for 30 minutes to prepare a quantum dot solution. Subsequently, the quantum dot solution was mixed with another solution containing the photopolymerization initiator, etc., and stirred at room temperature for 30 minutes. The product was filtered three times to remove impurities to prepare a solvent-based curable composition.

[0352] [Table 3] Example 5 Example 6 Example 7 Example 8 quantum dots (A-1) 9 - - - (A-2) - 9 - - (A-3) - - 9 - (A-4) - - - 9 polymerizable compounds 7 7 7 7 Photopolymerization initiator 7 7 7 7 Light diffusing agent 2 2 2 2 Adhesive resin 10 10 10 10 solvent (F-1) 30 30 30 30 (F-2) 35 35 35 35

[0353] [Table 4] Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 quantum dots (A-5) 9 - - - - (A-6) - 9 - - - (A-7) - - 9 - - (A-8) - - - 9 - (A-9) - - - - 9 polymerizable compounds 7 7 7 7 7 Photopolymerization initiator 7 7 7 7 7 Light diffusing agent 2 2 2 2 2 Adhesive resin 10 10 10 10 10 solvent (F-1) 30 30 30 30 30 (F-2) 35 35 35 35 35

[0354] Assessment: Evaluation of the lightfastness reliability of curable components

[0355] The lightfastness reliability of each curable component according to Examples 1 to 8 and Comparative Examples 1 to 10 was evaluated, and the results are shown in Table 5.

[0356] Lightfastness Reliability Assessment Method

[0357] The curable composition was prepared into a single film sample of 2 cm × 2 cm, and then the light efficiency as a function of time was measured by using a blue LED planar light source under a blue light emission condition of 100,000 nits.

[0358] Single film samples were used to measure the light efficiency and luminance as a function of time using integrating sphere equipment (QE-2100, Otsuka Electronics Co., Ltd.) and an in-line luminance meter (M7000, McScience Inc.).

[0359] Based on 100% of the initial measurement, compare and evaluate T90 (the time required for the initial light efficiency measurement result to drop from 100% to 90%).

[0360] [Table 5] T90 (hours) Example 1 220 Example 2 230 Example 3 215 Example 4 200 Example 5 150 Example 6 160 Example 7 140 Example 8 125 Comparative Example 1 <1 Comparative Example 2 15 Comparative Example 3 78 Comparative Example 4 100 Comparative Example 5 85 Comparative Example 6 <1 Comparative Example 7 8 Comparative Example 8 50 Comparative Example 9 80 Comparative Example 10 67

[0361] From Table 5, regardless of whether a solvent is included, the curable composition according to some exemplary embodiments can significantly improve lightfastness reliability. For example, according to Comparative Examples 5 and 10, because they include quantum dots that have been surface-modified with a surface-modifying material including ester linkage, there is a significant reduction in light efficiency due to the reduction in heat resistance, and thus the lightfastness reliability is reduced.

[0362] While the subject matter of this disclosure has been described in conjunction with what is now considered a practical, exemplary, passive embodiment, it should be understood that this disclosure is not limited to the disclosed exemplary embodiments, but rather is intended to cover various suitable modifications and equivalent configurations, and their equivalents, that fall within the spirit and scope of the appended claims. Therefore, the foregoing exemplary embodiments should be understood as examples, but not as limiting this disclosure in any way. [Simplified Explanation of the Diagram]

[0077] None.

Claims

1. A curable composition comprising: Quantum dots, including functional groups represented by chemical formula 1; And polymerizable compounds: [Formula 1] Wherein, in Formula 1, X is a sulfur atom or an oxygen atom, R1 is represented by any one of Formulas R-1 to R-3: [Formula R-1] [Formula R-2] [Formula R-3] Wherein, in Formulas R-1 to R-3, R2 is a substituted or unsubstituted vinyl, a substituted or unsubstituted epoxy, or a C1 to C20 alkyl substituted with epoxy and / or vinyl, L3 and L4 are each independently substituted or unsubstituted C1 to C10 alkyl, and m is 0 or 1, L1 and L2 are each independently substituted or unsubstituted C1 to C20 alkyl, and n is an integer between 2 and 10.

2. The curable composition as described in claim 1, wherein: The functional group represented by chemical formula 1 is selected from any one of chemical formulas 1-1 to 1-4: [chemical formula 1-1] [chemical formula 1-2] [chemical formula 1-3] [chemical formula 1-4] where, in chemical formulas 1-1 to 1-4, n is an integer between 2 and 10.

3. The curable composition as described in claim 1, wherein: The functional group represented by Formula 1 is derived from the compound represented by Formula 2: [Formula 2] Wherein, in Formula 2, X is a sulfur atom or an oxygen atom, and R1 is represented by any one of Formulas R-1 to R-3: [Formula R-1] [Formula R-2] [Formula R-3] Wherein, in Formulas R-1 to R-3, R2 is a substituted or unsubstituted vinyl, a substituted or unsubstituted epoxy, or a C1 to C20 alkyl substituted with an epoxy and / or vinyl, L3 and L4 are each independently substituted or unsubstituted C1 to C10 alkyl, and m is 0 or 1, L1 and L2 are each independently substituted or unsubstituted C1 to C20 alkyl, and n is an integer between 2 and 10.

4. The curable composition as described in claim 1, wherein: The curable component is a solvent-free curable component.

5. The curable composition as described in claim 4, wherein: The solvent-free curable composition comprises, based on the total amount of the solvent-free curable composition: 5% to 60% by weight of the quantum dots; and 40% to 95% by weight of the polymerizable compound.

6. The curable composition as claimed in claim 1, wherein: The curable component further includes polymerization initiators, light diffusing agents, polymerization inhibitors, or combinations thereof.

7. The curable composition as described in claim 6, wherein: The light diffusing agent includes barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

8. The curable composition as claimed in claim 1, wherein: The curable components further include malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorinated surfactants, or combinations thereof.

9. The curable composition as claimed in claim 1, wherein: The quantum dots include cadmium-free luminescent materials.

10. The curable composition as claimed in claim 9, wherein: The quantum dots have a core / shell structure of InP / ZnS or a core / first shell / second shell structure of InP / ZnSe / ZnS.

11. The curable composition as claimed in claim 1, wherein: The quantum dot comprises: a core consisting of Ag, In, Ga, and S; and a shell consisting of at least two of Ag, Ga, Zn, and S.

12. The curable composition as claimed in claim 1, wherein: The curable component further includes a solvent.

13. The curable composition as described in claim 12, wherein: The curable composition comprises, by weight, 1% to 40% of the quantum dots; 1% to 20% of the polymerizable compound; and 40% to 80% of the solvent.

14. A cured layer manufactured using a curable composition as described in claim 1.

15. A display device comprising a cured layer as described in claim 14.