Curable composition, cured layer using the composition, color filter comprising the cured layer, and display device comprising the color filter

Abstract

The present invention provides a curable composition, a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter, the curable composition including (A) quantum dots surface-modified with a first ligand and a second ligand having different structures; and (B) a polymerizable compound, wherein the first ligand is a silsesquithiol ligand.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0038278 filed in the Korean Intellectual Property Office on March 28, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a curable composition, a cured layer manufactured using the composition, a color filter including the cured layer, and a display device including the color filter. Background Art

[0004] In the case of ordinary quantum dots, due to the hydrophobic surface characteristics, the solvent in which the quantum dots are dispersed is limited, and thus it is difficult to introduce them into a polar system such as an adhesive or a curable monomer.

[0005] For example, even with the active development of quantum dot ink compositions, their polarity is relatively low in the initial stages, and they can be dispersed in the solvent used in the highly hydrophobic curable composition. Consequently, it is difficult to include 20% or more of quantum dots in the total composition, making it impossible to increase the optical efficiency of the ink above a certain level. Even if quantum dots are added and dispersed to improve optical efficiency, the viscosity exceeds the range that allows inkjet printing, and thus processability may not be satisfactory.

[0006] To achieve a viscosity range suitable for inkjetting, attempts have been made to reduce the ink solids content by dissolving 50% or more of a solvent, based on the total weight of the composition. This has also provided somewhat satisfactory results in terms of viscosity. However, while this may be considered satisfactory in terms of viscosity, nozzle drying and clogging due to solvent evaporation during inkjetting, as well as a decrease in single film thickness over time after inkjet, can be exacerbated. Furthermore, controlling thickness deviation after curing is difficult. Consequently, this approach has been difficult to apply to actual processes.

[0007] Therefore, solvent-free quantum dot inks that do not contain solvents are the most ideal form for application in practical processes. Current technologies for applying quantum dots themselves to solvent-based compositions are currently limited to a certain extent.

[0008] Quantum dots, on the other hand, must possess several key characteristics when used in quantum dot displays. The most important characteristics, from a product perspective, are high brightness and the reliability of maintaining that brightness. Brightness is likely to be achieved through the properties of the quantum dot particles themselves, but reliability, in particular, still faces many hurdles that need to be overcome.

[0009] Reliability can be broadly categorized into heat resistance and light resistance, which have been tried to be improved by various methods in many studies in the past.

[0010] For example, known techniques include methods of encapsulating quantum dots with inorganic materials such as aluminum, titanium, and oxides thereof.

[0011] However, all of these methods are still in academic research and difficult to apply to actual display products. Summary of the Invention

[0012] The embodiment provides a curable composition including quantum dots having excellent heat resistance reliability even after thermal curing.

[0013] Another embodiment provides a cured layer produced using the curable composition.

[0014] Another embodiment provides a color filter including a cured layer.

[0015] Another embodiment provides a display device including a color filter.

[0016] The embodiment provides a curable composition comprising (A) quantum dots surface-modified with a first ligand and a second ligand having different structures; and (B) a polymerizable compound, wherein the first ligand is a silsesquioxane-type thiol ligand.

[0017] The silsesquioxane thiol ligand may be a cage-type silsesquioxane thiol ligand.

[0018] The silsesquioxane-based thiol ligand may include a structural unit represented by Chemical Formula 1.

[0019] [Chemical Formula 1]

[0020]

[0021] In Chemical Formula 1,

[0022] L 1 is an ether linking group, a thioether linking group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof.

[0023] The first ligand may be represented by Chemical Formula 1-1.

[0024] [Chemical Formula 1-1]

[0025]

[0026] In Chemical Formula 1-1,

[0027] L1 is an ether linking group, a thioether linking group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and

[0028] R 2 ~R 8 Each is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0029] The content of the first ligand on the surface of the quantum dot may be less than or equal to the content of the second ligand.

[0030] The first ligand and the second ligand on the surface of the quantum dot may be included in a weight ratio of 1:9 to 5:5.

[0031] The second ligand may be a thiol ligand having a structure different from that of the first ligand.

[0032] The second ligand may be represented by Chemical Formula 2.

[0033] [Chemical Formula 2]

[0034]

[0035] In Chemical Formula 2,

[0036] R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof,

[0037] L 2 and L 3 are each independently a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and

[0038] n and m are each independently an integer from 0 to 100, provided that n+m≠0.

[0039] In Chemical Formula 2, R 1 It may be a substituted or unsubstituted C6-C20 aryl group.

[0040] In Chemical Formula 2, R 1 may be a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 Can be the same.

[0041] In Chemical Formula 2, R1 may be a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 Can be different from each other.

[0042] The curable composition may be a solvent-free curable composition.

[0043] The solvent-free curable composition may include 5 wt % to 60 wt % of quantum dots; and 40 wt % to 95 wt % of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0044] The curable composition may further include a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

[0045] The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0046] The curable composition may further include a solvent.

[0047] The curable composition may include 1 wt% to 40 wt% of quantum dots; 1 wt% to 20 wt% of the polymerizable compound; and 40 wt% to 80 wt% of the solvent, based on the total weight of the curable composition.

[0048] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0049] Another embodiment provides a cured layer produced using the curable composition.

[0050] Another embodiment provides a color filter including a cured layer.

[0051] Another embodiment provides a display device including a color filter.

[0052] Other embodiments of the invention are included in the detailed description below.

[0053] Surface modification of quantum dots with ligands of a composition previously unavailable in quantum dot-containing curable compositions can improve the heat resistance reliability of the quantum dot-containing curable composition after thermal curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 A diagram showing a quantum dot surface-modified with a first ligand and a second ligand.

[0055] Explanation of Figure Numbers

[0056] 1: first ligand;

[0057] 2: second ligand;

[0058] 3: Quantum dots. DETAILED DESCRIPTION

[0059] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary and the present invention is not limited thereto, but is defined by the scope of the claims.

[0060] As used herein, when a specific definition is not otherwise provided, “alkyl” refers to a C1-C20 alkyl group, “alkenyl” refers to a C2-C20 alkenyl group, “cycloalkenyl” refers to a C3-C20 cycloalkenyl group, “heterocycloalkenyl” refers to a C3-C20 heterocycloalkenyl group, “aryl” refers to a C6-C20 aryl group, “aralkyl” refers to a C6-C20 aralkyl group, “alkylene” refers to a C1-C20 alkylene group, “arylene” refers to a C6-C20 arylene group, “alkylarylene” refers to a C6-C20 alkylarylene group, “heteroarylene” refers to a C3-C20 heteroarylene group, and “alkyleneoxy” refers to a C1-C20 alkyleneoxy group.

[0061] As used herein, when a specific definition is not otherwise provided, “substituted” refers to replacement of at least one hydrogen atom by a substituent selected from the group consisting of a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1-C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, a carbamimido group, a hydrazine group, a hydrazo group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 cycloalkynyl group, a C2-C20 heterocycloalkyl group, a C2-C20 heterocycloalkenyl group, a C2-C20 heterocycloalkynyl group, a C3-C20 heteroaryl group, or a combination thereof.

[0062] As used herein, when a specific definition is not otherwise provided, "hetero" refers to a heteroatom containing at least one of N, O, S and P in a chemical formula.

[0063] As used herein, when a specific definition is not otherwise provided, “(meth)acrylate” refers to both “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.

[0064] As used herein, when no specific definition is otherwise provided, the term "combination" means mixing or copolymerization.

[0065] In the present specification, when a definition is not otherwise provided, in a chemical formula, when a chemical bond is not drawn at a position where it should be given, hydrogen is bonded at the position.

[0066] Furthermore, in the present specification, when no definition is otherwise provided, "*" means a point of connection with the same atom or chemical formula or a different atom or chemical formula.

[0067] The quantum dot-containing curable composition according to the present invention uses two or more types of ligands to modify the surface of the quantum dots, but by limiting the structure of the ligands and the weight ratio of the two or more ligands, it is possible to achieve excellent heat resistance reliability after thermal curing.

[0068] Specifically, the present invention primarily improves heat resistance reliability by passivating the surface of quantum dots with a thiol ligand containing a silsesquioxane component at a predetermined ratio to locally cover defect sites or dangling bonds in the quantum dots. Since conventionally known silicon or siloxane components are known to significantly degrade the dispersibility of quantum dots in practical applications and thus impair compatibility with curable compositions, the present inventors have reiterated that when conventionally known thiol ligands are used together with siloxane ligands (such as 3-mercaptopropyltrimethoxysilane) for surface modification of quantum dots, the dispersibility of the quantum dots cannot be ensured under any conditions.

[0069] However, the present inventors have confirmed that when a thiol ligand containing a silsesquioxane component, which is a silsesquioxane-type thiol ligand (first ligand), is applied to the surface modification of quantum dots together with a second ligand having a structure different from that of the first ligand, the silsesquioxane structure of the first ligand can form an affinity with the surface of the quantum dots in the form of a large number of siloxane cages with a large volume, and ultimately greatly improve the compatibility with the curable composition, thereby completing the present invention by repeating relevant studies.

[0070] Hereinafter, each component constituting the curable composition according to the embodiment will be described in detail.

[0071] quantum dots

[0072] The quantum dots in the curable composition according to the embodiment are surface-modified with at least two ligands, wherein the ligands include a silsesquioxane-based thiol ligand (first ligand) and a second ligand having a structure different from that of the first ligand.

[0073] As mentioned above, when the first ligand and the second ligand are used to simultaneously modify the surface of quantum dots, the surface-modified quantum dots can be easily prepared into highly densified or highly concentrated quantum dot dispersions (improving the dispersibility of quantum dots relative to polymerizable monomers, which will be described later), and therefore have a significant impact on improving low viscosity and heat resistance, and in particular, have a significant impact on achieving solvent-free curable compositions.

[0074] For example, the silsesquioxane thiol ligand may be a cage-type silsesquioxane thiol ligand. Silsesquioxanes generally have various structures, such as cage-type, random-type, and ladder-type. Cage-type structures produce almost no volatile components during thermal curing and exhibit excellent heat resistance due to their low equivalent weight of functional groups, thus advantageously maximizing affinity for the surface of quantum dots. (For example, random-type structures have high equivalent weights of functional groups and generate impurities during thermal curing, while ladder-type structures exhibit properties similar to silicon during thermal curing and may therefore be unsuitable for curable compositions containing quantum dots.)

[0075] For example, the silsesquioxane-based thiol ligand may include a structural unit represented by Chemical Formula 1, but is not necessarily limited thereto.

[0076] [Chemical Formula 1]

[0077]

[0078] In Chemical Formula 1,

[0079] L 1 is an ether linking group, a thioether linking group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof.

[0080] For example, the first ligand may be represented by Chemical Formula 1-1, but is not necessarily limited thereto.

[0081] [Chemical Formula 1-1]

[0082]

[0083] In Chemical Formula 1-1,

[0084] L 1 is an ether linking group (*-O-*), a thioether linking group (*-S-*), a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and

[0085] R 2 ~R 8 Each is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0086] For example, in Chemical Formula 1-1, R 2 ~R 8 Each independently may contain an alkyl substituent at its terminal. For example, in Chemical Formula 1-1, R2 ~R 8 Each of them may be independently a C1-C20 alkyl group containing a C1-C10 alkyl substituent at its terminal. For example, in Chemical Formula 1-1, R 2 ~R 8 Each of them may be independently a C1 to C20 alkyl group containing an isopropyl group or a tert-butyl group at its terminal. 2 ~R 8 Each further includes an alkyl substituent at the terminal end, so that a large volume of siloxane cage formation can be implemented, and thus, the affinity to the surface of the quantum dots in the curable composition can be maximized.

[0087] For example, the content of the first ligand on the surface of the quantum dots may be less than or equal to the content of the second ligand. For example, the first ligand and the second ligand on the surface of the quantum dots may be present in a weight ratio of 1:9 to 5:5. When the content of the first ligand is greater than the content of the second ligand, the viscosity of the curable composition containing the quantum dots may increase, which may be undesirable in terms of inkjet properties.

[0088] For example, the second ligand may be a thiol ligand having a structure different from that of the first ligand.

[0089] For example, the second ligand may be represented by Chemical Formula 2, but is not necessarily limited thereto.

[0090] [Chemical Formula 2]

[0091]

[0092] In Chemical Formula 2,

[0093] R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof,

[0094] L 2 and L 3 are each independently a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and

[0095] n and m are each independently an integer from 0 to 100, provided that n+m≠0.

[0096] For example, in Chemical Formula 2, R 1 The aryl group may be a substituted or unsubstituted C6 to C20 aryl group. In this case, the heat resistance reliability of the curable composition according to the embodiment can be maximized.

[0097] For example, in Chemical Formula 2, R 1 may be a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 In this case, the viscosity of the curable composition can be reduced without reducing the heat resistance reliability of the curable composition according to the embodiment.

[0098] For example, in Chemical Formula 2, R 1 may be a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 In this case, the viscosity of the curable composition can be greatly reduced without reducing the heat resistance reliability of the curable composition according to the embodiment.

[0099] For example, quantum dots may have a maximum fluorescence emission wavelength in the range of 500 nm to 680 nm.

[0100] For example, when the curable composition according to an embodiment is a solvent-free curable composition, the quantum dots may be included in an amount of 5% to 60% by weight, for example, 10% to 60% by weight, for example, 20% to 60% by weight, for example, 30% to 50% by weight. When the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0101] For example, when the curable composition according to an embodiment is a curable composition containing a solvent, the quantum dots may be included in an amount of 1% to 40% by weight, for example, 3% to 30% by weight, based on the total amount of the curable composition. When the quantum dots are included within the above range, the light conversion efficiency is improved without compromising pattern characteristics and development characteristics, thereby achieving excellent processability.

[0102] To date, curable compositions (inks) containing quantum dots have been developed specifically for thiol-based binders or monomers having good compatibility with quantum dots, and further, are being commercialized.

[0103] For example, quantum dots can absorb light in the wavelength range of 360 nm to 780 nm, such as in the wavelength range of 400 nm to 780 nm, and can emit fluorescence in the wavelength range of 500 nm to 700 nm, such as in the wavelength range of 500 nm to 580 nm, or emit fluorescence in the wavelength range of 600 nm to 680 nm. In other words, quantum dots can have a maximum fluorescence emission wavelength (fluorescence λ) at 500 nm to 680 nm. em ).

[0104] The quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum (FWHM) within this range, color reproducibility is improved when used as a color material in a color filter due to high color purity.

[0105] The quantum dots can independently be organic materials, inorganic materials, or hybrids (mixtures) of organic and inorganic materials.

[0106] Quantum dots can independently be composed of a core and a shell surrounding the core, and the core and the shell can independently have structures such as core, core / shell, core / first shell / second shell, alloy, alloy / shell, etc. composed of Group II to Group IV, Group III to Group V, etc., but are not limited thereto.

[0107] For example, the core may include at least one material selected from the following: 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 the core may include at least one material selected from the following: CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.

[0108] In an embodiment, since environmental concerns have greatly increased worldwide in recent years and restrictions on toxic materials have also been strengthened, cadmium-free luminescent materials (InP / ZnS, InP / ZnSe / ZnS, etc.) with extremely low quantum efficiency (quantum yield) but environmentally friendly are used instead of luminescent materials with cadmium-like cores, but it is not necessary to be limited to this.

[0109] In the case of core / shell structured quantum dots, the overall size (average particle size) including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

[0110] For example, the quantum dots may independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may independently have an average particle size of 10 nm to 15 nm. The green quantum dots may independently have an average particle size of 5 nm to 8 nm.

[0111] On the other hand, for the dispersion stability of quantum dots, the curable composition according to the embodiment may further include a dispersant. The dispersant contributes to the uniform dispersibility of the light-converting material such as quantum dots in the curable composition, and may include nonionic, anionic or cationic dispersants. Specifically, the dispersant may be a polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide addition product, alkylamine, etc., and it can be used alone or in the form of a mixture of two or more than two. According to the solid content of the light-converting material such as quantum dots, a dispersant can be used in an amount of 0.1% by weight to 100% by weight, for example, in an amount of 10% by weight to 20% by weight.

[0112] polymerizable compounds

[0113] The curable composition according to an embodiment includes a polymerizable compound, and the polymerizable compound may have a carbon-carbon double bond at a terminal thereof.

[0114] The polymerizable compound having a carbon-carbon double bond at the terminal can be included in an amount of 40% to 95% by weight, for example, 50% to 90% by weight, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, a solvent-free curable composition having a viscosity capable of inkjetting can be prepared, and the quantum dots in the prepared solvent-free curable composition have improved dispersibility and optical properties.

[0115] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may have a molecular weight of 170 to 1,000 g / mol. When the molecular weight of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, it may be advantageous for inkjet printing because the viscosity of the composition does not increase without suppressing the optical properties of the quantum dots.

[0116] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 3, but is not necessarily limited thereto.

[0117] [Chemical Formula 3]

[0118]

[0119] In Chemical Formula 3,

[0120] R 9 and R 10 are each independently a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group,

[0121] L 4 and L 6are each independently a single bond or a substituted or unsubstituted C1-C10 alkylene group, and

[0122] L 5 is a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, or an ether linking group (*-O-*).

[0123] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 3-1 or Chemical Formula 3-2, but is not necessarily limited thereto.

[0124] [Chemical Formula 3-1]

[0125]

[0126] [Chemical Formula 3-2]

[0127]

[0128] For example, in addition to the compound represented by Chemical Formula 3-1 or Chemical Formula 3-2, the polymerizable compound having a carbon-carbon double bond at the terminal may further include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

[0129] In addition, the polymerizable compound having a carbon-carbon double bond at the terminal may further include a monomer commonly used in conventional thermosetting or photocurable compositions. For example, the monomer may further include an oxetane compound such as bis[1-ethyl(3-oxetanyl)]methyl ether.

[0130] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1% to 20% by weight, for example, 1% to 15% by weight, for example, 5% to 15% by weight, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dots may be improved.

[0131] Light diffuser

[0132] The curable composition according to an embodiment may further include a light diffusing agent.

[0133] For example, the light diffuser may include barium sulfate (BaSO 4 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), zirconium oxide (ZrO 2 ), or a combination thereof.

[0134] The light diffusing agent can reflect the light not absorbed by the quantum dots and allow the quantum dots to absorb the reflected light again. In other words, 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.

[0135] The light diffusing agent may have an average particle size (D 50 ), and specifically has an average particle size (D 50 When the average particle size of the light diffusing agent is within the above range, it can have a better light diffusing effect and improve the light conversion efficiency.

[0136] The light diffusing agent may be included in an amount of 1% to 20% by weight, for example, 2% to 15% by weight, or 3% to 10% by weight, based on the total amount of the curable composition. When the light diffusing agent is included in an amount of less than 1% by weight, based on the total amount of the curable composition, it is difficult to expect the effect of improving the light conversion efficiency by using the light diffusing agent, and when the light diffusing agent is included in an amount of more than 20% by weight, quantum dot sedimentation may occur.

[0137] polymerization initiator

[0138] The curable composition according to an embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0139] The photopolymerization initiator is a common initiator for photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, aminoketone compounds, etc., but is not limited thereto.

[0140] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 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, and the like.

[0141] Examples of the benzophenone compound include benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0142] Examples of the thioxanthone compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0143] Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0144] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-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, s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxyphenylvinyl)-s-triazine, and the like.

[0145] Examples of oxime compounds include O-acyloximes, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetoxiime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one. Specific examples of O-acyloximes include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate.

[0146] Examples of aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like.

[0147] In addition to the above compounds, the photopolymerization initiator may further include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, and the like.

[0148] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transferring its energy.

[0149] Examples of the photosensitizer may include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0150] Examples of thermal polymerization initiators may be peroxides, specifically 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), tert-butyl perbenzoate, and the like, such as 2,2′-azobis-2-methylpropionitrile, but are not necessarily limited thereto, and any one well known in the art may be used.

[0151] The polymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 1% to 4% by weight, based on the total amount of the curable composition. When the polymerization initiator is included within this range, it is possible to obtain excellent reliability due to sufficient curing during exposure or thermal curing, and it is possible to prevent deterioration of transmittance due to non-reactive initiators, thereby preventing deterioration of the optical properties of quantum dots.

[0152] Binder resin

[0153] The curable composition according to an embodiment may further include a binder resin.

[0154] The binder resin may include an acrylic resin, a cardoline resin, an epoxy resin, or a combination thereof.

[0155] The acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including at least one acrylic repeating unit.

[0156] Specific examples of the acrylic binder resin may be 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, etc., but are not limited thereto, and may be used alone or in the form of a mixture of two or more.

[0157] The weight average molecular weight of the acrylic binder resin may be 5,000 to 15,000 g / mol. When the acrylic binder resin has a weight average molecular weight within the range, close contact properties with a substrate, physical and chemical properties are improved, and viscosity is appropriate.

[0158] The acrylic resin may have an acid value of 80 mg KOH / g to 130 mg KOH / g. When the acrylic resin has an acid value within the range, the pixel pattern may have excellent resolution.

[0159] The carbazole-based resin may be used in a conventional curable resin (or photosensitive resin) composition and may be generally used, for example, as disclosed in Korean Patent Application Laid-Open No. 10-2018-0067243, but is not limited thereto.

[0160] The carbazole resin can be prepared, for example, by mixing at least two of the following: a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; an acid anhydride compound such as pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride; a diol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; a phosphorus compound such as triphenylphosphine; and an amine or ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

[0161] The weight average molecular weight of the carbazole-based binder resin may be 500 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the carbazole-based binder resin is within the above range, a satisfactory pattern can be formed without leaving residue during the production of the cured layer and without losing film thickness during the development of the solvent-based curable composition.

[0162] When the binder resin is a carbole-based resin, developability of a curable composition (particularly, a photosensitive resin composition) containing the binder resin is improved, and sensitivity during photocuring is good, so that fine pattern forming properties are improved.

[0163] The epoxy resin may be a monomer or oligomer capable of being polymerized by heat, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0164] The epoxy resin may include, but is not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cycloaliphatic epoxy resin, and aliphatic polyglycidyl ether.

[0165] Currently available products of the epoxy resin may include bisphenyl epoxy resins, such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co., Ltd.; cresol novolac type epoxy resins, such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 of Nippon Kayaku Co., Ltd. and EPIKOTE 180S75 of Yuka Shell Epoxy Co., Ltd.; bisphenol A epoxy resins, such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1005 and EPIKOTE 1006 of Yuka Shell Epoxy Co., Ltd. 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010 and EPIKOTE 828; bisphenol F type epoxy resins, such as EPIKOTE 807 and EPIKOTE 834 from Shell Epoxy Resins Co., Ltd.; phenol novolac type epoxy resins, such as EPIKOTE 152, EPIKOTE 154 or EPIKOTE 157H65 from Shell Epoxy Resins Co., Ltd. and EPPN 201 and EPPN 202 from Nippon Kayaku Co., Ltd.; other cycloaliphatic epoxy resins, such as CIBA-GEIGY AG)'s CY175, CY177 and CY179, Union Carbide Corporation (UCC)'s ERL-4234, ERL-4299, ERL-4221 and ERL-4206, Showa Denko K.K.'s Showdyne 509, Ciba-Geigy's ARALDITE CY-182, CY-192 and CY-184, Dainippon Ink and Chemicals, Inc.'s EPICLON 200 and EPICLON 400, Shell Epoxy Resins Co., Ltd.'s EPIKOTE 871, EPIKOTE 872 and EP1032H60, Celanese Coatings Co., Ltd.) ED-5661 and ED-5662; aliphatic polyglycidyl ethers, such as EPIKOTE 190P and EPIKOTE 191P of Shell Epoxy Resins Co., Ltd., EPOLITE 100MF of Kyoesha Yushi Co., Ltd., Nippon Yushi Co., Ltd.)'s EPIOL TMP, etc. .

[0166] For example, when the curable composition according to an embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5% to 10% by weight, for example, 1% to 5% by weight, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

[0167] For example, when the curable composition according to an embodiment is a curable composition containing a solvent, the binder resin may be included in an amount of 1% to 30% by weight, for example, 3% to 20% by weight, based on the total amount of the curable composition. In this case, pattern characteristics, heat resistance, and chemical resistance can be improved.

[0168] Other additives

[0169] For improvement of stability and dispersibility of quantum dots, the curable composition according to an embodiment may further include a polymerization inhibitor.

[0170] The polymerization inhibitor may include a hydroquinone compound, a catechol compound, or a combination thereof, but is not limited thereto. When the curable composition according to an embodiment further includes a hydroquinone compound, a catechol compound, or a combination thereof, room temperature crosslinking during exposure after printing (coating) the curable composition can be prevented.

[0171] For example, the hydroquinone compound, the catechol compound, or a combination thereof may include hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, tert-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamine-O,O')aluminum, or a combination thereof, but is not necessarily limited thereto.

[0172] The hydroquinone compound, catechol compound, or combination thereof can be used in the form of a dispersion, and the polymerization inhibitor in the form of a dispersion can be included in an amount of 0.001 to 3% by weight, for example, 0.01 to 2% by weight, based on the total amount of the curable composition. When the polymerization inhibitor is included within the above range, the problem of aging at room temperature can be solved, and at the same time, sensitivity reduction and surface peeling can be prevented.

[0173] In addition, the curable composition according to an embodiment may further include malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof in order to improve heat resistance and reliability.

[0174] For example, the curable composition according to an embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc., in order to improve close contact characteristics with the substrate.

[0175] Examples of the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacrylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in a mixture of two or more.

[0176] The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable composition. When the silane-based coupling agent is included within the above range, close contact characteristics, storage ability, and the like are improved.

[0177] Furthermore, the curable composition may further contain a surfactant, such as a fluorine-based surfactant, as needed, in order to improve coating characteristics and suppress the generation of spots, that is, to improve leveling performance.

[0178] The fluorochemical surfactant may have a low weight average molecular weight of 4,000 to 10,000 g / mol, specifically 6,000 to 10,000 g / mol. Furthermore, the fluorochemical surfactant may have a surface tension of 18 to 23 mN / m (measured using a 0.1% polyethylene glycol monomethylether acetate (PGMEA) solution). When the fluorochemical surfactant has a weight average molecular weight and surface tension within the above ranges, leveling performance can be further improved, and excellent properties can be provided when applying slit coating as a high-speed coating method, because film defects can be reduced by preventing spot formation and suppressing vapor generation during high-speed coating.

[0179] Examples of fluorochemical surfactants include and (BM Chemie Inc.); MEGAFACE F McGuffins F McGuffins F and McGuffins F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD Fowlerard Fowlerard and Fowlerad (Sumitomo 3M Co., Ltd.); SURFLON Thrawn Thrawn Thrawn and Thrawn (ASAHI Glass Co., Ltd.); and as well as etc. (Toray Silicone Co., Ltd.); F-482, F-484, F-478, F-554, etc. of Dainippon Ink and Chemicals Co., Ltd. (DIC Co., Ltd.).

[0180] In addition, the solvent-free curable composition according to the embodiment may include a silicone surfactant in addition to the fluorine-based surfactant. Specific examples of the silicone surfactant may include TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba Silicone Co., Ltd., but are not limited thereto.

[0181] The surfactant may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant is included within the range, foreign matter is less generated in the spray coating composition.

[0182] In addition, unless characteristics are deteriorated, the curable composition according to the embodiment may further include a predetermined amount of other additives such as an antioxidant, a stabilizer, and the like.

[0183] solvent

[0184] Meanwhile, the curable composition according to an embodiment may further include a solvent.

[0185] The solvent may, for example, include: alcohols such as methanol, ethanol, etc.; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; ethylene glycol ethyl acetate, such as methyl ethylene glycol ethyl acetate, ethyl ethylene glycol ethyl acetate, diethyl ethylene glycol ethyl acetate, etc.; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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- butanone, methyl n-amyl ketone, 2-heptanone, etc.; alkyl esters of saturated aliphatic monocarboxylic acids, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; alkyl hydroxyacetic acid esters, such as methyl hydroxyacetic acid, ethyl hydroxyacetic acid, butyl hydroxyacetic acid, etc.; alkoxyalkyl acetates, such as methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, 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, ethyl 3-ethoxypropionic acid , 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-methylpropionate, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionate, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-propionic acid -hydroxy-2-methylethyl ester, hydroxyethyl acetate, 2-hydroxy-3-methylbutyric acid methyl ester, etc.; or ketoesters such as ethyl pyruvate, etc., and in addition, may be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, 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 glycol ethyl acetate, etc., but are not limited thereto.

[0186] For example, the solvent may be preferably glycol ethers, such as ethylene glycol monoethyl ether, ethylene diglycol methyl ethyl ether, etc.; ethylene glycol alkyl ether acetates, such as ethyl glycol ethyl ether acetate, etc.; esters, such as 2-hydroxyethyl propionate, etc.; carbitols, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; alcohols, such as ethanol, etc.; or combinations thereof.

[0187] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0188] The solvent may be included in an amount of 40% to 80% by weight, for example, 45% to 80% by weight, based on the total amount of the curable composition. When the solvent is within the above range, the solvent-based curable composition has an appropriate viscosity and thus can have excellent coating properties when applied to a large area by spin coating and slit coating.

[0189] Another embodiment provides a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter.

[0190] One of the methods of manufacturing a cured layer may include coating a curable composition on a substrate using an inkjet spraying method to form a pattern ( S1 ); and curing the pattern ( S2 ).

[0191] (S1) Pattern formation

[0192] The curable composition can be applied to the substrate in an ideal thickness of 0.5 to 20 microns using an inkjet coating method. The inkjet coating method can form a pattern by spraying a single color from each nozzle and repeating the spraying multiple times according to the desired number of colors. However, the pattern can be formed by simultaneously spraying the desired number of colors through each inkjet nozzle to reduce the process.

[0193] (S2) Curing

[0194] The obtained pattern is cured to obtain pixels. In this article, the curing method may be a thermal curing process or a photocuring process. The thermal curing process may be carried out at a temperature greater than or equal to 100° C., ideally in the range of 100° C. to 300° C., and more ideally in the range of 160° C. to 250° C. The photocuring process may include irradiating actinic rays, such as UV rays of 190 nm to 450 nm, for example UV rays of 200 nm to 400 nm. Irradiation is performed using a light source such as a mercury lamp, a metal halide lamp, an argon laser, etc. having low pressure, high pressure, or ultrahigh pressure. X-rays, electron beams, etc. may also be used as needed.

[0195] Another method of manufacturing a cured layer may include manufacturing a cured layer using the aforementioned curable composition by the following photolithography method.

[0196] (1) Coating and film formation

[0197] The curable composition is applied to a substrate subjected to a predetermined pretreatment using a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. to a desired thickness, for example, a thickness in the range of 2 to 10 microns. The coated substrate is then heated at a temperature of 70° C. to 90° C. for 1 to 10 minutes to remove the solvent and form a film.

[0198] (2) Exposure

[0199] After placing a mask having a predetermined shape, the resulting film is irradiated with actinic radiation, such as UV radiation of 190 to 450 nanometers, for example, UV radiation of 200 to 400 nanometers, to form a desired pattern. Irradiation is performed using a light source such as a low-pressure, high-pressure, or ultrahigh-pressure mercury lamp, a metal halide lamp, or an argon laser. X-rays, electron beams, and the like may also be used as needed.

[0200] When a high-pressure mercury lamp is used, the exposure process uses a light dose of, for example, 500 mJ / cm² or less (using a 365 nm sensor). However, the light dose may vary depending on the type of each component of the curable composition, its combination ratio, and dry film thickness.

[0201] (3) Development

[0202] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unnecessary parts except the exposed parts, thereby forming an image pattern. In other words, when an alkaline developing solution is used for development, the non-exposed areas are dissolved and an image color filter pattern is formed.

[0203] (4) Post-processing

[0204] The developed image pattern can be heated again or irradiated by actinic rays or the like to be cured so as to achieve excellent quality in terms of heat resistance, light resistance, close contact characteristics, crack resistance, chemical resistance, high strength, storage stability, and the like.

[0205] Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples should not be interpreted as limiting the scope of the present invention in any sense.

[0206] (Synthesis of Ligand)

[0207] [Synthesis of the compound represented by Chemical Formula E-2 (second ligand)]

[0208] 100 grams of PH-4 (Hannong Chemical Inc.) was added to a two-necked round-bottom flask and thoroughly dissolved in 300 milliliters of tetrahydrofuran (THF). 15.4 grams of NaOH and 100 milliliters of water were injected at 0°C and then thoroughly dissolved until a clear solution was obtained. A solution obtained by dissolving 73 grams of p-toluenesulfonyl chloride in 100 milliliters 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, an excess of dichloromethane was added thereto and then stirred, and a saturated solution of NaHCO3 was added thereto, followed by extraction, titration, and dehydration. After removing the solvent, the residue was dried in a drying oven for 24 hours. 50 grams of the dried product was placed in a two-necked round-bottom flask and thoroughly stirred in 300 milliliters of ethanol. Subsequently, 27 grams of thiourea was added thereto and dispersed therein, and then refluxed at 80°C for 12 hours. Next, an aqueous solution prepared by dissolving 4.4 g of NaOH in 20 ml of water was injected thereinto, and the mixture was further stirred for 5 hours. An excess of dichloromethane was added thereto, and then an aqueous hydrochloric acid solution was added thereto. Extraction, titration, water removal, and solvent removal were then performed in this order. The obtained product was dried in a vacuum oven for 24 hours to obtain a compound represented by Chemical Formula E-2.

[0209] [Chemical Formula E-2]

[0210]

[0211] [Synthesis of the compound represented by Chemical Formula E-3 (second ligand)]

[0212] 100 grams of triethylene glycol monomethyl ether is added to a two-necked round-bottom flask and fully dissolved in 300 milliliters of THF. At 0°C, 36.6 grams of NaOH and 100 milliliters of water are added thereto, and then fully dissolved until a clear solution is obtained. At 0°C, a solution obtained by dissolving 127 grams of p-toluenesulfonyl chloride in 100 milliliters of THF is slowly injected. The injection is carried out for 1 hour, and the resulting mixture is stirred at room temperature for 12 hours. When the reaction is complete, excess dichloromethane is added thereto and then stirred, and a saturated solution of NaHCO3 is added thereto, followed by extraction, titration, and dehydration. After removing the solvent, the residue is dried in a drying oven for 24 hours. 50 grams of the dried product is placed in a two-necked round-bottom flask and fully stirred in 300 milliliters of ethanol. Subsequently, 58 grams of thiourea are added thereto and dispersed therein, and then refluxed at 80°C for 12 hours. Next, an aqueous solution prepared by dissolving 18.5 g of NaOH in 20 ml of water was injected thereinto, and the mixture was further stirred for 5 hours. An excess of dichloromethane was added thereto, and then an aqueous hydrochloric acid solution was added thereto. Extraction, titration, water removal, and solvent removal were then performed in this order. The obtained product was dried in a vacuum oven for 24 hours to obtain a compound represented by Chemical Formula E-3.

[0213] [Chemical Formula E-3]

[0214]

[0215] [Synthesis of the compound represented by Chemical Formula E-4 (second ligand)]

[0216] 100 g of MePO(EO)2 (Han Nong Chemical Co., Ltd.) was added to a two-necked round-bottom flask and fully dissolved in 300 ml of THF. 1.5 equivalents of NaOH and 150 ml of water were added thereto, and the resultant was fully stirred under ice bath conditions. A solution obtained by dissolving 1.2 equivalents of p-toluenesulfonyl chloride 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 15 hours. When the reaction was complete, 300 ml of water and 500 ml of dichloromethane were added thereto and then stirred, and a saturated solution of NaHCO3 was added thereto, followed by extraction, titration, and dehydration. After removing the solvent, the residue was dried in a drying oven for 24 hours. 50 g of the dried product was placed in a two-necked round-bottom flask and fully stirred in 300 ml of ethanol. Then, 3.5 equivalents of thiourea (TCI (Tokyo Chemical Industry)) were added thereto, and then refluxed at 100°C for 15 hours. Next, an aqueous solution prepared by dissolving 4.4 g of NaOH in 20 ml of water was injected thereinto, and the mixture was further stirred for 6 hours. An excess of dichloromethane was added thereto, and then an aqueous hydrochloric acid solution was added thereto. Extraction, titration, water removal, and solvent removal were then performed in this order. The obtained product was dried in a vacuum oven for 24 hours to obtain a compound represented by Chemical Formula E-4.

[0217] [Chemical Formula E-4]

[0218]

[0219] (Preparation of Surface-Modified Quantum Dots)

[0220] Preparation Example 1

[0221] After the magnetic bar is placed in a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical; 23% by weight of quantum dot solid content) is placed therein. Here, a compound represented by chemical formula E-1 (TH1550-mercaptopropyl isobutyl POSS (polyhedral oligomeric silsesquioxane), Hybrid plastics) and a compound represented by chemical formula E-2 are added in a weight ratio of 1:9 and stirred at 80°C in a nitrogen atmosphere. When the reaction is complete, after lowering the temperature to room temperature (23°C), the quantum dot reaction solution is added to cyclohexane to capture the precipitate. The precipitate is separated from the cyclohexane by centrifugation and then fully dried in a vacuum oven for one day to obtain surface-modified green quantum dots.

[0222] [Chemical Formula E-1]

[0223]

[0224] Preparation Example 2

[0225] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula E-1 and the compound represented by Chemical Formula E-2 were used at a weight ratio of 2:8 instead of 1:9.

[0226] Preparation Example 3

[0227] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula E-1 and the compound represented by Chemical Formula E-2 were used at a weight ratio of 3:7 instead of 1:9.

[0228] Preparation Example 4

[0229] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula E-1 and the compound represented by Chemical Formula E-2 were used at a weight ratio of 5:5 instead of 1:9.

[0230] Preparation Example 5

[0231] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 2, except that the compound represented by Chemical Formula E-3 was used instead of the compound represented by Chemical Formula E-2.

[0232] Preparation Example 6

[0233] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 2, except that the compound represented by Chemical Formula E-4 was used instead of the compound represented by Chemical Formula E-2.

[0234] Comparative Preparation Example 1

[0235] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula E-1 was not included.

[0236] Comparative Preparation Example 2

[0237] Surface-modified green quantum dots were prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula E-2 was not used.

[0238] (Preparation of Curable Composition)

[0239] Curable compositions according to Examples 1 to 6 and Comparative Examples 1 and 2 were prepared based on each of the following components.

[0240] (A)Quantum dots

[0241] (A-1) Preparation of surface-modified green quantum dots prepared in Example 1

[0242] (A-2) Preparation of surface-modified green quantum dots prepared in Example 2

[0243] (A-3) Preparation of surface-modified green quantum dots prepared in Example 3

[0244] (A-4) Preparation of surface-modified green quantum dots prepared in Example 4

[0245] (A-5) Preparation of surface-modified green quantum dots prepared in Example 5

[0246] (A-6) Preparation of surface-modified green quantum dots prepared in Example 6

[0247] (A-7) Comparative Preparation of Surface-Modified Green Quantum Dots Prepared in Example 1

[0248] (A-8) Comparative Preparation of Surface-Modified Green Quantum Dots Prepared in Example 2

[0249] (B) polymerizable compound

[0250] Compound represented by Chemical Formula 3-2 (M200, Miwon Chemical)

[0251] [Chemical Formula 3-2]

[0252]

[0253] (C) Photopolymerization initiator

[0254] TPO-L (Polynetron)

[0255] (D) Light Diffuser

[0256] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0257] (E) Polymerization inhibitor

[0258] Methylhydroquinone (Tokyo Chemical Industry Co., Ltd.)

[0259] Examples 1 to 6 and Comparative Examples 1 and 2

[0260] Specifically, the surface-modified green quantum dots were mixed with a polymerizable compound and stirred for 12 hours. A polymerization inhibitor was added and stirred for 5 minutes. Then, if necessary, a photopolymerization initiator was added, and then a light diffusing agent was added.

[0261] (Take Example 1 as an example, 41 g of surface-modified green quantum dots and 41 g of the compound represented by Chemical Formula 3-2 as a polymerizable compound were mixed and then stirred to prepare a green quantum dot dispersion, 10.95 g of another curable monomer represented by Chemical Formula 3-2 and 0.05 g of a polymerization inhibitor were added thereto, and then stirred for 5 minutes, and then 3 g of a photopolymerization initiator and 4 g of a light diffuser were added thereto, and then stirred, thereby preparing a curable composition (ink).)

[0262] Specific compositions are shown in Table 1.

[0263] (Table 1)

[0264]

[0265] Evaluate

[0266] 2 ml of each curable composition according to Examples 1 to 6 and Comparative Examples 1 and 2 was spin-coated on a glass substrate at 1,500 rpm, and then exposed to 5 joules for 9 seconds in a nitrogen UV exposure device to form a 9-micron-thick QD film. The initial blue light conversion rate (initial retention rate) of the QD film was measured using a light efficiency meter (QE-2100, Otsuka Electronics Co., Ltd.), and then the substrate with the QD film was baked on a hot plate at 180° C. under a nitrogen atmosphere for 30 minutes and 1 hour, respectively, and cooled to room temperature (23° C.) for 3 hours. Subsequently, the blue light conversion rate (retention rate after baking) thereof was re-measured using the light efficiency meter, which was used to calculate the thermal process retention rate (%) according to the following calculation formula, and the results are shown in Table 2.

[0267] Thermal process retention rate (%) = [retention rate after baking / initial retention rate] * 100

[0268] (Table 2)

[0269]

[0270] Referring to Table 2, the curable compositions according to Examples 1 to 6 exhibited excellent heat resistance reliability due to minimized deterioration of thermal process retention after the thermal curing process, compared to the curable compositions according to Comparative Examples 1 and 2.

[0271] Although the present invention has been described in conjunction with what are presently considered to be practical example embodiments, it should be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood as illustrative and not limiting of the present invention in any way.

Claims

1. A curable composition comprising: (A) Quantum dots, surface-modified with a first ligand and a second ligand having different structures; as well as (B) polymerizable compound wherein the first ligand is a silsesquioxane thiol ligand, wherein the content of the first ligand on the surface of the quantum dot is less than or equal to the content of the second ligand, The first ligand is represented by Chemical Formula 1-1: [Chemical Formula 1-1] In Chemical Formula 1-1, L 1 is an ether linking group, a thioether linking group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and R 2 ~R 8 Each is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, The second ligand is represented by Chemical Formula 2: [Chemical Formula 2] Wherein, in Chemical Formula 2, R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof, L 2 and L 3 are each independently a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, and n and m are each independently an integer from 0 to 100, provided that n+m≠0. 2 . The curable composition according to claim 1 , wherein the silsesquioxane thiol ligand is a cage-type silsesquioxane thiol ligand. 3 . The curable composition according to claim 1 , wherein the first ligand and the second ligand on the surface of the quantum dot are included in a weight ratio of 1:9 to 5:

5.

4. The curable composition according to claim 1, wherein in Chemical Formula 2, R 1 is a substituted or unsubstituted C6-C20 aryl group.

5. The curable composition according to claim 1, wherein in Chemical Formula 2, R 1 is a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 same.

6. The curable composition according to claim 1, wherein in Chemical Formula 2, R 1 is a substituted or unsubstituted C1-C20 alkyl group, and L 2 and L 3 Different from each other.

7. The curable composition according to claim 1, wherein the curable composition is a solvent-free curable composition.

8. The curable composition according to claim 7, wherein the solvent-free curable composition comprises, based on the total amount of the solvent-free curable composition: 5 wt% to 60 wt% of the quantum dots; and 40% to 95% by weight of the polymerizable compound. 9 . The curable composition of claim 1 , wherein the curable composition further comprises a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

10. The curable composition of claim 9, wherein the light diffuser comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

11. The curable composition according to claim 1, wherein the curable composition further comprises a solvent.

12. The curable composition of claim 11, wherein the curable composition comprises, based on the total weight of the curable composition: 1 wt% to 40 wt% of the quantum dots; 1 wt% to 20 wt% of the polymerizable compound; and 40 wt% to 80 wt% of the solvent.

13. The curable composition according to claim 1, wherein the curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof. 14 . A cured layer produced using the curable composition according to claim 1 .

15. A color filter comprising the cured layer according to claim 14.

16. A display device comprising the color filter according to claim 15.

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