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

Abstract

Provided are a curable composition, a cured layer manufactured using the composition, a color filter including the cured layer, and a display device including the cured layer, the curable composition including (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound includes a first polymerizable compound having a high refractive index and a high viscosity characteristic.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0043582, filed on March 29, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a curable composition, a cured layer 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 research into 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 can be considered satisfactory in terms of viscosity, nozzle drying due to solvent evaporation and nozzle clogging during inkjetting, as well as a decrease in single film thickness over time after inkjet, can be deteriorating. 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] Solvent-free curable compositions (quantum dot ink compositions) contain excessive polymerizable compounds and cause nozzle clogging and jetting failure problems due to nozzle drying caused by volatility, as well as a decrease in the thickness of the monolayer film due to the volatilization of the ink composition sprayed in the patterned partition wall pixels. Therefore, efforts are being made to improve the optical properties of solvent-free curable compositions from various angles. In order to improve the optical properties of solvent-free curable compositions, a method for increasing the content of inorganic materials is generally used, but the problem is that as the content of inorganic materials increases, the reflectivity also increases. In other words, the problem of improving optical properties and reducing the reflectivity of solvent-free curable compositions is in a trade-off relationship, and the demand for technology that can simultaneously improve these two properties (improving optical properties and reducing reflectivity) is growing. Summary of the Invention

[0009] Some embodiments provide a curable composition that can simultaneously improve optical properties and reduce reflectivity.

[0010] Some embodiments provide a cured layer produced using the curable composition.

[0011] Some embodiments provide a color filter including the cured layer.

[0012] Some embodiments provide a display device including the color filter.

[0013] Some embodiments provide a curable composition including (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound includes a first polymerizable compound represented by Chemical Formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] In Chemical Formula 1,

[0017] R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0018] L 1 To L 3 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0019] X 1 and X 2 are each independently an ether group (*-O-*) or a thioether group (*-S-*), provided that X 1 and X 2 At least one of them must be a thioether group (*-S-*).

[0020] L 1 It may be a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group.

[0021] L 2 and L 3 Each independently may be a substituted or unsubstituted C1 to C20 alkylene group.

[0022] The first polymerizable compound may have a refractive index of about 1.49 or greater and a viscosity of about 7.0 or greater.

[0023] The first polymerizable compound may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3.

[0024] [Chemical Formula 1-1]

[0025]

[0026] [Chemical formula 1-2]

[0027]

[0028] [Chemical formula 1-3]

[0029]

[0030] The polymerizable compound may further include a second polymerizable compound having a different structure from the first polymerizable compound.

[0031] The second polymerizable compound may include a compound represented by Chemical Formula 2.

[0032] [Chemical Formula 2]

[0033]

[0034] In Chemical Formula 2,

[0035] L 4 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*),

[0036] L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0037] R 3 and R 4 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0038] A weight ratio of the first polymerizable compound to the second polymerizable compound may be about 1:9 to about 9:1.

[0039] A weight ratio of the first polymerizable compound to the second polymerizable compound may be about 1:9 to about 5:5.

[0040] The curable composition may be a solvent-free curable composition.

[0041] The solvent-free curable composition may include about 5 wt % to about 60 wt % of the quantum dots; and about 40 wt % to about 95 wt % of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0042] The curable composition may further include a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

[0043] The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0044] The curable composition may further include a solvent.

[0045] The curable composition may include about 1 wt % to about 40 wt % of quantum dots, about 1 wt % to about 20 wt % of a polymerizable compound, and about 40 wt % to about 80 wt % of a solvent, based on the total weight of the curable composition.

[0046] 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.

[0047] Some embodiments provide a cured layer produced using the curable composition.

[0048] Some embodiments provide a color filter including the cured layer.

[0049] Some embodiments provide a display device including the color filter.

[0050] Other embodiments of the invention are included in the detailed description below.

[0051] By including a polymerizable compound having high refractive index and high viscosity characteristics in the curable composition containing quantum dots, the optical characteristics of the curable composition containing quantum dots can be improved while reducing reflectivity. DETAILED DESCRIPTION

[0052] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary and the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0053] As used herein, when a specific definition is not otherwise provided, “alkyl” refers to a C1 to C20 alkyl group, “alkenyl” refers to a C2 to C20 alkenyl group, “cycloalkenyl” refers to a C3 to C20 cycloalkenyl group, “heterocycloalkenyl” refers to a C3 to C20 heterocycloalkenyl group, “aryl” refers to a C6 to C20 aryl group, “aralkyl” refers to a C6 to C20 aralkyl group, “alkylene” refers to a C1 to C20 alkylene group, “arylene” refers to a C6 to C20 arylene group, “alkylarylene” refers to a C6 to C20 alkylarylene group, “heteroarylene” refers to a C3 to C20 heteroarylene group, and “alkyleneoxy” refers to a C1 to C20 alkyleneoxy group.

[0054] As used herein, when a specific definition is not otherwise provided, “substituted” means that at least one hydrogen atom is replaced by a substituent selected from a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azido group, an amide group, a hydrazine group, a hydrazine keto 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 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0055] As used herein, when a specific definition is not otherwise provided, "hetero" refers to a heteroatom including at least one of N, O, S and P in a chemical formula.

[0056] As used herein, when no specific definition is otherwise provided, “(meth)acrylate” refers to both “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.

[0057] As used herein, when no specific definition is otherwise provided, the term "combination" means mixing or copolymerization.

[0058] 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.

[0059] 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.

[0060] Furthermore, unless otherwise specified herein, viscosity refers to viscosity at about 20°C.

[0061] Hereinafter, each component constituting the curable composition according to some embodiments will be described in detail.

[0062] polymerizable compounds

[0063] In the case of a panel using quantum dots, there is a technical challenge of increasing pixel brightness and reducing external light reflection to improve front brightness. To solve this problem, attempts have been made to increase the absorptivity (absorption rate, abs.) and light efficiency (light efficiency, EQE) of the curable composition including quantum dots. Typically, as the amount of inorganic material in the composition increases, the optical properties of the curable composition including quantum dots are improved. For example, by increasing the amount of quantum dot particles or increasing the content of a light diffusing agent as a scattering agent, light efficiency can be improved. However, in this case, there is a problem of increased reflectivity.

[0064] In addition to the amount of inorganic material, the present inventors have determined that the use of high-refractive-index monomers can improve light efficiency, while the use of high-viscosity monomers can improve optical properties. After extensive research, they have developed a novel high-refractive-index / high-viscosity polymerizable compound structure suitable for use in curable compositions containing quantum dots (including both solvent-free and solvent-based compositions), thereby completing the present invention. Specifically, according to some embodiments, the use of novel high-refractive-index / high-viscosity curable monomers capable of improving optical properties and reducing the reflectivity of curable compositions containing quantum dots can significantly improve light efficiency.

[0065] According to some embodiments, the quantum dot-containing curable composition includes a (meth)acrylate compound having high refractive index and high viscosity as a polymerizable compound, thereby simultaneously achieving the effects of improving the optical properties of the curable composition and reducing reflectivity. In particular, since the (meth)acrylate compound having high refractive index and high viscosity in the quantum dot-containing curable composition according to some embodiments is a thioacrylate monomer, the effect of improving the optical properties can be maximized.

[0066] Specifically, a (meth)acrylate compound having high refractive index and high viscosity characteristics may be represented by Chemical Formula 1, and may be expressed as the first polymerizable compound.

[0067] [Chemical Formula 1]

[0068]

[0069] In Chemical Formula 1,

[0070] R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0071] L 1 To L 3are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0072] X 1 and X 2 are each independently an ether group (*-O-*) or a thioether group (*-S-*), provided that X 1 and X 2 At least one of them must be a thioether group (*-S-*).

[0073] The first polymerizable compound represented by Chemical Formula 1 must be a thioacrylate monomer. In this case, regardless of the presence of a solvent, solvent-free or solvent-based, both high refractive index and high viscosity characteristics can be achieved. The compound can be applied as a high-refractive-index monomer to all types of quantum-dot-containing curable compositions. The optical properties of the cured layer produced using this quantum-dot-containing curable composition can be maximized.

[0074] In addition, the linking group L in the first polymerizable compound represented by Chemical Formula 1 1 To L 3 The thioether group should not be included, and it may be desirable for the thioether group to be directly bonded to the carbon atom constituting the carbonyl group. 1 To L 3 Including thioether groups reduces both the refractive index and viscosity, which may not be desirable.

[0075] For example, in Chemical Formula 1, L 1 It can be a single bond, an ether group (*-O-*) or a substituted or unsubstituted C1 to C20 alkylene group, L 2 and L 3 Each independently may be a substituted or unsubstituted C1 to C20 alkylene group. In this case, the dispersibility of the quantum dots described later in the polymerizable compound can be further improved.

[0076] For example, the first polymerizable compound may have a refractive index greater than or equal to about 1.49, eg, greater than or equal to about 1.49 and less than or equal to about 1.7.

[0077] For example, the first polymerizable compound can have a viscosity greater than or equal to about 7.0, eg, greater than or equal to about 7.0 and less than or equal to about 15.

[0078] Since the first polymerizable compound represented by Chemical Formula 1 has a high refractive index and viscosity within the above ranges, the optical characteristics of a curable composition including the first polymerizable compound as a quantum dot can be greatly improved while reducing reflectivity.

[0079] On the other hand, curable compositions containing green quantum dots have relatively lower absorptivity (ABS) and luminous efficiency (EQE) compared to curable compositions containing red quantum dots, and their reflectivity is almost doubled. Therefore, the technical challenges of improving the brightness of green quantum dot pixels in panels and further increasing frontal brightness by reducing external light reflection remain unresolved.

[0080] The present inventors have clearly solved the above problems, conducted relevant research for a long time and experienced hundreds of trial and error to improve the optical properties of a curable composition containing green quantum dots and reduce its reflectivity. By applying the compound represented by Chemical Formula 1 as a polymerizable compound, the above technical problems have been solved.

[0081] Typically, the primary method for improving the optical properties of curable compositions containing green quantum dots is to increase the amount of inorganic material. Conversely, the primary method for reducing the reflectivity of curable compositions containing green quantum dots is to increase the amount of organic material. Because improving optical properties and reducing reflectivity are opposing physical properties—that is, they are in a trade-off relationship—simultaneously achieving both properties is very difficult.

[0082] According to some embodiments, by applying the first polymerizable compound represented by Chemical Formula 1 to the curable composition, the effects of improving optical properties and reducing reflectivity can be simultaneously achieved not only in the curable composition containing red quantum dots but also in the curable composition containing green quantum dots.

[0083] For example, the compound represented by Chemical Formula 1 may be represented by any one of Chemical Formulas 1-1 to 1-3, but is not necessarily limited thereto.

[0084] [Chemical Formula 1-1]

[0085]

[0086] [Chemical formula 1-2]

[0087]

[0088] [Chemical formula 1-3]

[0089]

[0090] For example, the polymerizable compound may further include a compound (second polymerizable compound) having a different structure from the compound represented by Chemical Formula 1. That is, the polymerizable compound may include the compound represented by Chemical Formula 1 (first polymerizable compound) and another compound (second polymerizable compound) having a different structure.

[0091] For example, the second polymerizable compound having a different structure from the compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 2.

[0092] [Chemical Formula 2]

[0093]

[0094] In Chemical Formula 2,

[0095] L 4 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*),

[0096] L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0097] R 3 and R 4 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0098] When the curable composition according to some embodiments may further include a high refractive index / high viscosity compound represented by Chemical Formula 1 and additionally include a compound represented by Chemical Formula 2 as a polymerizable compound, the effects of improving the optical properties of the curable composition, reducing reflectivity, and improving inkjet performance may also be simultaneously achieved, as in the case of using the compound represented by Chemical Formula 1 alone.

[0099] For example, the compound represented by Chemical Formula 2 may have a refractive index less than or equal to about 1.455. If the compound represented by Chemical Formula 2 has a refractive index exceeding about 1.455, this is advantageous in improving optical characteristics but may be disadvantageous in reducing reflectivity.

[0100] For example, the compound represented by Chemical Formula 1 and a compound having a different structure from the compound represented by Chemical Formula 1 (e.g., a compound represented by Chemical Formula 2, etc.) may be included in a weight ratio of about 1:9 to about 9:1 (e.g., about 1:9 to about 5:5).

[0101] For example, the content of the compound represented by Chemical Formula 1 may be equal to or less than a compound having a different structure from the compound represented by Chemical Formula 1 (eg, a compound represented by Chemical Formula 2, etc.).

[0102] When the content of the compound represented by Chemical Formula 1 is equal to or less than the compound having a structure different from the compound represented by Chemical Formula 1 (e.g., the compound represented by Chemical Formula 2, etc.), for example, when the compound represented by Chemical Formula 1 and the compound having a structure different from the compound represented by Chemical Formula 1 (e.g., the compound represented by Chemical Formula 2, etc.) are included in a weight ratio of about 1:9 to about 5:5, the curing rate of the curable composition according to some embodiments is increased, and both effects of improving optical properties and reducing reflectivity can be maximized.

[0103] For example, the compound represented by Chemical Formula 2 may be represented by Chemical Formula 2-1, 2-2, or 2-3, but is not necessarily limited thereto.

[0104] [Chemical Formula 2-1]

[0105]

[0106] [Chemical Formula 2-2]

[0107]

[0108] [Chemical formula 2-3]

[0109]

[0110] For example, in addition to the compounds represented by Chemical Formulas 2-1 to 2-3, the compound having a structure different from that of the compound represented by Chemical Formula 1 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.

[0111] In addition, in addition to the polymerizable compound, monomers commonly used in conventional heat-curing or light-curing compositions can also be further used. For example, the monomers can further include oxetane compounds, such as bis[1-ethyl(3-oxetane)]methyl ether.

[0112] For example, the curable composition can be a solvent-free curable composition. In this case, based on the total amount of the solvent-free curable composition, the amount of about 40 % by weight to about 95 % by weight (such as about 50 % by weight to about 90 % by weight) can comprise polymerizable compound. If the amount of polymerizable compound is within the above range, the solvent-free curable composition with the viscosity that can carry out inkjet can be manufactured. In addition, the quantum dot in the solvent-free curable composition of preparation can have excellent dispersibility, thereby improving optical properties.

[0113] For example, the polymerizable compound may have a molecular weight of about 170 g / mol to about 1,000 g / mol. If the molecular weight of the polymerizable compound is within the above range, it may be advantageous for inkjet because it does not impair the optical properties of the quantum dots or increase the viscosity of the composition.

[0114] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of about 1 wt % to about 20 wt % (e.g., about 5 wt % to about 15 wt %) based on the total amount of the curable composition. If the polymerizable compound is included within the above range, the optical properties of the quantum dots may be improved.

[0115] quantum dots

[0116] For example, quantum dots can have a maximum fluorescence emission wavelength of about 500 nanometers to about 680 nanometers.

[0117] For example, when the curable composition according to some embodiments is a solvent-free curable composition, the quantum dots may be included in an amount of about 5 wt % to about 60 wt %, such as about 10 wt % to about 60 wt %, such as about 20 wt % to about 60 wt %, such as about 30 wt % to about 50 wt %. If the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0118] For example, when the curable composition according to some embodiments is a curable composition including a solvent, the quantum dots may be included in an amount of about 1 wt % to about 40 wt %, for example, about 3 wt % to about 30 wt %, based on the total amount of the curable composition. If 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.

[0119] For example, quantum dots absorb light in a wavelength region of about 360 nm to about 780 nm (e.g., about 400 nm to about 780 nm), and emit fluorescence in a wavelength region of about 500 nm to about 700 nm (e.g., about 500 nm to about 580 nm, or about 600 nm to about 680 nm). That is, the quantum dots may have a maximum fluorescence emission wavelength (fluorescence λ) at about 500 nm to about 680 nm. em ).

[0120] 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) in this range, the color gamut is increased when used as a color material in a color filter due to high color purity.

[0121] The quantum dots may each independently be an organic material, an inorganic material, or a hybrid (mixture) of an organic material and an inorganic material.

[0122] The quantum dots can each independently consist of a core and a shell surrounding the core, and the core and the shell can each independently have a structure of 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 to.

[0123] For example, the core may include at least one material selected from the group consisting of 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 group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.

[0124] In some embodiments, 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.

[0125] 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.

[0126] For example, the quantum dots can each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots can each independently have an average particle size of about 10 nanometers to about 15 nanometers. The green quantum dots can each independently have an average particle size of about 5 nanometers to about 8 nanometers.

[0127] On the other hand, for the dispersion stability of quantum dots, the curable composition according to the embodiment may further include a dispersant. 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 may be used alone or in the form of a mixture greater than two kinds. By the solid content of the light-converting material such as quantum dots, a dispersant may be used in an amount of 0.1 wt % to 100 wt %, for example, 10 wt % to 20 wt %.

[0128] For example, quantum dots can be surface-modified with ligands having polar groups (e.g., ligands with high affinity for polymerizable compounds). In the case of surface-modified quantum dots as described above, it is very easy to produce highly concentrated or concentrated quantum dot dispersions (to improve the dispersibility of the quantum dots in the polymerizable compound), which can have a significant impact on improving light efficiency, especially when achieving solvent-free curable compositions.

[0129] For example, a ligand having a polar group may have a structure having a high affinity for the chemical structure of a polymerizable compound.

[0130] For example, the ligand having a polar group may be represented by any one of the compounds represented by Chemical Formula A to Chemical Formula Q, but is not necessarily limited thereto.

[0131] [Chemical Formula A]

[0132]

[0133] [Chemical Formula B]

[0134]

[0135] [Chemical Formula C]

[0136]

[0137] [Chemical Formula D]

[0138]

[0139] In Chemical Formula D, m1 is an integer from 0 to 10.

[0140] [Chemical Formula E]

[0141]

[0142] [Chemical Formula F]

[0143]

[0144] [Chemical formula G]

[0145]

[0146] [Chemical formula H]

[0147]

[0148] [Chemical Formula I]

[0149]

[0150] [Chemical Formula J]

[0151]

[0152] [Chemical formula K]

[0153]

[0154] [Chemical formula L]

[0155]

[0156] [Chemical Formula M]

[0157]

[0158] [Chemical formula N]

[0159]

[0160] [Chemical formula O]

[0161]

[0162] [Chemical formula P]

[0163]

[0164] [Chemical formula Q]

[0165]

[0166] When the above ligand is used, surface modification of quantum dots is easier, and when the quantum dots surface-modified with the above ligand are added to the above polymerizable compound and stirred, a very transparent dispersion can be obtained, which serves as a measure to confirm that the surface modification of the quantum dots is very successful.

[0167] Light diffuser

[0168] The curable composition according to some embodiments may further include a light diffusing agent.

[0169] 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.

[0170] The light diffusing agent can reflect the light not absorbed by the quantum dots and make the quantum dots absorb the reflected light again. In other words, the light diffusing agent can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

[0171] The average particle size of the light diffusing agent (D 50 ) can be about 150 nm to about 250 nm, specifically about 180 nm to about 230 nm. If the average particle size of the light diffusing agent is within these ranges, it can have a better light diffusing effect and improve the light conversion efficiency.

[0172] The amount of the light diffuser may be from about 1% to about 20% by weight, for example, from about 2% to about 15% by weight, or from about 3% to about 10% by weight, based on the total amount of the curable composition. If the amount of the light diffuser is less than about 1% by weight, it is difficult to expect an improvement in light conversion efficiency by using the light diffuser, while if the amount is greater than about 20% by weight, the quantum dots may precipitate.

[0173] polymerization initiator

[0174] The curable composition according to some embodiments may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0175] The photopolymerization initiator is an initiator commonly used in 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.

[0176] 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.

[0177] 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.

[0178] Examples of the thioxanthone compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] Examples of aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like.

[0183] In addition to the above compounds, the photopolymerization initiator may further include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and the like.

[0184] 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.

[0185] Examples of the photosensitizer may include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0186] 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.

[0187] The amount of the polymerization initiator may be about 0.1 wt % to about 5 wt %, for example, about 1 wt % to about 4 wt %, based on the total amount of the curable composition. If the polymerization initiator is included within the above range, excellent reliability may be obtained due to sufficient curing during exposure or thermal curing, and it is possible to prevent transmittance degradation due to non-reactive initiators, thereby preventing degradation of optical properties of quantum dots.

[0188] Adhesive resin

[0189] The curable composition according to some embodiments may further include a binder resin.

[0190] The binder resin may include acrylic resin, carbazole resin, epoxy resin, or a combination thereof.

[0191] 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.

[0192] Specific examples of acrylic resins 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.

[0193] The weight average molecular weight of the acrylic resin may be about 5,000 g / mol to about 15,000 g / mol. If the weight average molecular weight of the acrylic resin is within these ranges, close contact characteristics with the substrate, physical and chemical characteristics are improved, and viscosity is appropriate.

[0194] The acid value of the acrylic resin may be about 80 mg KOH / g to about 130 mg KOH / g. If the acid value of the acrylic resin is within these ranges, excellent pixel resolution may be achieved.

[0195] The carbazole-based resin may be used in a conventional curable resin (or photosensitive resin) composition and may be generally used as disclosed in, for example, Korean Patent Application Laid-Open No. 10-2018-0067243, but is not limited thereto.

[0196] 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.

[0197] 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. If the weight average molecular weight of the carbazole-based binder resin is within this range, a satisfactory pattern can be formed without residue during the production of the cured layer and without loss of film thickness during the development of the curable composition.

[0198] If the binder resin is a carbole-based resin, a curable composition (particularly a photosensitive resin composition) containing the same has excellent developability and sensitivity during photocuring, and thus has fine pattern forming capability.

[0199] The epoxy resin may be a thermally polymerizable monomer or oligomer, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0200] The epoxy resin may further include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cycloaliphatic epoxy resin, and aliphatic polyglycidyl ether, but is not necessarily limited thereto.

[0201] As commercially available products of these compounds, the biphenyl epoxy resin may be YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co., Ltd.; the cresol novolac type epoxy resin may be EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 of Nippon Kayaku Co., Ltd. and EPIKOTE180S75 of Yuka Shell Epoxy Co., Ltd.; the bisphenol A epoxy resin may be EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010 and EPIKOTE 828; bisphenol F type epoxy resins can be EPIKOTE 807 and EPIKOTE 834 of Shell Epoxy Resins Co., Ltd.; phenol novolac type epoxy resins can be EPIKOTE 152, EPIKOTE 154 or EPIKOTE 157H65 of Shell Epoxy Resins Co., Ltd. and EPPN 201, EPPN 202 of Nippon Kayaku Co., Ltd.; other cycloaliphatic epoxy resins can be CY175, CY177 and CY179 of CIBA-GEIGY AG, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 of Union Carbide Corporation (UCC), and ERL-4206 of Showa Denko K.K. KK) Showdyne 509, Ciba-Geigy Group'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.'s ED-5661 and ED-5662; the aliphatic polyglycidyl ether may be Shell Epoxy Resins Co., Ltd.'s EPIKOTE 190P and EPIKOTE191P, Kyoesha Yushi Co., Ltd.'s EPOLITE 100MF, Nippon Yushi Co.,Ltd.)'s EPIOL TMP, etc. .

[0202] For example, when the curable composition according to some embodiments is a solvent-free curable composition, the amount of the binder resin may be about 0.5 wt % to about 10 wt %, for example, about 1 wt % to about 5 wt %, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition may be improved, as well as the storage stability of the composition.

[0203] For example, when the curable composition according to some embodiments is a curable composition including a solvent, the amount of the binder resin may be about 1 wt % to about 30 wt %, for example, about 3 wt % to about 20 wt %, based on the total amount of the curable composition. In this case, it is possible to improve pattern characteristics, heat resistance, and chemical resistance.

[0204] Other additives

[0205] To improve the stability and dispersibility of quantum dots, the curable composition according to some embodiments may further include a polymerization inhibitor.

[0206] The polymerization inhibitor may include, but is not limited to, a hydroquinone compound, a catechol compound, or a combination thereof. When the curable composition according to some embodiments further includes a hydroquinone compound, a catechol compound, or a combination thereof, room temperature crosslinking during exposure after coating the curable composition may be prevented.

[0207] 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.

[0208] The hydroquinone compound, catechol compound, or combination thereof can be used in a dispersed form. A polymerization inhibitor in the form of a dispersion can be included in an amount of about 0.001 to about 3 weight percent, for example, about 0.01 to about 2 weight percent, based on the total weight of the curable composition. If the polymerization inhibitor is included within this range, the problem of aging at room temperature can be resolved while also preventing sensitivity deterioration and surface peeling.

[0209] In addition, the curable composition according to some embodiments 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 to improve heat resistance and reliability.

[0210] For example, the curable composition according to an embodiment may further include a silane-based coupling agent having a reactive substituent (eg, a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc.) to improve close contact performance with the substrate.

[0211] Examples of the silane coupling agent may include trimethoxysilylbenzoic acid, γ-methacrylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, and the like, which may be used alone or in mixtures of two or more.

[0212] The silane-based coupling agent may be used in an amount of about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the curable composition. If the silane-based coupling agent is included within the range, close contact properties, storage ability, etc. are improved.

[0213] In addition, the curable composition may further include a surfactant, such as a fluorine-based surfactant, as needed to improve coating properties and suppress the generation of spots, that is, to improve leveling properties.

[0214] The fluorochemical surfactant may have a low weight average molecular weight of about 4,000 g / mol to about 10,000 g / mol, specifically about 6,000 g / mol to about 10,000 g / mol. In addition, the fluorochemical surfactant may have a surface tension of about 18 millinewtons / meter to about 23 millinewtons / meter (measured in a 0.1% polyethylene glycol monomethylether acetate (PGMEA) solution). If the fluorochemical surfactant has a weight average molecular weight and surface tension within these ranges, the leveling performance can be further improved, and when applied as a slit coating for high-speed coating, excellent properties can be provided because the generation of film defects can be reduced by preventing spot generation and suppressing vapor generation during high-speed coating.

[0215] 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 of Dainippon Ink & Chemicals Co., Ltd. (DIC Co., Ltd.).

[0216] In addition, the curable composition according to some embodiments 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., manufactured by Toshiba Silicon Corporation, but are not limited thereto.

[0217] The amount of the surfactant can be about 0.01 to about 5 parts by weight, such as about 0.1 to about 2 parts by weight, based on 100 parts by weight of the curable composition. If the surfactant is included within these ranges, less impurities are generated in the sprayed composition.

[0218] In addition, unless characteristics are deteriorated, the curable composition according to some embodiments may further include a predetermined amount of other additives such as an antioxidant, a stabilizer, and the like.

[0219] solvent

[0220] Meanwhile, the curable composition according to some embodiments may further include a solvent.

[0221] 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.

[0222] For example, the solvent may preferably be glycol ethers, such as ethylene glycol monoethyl ether, ethylene diglycol methyl ethyl ether, etc.; ethylene glycol alkyl ether acetates, such as ethyl glycol ethyl 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.

[0223] 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.

[0224] The amount of the solvent may be about 40 wt % to about 80 wt %, e.g., about 45 wt % to about 80 wt %, based on the total amount of the curable composition. If the solvent is within the above range, the solvent-based curable composition has an appropriate viscosity and thus may have excellent coating properties when applied to a large area by spin coating and slit coating.

[0225] Some embodiments provide a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter.

[0226] One of the methods of manufacturing a cured layer may include coating a curable composition and a solvent-based curable composition on a substrate using an inkjet spraying method to form a pattern ( S1 ); and curing the pattern ( S2 ).

[0227] (S1) Pattern formation

[0228] The curable composition can be preferably applied to the substrate by an inkjet coating method to a thickness of about 0.5 μm to about 20 μm. The inkjet coating method can form a pattern by spraying a single color per nozzle and repeating the spraying of the desired number of colors. However, in order to reduce the number of steps, the pattern can also be formed by spraying the desired number of colors simultaneously per inkjet nozzle.

[0229] (S2) Curing

[0230] The obtained pattern is cured to obtain pixels. Here, the curing method may be a thermal curing or a photocuring process. The thermal curing process may be performed at a temperature greater than or equal to about 100°C, preferably in the range of about 100°C to about 300°C, and more preferably in the range of about 160°C to about 250°C. The photocuring process may include irradiating actinic rays of about 190nm to about 450nm, such as ultraviolet rays of about 200nm to about 500nm. Light sources for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and in some cases, X-rays and electron beams.

[0231] Another method of manufacturing a cured layer may include manufacturing a cured layer by the following photolithography method using the above-mentioned curable composition or solvent-based curable composition.

[0232] (1) Coating and film formation

[0233] The curable composition is applied to a substrate that has undergone a predetermined pretreatment to a desired thickness, for example, a thickness ranging from about 2 μm to about 10 μm, using a spin coating or slit coating method, a roll coating method, a screen printing method, an applicator method, etc. The coated substrate is then heated at a temperature of about 70° C. to about 90° C. for about 1 minute to about 10 minutes to remove the solvent and form a thin film.

[0234] (2) Exposure

[0235] A mask having a predetermined shape is placed on the resulting film, and then irradiated with actinic radiation of about 190 nm to about 450 nm, such as ultraviolet radiation of about 200 nm to about 500 nm, to form the desired pattern. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, and in some cases, X-rays and electron beams.

[0236] When a high pressure mercury lamp is used, the exposure process uses, for example, 500 mJ / cm 2 or lower light dose (using a 365 nm sensor). However, the light dose may vary depending on the types of components of the curable composition, their combination ratio, and dry film thickness.

[0237] (3) Development

[0238] After the exposure process, the exposed film is developed using an alkaline aqueous solution by dissolving and removing unnecessary portions other than the exposed portions, thereby forming an image pattern. In other words, when developing using an alkaline developer, the unexposed areas are dissolved and an image color filter pattern is formed.

[0239] (4) Post-processing

[0240] The developed image pattern can be heated again or irradiated with actinic rays or the like to be cured to achieve excellent heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability and the like qualities.

[0241] 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.

[0242] Preparation of curable compositions

[0243] Preparation Example 1

[0244] Dissolve 16.3 g of 1,4-butanedithiol in 100 ml of toluene. Add 47.34 g of 3-chloropropionyl chloride and stir at 50°C for 12 hours to terminate the reaction. Extract the reaction solution with 100 ml of water and 150 ml of dichloromethane. Add MgSO₄ to the separated organic layer, stir for 5 minutes, filter, and concentrate the filtrate. Purify by column chromatography, concentrate, and dry in vacuo.

[0245] 33 g of the dried intermediate was fully dissolved in 150 ml of acetone and stirred at 0°C for 10 minutes. 45.5 g of triethylamine was added, and the mixture was stirred for an additional 10 minutes, followed by stirring at 50°C for 12 hours to terminate the reaction. The reaction solution was extracted with 100 ml of 1N aqueous hydrochloric acid and 150 ml of dichloromethane. MgSO₄ was added to the separated organic layer, stirred for 5 minutes, filtered, and the filtrate was concentrated. After purification by column chromatography, concentration, and vacuum drying, the compound represented by Chemical Formula 1-1 (refractive index: 1.5508, viscosity: 7.3) was prepared.

[0246] [Chemical Formula 1-1]

[0247]

[0248] Preparation Example 2

[0249] Dissolve 18.6 g of bis(2-mercaptoethyl)ether in 100 ml of toluene. Add 51.3 g of 3-chloropropionyl chloride and stir at 50°C for 12 hours to terminate the reaction. Extract the reaction solution with 100 ml of water and 150 ml of dichloromethane. Add MgSO₄ to the separated organic layer, stir for 5 minutes, filter, and concentrate the filtrate. Purify by column chromatography, concentrate, and dry in vacuo.

[0250] 34 g of the dried intermediate was thoroughly dissolved in 150 ml of acetone and stirred at 0°C for 10 minutes. 44.5 g of triethylamine was added, followed by stirring for an additional 10 minutes, and then the reaction was terminated by stirring at 50°C for 12 hours. The reaction solution was extracted with 100 ml of 1N aqueous hydrochloric acid and 150 ml of dichloromethane. MgSO₄ was added to the separated organic layer, stirred for 5 minutes, filtered, and the filtrate concentrated. After purification by column chromatography, concentration, and vacuum drying, the compound represented by Chemical Formula 1-2 (refractive index: 1.5455, viscosity: 10.1) was prepared.

[0251] [Chemical formula 1-2]

[0252]

[0253] Preparation Example 3

[0254] 24 g of 6-mercapto-1-hexanol was thoroughly dissolved in 100 ml of toluene. 62.41 g of 3-chloropropionyl chloride was added and the reaction was terminated after stirring at 50°C for 12 hours. The reaction solution was extracted with 100 ml of water and 150 ml of dichloromethane. MgSO₄ was added to the separated organic layer, stirred for 5 minutes, filtered, and the filtrate was concentrated. After purification by column chromatography, the mixture was concentrated and dried under vacuum.

[0255] 50 g of the dried intermediate was thoroughly dissolved in 150 ml of acetone and stirred at 0°C for 10 minutes. 44.5 g of triethylamine was added, and the mixture was stirred for an additional 10 minutes. The reaction was then terminated by stirring at 50°C for 12 hours. The reaction solution was extracted with 100 ml of 1N aqueous hydrochloric acid and 150 ml of dichloromethane. MgSO₄ was added to the separated organic layer, stirred for 5 minutes, filtered, and the filtrate concentrated. After purification by column chromatography, concentration, and vacuum drying, the compound represented by Chemical Formula 1-3 (refractive index: 1.4987, viscosity: 7.1) was prepared.

[0256] [Chemical formula 1-3]

[0257]

[0258] Preparation of surface-modified quantum dot dispersion

[0259] Preparation Example 4

[0260] After placing a magnetic stirrer in a three-necked round-bottom flask, a green quantum dot dispersion (InP / ZnSe / ZnS, Hansong Chemical, quantum dot solid content: 23 wt%) was added thereto. Subsequently, the compound (ligand) represented by the chemical formula Q was added and then stirred at 80 ° C under a nitrogen atmosphere. After the reaction was completed, it was cooled to room temperature (23 ° C), and the quantum dot reaction solution was added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and then fully dried in a vacuum oven for 24 hours to obtain surface-modified quantum dots.

[0261] The surface-modified green quantum dots were stirred with the polymerizable compound for 12 hours to obtain a surface-modified quantum dot dispersion (quantum dot solid content: 23 wt %).

[0262] (*Synthesis of the compound represented by Chemical Formula Q: 100 g of PH-4 (Hannong Chemical Co., Ltd.) was placed in a two-necked round-bottom flask and then fully dissolved in 300 ml of tetrahydrofuran. Subsequently, 15.4 g of sodium hydroxide and 100 ml of water were added at 0°C and then fully dissolved until a clear solution was obtained. A solution prepared by dissolving 73 g of p-toluenesulfonyl chloride in 100 ml of tetrahydrofuran was slowly injected thereinto at 0°C. The injection process was continued for 1 hour, and the obtained mixture was then stirred at room temperature for 12 hours. When the reaction was completed, an excess of dichloromethane was added thereto and stirred, and then saturated NaHCO3 was added thereto. The solution was extracted, titrated, and dehydrated. After removing the solvent, the residue 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 thoroughly stirred with 300 ml of ethanol. Subsequently, 27 g of thiourea was added and dispersed therein, and then refluxed at 80°C for 12 hours. Subsequently, an aqueous solution of 4.4 g of sodium hydroxide dissolved in 20 ml of water was injected therein, while continuing to stir for 5 hours, an excess of dichloromethane was added and stirred, and then an aqueous hydrochloric acid solution was added, and extraction, titration, dehydration, and solvent removal were carried out in sequence. It was then dried in a vacuum oven for 24 hours to obtain the compound represented by the chemical formula Q.)

[0263] [Chemical formula Q]

[0264]

[0265] (Preparation of Curable Composition)

[0266] Examples 1 to 5 and Comparative Examples 1 and 2

[0267] Each curable composition of Examples 1 to 5 and Comparative Examples 1 and 2 was prepared using the following components to obtain the respective compositions shown in Tables 1 and 2.

[0268] Specifically, a quantum dot dispersion was weighed, diluted by mixing with a polymerizable compound, and a polymerization inhibitor was added thereto, followed by stirring for 5 minutes. Subsequently, a photoinitiator was added thereto, followed by a light diffuser. The resulting composition was then stirred for 1 hour to prepare a curable composition.

[0269] (A)Quantum dots

[0270] Surface modified green quantum dot dispersion prepared from Preparation Example 4

[0271] (B) polymerizable compound

[0272] (B-1) Compound of Preparation Example 1 (First Polymerizable Compound)

[0273] (B-2) Compound of Preparation Example 2 (First Polymerizable Compound)

[0274] (B-3) Compound of Preparation Example 3 (First Polymerizable Compound)

[0275] (B-4) Compound represented by Chemical Formula 2-2 (M200, Miwon Chemical Co., Ltd.) (refractive index: 1.455, viscosity: 6.1 cps) (second polymerizable compound)

[0276] [Chemical Formula 2-2]

[0277]

[0278] (C) Photopolymerization initiator

[0279] TPO-L (Polynetron Co., Ltd.)

[0280] (D) Light Diffuser

[0281] Titanium dioxide dispersion (TiO2 solid content: 20 wt%, average particle size: 200 nm, Dito Technology Co., Ltd.)

[0282] (E) Polymerization inhibitor

[0283] Methylhydroquinone (TOKYO CHEMICAL Co., Ltd.)

[0284] (Table 1)

[0285] (Unit: wt%)

[0286]

[0287] Evaluation: Evaluation of optical properties and diffuse reflectance of curable compositions

[0288] For each of the curable compositions of Examples 1 to 5 and Comparative Examples 1 and 2, the quantum efficiency (EQE) after exposure and the diffuse reflectance (SCE) after curing were measured using a spectrophotometer (CM-3600A, Konica Minolta). The results are shown in Table 2.

[0289] (Table 2)

[0290]

[0291] Referring to Table 2, the curable compositions of Examples 1 to 5 exhibited improved optical properties compared to the curable compositions of Comparative Examples 1 and 2 due to high quantum efficiency after exposure, while reducing reflection effects due to low diffuse reflectivity after curing.

[0292] 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 is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the above embodiments should be understood as illustrative and not limiting in any way.

Claims

1. A curable composition comprising: (A) Quantum dots; as well as (B) a polymerizable compound including a first polymerizable compound represented by Chemical Formula 1: [Chemical Formula 1] Wherein, in Chemical Formula 1, R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, L 1 To L 3 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and X 1 and X 2 are each independently an ether group (*-O-*) or a thioether group (*-S-*), provided that X 1 and X 2 At least one of them must be a thioether group (*-S-*).

2. The curable composition according to claim 1, wherein L 1 is a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group.

3. The curable composition according to claim 1, wherein L 2 and L 3 Each is independently a substituted or unsubstituted C1 to C20 alkylene group. 4 . The curable composition of claim 1 , wherein the first polymerizable compound has a refractive index greater than or equal to 1.49 and a viscosity greater than or equal to 7.

0.

5. The curable composition according to claim 1, wherein the first polymerizable compound is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3: [Chemical Formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] 6 . The curable composition according to claim 1 , wherein the polymerizable compound further comprises a second polymerizable compound having a different structure from that of the first polymerizable compound.

7. The curable composition according to claim 6, wherein the second polymerizable compound comprises a compound represented by Chemical Formula 2: [Chemical Formula 2] in, In Chemical Formula 2, L 4 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*), L 5 and L 6 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and R 3 and R 4 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. 8 . The curable composition according to claim 7 , wherein the first polymerizable compound and the second polymerizable compound are included in a weight ratio of 1:9 to 9:

1. 9 . The curable composition of claim 8 , wherein the first polymerizable compound and the second polymerizable compound are included in a weight ratio of 1:9 to 5:

5.

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

11. The curable composition according to claim 10, wherein the solvent-free curable composition comprises, based on the total amount of the solvent-free curable composition: 5 wt % to 60 wt % of said quantum dots; as well as 40% to 95% by weight of the polymerizable compound.

12. The curable composition according to claim 1, wherein The curable composition further includes a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

13. The curable composition of claim 12, wherein the light diffuser comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

14. The curable composition of claim 1, wherein the curable composition further comprises a solvent.

15. The curable composition of claim 14, wherein the curable composition comprises, based on the total weight of the curable composition: 1 wt% to 40 wt% of said quantum dots: 1 to 20 wt% of the polymerizable compound; and 40 wt % to 80 wt % of the solvent.

16. 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.

17. A cured layer produced using the curable composition according to any one of claims 1 to 16.

18. A color filter comprising the cured layer according to claim 17.

19. A display device comprising the cured layer according to claim 17.

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