Curable composition, cured layer using the same, and display device comprising the cured layer

Abstract

The present invention provides a curable composition, a cured layer manufactured using the same, and a display device including the cured layer. The curable composition includes (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound is a compound represented by Chemical Formula 1. In Chemical Formula 1, each substituent is the same as defined in the specification.[Chemical Formula 1]

Description

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2020-0104367, filed on August 20, 2020, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to a curable composition, a cured layer manufactured using the same, and a display device comprising the cured layer. Background Technology

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

[0005] For example, even with active research into quantum dot ink compositions, the polarity is relatively low in the initial steps, and they can be dispersed in solvents used in curable compositions with high hydrophobicity. Therefore, since it is difficult to contain 20% by weight or more of quantum dots in the total composition, it is impossible to improve the light efficiency of the ink above a certain level. Even if additional quantum dots are added and dispersed to improve light efficiency, the viscosity exceeds the range suitable for inkjet printing (12 centipoise), and therefore the processability may be unsatisfactory.

[0006] To achieve a viscosity range suitable for inkjet printing, reducing the ink solids content by dissolving 50% or more of a solvent by weight of the total composition provides slightly satisfactory results in terms of viscosity. However, while the viscosity may be considered satisfactory, issues such as nozzle drying and clogging due to solvent evaporation, as well as layer reduction over time after printing, can worsen, and thickness deviations are difficult to control after curing. Therefore, it is difficult to apply this method to practical processes.

[0007] Therefore, solvent-free quantum dot inks are the most ideal form for practical applications. Existing techniques for incorporating quantum dots themselves into solvent-based compositions are currently subject to certain limitations.

[0008] As reported to date, when applying the most ideal solvent-based composition to practical processes, the content of unmodified quantum dots, such as ligand-substituted ones, is 20% to 25% by weight, based on the total amount of the solvent-based composition. Therefore, it is difficult to improve light efficiency and absorptivity due to viscosity limitations. Furthermore, attempts have been made to reduce the quantum dot content and increase the content of light diffusing agents (scatterers) in other improvement methods, but these have also failed to solve the precipitation problem and the low light efficiency problem.

[0009] Therefore, the demand for solvent-free compositions is increasing. In the case of solvent-free compositions, there is a problem of pattern separation because the close contact force between the curing process or subsequent processes is reduced due to high shrinkage during curing. Summary of the Invention

[0010] The embodiments provide a curable composition that minimizes processability problems such as pattern lifting through a tight contact force with high light efficiency and improved patterning.

[0011] Another embodiment provides a cured layer manufactured using a curable composition.

[0012] Another embodiment provides a display device including a cured layer.

[0013] An embodiment provides a curable composition comprising (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound comprises a compound represented by chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] In chemical formula 1,

[0017] R a It is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0018] L a and L b Each is independently a substituted or unsubstituted C1 to C20 alkylene oxide or a substituted or unsubstituted C1 to C20 alkylene oxide, but L a With L b different.

[0019] Substituted or unsubstituted C1 to C20 oxyalkylene groups can be represented by chemical formula 2.

[0020] [Chemical Formula 2]

[0021]

[0022] In chemical formula 2,

[0023] L c It is a substituted or unsubstituted C1 to C20 alkylene group, and

[0024] n is an integer from 1 to 10.

[0025] The compound represented by chemical formula 1 may be included in an amount from 0.5% to 10% by weight, based on the total amount of the curable composition.

[0026] The polymerizable compound may further include polymerizable compounds having carbon-carbon double bonds at both ends.

[0027] Polymerizable compounds with carbon-carbon double bonds at both ends can have a weight average molecular weight of 200 g / mol to 1,000 g / mol.

[0028] Polymerizable compounds with carbon-carbon double bonds at both ends can be represented by chemical formula 3.

[0029] [Chemical Formula 3]

[0030]

[0031] In chemical formula 3,

[0032] R' and R'' are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0033] L d It is a substituted or unsubstituted C5 to C20 alkylene group.

[0034] The polymerizable compound may be included in an amount of 1% to 15% by weight, representing a polymerizable compound of chemical formula 1, and may be included in an amount of 85% to 99% by weight, representing a polymerizable compound having carbon-carbon double bonds at both ends.

[0035] Quantum dots can be surface modified using any of the compounds represented by chemical formulas 4 to 17 or combinations thereof.

[0036] [Chemical Formula 4]

[0037]

[0038] [Chemical Formula 5]

[0039]

[0040] [Chemical Formula 6]

[0041]

[0042] [Chemical Formula 7]

[0043]

[0044] [Chemical Formula 8]

[0045]

[0046] [Chemical Formula 9]

[0047]

[0048] In chemical formulas 4 to 9

[0049] R 1 To R 7 Each is independently a substituted or unsubstituted C1 to C10 alkyl or a substituted or unsubstituted C6 to C20 aryl, L 1 To L 16 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0050] n1 to n7 are each an independent integer from 0 to 10.

[0051] [Chemical Formula 10]

[0052]

[0053] [Chemical Formula 11]

[0054]

[0055] [Chemical Formula 12]

[0056]

[0057] In chemical formulas 10 to 12,

[0058] R 8 and R 9 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0059] L 17 To L 23 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and each of n8 to n10 is independently an integer from 0 to 10.

[0060] [Chemical Formula 13]

[0061]

[0062] [Chemical Formula 14]

[0063]

[0064] [Chemical Formula 15]

[0065]

[0066] [Chemical Formula 16]

[0067]

[0068] In chemical formulas 13 to 16

[0069] R 10 To R 15 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0070] L 24 To L 29 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0071] n11 to n16 are each an independent integer from 0 to 10.

[0072] [Chemical Formula 17]

[0073]

[0074] In chemical formula 17,

[0075] R 16 To R 18 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0076] L 30 To L 32 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0077] n17 to n19 are each an independent integer from 0 to 10.

[0078] Quantum dots can have the maximum fluorescence emission wavelength in the range of 500 nanometers to 680 nanometers.

[0079] The curable composition may further comprise a polymerization initiator, a light diffuser, a polymerization inhibitor, an adhesive resin, or a combination thereof.

[0080] Light diffusers may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or combinations thereof.

[0081] The curable composition can be a solvent-free curable composition.

[0082] Based on the total weight of the solvent-free curable composition, the solvent-free curable composition comprises 1 wt% to 60 wt% of (A) quantum dots; and 40 wt% to 99 wt% of (B) polymerizable compounds.

[0083] Curable compositions include malonic acid; 3-amino-1,2-propanediol; silane coupling agents; leveling agents; fluorinated surfactants; or combinations thereof.

[0084] The curable composition may further contain a solvent. In this document, the curable composition may contain 1 wt% to 40 wt% of (A) quantum dots; 1 wt% to 20 wt% of (B) polymerizable compound; and 40 wt% to 80 wt% of solvent, based on the total weight of the curable composition.

[0085] Another embodiment provides a cured layer manufactured using a curable composition.

[0086] Another embodiment provides a display device including a cured layer.

[0087] Other embodiments of the present invention are described in detail below.

[0088] Curable compositions may be able to address processability issues such as pattern lifting by increasing the tight contact force of the pattern while maintaining high gloss efficiency. Attached Figure Description

[0089] Figure 1 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Example 1 has been applied to a substrate and developed.

[0090] Figure 2 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Example 2 has been applied to a substrate and developed.

[0091] Figure 3 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Example 3 has been applied to a substrate and developed.

[0092] Figure 4 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Comparative Example 1 has been applied to a substrate and developed.

[0093] Figure 5 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Comparative Example 2 has been applied to a substrate and developed.

[0094] Figure 6 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Comparative Example 3 has been applied to a substrate and developed.

[0095] Figure 7 The image is a cross-sectional evaluation photograph of the pattern after the curable composition according to Comparative Example 4 has been applied to a substrate and developed. Detailed Implementation

[0096] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto, and is defined by the scope of the claims.

[0097] As used herein, unless otherwise specifically defined, “alkyl” refers to C1 to C20 alkyl, “alkenyl” refers to C2 to C20 alkenyl, “cycloalkenyl” refers to C3 to C20 cycloalkenyl, “heterocyclic alkenyl” refers to C3 to C20 heterocyclic alkenyl, “aryl” refers to C6 to C20 aryl, “aranealkyl” refers to C6 to C20 aranealkyl, “alkylene” refers to C1 to C20 alkylene, “arylene” refers to C6 to C20 arylene, “alkylarylene” refers to C6 to C20 alkylarylene, “heteroarylene” refers to C3 to C20 heteroarylene, and “alkoxide” refers to C1 to C20 alkoxide.

[0098] As used herein, unless otherwise specifically defined, “substitution” means the replacement of at least one hydrogen atom with 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 azide group, a formamidinyl group, a hydrazinyl group, a hydrazineyl 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 heterocyclic alkyl group, a C2 to C20 heterocyclic alkenyl group, a C2 to C20 heterocyclic alkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0099] As used herein, unless otherwise specifically defined, “heterogeneous” refers to a chemical formula containing at least one heteroatom of N, O, S, and P.

[0100] As used herein, unless otherwise specifically defined, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0101] As used herein, unless otherwise specifically defined, the term “combination” refers to a mixture or copolymerization.

[0102] In this specification, unless otherwise defined, in a chemical formula, when no chemical bond is drawn at the position that should be given, hydrogen is bonded at said position.

[0103] Furthermore, in this specification, unless otherwise defined, "*" refers to a bond point with the same atom or chemical formula or a different atom or chemical formula.

[0104] The curable composition according to the embodiments comprises (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound comprises a compound represented by chemical formula 1.

[0105] [Chemical Formula 1]

[0106]

[0107] In chemical formula 1,

[0108] R a It is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0109] L a and L b Each is independently a substituted or unsubstituted C1 to C20 alkylene oxide or a substituted or unsubstituted C1 to C20 alkylene oxide, but L a With L b different.

[0110] As described above, due to the high shrinkage rate of curable compositions during curing, the pattern continuously lifts and separates as the tight contact force of the formed pattern decreases. To address this issue, current methods often employ methods that reduce the core size of quantum dots during synthesis to induce a blue shift in wavelength during luminescence. However, when cured after coating, curable compositions have the disadvantage of degrading the lightfastness and heat resistance of individual films. Therefore, the inventors have addressed the problem of lightfastness and heat resistance degradation by repeatedly experimenting with polymerizable compounds represented by Formula 1 to prevent pattern separation and thus increase the tight contact force with the pattern on the interface. Furthermore, the quantum dots are surface-modified with specific ligands to improve their aggregation during curing.

[0111] Each component is described in detail below.

[0112] (B) Polymerizable compounds

[0113] For example, a compound represented by chemical formula 1 may contain an alkylene oxide, and the alkylene oxide may be represented by chemical formula 2.

[0114] [Chemical Formula 2]

[0115]

[0116] In chemical formula 2,

[0117] L c It is a substituted or unsubstituted C1 to C20 alkylene group, and

[0118] n is an integer from 1 to 10.

[0119] The curable composition according to the embodiments comprises a compound represented by chemical formula 1, thereby achieving a high degree of tight contact, which leads to improved processability.

[0120] For example, the compound represented by Formula 1 may be included in the total amount of the curable composition at amounts ranging from 0.5% to 10% by weight, such as 1% to 5% by weight. When the compound represented by Formula 1 is included in less than 0.5% by weight of the total amount of the curable composition, the effect of increasing the tightness of the pattern cannot be achieved. When the compound represented by Formula 1 is included in more than 10% by weight, it is difficult to achieve the effect of increasing the tightness of the additional pattern, which is uneconomical, and the viscosity change can become drastic over time, which can actually lead to a deterioration in processability.

[0121] The polymerizable compound may further comprise, for example, a polymerizable compound having carbon-carbon double bonds at both ends.

[0122] When the curable composition is a solvent-free curable composition, it may contain a polymerizable compound having carbon-carbon double bonds at both ends in an amount ranging from 39% to 98% by weight, for example, from 40% to 85% by weight, for example, from 40% to 80% by weight, based on the total amount of the curable composition. When the content of the polymerizable compound having carbon-carbon double bonds at both ends is within the above range, it is possible to prepare a solvent-free curable composition with an inkjet-capable viscosity, and the quantum dots in the prepared solvent-free curable composition exhibit excellent dispersibility to improve optical properties.

[0123] Furthermore, when the curable composition is a solvent-based curable composition, it may include, in an amount of 1% to 20% by weight, for example, 5% to 20% by weight, of the total amount of the curable composition. When a compound having carbon-carbon double bonds at both ends is included within the above range, the optical properties of the quantum dots can be improved.

[0124] For example, polymerizable compounds with carbon-carbon double bonds at both ends can have a weight-average molecular weight of 200 g / mol to 1,000 g / mol. When the weight-average molecular weight of polymerizable compounds with carbon-carbon double bonds at both ends is within this range, it is advantageous for inkjet printing because the viscosity of the composition does not increase without impairing the optical properties of the quantum dots.

[0125] For example, a polymerizable compound having carbon-carbon double bonds at both ends can be represented by chemical formula 3, but is not limited to this.

[0126] [Chemical Formula 3]

[0127]

[0128] In chemical formula 3,

[0129] R' and R'' are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0130] L d It is a substituted or unsubstituted C5 to C20 alkylene group.

[0131] For example, a compound having carbon-carbon double bonds at both ends can be represented by chemical formula 3-1 or chemical formula 3-2, but is not limited to these.

[0132] [Chemical Formula 3-1]

[0133]

[0134] [Chemical Formula 3-2]

[0135]

[0136] For example, in addition to compounds represented by chemical formula 3-1 or chemical formula 3-2, compounds having carbon-carbon double bonds at both ends may 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 tripropionate, novolacepoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or combinations thereof.

[0137] In addition to polymerizable compounds having carbon-carbon double bonds at both ends, commonly used monomers in conventional thermosetting or photocurable compositions can be further used as polymerizable compounds, and the monomers can further include oxetane compounds, such as bis[1-ethyl(3-oxetane)]methyl ether.

[0138] For example, based on the total amount of polymerizable compounds, the compound represented by Formula 1 may be included in an amount of 1.5% to 15% by weight, and the compound having carbon-carbon double bonds at both ends may be included in an amount of 85% to 98.5% by weight. When the compounds are included within the content range, the close contact force between the pattern and the interface is maximized.

[0139] (A)Quantum dots

[0140] The quantum dots in the curable composition according to the embodiments can be, for example, surface-modified quantum dots with ligands having polar groups, such as ligands with high affinity for polymerizable compounds. In the case of surface-modified quantum dots as described above, it is extremely easy to prepare high-concentration or highly concentrated quantum dot dispersions (improving the dispersibility of quantum dots relative to polymerizable compounds), which can have a significant impact on improving light efficiency, and more specifically, can be advantageous for implementing solvent-free curable compositions.

[0141] For example, ligands with polar groups can have structures that have a high affinity for the chemical structure of polymerizable compounds.

[0142] For example, a ligand with a polar group can be represented by any of the chemical formulas 4 to 17, but is not limited to them.

[0143] [Chemical Formula 4]

[0144]

[0145] [Chemical Formula 5]

[0146]

[0147] [Chemical Formula 6]

[0148]

[0149] [Chemical Formula 7]

[0150]

[0151] [Chemical Formula 8]

[0152]

[0153] [Chemical Formula 9]

[0154]

[0155] In chemical formulas 4 to 9

[0156] R 1 To R 7 Each is independently a substituted or unsubstituted C1 to C10 alkyl or a substituted or unsubstituted C6 to C20 aryl, L 1 To L 16 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0157] n1 to n7 are each an independent integer from 0 to 10.

[0158] [Chemical Formula 10]

[0159]

[0160] [Chemical Formula 11]

[0161]

[0162] [Chemical Formula 12]

[0163]

[0164] In chemical formulas 10 to 12,

[0165] R 8 and R 9 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0166] L 17 To L 23 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0167] n8 to n10 are each an independent integer from 0 to 10.

[0168] [Chemical Formula 13]

[0169]

[0170] [Chemical Formula 14]

[0171]

[0172] [Chemical Formula 15]

[0173]

[0174] [Chemical Formula 16]

[0175]

[0176] In chemical formulas 13 to 16

[0177] R 10 To R 15 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0178] L 24 To L 29 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0179] n11 to n16 are each an independent integer from 0 to 10.

[0180] [Chemical Formula 17]

[0181]

[0182] In chemical formula 17,

[0183] R 16 To R 18 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0184] L 30 To L 32 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0185] n17 to n19 are each an independent integer from 0 to 10.

[0186] For example, compounds represented by chemical formulas 4 to 17 can be represented by any of the compounds represented by chemical formulas A to Q, but are not limited to these.

[0187] [Chemical Formula A]

[0188]

[0189] [Chemical Formula B]

[0190]

[0191] [Chemical formula C]

[0192]

[0193] [Chemical formula D]

[0194]

[0195] In chemical formula D, m1 is an integer from 0 to 10.

[0196] [Chemical Formula E]

[0197]

[0198] [Chemical formula F]

[0199]

[0200] [Chemical formula G]

[0201]

[0202] [Chemical formula H]

[0203]

[0204] [Chemical Formula I]

[0205]

[0206] [Chemical Formula J]

[0207]

[0208] [Chemical formula K]

[0209]

[0210] [Chemical formula L]

[0211]

[0212] [Chemical formula M]

[0213]

[0214] [Chemical formula N]

[0215]

[0216] [Chemical formula O]

[0217]

[0218] [Chemical formula P]

[0219]

[0220] [Chemical Formula Q]

[0221]

[0222] When using ligands, surface modification of quantum dots becomes easier, and when quantum dots that will be surface modified with ligands are added to the aforementioned monomers and then stirred, an extremely transparent dispersion is obtained, which confirms that surface modification of quantum dots is carried out very well.

[0223] For example, quantum dots can have the maximum fluorescence emission wavelength in the range of 500 nanometers to 680 nanometers.

[0224] For example, when the curable composition according to the embodiments is a solvent-free curable composition, quantum dots may be included in an amount from 1 wt% to 60 wt%, for example, 5 wt% to 60 wt%, for example, 10 wt% to 60 wt%, for example, 20 wt% to 60 wt%, for example, 30 wt% to 50 wt%. When quantum dots are included within the above ranges, high light retention and light efficiency can be achieved even after curing.

[0225] For example, when the curable composition according to the embodiment is a solvent-containing curable composition, quantum dots may be included in an amount from 1% to 40% by weight, for example from 1% to 30% by weight, for example from 3% to 20% by weight, based on the total amount of the curable composition. When quantum dots are included within the above range, the light conversion rate is improved without impairing the patterning and developing properties, and thus improved processability is obtained.

[0226] For example, quantum dots absorb light in the wavelength range of 360 nm to 780 nm, such as 400 nm to 780 nm, and emit fluorescence in the wavelength range of 500 nm to 700 nm, such as 500 nm to 580 nm, or in the wavelength range of 600 nm to 680 nm. In other words, quantum dots can have a maximum fluorescence emission wavelength (fluorescence λ) in the 500 nm to 680 nm range. em ).

[0227] Quantum dots can independently have a full width at half maximum (FWHM) of 20 to 100 nanometers, for example, 20 to 50 nanometers. When quantum dots have a full width at half maximum (FWHM) within this range, color reproducibility is increased when used as color materials in color filters due to high color purity.

[0228] Quantum dots can be organic materials, inorganic materials, or hybrids of organic and inorganic materials.

[0229] Quantum dots can be independently composed of a core and a shell surrounding the core, and the core and shell can independently have structures such as core, core / shell, core / first shell / second shell, alloy, alloy / shell, etc., consisting of groups II to IV, III to V, etc., but are not limited to these.

[0230] For example, the core may comprise 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 comprise 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.

[0231] In this embodiment, due to the significant increase in environmental concerns worldwide and the strengthening of restrictions on toxic materials, environmentally friendly cadmium-free luminescent materials (InP / ZnS, InP / ZeSe / ZnS, etc.) with extremely low quantum efficiency (quantum yield) are used instead of luminescent materials with cadmium-based cores, but are not limited to this.

[0232] In the case of quantum dots with a core / shell structure, the overall size (average particle diameter) including the shell can be from 1 nanometer to 15 nanometers, for example, from 5 nanometers to 15 nanometers.

[0233] For example, quantum dots can independently comprise red quantum dots, green quantum dots, or combinations thereof. Red quantum dots can independently have an average particle diameter of 10 nanometers to 15 nanometers. Green quantum dots can independently have an average particle diameter of 5 nanometers to 8 nanometers.

[0234] On the other hand, regarding the dispersion stability of quantum dots, the curable composition according to the embodiments may further include a dispersant. The dispersant contributes to the uniform dispersion of the light conversion material of 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 epoxy alkyl addition product, alcohol epoxy alkyl addition product, sulfonate, sulfonate, carboxylic acid ester, carboxylate, alkylamide epoxy alkyl addition product, alkylamine, etc., and may be used alone or in mixtures of two or more. The amount of dispersant used may be from 0.1% to 100% by weight, for example, from 10% to 20% by weight, based on the solids content of the light conversion material of quantum dots.

[0235] Light diffusing agent (or light diffusing agent dispersion)

[0236] The curable composition according to the embodiments may further include a light diffuser.

[0237] For example, light diffusers may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0238] Light diffusers can reflect light that has not been absorbed by the quantum dots and allow the quantum dots to reabsorb the reflected light. In other words, light diffusers can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

[0239] Light diffusers can have an average particle diameter (D) of 150 nm to 250 nm, and specifically 180 nm to 230 nm. 50 When the average particle diameter of the light diffuser is within the specified range, it can have a better light diffusion effect and improve light conversion efficiency.

[0240] The light diffusing agent may be included in an amount from 0.01 wt% to 20 wt%, for example, from 5 wt% to 10 wt%, based on the total amount of the curable composition. For example, as a solid content, the light diffusing agent may be included in an amount from 0.01 wt% to 10 wt%, based on the solid content constituting the solvent-free curable composition. When less than 0.01 wt% of light diffusing agent is included in the total amount of the curable composition, it is difficult to expect an effect on improving light conversion efficiency by using the light diffusing agent, and when more than 20 wt% of light diffusing agent is included, quantum dot precipitation problems may occur.

[0241] Polymerization initiator

[0242] The curable composition according to the embodiments may further comprise a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0243] Photopolymerization initiators are commonly used initiators for resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, amino ketone compounds, etc., but are not limited to these.

[0244] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one.

[0245] Examples of benzophenone compounds include benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, benzoyl acrylate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0246] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0247] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0248] Examples of triazine compounds include 2,4,6-trichlorotriazine, 2-phenyl-4,6-bis(trichloromethyl)triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)triazine, 2-biphenyl-4,6-bis(trichloromethyl)triazine, bis(trichloromethyl)-6-styryltriazine, and 2-(naphthol- Examples of trichloromethyl s-triazine include 2-(naphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0249] Examples of oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone, O-ethoxycarbonyl-α-oxoamino-1-phenylprop-1-one, etc. Specific examples of O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-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)-octane-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-but-1-one oxime-O-acetate, etc.

[0250] Examples of aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc.

[0251] In addition to the compounds mentioned above, the photopolymerization initiator may further include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, etc.

[0252] Photopolymerization initiators can be used in conjunction with photosensitizers that can induce a chemical reaction by absorbing light, becoming excited, and then transferring their energy.

[0253] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0254] Examples of thermal polymerization initiators can 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 hydrogen peroxide, cumene hydroperoxide), dicyclohexylperoxydicarbonate, 2,2-azobis(isobutyronitrile), tert-butyl perbenzoate, and analogs such as 2,2'-azobis-2-methylpropinonitrile, but are not limited thereto, and any peroxide well known in the art can be used.

[0255] The polymerization initiator may be included in an amount from 0.01 wt% to 5 wt%, for example, from 0.1 wt% to 4 wt%, based on the total amount of the curable composition. When the polymerization initiator is included in the range described above, it is possible to obtain excellent reliability due to sufficient curing during exposure or thermal curing, and it is possible to prevent the degradation of transmittance due to non-reactive initiators, thereby preventing the degradation of the optical properties of the quantum dots.

[0256] Polymer inhibitors

[0257] To improve the stability and dispersion of quantum dots, the curable composition according to the embodiments may further contain polymerization inhibitors.

[0258] The polymerization inhibitor may comprise hydroquinone compounds, catechol compounds, or combinations thereof, but is not limited thereto. When the curable composition according to the embodiments further comprises hydroquinone compounds, catechol compounds, or combinations thereof, room temperature crosslinking during exposure after coating the curable composition can be prevented.

[0259] For example, hydroquinone compounds, catechol compounds, or combinations thereof may include hydroquinone, methyl hydroquinone, methoxy hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 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 combinations thereof, but are not necessarily limited thereto.

[0260] Hydroquinone compounds, catechol compounds, or combinations thereof may be used in the form of dispersions, and may contain polymerization inhibitors in dispersion form in an amount from 0.001% to 3% by weight, for example, from 0.1% to 2% by weight, based on the total amount of the curable composition. When polymerization inhibitors are included within the above range, the problem of aging at room temperature can be solved, while simultaneously preventing decreased sensitivity and surface peeling.

[0261] Adhesive resin

[0262] The adhesive resin may include acryloyl resins, carbole resins, epoxy resins, or combinations thereof.

[0263] Acrylamide resins can be copolymers of a first ethylene-based unsaturated monomer and a second ethylene-based unsaturated monomer that can be copolymerized therewith, and can be resins containing at least one acrylamide repeating unit.

[0264] Specific examples of acrylic adhesive resins may include polyphenylmethyl methacrylate, (meth)acrylic acid / phenyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene copolymer, (meth)acrylic acid / phenyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but are not limited thereto, and may be used alone or in mixtures of two or more.

[0265] Acrylamide adhesive resins can have a weight-average molecular weight ranging from 5,000 g / mol to 15,000 g / mol. When acrylamide adhesive resins have a weight-average molecular weight within this range, their adhesion to the substrate, physical properties, and chemical properties are improved, and their viscosity is appropriate.

[0266] Acrylamide resins can have an acid value ranging from 80 mg / g to 130 mg / g. When acrylamide resins have an acid value within this range, pixel patterns can have excellent resolution.

[0267] Carbole resins can be used in conventional curable resin (or photosensitive resin) compositions, and can be used in general, for example, as disclosed in Korean Patent Application Publication No. 10-2018-0067243, but are not limited thereto.

[0268] Cardole resins can be prepared, for example, by mixing at least two of the following: fluorene-containing compounds, such as 9,9-bis(4-epoxyethylene methoxyphenyl)fluorene; acid anhydride compounds, such as phenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, benzopyrenetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride; diol compounds, such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds, such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds, such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds, such as triphenylphosphine; and amine or ammonium salt compounds, such as tetramethylammonium chloride, tetraethylammonium bromide, benzyl diethylamine, triethylamine, tributylamine, or benzyl triethylammonium chloride.

[0269] The weight-average molecular weight of carbole-based adhesive resins can range from 500 g / mol to 50,000 g / mol, for example, from 1,000 g / mol to 30,000 g / mol. When the weight-average molecular weight of the carbole-based adhesive resin is within this range, satisfactory patterns can be formed without residue during the formation of the cured layer and without loss of film thickness during the development of the solvent-based curable composition.

[0270] When the adhesive resin is a carbole-based resin, it improves the developability of the curable composition (more precisely, the photosensitive resin composition) containing the adhesive resin and provides good sensitivity during photocuring, thereby improving the fine patterning properties.

[0271] Epoxy resins can be monomers or oligomers that can be thermally polymerized, and can contain compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0272] Epoxy resins may include, but are not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenolic aldehyde type epoxy resins, cyclic aliphatic epoxy resins, and aliphatic polyglycidyl ethers.

[0273] Currently available epoxy resins may include diphenyl epoxy resins, such as YX4000, YX4000H, YL6121H, YL6640, or YL6677 from Yuka Shell Epoxy Co., Ltd.; cresol-phenolic epoxy resins, such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 from Nippon Kayaku Co., Ltd., and EPIKOTE 180S75 from Yuka Shell Epoxy Co., Ltd.; and bisphenol A epoxy resins, such as EPIKOTE1001, EPIKOTE1002, EPIKOTE 1003, and EPIKOTE from Yuka Shell Epoxy Co., Ltd. EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010, and EPIKOTE 828; bisphenol F type epoxy resins, such as EPIKOTE 807 and EPIKOTE 834 from EPIKOTE Epoxy Resin Co., Ltd.; phenolic resins, such as EPIKOTE 152, EPIKOTE 154, or EPIKOTE 157H65 from EPIKOTE Epoxy Resin Co., Ltd., and EPPN 201 and EPPN202 from Nippon Kayaku Co., Ltd.; other cyclic aliphatic epoxy resins, such as those from Ciba-Geigy Corporation. AG's CY175, CY177, and CY179; United Carbon Corporation (UCC)'s ERL-4234, ERL-4299, ERL-4221, and ERL-4206; Showa Denko K.K.'s Showdyne 509; Ciba-Geigy Corporation's ARALDITE CY-182, CY-192, and CY-184; Dainippon Ink and Chemicals, Inc.'s EPICLON 200 and EPICLON 400; Oilshell Epoxy Resin Co., Ltd.'s EPIKOTE 871, EPIKOTE 872, and EP1032H60; Celanese Coatings, Ltd. ED-5661 and ED-5662 from Co., Ltd.; aliphatic polyglycidyl ethers, such as EPIKOTE 190P and EPIKOTE 191P from Oil-based Shell Epoxy Resin Co., Ltd., EPOLITE 100MF from Kyoesha Yushi Co., Ltd., and EPIOL TMP from Nippon Yushi Co., Ltd.

[0274] For example, when the curable composition according to the embodiments is a solvent-free curable composition, the adhesive 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.

[0275] For example, when the curable composition according to the embodiments is a solvent-containing curable composition, the adhesive 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, patterning properties, heat resistance, and chemical resistance can be improved.

[0276] Other additives

[0277] The curable composition according to the embodiments may further comprise malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorinated surfactant; or combinations thereof, to improve heat resistance and reliability.

[0278] For example, the curable composition according to the embodiments may further comprise a silane coupling agent having reactive substituents (such as vinyl, carboxyl, methacryloyloxy, isocyanate, epoxy, etc.) to improve the tight contact properties with the substrate.

[0279] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methpropenylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, etc., and these can be used alone or in mixtures of two or more.

[0280] Based on 100 parts by weight of the curable composition, a silane coupling agent may be included in an amount from 0.01 parts by weight to 10 parts by weight. When a silane coupling agent is included within the range described above, it improves the close contact properties, storage capacity, etc.

[0281] In addition, the curable composition may further contain surfactants, such as fluorinated surfactants as needed, to improve coating properties and inhibit spot formation, that is, improve leveling performance.

[0282] Fluorinated surfactants can have a low weight-average molecular weight of 4,000 g / mol to 10,000 g / mol, and specifically 6,000 g / mol to 10,000 g / mol. Furthermore, fluorinated surfactants can have a surface tension of 18 mN / m to 23 mN / m (measured with a 0.1% polyethylene glycol monomethyl ether acetate (PGMEA) solution). When fluorinated surfactants have a weight-average molecular weight and surface tension within the aforementioned range, leveling properties can be further improved, and excellent properties can be provided when applying slit coating as a high-speed coating process, because fewer film defects are generated by preventing spot formation and suppressing vapor generation during high-speed coating.

[0283] Examples of fluorinated surfactants can be... and (BM Chemie Inc.); MEGAFACE F Ma Jiafeisi F Ma Jiafeisi F And Magafis F (Dainippon Ink Kagaku Kogyo Co., Ltd., Japan); FULORAD Fowlerard Fowlerard and Fowlerard (Sumitomo 3M Co., Ltd.); SURFLON Soron Soron Soron And Thrall (ASAHI Glass Co., Ltd.); and as well as Examples include F-482, F-484, F-478, and F-554 from Toray Silicone Co., Ltd., and DIC Co., Ltd.

[0284] Furthermore, the solvent-free curable composition according to the embodiments may contain silicone surfactants other than fluorinated surfactants. Specific examples of silicone surfactants may be, but are not limited to, TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba Silicone Co., Ltd.

[0285] A surfactant may be included in an amount of 0.01 to 5 parts by weight (e.g., 0.1 to 2 parts by weight) per 100 parts by weight of the curable composition. When a surfactant is included in the range described above, fewer foreign matter is generated in the spray composition.

[0286] Furthermore, unless the properties deteriorate, the curable composition according to the embodiments may further contain a predetermined amount of other additives, such as antioxidants, stabilizers, etc.

[0287] solvent

[0288] Meanwhile, the curable composition according to the embodiments may be a solvent-based curable composition that further includes a solvent.

[0289] Solvents may include, for example: alcohols, such as methanol, ethanol, etc.; glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; ethylene glycol acetate ethyl ethers, such as methyl ethylene glycol acetate ethyl ether, ethyl ethylene glycol acetate ethyl ether, diethyl ethylene glycol acetate ethyl ether, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether... Ether acetates, propylene glycol propyl ether acetate, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, methyl n-butyl ketone, methyl n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; alkyl glycolic acid esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkyl acetate alkoxylates, such as methyl methoxyacetate, methyl methoxyacetate, etc. Ethyl oxyacetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionic acid esters, such as methyl 3-hydroxypropionic acid, ethyl 3-hydroxypropionic acid, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid, methyl 3-ethoxypropionic acid, etc.; alkyl 2-hydroxypropionic acid esters, such as methyl 2-hydroxypropionic acid, ethyl 2-hydroxypropionic acid, propyl 2-hydroxypropionic acid, etc.; alkyl 2-alkoxypropionic acid... Esters, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionate esters, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionate esters, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate (2-hydroxyethyl... Propionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, methyl2-hydroxy-3-methylbutanoate, etc.; or keto esters, such as ethyl pyruvate, etc., and in addition, it can be N-methylformamide, N,N-dimethylformamide, N-methylformaniline, 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, phenylethylene glycol acetate, etc., but not limited to these.

[0290] For example, the solvent may be a glycol ether, such as ethylene glycol monoethyl ether, ethylene diglycol methyl ethyl ether, etc.; ethylene glycol alkyl ether acetate, such as ethyl ethylene glycol acetate, etc.; ester, such as 2-hydroxyethyl propionate, etc.; carbitol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; alcohol, such as ethanol, etc.; or combinations thereof.

[0291] For example, the solvent can 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 combinations thereof.

[0292] The solvent may be included in the total amount of the solvent-based curable composition, for example, from 30% to 80% by weight, and the remainder from 35% to 70% by weight. When the solvent is within the range described, the solvent-based curable composition has a suitable viscosity and therefore exhibits excellent coating properties when applied over large areas by spin coating and slot coating.

[0293] Another embodiment provides a cured layer manufactured using the aforementioned curable composition and a display device comprising the cured layer.

[0294] One method of manufacturing a cured layer may include applying the aforementioned curable composition onto a substrate using an inkjet printing method to form a pattern (S1); and curing the pattern (S2).

[0295] (S1) Pattern Formation

[0296] Curable compositions can be ideally coated onto a substrate at a depth of 0.5 to 20 micrometers using inkjet printing. Inkjet printing can form patterns by spraying a single color through each nozzle and thus repeating the spraying multiple times according to the desired number of colors, but patterns can also be formed by spraying the desired number of colors simultaneously through each inkjet nozzle to reduce the process.

[0297] (S2) Curing

[0298] The resulting pattern is cured to obtain pixels. In this document, the curing method can be either a thermosetting process or a photopolymerization process. Thermosetting processes can be performed at or above 100°C, ideally in the range of 100°C to 300°C, and more ideally in the range of 160°C to 250°C. Photopolymerization processes can involve radiation photochemical rays, such as UV rays of 190 nm to 450 nm (e.g., 200 nm to 500 nm). Irradiation is achieved using light sources such as mercury lamps, metal halide lamps, argon lasers, etc., with low, high, or ultra-high pressure. X-rays, electron beams, etc., may also be used as needed.

[0299] Another method for producing a cured layer may include manufacturing the cured layer using the aforementioned curable composition by means of a photolithography method.

[0300] (1) Coating and film formation

[0301] The aforementioned curable composition is applied to a pre-treated substrate using spin coating, slot coating, roller coating, screen printing, or smearing methods to achieve a desired thickness, for example, between 2 and 10 micrometers. The coated substrate is then heated at 70°C to 90°C for 1 to 10 minutes to remove the solvent and form a film.

[0302] (2) Exposure

[0303] After a mask of a predetermined shape is placed on the resulting film, it is irradiated with photochemical rays of UV lines, such as 190 nm to 450 nm (e.g., 200 nm to 500 nm), to form the desired pattern. Irradiation can be performed using light sources such as mercury lamps, metal halide lamps, or argon lasers with low, high, or ultra-high pressure. X-rays, electron beams, etc., may also be used as needed.

[0304] When using a high-pressure mercury lamp, the exposure process uses a light dose of, for example, 500 mJ / cm² or less (using a 365 nm sensor). However, the light dose can vary depending on the type of each component of the curable composition, their combination ratio, and the dry film thickness.

[0305] (3) Development

[0306] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unwanted portions other than the exposed areas, thereby forming an image pattern. In other words, when the alkaline developing solution is used for development, the unexposed areas are dissolved and an image filter pattern is formed.

[0307] (4) Post-processing

[0308] The developed image pattern can be cured by heating or radiation such as photochemical rays to achieve excellent quality in terms of heat resistance, light resistance, contact properties, crack resistance, chemical resistance, high strength, and storage stability.

[0309] The invention is described in more detail below with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.

[0310] Preparation of polymerizable compounds

[0311] Preparation Example 1

[0312] 100 g of triethylene glycol and 14.4 g of acrylic acid were added to 500 mL of cyclohexane, and the mixture was stirred. 0.15 g of CuCl2 and 15 g of p-toluenesulfonic acid were then added, and the mixture was stirred for 8 hours after securing a Dean-Stark condenser and raising the temperature to a maximum of 100 °C to complete the reaction. Subsequently, 200 mL of ethyl acetate and NaOH dilution were added for extraction, followed by the addition of dichloromethane, and extraction, neutralization, and solvent removal were performed sequentially. After redissolving in 100 mL of ethyl acetate, the solvent was removed, and the mixture was dried in a vacuum oven for 24 hours to prepare the polymerizable compound represented by chemical formula E-1.

[0313] [Chemical Formula E-1]

[0314]

[0315] Comparative Preparation Example 1

[0316] 100 g of 1,6-hexanediol and 20 g of acrylic acid were thoroughly stirred in 500 mL of cyclohexane. Then, 0.14 g of CuCl2 and 14 g of p-toluenesulfonic acid were added, and the mixture was stirred for 8 hours after securing the Dean Stark concentrator and raising the temperature to a maximum of 100°C to complete the reaction. Subsequently, the same process as in Preparation Example 1 was performed to obtain the polymerizable compound represented by the chemical formula C-1.

[0317] [Chemical formula C-1]

[0318]

[0319] Comparative preparation example 2

[0320] 100 g of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol and 17.7 g of acrylic acid were thoroughly stirred in 500 mL of cyclohexane. Subsequently, 0.16 g of CuCl2 and 12.8 g of p-toluenesulfonic acid were added, and the mixture was stirred for 8 hours after securing the Dean Stark concentrator and raising the temperature to a maximum of 100°C to complete the reaction. The same process as in Preparation Example 1 was then performed to prepare the polymerizable compound represented by the chemical formula C-2.

[0321] [Chemical formula C-2]

[0322]

[0323] Preparation of surface-modified quantum dot dispersions

[0324] Preparation Example 2

[0325] After placing a magnetic rod in a three-necked round-bottom flask, either a green quantum dot dispersion (InP / ZnSe / ZnS, Hansol Chemical) or a red quantum dot dispersion (InP / ZnSe / ZnS, Hansol Chemical) was added. A compound (ligand) represented by the chemical formula Q was then added, and the mixture was stirred at 80°C under a nitrogen atmosphere. Upon completion of the reaction, the temperature was lowered to room temperature (23°C), and the quantum dot reactant was added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and then thoroughly dried in a vacuum oven for 24 hours to obtain quantum dots as a surface-modified solid.

[0326] Surface-modified solid green or red quantum dots are mixed with a compound represented by chemical formula 3-1 (triethylene glycol dimethacrylate, Miwon Commercial Co., Ltd.) in the same weight ratio, and then stirred for 12 hours to obtain a surface-modified quantum dot dispersion.

[0327] (*Synthesis of the compound represented by the chemical formula Q: 100 g of PH-4 (Hannong Chemical Inc.) was placed in a two-necked round-bottom flask and then completely dissolved in 300 mL of THF. Subsequently, 15.4 g of NaOH and 100 mL of water were added at 0 °C, and the solution was completely dissolved until a clear solution was obtained.)

[0328] Next, a solution obtained by dissolving 73 g 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 12 hours. When the reaction was complete, excess dichloromethane was added and stirring continued, followed by the addition of a saturated solution of NaHCO3, followed by extraction, titration, and dehydration. After solvent removal, 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 stirred thoroughly in 300 mL of ethanol. Subsequently, 27 g of thiourea was added and dispersed, followed by reflux at 80 °C for 12 hours. Then, an aqueous solution prepared by dissolving 4.4 g of NaOH in 20 mL of water was injected, with further stirring for 5 hours, followed by the addition of excess dichloromethane, followed by the addition of an aqueous hydrochloric acid solution, and then extraction, titration, dehydration, and solvent removal were performed sequentially. The obtained product was dried in a vacuum oven for 24 hours to obtain the compound represented by the chemical formula Q.

[0329] [Chemical Formula Q]

[0330]

[0331] [Chemical Formula 3-1]

[0332]

[0333] (Preparation of curable compositions)

[0334] Examples 1 to 3 and Comparative Examples 1 to 4

[0335] Each curable composition according to Examples 1 to 3 and Comparative Examples 1 to 4 was prepared by using the compositions shown in Table 1.

[0336] Specifically, the quantum dot dispersion was prepared by mixing and diluting a polymerizable compound represented by Chemical Formula E-1 and a polymerizable compound represented by Chemical Formula 3-1, adding a polymerization inhibitor, and then stirring for 5 minutes. Subsequently, a photoinitiator (TPO-L, PolyNetron Co., Ltd.) was injected, and a light diffusing agent dispersion was added. The resulting crude solution was then stirred for 1 hour to prepare a curable composition. (For example, the curable composition of Example 1 was prepared by mixing 40 grams of surface-modified green quantum dot solids with 40 grams of a polymerizable compound represented by Chemical Formula 3-1 to prepare a quantum dot dispersion; adding 7 grams of a polymerizable compound represented by Chemical Formula 3-1, 1 gram of a polymerizable compound represented by Chemical Formula E-1, and 1 gram of a polymerization inhibitor to the quantum dot dispersion and stirring for 5 minutes; subsequently, adding 3 grams of a photoinitiator and 8 grams of a light diffusing agent dispersion and stirring.)

[0337] (A)Quantum dots

[0338] (A-1) Content of surface-modified green quantum dot solids prepared in Preparation Example 2

[0339] (A-2) Content of surface-modified red quantum dot solids prepared in Preparation Example 2

[0340] (B) Polymerizable compounds

[0341] (B-1) Polymerizable compound represented by chemical formula E-1

[0342] (B-2) Polymerizable compounds represented by chemical formula C-1

[0343] (B-3) Polymerizable compounds represented by the chemical formula C-2

[0344] (B-4) Compounds represented by chemical formula 3-1

[0345] (C) Photopolymerization initiator

[0346] OXE01 (BASF)

[0347] (D) Light diffusing agent

[0348] Titanium dioxide dispersion (20% by weight solid TiO2, average particle diameter: 200 nm, Ditto Technology Co., Ltd.)

[0349] (E) Polymerization inhibitor

[0350] Methylhydroquinone (5% by weight of monomers represented by chemical formula 3-1, Tokyo Chemical Industry Co., Ltd.)

[0351] (Table 1)

[0352] (Unit: % by weight)

[0353]

[0354] Assessment 1: Evaluation of optical properties

[0355] Curable compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 were coated to a thickness of 15 μm on glass substrates or yellow photoresist (YPR) substrates using a spin coater (800 rpm, 5 seconds, Opticoat MS-A150, Mikasa Co., Ltd.). The coatings were exposed at 5000 mJ (83°C, 10 seconds) using a 395 nm UV illuminator under a nitrogen atmosphere and dried at 180°C for 30 minutes in a forced convection drying oven under a nitrogen atmosphere. Subsequently, each 2 cm × 2 cm monolayer film sample was loaded into an integrating sphere apparatus (QE-2100, Otsuka Electronics, Co., Ltd.) and evaluated relative to optical efficiency retention, quantum efficiency, maximum emission wavelength, and full width at half maximum (FWHM). The results are shown in Table 2.

[0356] Assessment 2: Assessment of the tight contact force of the pattern

[0357] Using a spin coater (800 rpm, 5 seconds, optical coating MS-A150, Mikasa Corporation), the curable compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 were coated to a thickness of 15 μm on a clean SiOx substrate. The coatings were exposed at 5000 mJ (83°C, 10 seconds) using a 395 nm UV illuminator under a nitrogen atmosphere, and then dried at 180°C for 30 minutes in a forced convection drying oven under a nitrogen atmosphere. Subsequently, monolayer film samples were engraved into 2 mm × 2 mm lattice patterns using a cross-hatching cutter. The peel condition was visually evaluated after a tape peel test, and then determined based on a cross-cutting reference. Furthermore, the pattern tightness was evaluated by fixing the column bolts to each 1 cm × 1 cm monolayer film sample formed using the same method as above, and by using the UTM peel assessment method (Inspekt 10-1, Hegewald & Peschke GmbH, Germany). The results are shown in Table 2 and... Figures 1 to 7middle.

[0358] (Table 2)

[0359]

[0360] See Table 2 and Figures 1 to 7 The curable compositions according to the embodiments maintain high light efficiency retention and quantum efficiency, while exhibiting sufficient processability due to the increased tight contact force of the patterns.

[0361] While the invention has been described in conjunction with what are now considered practical examples, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements contained within the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood as exemplary and not as limiting the invention in any way.

Claims

1. A curable composition, comprising: quantum dots; and a polymerizable compound, wherein the curable composition is a solvent-free curable composition, wherein the polymerizable compound comprises a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 3: [Chemical Formula 1] wherein, in Chemical Formula 1, R a is a hydrogen atom or a substituted or unsubstituted C1to C20alkyl group, and L a and L b each independently is substituted or unsubstituted C1to C20oxyalkylene or substituted or unsubstituted C1to C20alkylene, but L a and L b are different, wherein L a and L b at least one of which is said substituted or unsubstituted C1to C20oxyalkylene group, [Chemical Formula 3] wherein, in Chemical Formula 3, R' and R'' are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and Ld is a substituted or unsubstituted C5 to C20 alkylene group, wherein, based on the total amount of the polymerizable compound, the compound represented by Chemical Formula 1 is contained in an amount of 1.5 wt% to 15 wt%, and the compound represented by Chemical Formula 3 is contained in an amount of 85 wt% to 98.5 wt%. 2.The curable composition according to claim 1, wherein the substituted or unsubstituted C1 to C20 oxyalkylene group is represented by Chemical Formula 2: [Chemical Formula 2] wherein wherein, in Chemical Formula 2, L c is substituted or unsubstituted C1to C20alkylene, and n is an integer of 1 to 10. 3.The curable composition according to claim 1, wherein the compound represented by Chemical Formula 1 is contained in an amount of 0.5 wt% to 10 wt%, based on the total amount of the curable composition. 4.The curable composition according to claim 1, wherein the compound represented by Chemical Formula 3 has a weight average molecular weight of 200 g / mol to 1,000 g / mol. 5.The curable composition according to claim 1, wherein the quantum dots are quantum dots surface-modified with one compound represented by Chemical Formula 4 to Chemical Formula 17 or a combination thereof: [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] wherein, wherein, in Chemical Formula 4 to Chemical Formula 9, R 1 to R 7 each independently is substituted or unsubstituted C1to C10alkyl or substituted or unsubstituted C6to C20aryl, L 1 to L 16 each independently is substituted or unsubstituted C1to C10alkylene, and n1 to n7 are each independently an integer of 0 to 10, [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] wherein, in Chemical Formula 10 to Chemical Formula 12, R 8 and R 9 each independently is a substituted or unsubstituted C1to C10alkyl, L 17 to L 23 each independently is a substituted or unsubstituted C1to C10alkylene, and n8to n10each independently is an integer of 0 to 10, [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] wherein, in Chemical Formula 13 to Chemical Formula 16, R 10 to R 15 each independently is a hydrogen atom or a substituted or unsubstituted C1to C10alkyl group, L 24 to L 29 each independently is substituted or unsubstituted C1to C10alkylene, and n11 to n16 are each independently an integer of 0 to 10, [Chemical Formula 17] wherein, in Chemical Formula 17, R 16 to R 18 each independently is substituted or unsubstituted C1to C10alkyl, L 30 to L 32 each independently is substituted or unsubstituted C1to C10alkylene, and n17 to n19 are each independently an integer of 0 to 10. 6.The curable composition according to claim 1, wherein the quantum dots have a maximum fluorescence emission wavelength in the range of 500 nm to 680 nm. 7.The curable composition according to claim 1, wherein the curable composition further comprises a polymerization initiator, a light diffusing agent, a polymerization inhibitor, an adhesive resin, or a combination thereof. 8.The curable composition according to claim 7, wherein the light diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof. 9.The curable composition according to claim 1, wherein based on the total weight of the solvent-free curable composition, the solvent-free curable composition comprises: 1 wt% to 60 wt% of the quantum dots; and 40 wt% to 99 wt% of the polymerizable compound.

10. The curable composition of claim 1, wherein the curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

11. A cured layer made using the curable composition of claim 1.

12. A display device comprising the cured layer of claim 11.

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