Curable composition, cured layer manufactured using the composition, and display device including the cured layer

Abstract

Provided are a curable composition, a cured layer manufactured using the curable composition, and a display device including the cured layer, the curable composition including (A) quantum dots and (B) a polymerizable compound, in which the polymerizable compound includes a first polymerizable compound having a refractive index of 1.5 or more and a viscosity of 10 cps or more.

Description

Technical Field

[0001] This disclosure relates to curable compositions, curable layers using said compositions, and display devices including said curable layers. Background Technology

[0002] In general, quantum dots are limited by their hydrophobic surface properties, making it difficult to introduce them into polar systems such as adhesives or curable monomers.

[0003] For example, even with regard to quantum dot ink compositions that are currently under active investigation, the polarity is relatively low in the initial steps, and it can be dispersed in highly hydrophobic solvents used in curable compositions. Therefore, it is impossible to improve the light efficiency of the ink beyond a certain level because it is difficult to include 20 wt% or more of quantum dots based on the total composition. Although quantum dots may be added and dispersed to improve light efficiency, the viscosity exceeds the range suitable for inkjet printing and therefore may not meet processability requirements.

[0004] To achieve a viscosity range suitable for inkjet printing, reducing the ink solids content by dissolving 50 wt% or more of solvent based on the total composition provides somewhat satisfactory results in terms of viscosity. However, while this is a satisfactory result in terms of viscosity, it is difficult to apply to practical processes due to nozzle drying and clogging caused by solvent evaporation during inkjet printing, as well as the potential for deterioration in single-layer thickness over time after inkjet printing, and the difficulty in controlling thickness deviation after curing.

[0005] Therefore, solvent-free quantum dot inks, which do not contain solvents, are the most desirable form for practical applications. Currently, existing technologies for applying quantum dots themselves to solvent-based compositions are somewhat limited.

[0006] In the case of solvent-free curable compositions (quantum dot ink compositions), the presence of excessive polymerizable compounds can lead to nozzle drying due to volatility, resulting in clogging and spraying failures. Furthermore, the evaporation of the ink composition sprayed into the patterned separator pixels can cause a reduction in single-film thickness. Therefore, efforts are being made from various angles to improve the optical properties of solvent-free curable compositions. Increasing the inorganic material content is a common method to improve the optical properties of solvent-free curable compositions; however, the problem is that reflectivity increases with increasing inorganic material content. In other words, there is a trade-off between improving the optical properties of solvent-free curable compositions and reducing reflectivity, and the demand for technologies that can simultaneously improve both properties (improved optical properties and reduced reflectivity) is growing. Summary of the Invention

[0007] Technical issues

[0008] One embodiment provides a curable composition that can improve light absorption and light efficiency.

[0009] Another embodiment provides a cured layer manufactured using the said curable composition.

[0010] Another embodiment provides a display device including the cured layer.

[0011] Technical solution

[0012] One embodiment provides a curable composition comprising (A) quantum dots and (B) a polymerizable compound, wherein the polymerizable compound comprises a first polymerizable compound having a refractive index greater than or equal to 1.5 and a viscosity greater than or equal to 10 cps.

[0013] The first polymerizable compound can be represented by chemical formula 1.

[0014] [Chemical Formula 1]

[0015] In chemical formula 1, R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 and L 2 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group (oxidized alkenyl group), or a substituted or unsubstituted C3 to C20 cycloalkylene group, provided that L 1 and L 2 They are not both single keys.

[0016] In chemical formula 1, L 1 It can be a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 2 It can be a single bond or an alkylene oxide.

[0017] Chemical formula 1 can be represented by chemical formulas 2-1 to 2-3.

[0018] [Chemical Formula 2-1]

[0019] [Chemical Formula 2-2]

[0020] [Chemical Formula 2-3]

[0021] In chemical formulas 2-1 to 2-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group.

[0022] Chemical formula 1 can be represented by chemical formulas 3-1 to 3-3.

[0023] [Chemical Formula 3-1]

[0024] [Chemical Formula 3-2]

[0025] [Chemical Formula 3-3]

[0026] In chemical formulas 3-1 to 3-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 3 It is a substituted or unsubstituted C1 to C20 alkylene group.

[0027] The polymerizable compound may also include a second polymerizable compound having a structure different from that of the first polymerizable compound.

[0028] The second polymerizable compound may include a compound represented by chemical formula 4.

[0029] [Chemical Formula 4]

[0030] In chemical formula 4, L 4 It 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 6Each is 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.

[0031] The second polymerizable compound may include a compound represented by chemical formula 5.

[0032] [Chemical Formula 5]

[0033] In chemical formula 5, L 7 It is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and R 5 It is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0034] The second polymerizable compound may have a refractive index of less than 1.5 or a viscosity of less than 10 cps.

[0035] The first polymerizable compound and the second polymerizable compound may be contained in a weight ratio of 1:9 to 9:1.

[0036] The curable composition may be a solvent-free curable composition.

[0037] The solvent-free curable composition comprises 5 wt% to 60 wt% of quantum dots and 40 wt% to 95 wt% of polymerizable compounds based on the total amount of the solvent-free curable composition.

[0038] The curable composition may also contain a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0039] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0040] The curable composition may also contain a solvent.

[0041] The curable composition may comprise 1 wt% to 40 wt% of quantum dots, 1 wt% to 20 wt% of polymerizable compound and 40 wt% to 80 wt% of solvent, based on the total weight of the curable composition.

[0042] The curable composition may further include malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorinated surfactants, or combinations thereof.

[0043] Another embodiment provides a cured layer manufactured using the said curable composition.

[0044] Another embodiment provides a display device including the cured layer.

[0045] Other embodiments of the present invention are included in the following detailed description.

[0046] Beneficial effects

[0047] By incorporating a high-refractive-index and high-viscosity (meth)acrylate compound with a novel structure into a curable composition containing quantum dots, the light absorption rate and light efficiency of the curable composition containing quantum dots can be improved. Therefore, in terms of display panels manufactured using it, pixel brightness can be improved, external light reflection can be reduced, and front brightness can be improved. Detailed Implementation

[0048] Embodiments of the present 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.

[0049] 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.

[0050] As used herein, unless otherwise specifically defined, “substituted” means that at least one hydrogen atom is replaced by a substituent selected from the following: halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, imino, azide, amido, hydrazyl, hydrazine, carbonyl, carbamoyl, thiol, ester, ether, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocyclic alkyl, C2 to C20 heterocyclic alkenyl, C2 to C20 heterocyclic alkynyl, C3 to C20 heterocyclic aryl, or combinations thereof.

[0051] As used herein, unless otherwise specifically defined, “heterogeneous” means a chemical formula containing at least one heteroatom of N, O, S, and P.

[0052] 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”.

[0053] As used herein, unless otherwise specifically defined, the term "combination" refers to a mixture or copolymer.

[0054] In this specification, unless otherwise defined, if a chemical bond is not drawn at the position where it should be shown in the chemical formula, then hydrogen bonding is at that position.

[0055] Additionally, unless otherwise defined in this specification, " "" refers to the connection point with the same or different atoms or chemical formulas.

[0056] In the following text, each component constituting a curable composition according to one embodiment will be described in detail.

[0057] polymerizable compounds

[0058] (First polymerizable compound)

[0059] According to one embodiment, a curable composition containing quantum dots comprises a (meth)acrylate compound (a first polymerizable compound) having a high refractive index and high viscosity as the polymerizable compound, and more specifically, having a refractive index of 1.5 or greater and a viscosity of 10 cps or greater. The high refractive index and high viscosity of the (meth)acrylate compound result in the curable composition having improved light absorption and light efficiency, ultimately providing a display panel with improved brightness on the front side.

[0060] For example, the first polymerizable compound can be represented by chemical formula 1.

[0061] [Chemical Formula 1]

[0062] In chemical formula 1, R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 and L 2 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group, provided that L 1 and L 2 They are not both single keys.

[0063] Compared to curable compositions containing red quantum dots, curable compositions containing green quantum dots have the disadvantages of relatively low absorptivity (abs.) and luminous efficacy (EQE), and almost twice the reflectivity. Therefore, the technical challenge of improving the brightness of green quantum dot pixels in display panels by reducing external light reflection, and further improving front-side brightness, remains unresolved.

[0064] The inventors clearly recognized the above-mentioned problems and conducted extensive research and hundreds of trials and errors in order to improve the optical properties of curable compositions containing green quantum dots and reduce their reflectivity. The above-mentioned technical problems have been solved by applying the compound represented by Chemical Formula 1 as a polymerizable compound, which has a high refractive index of 1.5 or greater and a viscosity of 10 cps or greater.

[0065] Typically, the main method for improving the optical properties of curable compositions containing green quantum dots is to increase the content of inorganic substances, and conversely, the main method for reducing the reflectivity of curable compositions containing green quantum dots is to reduce the content of inorganic substances. Since improving optical properties and reducing reflectivity are opposite physical properties—that is, they are in a trade-off—achieving both properties simultaneously is very difficult.

[0066] According to one embodiment, a (meth)acrylate compound represented by Formula 1, having a high refractive index of 1.5 or greater and a viscosity of 10 cps or greater, is applied as a polymerizable compound to a curable composition, thereby simultaneously achieving the effects of improved optical properties and reduced reflectivity in both curable compositions containing green quantum dots and curable compositions containing red quantum dots.

[0067] Specifically, the improvement in optical properties is due to the fact that compounds represented by Formula 1 have both high refractive index and high viscosity. For example, compounds represented by Formula 1 can have a refractive index of 1.5 or greater, such as 1.5 to 1.7, and simultaneously have a viscosity of 10 cps or greater, such as 10 cps to 100 cps, thus greatly improving the optical properties of curable compositions containing quantum dots that include it as a polymerizable compound.

[0068] Furthermore, the reflectivity reduction effect can be achieved by thermosetting a curable composition according to one embodiment. When the compound represented by Formula 1, used as the polymerizable compound, undergoes thermal decomposition to expose thiol groups, these thiol groups readily induce a thiol-ene reaction between the carbon-carbon double bond of the (meth)acrylate group and the thiol group. This promotes surface curing of the thermosetting monofilm of the curable composition according to one embodiment and ultimately significantly reduces the reflectivity of the cured layer, especially the diffuse reflectivity. For example, the diffuse reflectivity of the cured layer can be reduced to 55% or less, such as 50% to 55%.

[0069] In chemical formula 1, when L 2 Including sulfides ( -S- When the structure is connected, the refractive index of the compound decreases, which is detrimental to improving optical properties, and the thiol-ene reaction cannot occur smoothly, so the effect of reducing reflectivity is halved, which may be undesirable.

[0070] For example, L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 2 It is a single bond or an alkylene oxide (substituted or unsubstituted C1 to C20 alkylene oxide). In this case, chemical formula 1 can be represented by chemical formula 2-1 to chemical formula 2-3, but is not limited to this.

[0071] [Chemical Formula 2-1]

[0072] [Chemical Formula 2-2]

[0073] [Chemical Formula 2-3]

[0074] In chemical formulas 2-1 to 2-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group.

[0075] For example, L 1 It can be a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 2It can be a substituted or unsubstituted C1 to C20 alkylene oxide. In this case, chemical formula 1 can be represented by chemical formulas 3-1 to 3-3, but is not limited to them.

[0076] [Chemical Formula 3-1]

[0077] [Chemical Formula 3-2]

[0078] [Chemical Formula 3-3]

[0079] In chemical formulas 3-1 to 3-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group. L 3 It is a substituted or unsubstituted C1 to C20 alkylene group.

[0080] For example, when chemical formula 1 is represented by any one of chemical formulas 2-1 to 2-3 and 3-1 to 3-3, it is very advantageous to simultaneously improve the optical properties of the curable composition according to one embodiment and reduce the reflectivity (diffuse reflectivity).

[0081] For example, a compound represented by chemical formula 1 can be represented by any one of chemical formulas 11 to 15, but is not limited to this.

[0082] [Chemical Formula 11]

[0083] [Chemical Formula 12]

[0084] [Chemical Formula 13]

[0085] [Chemical Formula 14]

[0086] [Chemical Formula 15]

[0087] (Second polymerizable compound)

[0088] For example, the polymerizable compound may also include a second polymerizable compound having a structure different from that of the first polymerizable compound.

[0089] For example, a second polymerizable compound having a structure different from that of the first polymerizable compound represented by chemical formula 1 can be represented by chemical formula 4 or chemical formula 5.

[0090] [Chemical Formula 4]

[0091] In chemical formula 4, L 4 It 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 Each is 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.

[0092] [Chemical Formula 5]

[0093] In chemical formula 5, L 7 It is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group. R 5 It is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0094] When the curable composition according to one embodiment may further include a compound represented by chemical formula 4 or chemical formula 5 as a polymerizable compound, which is present together with a high refractive / high viscosity compound represented by chemical formula 1, the effects of improved optical properties and reduced reflectivity of the curable composition can be achieved simultaneously, as with the case where the compound is used alone.

[0095] For example, compounds represented by Formula 4 or Formula 5 can have a refractive index less than 1.5 or a viscosity less than 10 cps. When compounds represented by Formula 4 or Formula 5 have a refractive index greater than or equal to 1.5 and a viscosity less than 10 cps, they are advantageous in improving optical properties, but disadvantageous in reducing reflectivity.

[0096] For example, the first polymerizable compound and the second polymerizable compound may be contained in a weight ratio of 1:9 to 9:1, such as 5:5 to 9:1.

[0097] For example, the first polymerizable compound represented by chemical formula 1 may be contained in an amount greater than that of a second polymerizable compound having a structure different from that of the compound represented by chemical formula 1 (e.g., a compound represented by chemical formula 4 or chemical formula 5).

[0098] For example, a first polymerizable compound represented by chemical formula 1 and a second polymerizable compound having a structure different from that of the compound represented by chemical formula 1 (e.g., a compound represented by chemical formula 4 or chemical formula 5, etc.) may be included in a weight ratio of 6:4 to 9:1.

[0099] The first polymerizable compound represented by chemical formula 1 is contained in an amount greater than that of a second polymerizable compound having a structure different from that of the compound represented by chemical formula 1 (e.g., a compound represented by chemical formula 4 or chemical formula 5). For example, when the first polymerizable compound and the second polymerizable compound are contained in a weight ratio of 6:4 to 9:1, the improvement in both optical properties and the reduction in reflectivity can be maximized simultaneously.

[0100] For example, a compound represented by chemical formula 4 or chemical formula 5 may be represented by chemical formula 4-1, chemical formula 4-2, chemical formula 4-3 or chemical formula 5-1, but is not limited to these.

[0101] [Chemical Formula 4-1]

[0102] [Chemical Formula 4-2]

[0103] [Chemical Formula 4-3]

[0104] [Chemical Formula 5-1]

[0105] For example, in addition to compounds represented by chemical formulas 4-1, 4-2, 4-3, and 5-1, a second polymerizable compound having a structure different from that of the first polymerizable compound may also include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolacepoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or combinations thereof.

[0106] In addition to the polymerizable compounds, monomers commonly used in conventional thermosetting or photocurable compositions, such as epoxy compounds, oxetane compounds, vinyl ether compounds, etc., can also be used.

[0107] For example, epoxy compounds may include aliphatic epoxy compounds, such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenolic varnish type epoxy compounds, trimethylolpropane polyglycidyl ether and neopentyl glycol diglycidyl ether; and alicyclic epoxy compounds, such as 1,2-epoxy-4-vinylcyclohexane and 1-methyl-4-(2-methylepoxyethoxy)-7-oxabicyclo[4.1.0]heptane.

[0108] Commercially available products can also be used as epoxy compounds. Examples of commercially available epoxy compounds include “Celloxide 2000,” “Celloxide 3000,” and “Celloxide 4000” manufactured by Daicel Chemical Co., Ltd.

[0109] For example, oxetane compounds may include bis[1-ethyl(3-oxetane)] methyl ether, 2-ethylhexyloxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, 3-hydroxymethyl-3-phenyloxetane, and 3-hydroxymethyl-3-phenylmethyloxetane. 3-Hydroxyethyl-3-methyloxetane, 3-Hydroxyethyl-3-ethyloxetane, 3-Hydroxyethyl-3-propyloxetane, 3-Hydroxyethyl-3-phenyloxetane, 3-Hydroxypropyl-3-methyloxetane, 3-Hydroxypropyl-3-ethyloxetane, 3-Hydroxypropyl-3-propyloxetane, 3-Hydroxypropyl-3-phenyloxetane, 3-Hydroxybutyl-3-methyloxetane, etc.

[0110] Commercial products can also be used as oxetane compounds. Commercially available oxetane compounds may include, for example, the Aaron Oxetane series (“OXT-101”, “OXT-212”, “OXT-121”, “OXT-221”, etc.) manufactured by Toagosei Co., Ltd.; “Celloxide 2021”, “Celloxide 2021A”, “Celloxide 2021P”, “Celloxide 2080”, “Celloxide 2081”, “Celloxide 2083”, “Celloxide 2085”, “Epolyde GT300”, “Epolyde GT301”, “Epolyde GT302”, “Epolyde GT400”, “Epolyde GT401”, and “Epolyde GT403”) manufactured by Daicel Chemical Co., Ltd.; and “Scyracure UVR-6105”, “Scyracure UVR-6107”, “Scyracure UVR-6107”, etc. manufactured by Dow Chemical Nippon Co., Ltd. UVR-6110, ScyracureUVR-6128, ERL4289, ERL4299, etc. In addition, known oxetane compounds (e.g., oxetane compounds described in Japanese Patent Application Publication No. 2009-40830) can also be used.

[0111] For example, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, etc., can be used as vinyl ether compounds.

[0112] Based on the total amount of the solvent-free curable composition, the polymerizable compound can be included in an amount of 40 wt% to 95 wt%, for example, 50 wt% to 90 wt%. When the polymerizable compound is included within this range, a solvent-free curable composition having an inkjet-capable viscosity can be prepared, and the quantum dots in the prepared solvent-free curable composition can have improved dispersibility, thereby improving optical properties.

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

[0114] Furthermore, when the curable composition contains a solvent, the polymerizable compound can be included in amounts ranging from 1 wt% to 20 wt%, 1 wt% to 15 wt%, or, for example, 5 wt% to 15 wt%, depending on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved.

[0115] quantum dots

[0116] For example, quantum dots can have maximum fluorescence emission wavelengths at approximately 500 nm to approximately 680 nm.

[0117] For example, when the curable composition according to one embodiment is a solvent-free curable composition, quantum dots may be included in amounts from 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 range, high light retention and light efficiency can be achieved even after curing.

[0118] For example, when the curable composition according to one embodiment is a solvent-containing curable composition, quantum dots can be included in an amount of 1 wt% to 40 wt%, for example, 3 wt% to 30 wt%, based on the total amount of the curable composition. When quantum dots are included within the above range, the light conversion efficiency is improved, and the patterning and developing properties are not impaired, thus improving processability can be obtained.

[0119] 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 600 nm to 680 nm. That is, quantum dots can have a maximum fluorescence emission wavelength (fluorescence λ) in the 500 nm to 680 nm range. em ).

[0120] Quantum dots can each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When quantum dots have a full width at half maximum (FWHM) of 20 nm to 100 nm, color reproducibility is improved due to high color purity when used as color materials in color filters.

[0121] Quantum dots can be organic materials, inorganic materials, or mixtures of organic and inorganic materials, each independently.

[0122] Quantum dots can each be independently composed of a core and a shell surrounding the core, and the core and the shell can each independently have a core / shell, core / first shell / second shell, alloy, alloy / shell, etc., structure composed of II-IV group, III-V group, etc., but are not limited thereto.

[0123] For example, the core may include at least one material selected from the following: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but are not limited thereto. The shell surrounding the core may include at least one material selected from the following: CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but are not limited thereto.

[0124] In one implementation, due to the recent increase in global environmental concern and the strengthening of restrictions on toxic materials, cadmium-free luminescent materials (InP / ZnS, InP / ZeSe / ZnS, etc.) that are environmentally friendly but have low quantum efficiency (quantum yield) are used instead of luminescent materials with cadmium-like cores, but are not limited to this.

[0125] In the case of core / shell structured quantum dots, the size (average particle size) of each quantum dot, including the shell, can be from 1 nm to 15 nm, for example, from 5 nm to 15 nm.

[0126] For example, quantum dots can independently include red quantum dots, green quantum dots, or combinations thereof. Red quantum dots can independently have an average particle size of 10 nm to 15 nm. Green quantum dots can independently have an average particle size of 5 nm to 8 nm.

[0127] On the other hand, for the dispersion stability of quantum dots, the curable composition according to one embodiment may also contain a dispersant. The dispersant contributes to the uniform dispersion of light-conversion materials, such as quantum dots, in the photosensitive resin composition, and may include nonionic, anionic, or cationic dispersants. Specifically, the dispersant may be a polyalkylene glycol or its ester, polyoxyalkylene oxide, polyol ester epoxy alkylation adduct, alcohol epoxy alkylation adduct, sulfonate, sulfonate, carboxylic acid ester, carboxylate, alkylamide epoxy alkylation adduct, alkylamine, etc., and they may be used alone or in mixtures of two or more. Depending on the solids content of the light-conversion material, such as quantum dots, the dispersant may be used in amounts from 0.1 wt% to 100 wt%, for example, from 10 wt% to 20 wt%.

[0128] For example, quantum dots can be surface-modified with ligands having polar groups, such as ligands with high affinity for polymerizable compounds. With regard to the aforementioned surface-modified quantum dots, it is very easy to prepare high-concentration or highly concentrated quantum dot dispersions (improved dispersibility of quantum dots in polymerizable compounds), which can have a significant impact on improving light efficiency and are particularly desirable in achieving solvent-free curable compositions.

[0129] For example, ligands with polar groups can have structures that have a high affinity for the chemical structure of polymerizable compounds.

[0130] For example, ligands with polar groups can be represented by any of the compounds represented by chemical formulas A to Q, but are not limited to this.

[0131] [Chemical Formula A]

[0132] [Chemical Formula B]

[0133] [Chemical formula C]

[0134] [Chemical formula D]

[0135] (In chemical formula D, m1 is an integer from 0 to 10.)

[0136] [Chemical Formula E]

[0137] [Chemical formula F]

[0138] [Chemical formula G]

[0139] [Chemical formula H]

[0140] [Chemical Formula I]

[0141] [Chemical Formula J]

[0142] [Chemical formula K]

[0143] [Chemical formula L]

[0144] [Chemical Formula M]

[0145] [Chemical formula N]

[0146] [Chemical formula O]

[0147] [Chemical formula P]

[0148] [Chemical Formula Q]

[0149] When using the above ligands, the surface modification of quantum dots is easier, and when the surface-modified quantum dots using the above ligands are added to the above polymerizable compound and stirred, a very transparent dispersion can be obtained, which shows that the surface modification of quantum dots has been very successful.

[0150] Light diffusing agent

[0151] The curable composition according to one embodiment may also contain a light diffusing agent.

[0152] For example, light diffusing agents may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0153] Light diffusing agents can reflect unabsorbed light from the quantum dots and allow the quantum dots to reabsorb the reflected light. In other words, light diffusing agents can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

[0154] Light diffusing agents can have an average particle size (D) of 150 nm to 250 nm, specifically 180 nm to 230 nm. 50 When the average particle size of the light diffusing agent is within this range, it can have a better light diffusion effect and improve the light conversion efficiency.

[0155] Based on the total amount of the curable composition, the light diffusing agent can be included in amounts from 1 wt% to 20 wt%, for example 2 wt% to 15 wt%, for example 3 wt% to 10 wt%. When the light diffusing agent is included in an amount less than 1 wt% of 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 it is included in an amount greater than 20 wt%, quantum dot deposition problems may occur.

[0156] Polymerization initiator

[0157] The curable composition according to one embodiment may also contain a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0158] The polymerization initiator can be an initiator commonly used in photosensitive resin compositions, and may include, for example, acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, amino ketone compounds, etc., but is not limited to these.

[0159] 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-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one, etc.

[0160] Examples of benzophenone compounds include benzophenone, 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, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0161] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0162] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0163] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-helianyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0164] 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-oxoamine-1-phenylprop-1-one, etc. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylhydrothiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylhydrothiophenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylhydrothiophenyl)-but-1-one oxime-O-acetate.

[0165] Examples of aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc.

[0166] In addition to the compounds mentioned above, photopolymerization initiators may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, etc.

[0167] The photopolymerization initiator can be used with a photosensitizer that can induce a chemical reaction by absorbing light and be excited, and then transfer its energy.

[0168] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0169] 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, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azobis(isobutyronitrile), tert-butyl perbenzoate, etc., such as 2,2'-azobis-2-methylpropionitrile, but not limited thereto, and any known in the art can be used.

[0170] Based on the total amount of the curable composition, the polymerization initiator can be included in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 4 wt%. When the polymerization initiator is included in this range, excellent reliability can be obtained due to sufficient curing during exposure or thermal curing, and the degradation of transmittance due to unreacted initiator can be prevented, thereby preventing the degradation of the optical properties of the quantum dots.

[0171] Adhesive resin

[0172] The curable composition according to one embodiment may also contain an adhesive resin.

[0173] The adhesive resin may include acrylamide-based resin, cardo-based resin, epoxy resin, or a combination thereof.

[0174] Acrylamide resins can be copolymers of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer that can be copolymerized therewith, and can be resins comprising at least one acrylate repeating unit.

[0175] Specific examples of acryloyl adhesive resins may be polymethyl methacrylate, (meth)acrylic acid / phenyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene copolymer, (meth)acrylic acid / phenyl methacrylate / hydroxyethyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene / hydroxyethyl methacrylate copolymer, etc., but are not limited thereto, and these may be used alone or as a mixture of two or more.

[0176] 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 and chemical properties are improved, and the viscosity is appropriate.

[0177] Acrylamide resins can have acid values ​​ranging from 80 mgKOH / g to 130 mgKOH / g. When acrylamide resins have acid values ​​within this range, pixel patterns can exhibit excellent resolution.

[0178] Carbole resins can be used in conventional curable resin (or photosensitive resin) compositions, and can be used, for example, as disclosed in Korean Patent Application Publication No. 10-2018-0067243, but are not limited thereto.

[0179] The carbadoid resin 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.

[0180] The weight-average molecular weight of carbole-based adhesive resins can be 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 manufacture of the cured layer and without loss of film thickness during the development of the solvent-based curable composition.

[0181] When the adhesive resin is a carbole-based resin, the developability of curable compositions containing the adhesive resin, especially photosensitive resin compositions, is improved, and the sensitivity during photocuring is good, thus improving the micro-patterning characteristics.

[0182] Epoxy resins can be monomers or oligomers that can be thermally polymerized, and can include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0183] Epoxy resins may include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cyclic aliphatic epoxy resin and aliphatic polyglycidyl ether.

[0184] Its currently available products may include bisphenol epoxy resins, such as YX4000, YX4000H, YL6121H, YL6640, or YL6677 from Yuka Shell Epoxy Co., Ltd.; cresol phenolic varnish-type 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.; bisphenol A epoxy resins, such as EPIKOTE 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 from Yuka Shell Epoxy Co., Ltd.; and bisphenol F type epoxy resins, such as those from Yuka Shell Epoxy... EPIKOTE 807 and 834 from Yuka Shell Epoxy Co., Ltd.; phenolic varnish-type epoxy resins, such as EPIKOTE 152, 154 and 157H65 from Yuka Shell Epoxy Co., Ltd., and EPPN 201 and 202 from Nippon Kayaku Co., Ltd.; other cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 from CIBA-GEIGY AG, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from UCC, Shodyne 509 from Showa Denko KK, ARALDITE CY-182, CY-192 and CY-184 from CIBA-GEIGY AG, Epichron 200 and 400 from Dainippon Ink and Chemicals, Inc., and from Yuka Shell Epoxy Co., Ltd. EPIKOTE 871, 872 and EP1032H60 from CelaneseCoatings Co., Ltd.; ED-5661 and ED-5662 from CelaneseCoatings Co., Ltd.; aliphatic polyglycidyl ethers, such as EPIKOTE 190P and 191P from Yuka ShellEpoxy Co., Ltd.; Epolite100MF from Kyoesha Yushi Co., Ltd.; Epiol TMP from Nippon Yushi Co., Ltd., etc.

[0185] For example, when the curable composition according to one embodiment is a solvent-free curable composition, it may contain an amount of the adhesive resin in the form of 0.5 wt% to 10 wt%, for example, 1 wt% to 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 can be improved, and the storage stability of the composition can also be improved.

[0186] For example, when the curable composition according to one embodiment is a solvent-containing curable composition, it may contain an amount of the adhesive resin in the form of 1 wt% to 30 wt%, for example, 3 wt% to 20 wt%, based on the total amount of the curable composition. In this case, patterning properties, heat resistance, and chemical resistance can be improved.

[0187] Other additives

[0188] To improve the stability and dispersibility of quantum dots, the curable composition according to one embodiment may also contain a polymerization inhibitor.

[0189] The polymerization inhibitor may include, but is not limited to, hydroquinone compounds, catechol compounds, or combinations thereof. If the curable composition according to one embodiment further comprises hydroquinone compounds, catechol compounds, or combinations thereof, room-temperature crosslinking during exposure can be prevented after coating the curable composition.

[0190] For example, hydroquinone compounds, catechol compounds, or combinations thereof can be 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-cresol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamine-O,O')aluminum, or combinations thereof, but are not necessarily limited thereto.

[0191] Hydroquinone compounds, catechol compounds, or combinations thereof can be used in the form of dispersions. A polymerization inhibitor in dispersion form may be included in an amount of 0.001 wt% to 3 wt%, for example, 0.01 wt% to 2 wt%, based on the total amount of the curable composition. When a polymerization inhibitor is included within this range, aging problems at room temperature can be addressed, while simultaneously preventing sensitivity degradation and surface delamination.

[0192] Furthermore, the curable composition according to one embodiment may also contain malonic acid; 3-amino-1,2-propanediol; silane coupling agents; leveling agents; fluorinated surfactants; or combinations thereof, thereby improving heat resistance and reliability.

[0193] For example, the curable composition according to one embodiment may also contain a silane coupling agent having reactive substituents such as vinyl, carboxyl, methacryloyloxy, isocyanate, epoxy, etc., thereby improving the tight contact properties with the substrate.

[0194] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc., and these can be used alone or in mixtures of two or more.

[0195] Based on 100 parts by weight of the curable composition, silane coupling agents can be used in amounts from 0.01 parts by weight to 10 parts by weight. When silane coupling agents are included within this range, close contact properties, storage capacity, etc., are improved.

[0196] In addition, the curable composition may, as needed, contain surfactants, such as fluorinated surfactants, to improve coating performance and inhibit spot formation, i.e., improve leveling performance.

[0197] Fluorinated surfactants can have low weight-average molecular weights ranging from 4,000 g / mol to 10,000 g / mol, and specifically from 6,000 g / mol to 10,000 g / mol. Additionally, fluorinated surfactants can have surface tensions ranging from 18 mN / m to 23 mN / m (measured in a 0.1% polyethylene glycol monomethyl ether acetate (PGMEA) solution). When fluorinated surfactants have weight-average molecular weights and surface tensions within this range, leveling properties can be further improved, and excellent properties can be provided when used in slot coating applications for high-speed coating, as fewer film defects are generated by preventing spot formation and suppressing vapor generation during high-speed coating.

[0198] An example of a fluorinated surfactant is BM-1000. ® and BM-1100 ® (BM Chemie Inc.);MEGAFACEF 142D ® F 172 ® F 173 ® and F 183 ®(Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORADFC-135 ® FULORAD FC-170C ® FULORAD FC-430 ® and FULORAD FC-431 ® (Sumitomo 3M Co., Ltd.); SURFLON S-112 ® SURFLON S-113 ® SURFLON S-131 ® SURFLON S-141 ® and SURFLON S-145 ® (ASAHI Glass Co., Ltd.); and SH-28PA ® SH-190 ® SH-193 ® SZ-6032 ® and SF-8428 ® Examples include Toray Silicone Co., Ltd.; and DIC Co., Ltd.'s F-482, F-484, F-478, and F-554.

[0199] In addition to fluorinated surfactants, the curable composition according to one embodiment may contain silicone surfactants. Specific examples of silicone surfactants may be, but are not limited to, TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba silicone Co., Ltd.

[0200] Based on 100 parts by weight of the curable composition, a surfactant may be included in an amount of 0.01 parts by weight to 5 parts by weight, for example, 0.1 parts by weight to 2 parts by weight. If a surfactant is included within this range, less foreign matter is generated in the sprayed composition.

[0201] Furthermore, the curable composition according to one embodiment may also contain a predetermined amount of other additives, such as antioxidants, stabilizers, etc., unless the properties deteriorate.

[0202] solvent

[0203] Additionally, the curable composition according to one embodiment may also contain a solvent.

[0204] The solvent may include, for example, alcohols such as methanol and ethanol; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; celecoxib acetate such as methyl celecoxib acetate, ethyl celecoxib acetate, and diethyl celecoxib acetate; carbitol such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, and methyl n-butanone. Methyl pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters, such as methyl lactate, ethyl lactate, etc.; alkyl glycolic acid esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkyl acetate alkoxy esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionic acid esters, such as methyl 3-hydroxypropionic acid, ethyl 3-hydroxypropionic acid, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid. Esters, such as methyl 3-ethoxypropionate; alkyl 2-hydroxypropionates, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, etc. The following are possible esters: 2-hydroxy-2-methylethyl ester, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, etc.; or keto esters, such as ethyl pyruvate, etc., and additionally, 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, phenyl celecoxalate, etc., but not limited to these.

[0205] For example, the solvent may preferably be a glycol ether, such as ethylene glycol monoethyl ether, ethylene glycol methyl ethyl ether, etc.; ethylene glycol alkyl ether acetate, such as ethyl celusyl 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.

[0206] 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 glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, propylene carbonate, γ-butyrolactone, or combinations thereof.

[0207] Based on the total amount of the curable composition, the solvent can be included in an amount of 40 wt% to 80 wt%, for example, 45 wt% to 80 wt%. When the solvent is within this range, the solvent-based curable composition has a suitable viscosity, and therefore can have excellent coating characteristics when applied over large areas by spin coating and slot coating.

[0208] Another embodiment provides a cured layer produced using the curable composition and a display device including the cured layer. In this case, the cured layer can have a diffuse reflectance of 50% to 55% as described above.

[0209] One method of producing a cured layer may include applying the curable composition onto a substrate using an inkjet printing method to form a pattern (S1); and curing the pattern (S2).

[0210] (S1) Pattern Formation

[0211] Ideally, a curable composition can be applied to a substrate to a thickness of 0.5 μm to 20 μm using inkjet printing. While inkjet printing can form patterns by spraying a single color from each nozzle and thus repeating the spraying process the same number of times as the desired color, it can also form patterns by simultaneously spraying the desired number of colors from each inkjet nozzle, thus reducing the number of steps.

[0212] (S2) Curing

[0213] The obtained pattern is cured to obtain pixels. In this document, the curing method can be a thermal curing or a photocuring process. Thermal curing processes can be performed at or above 100°C, preferably in the range of 100°C to 300°C, and more preferably in the range of 160°C to 250°C. Photocuring processes can include radiation photochemical rays, such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm. Radiation is performed using light sources such as mercury lamps (with low, high, or ultra-high pressure), metal halide lamps, argon lasers, etc. X-rays, electron beams, etc., may also be used as needed.

[0214] Another method for producing a cured layer may include producing a cured layer using the above-described curable composition via photolithography.

[0215] (1) Coating and film formation

[0216] A curable composition is applied to a pre-treated substrate to a desired thickness, such as 2 μm to 10 μm, using spin coating, slot coating, roller coating, screen printing, or a coater method. 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.

[0217] (2) Exposure

[0218] After placing a mask of a predetermined shape, the resulting film is irradiated with photochemical rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, to form a desired pattern. Irradiation is performed using a light source such as a mercury lamp (with low pressure, high pressure, or ultra-high pressure), a metal halide lamp, or an argon laser. X-rays, electron beams, etc., may also be used as needed.

[0219] When using a high-pressure mercury lamp, the exposure process uses, for example, 500 mJ / cm. 2 Or a lower light dose (using a 365 nm sensor). However, the light dose can be varied depending on the type of each component of the curable composition, their combination ratio, and the dry film thickness.

[0220] (3) Development

[0221] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unwanted portions outside the exposed areas, thereby forming an image pattern. In other words, when the alkaline developing solution is used for development, the unexposed areas dissolve and form an image filter pattern.

[0222] (4) Post-processing

[0223] To achieve excellent quality in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, and storage stability, the image pattern can be cured by reheating or by radiation development such as photochemical rays.

[0224] Invention Model

[0225] The invention is described in more detail below with reference to embodiments. However, these embodiments should not be construed in any way as limiting the scope of the invention.

[0226] Preparation of polymerizable compounds

[0227] Preparation Example 1

[0228] 20 g of 2-hydroxybenzenethiol was dissolved thoroughly in 200 mL of dimethylformamide (DMF). Then, 32.9 g of K₂CO₃ and 20.8 g of 2-bromoethanol were added sequentially, and the mixture was stirred at room temperature (23°C) for 12 hours to complete the reaction. The result was diluted with 200 mL of ethyl acetate and then extracted three times with 1N HCl aqueous solution. MgSO₄ was added to the extracted organic layer, the mixture was stirred for 5 minutes, filtered, and the resulting filtrate was concentrated. After column purification, the solution was concentrated and dried under vacuum.

[0229] The dried intermediate was thoroughly dissolved in 230 mL of dichloromethane and stirred at 0°C for 10 minutes. 41.0 g of triethylamine was added, and the mixture was stirred for another 10 minutes. 26.9 g of acryloyl chloride was slowly added dropwise at 0°C, and the mixture was stirred for 30 minutes to complete the reaction. The reaction solution was extracted sequentially with 200 mL of 1N HCl aqueous solution and 200 mL of water. MgSO4 was added to the resulting organic layer, the mixture was stirred and filtered, and the filtrate was concentrated. After column purification, the filtrate was concentrated and dried under vacuum to obtain the compound represented by Formula 11 (refractive index: 1.553, viscosity: 63 cps).

[0230] [Chemical Formula 11]

[0231] Preparation Example 2

[0232] The compound represented by chemical formula 12 (refractive index: 1.556, viscosity: 42 cps) was prepared in the same manner as in Preparation Example 1, except that 220 mL of dichloromethane, 39.2 g of triethylamine and 25.7 g of acryloyl chloride were used.

[0233] [Chemical Formula 12]

[0234] Preparation Example 3

[0235] The compound represented by chemical formula 13 (refractive index: 1.554, viscosity: 33 cps) was prepared in the same manner as in Preparation Example 1, except that 200 mL of dichloromethane, 35.7 g of triethylamine and 23.4 g of acryloyl chloride were used.

[0236] [Chemical Formula 13]

[0237] Preparation Example 4

[0238] 20 g of 4-hydroxythiophenol was completely dissolved in 200 mL of DMF. 129.1 g of Ca₂CO₃ and 43.6 g of 2-bromoethanol were added sequentially, and the mixture was stirred at 60°C for 12 hours to complete the reaction. The product was diluted with 200 mL of ethyl acetate and then extracted three times with 1N HCl aqueous solution. MgSO₄ was added to the separated organic layer, the mixture was stirred for 5 minutes, filtered, and the resulting filtrate was concentrated. After column purification, the solution was concentrated and dried under vacuum.

[0239] The dried intermediate was thoroughly dissolved in 300 mL of dichloromethane and stirred at 0°C for 10 minutes. 22.1 g of triethylamine was added, and the mixture was stirred for another 10 minutes. 17.1 g of acryloyl chloride was slowly added dropwise at 0°C, and the mixture was stirred for 30 minutes to complete the reaction. The reaction solution was extracted sequentially with 300 mL of 1N HCl aqueous solution and 300 mL of water. MgSO4 was added to the resulting organic layer, the mixture was stirred and filtered, and the filtrate was concentrated. After column purification, the filtrate was concentrated and dried under vacuum to obtain the compound represented by Formula 14 (refractive index: 1.546, viscosity: 71 cps).

[0240] [Chemical Formula 14]

[0241] Preparation Example 5

[0242] The compound represented by chemical formula 15 (refractive index: 1.529, viscosity: 100 cps) was prepared in the same manner as in Preparation Example 4, except that 52.9 g of 1-bromo-2-propanol was used instead of 2-bromoethanol.

[0243] [Chemical Formula 15]

[0244] Preparation Example 6

[0245] 20 g of 1,4-benzenedithiol was completely dissolved in 200 mL of dichloromethane. 22.5 g of 2-chloroethyl acrylate was added, and the mixture was stirred for 10 minutes. Then, 17 g of triethylamine was slowly added dropwise at 0°C, and the mixture was stirred for 12 hours to complete the reaction. The mixture was extracted with 300 mL of dichloromethane and 300 mL of water, separating the organic layer, which was then extracted three times with dilute hydrochloric acid solution. The dichloromethane layer was then separated, and MgSO4 was added, followed by stirring for 5 minutes. After filtration, the resulting filtrate was concentrated. After column purification, the filtrate was concentrated and dried under vacuum to obtain the compound represented by Formula 16 (refractive index: 1.579, viscosity: 56 cps).

[0246] [Chemical Formula 16]

[0247] Preparation of surface-modified quantum dot dispersions

[0248] Preparation Example 7

[0249] A magnetic rod was placed in a 3-necked round-bottom flask, and a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical, quantum dot solid content: 23 wt%) was added. Subsequently, a compound (ligand) represented by the chemical formula Q was added, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, after cooling to room temperature (23°C), the quantum dot reaction solution 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 surface-modified quantum dots.

[0250] Surface-modified green quantum dots were stirred with a polymerizable compound for 12 hours to obtain a surface-modified quantum dot dispersion (QD solids content: 23 wt%).

[0251] ( Synthesis of the compound represented by chemical formula Q: 100 g of PH-4 (Hannong Chemicals Inc.) was placed in a 2-necked round-bottom flask and thoroughly dissolved in 300 mL of THF. Then, 15.4 g of NaOH and 100 mL of water were added at 0°C, and the solution was thoroughly dissolved until a clear solution was obtained. At 0°C, a solution prepared by dissolving 73 g of p-toluenesulfonyl chloride in 100 mL of THF was slowly injected. The injection was carried out for 1 hour, and the resulting mixture was then stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added, followed by stirring, and a saturated solution of NaHCO3 was added for extraction, titration, and water removal. After solvent removal, the residue was dried in an oven for 24 hours. 50 g of the dried product was added to a 2-necked round-bottom flask and thoroughly stirred with 300 mL of ethanol. Subsequently, 27 g of thiourea was added and dispersed therein, and the mixture was refluxed at 80°C for 12 hours. Subsequently, an aqueous solution of 4.4 g NaOH dissolved in 20 mL of water was added, and the mixture was stirred for 5 hours. Excess dichloromethane was then added, followed by stirring. Hydrochloric acid aqueous solution was then added, and extraction, titration, water removal, and solvent removal were performed sequentially. Finally, the mixture was dried in a vacuum oven for 24 hours to obtain the compound represented by the chemical formula Q.

[0252] [Chemical Formula Q]

[0253] (Preparation of curable compositions)

[0254] Examples 1 to 8 and Comparative Examples 1 and 2

[0255] Each curable composition of Examples 1 to 8 and Comparative Examples 1 and 2 was prepared by using the following components to have each composition shown in Table 1.

[0256] Specifically, the quantum dot dispersion was weighed, diluted by mixing with a polymerizable compound, and a polymerization inhibitor was added, followed by stirring for 5 minutes. Subsequently, a photoinitiator was added, followed by a light diffusing agent. The resulting composition was then stirred for 1 hour to prepare a curable composition.

[0257] (A) Quantum dots

[0258] Surface-modified green quantum dot dispersion prepared by Preparation Example 7

[0259] (B) Polymerizable compounds

[0260] (B-1) Preparation of the compound of Example 1

[0261] (B-2) Preparation of the compound of Example 2

[0262] (B-3) Preparation of the compound of Example 3

[0263] (B-4) Preparation of the compound of Example 4

[0264] (B-5) Preparation of the compound of Example 5

[0265] (B-6) Preparation of the compound of Example 6

[0266] (B-7) Compound represented by chemical formula 4-2 (refractive index: 1.455, viscosity: 6.1 cps) (HannongChemicals Inc., HD002S)

[0267] [Chemical Formula 4-2]

[0268] (C) Photopolymerization initiator

[0269] TPO-L (Polynetron Co., Ltd.)

[0270] (D) Light diffusing agent

[0271] Titanium dioxide dispersion (TiO2 solid content: 20% by weight, average particle size: 200 nm, DitoTechnology Co., Ltd.)

[0272] (E) Polymerization inhibitor

[0273] Hydroquinone (TOKYO CHEMICAL)

[0274] [Table 1]

[0275] (Unit: wt%)

[0276] Evaluation: Evaluation of the optical properties and diffuse reflectance of the curable composition.

[0277] The quantum efficiency (EQE) and diffuse reflectance (SCE) after exposure for each curable composition according to Examples 1 to 8 and Comparative Examples 1 and 2 were measured using a spectrophotometer (CM-3600A, Konica Minolta, Inc.), and the results are shown in Table 2.

[0278] [Table 2]

[0279] Referring to Table 2, compared with the curable compositions according to Comparative Examples 1 and 2, the curable compositions according to Examples 1 to 10 exhibit high quantum efficiency after exposure, thus showing improved optical properties, and at the same time exhibit low diffuse reflectance after curing, thus showing a reflectance reduction effect.

[0280] Although the invention has been described in conjunction with exemplary embodiments now considered practical, 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 included within the spirit and scope of the appended claims. Therefore, the above embodiments should be understood as exemplary and not as limiting the invention in any way.

Claims

1. A curable composition comprising: (A) Quantum dots, and (B) Polymerizable compounds; in, The polymerizable compound comprises a first polymerizable compound having a refractive index greater than or equal to 1.5 and a viscosity greater than or equal to 10 cps.

2. The curable composition according to claim 1, wherein, The first polymerizable compound is represented by chemical formula 1: [Chemical Formula 1] In chemical formula 1, R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 and L 2 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group, provided that L 1 and L 2 They are not both single keys.

3. The curable composition according to claim 2, wherein, L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 2 It is a single bond or an alkylene oxide.

4. The curable composition according to claim 3, wherein, Chemical formula 1 is represented by chemical formulas 2-1 to 2-3: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] In chemical formulas 2-1 to 2-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group.

5. The curable composition according to claim 3, wherein, Chemical formula 1 is represented by chemical formulas 3-1 to 3-3: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] In chemical formulas 3-1 to 3-3 R 1 and R 2 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. L 1 It is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and L 3 It is a substituted or unsubstituted C1 to C20 alkylene group.

6. The curable composition according to claim 1, wherein, The polymerizable compound further comprises a second polymerizable compound having a structure different from that of the first polymerizable compound.

7. The curable composition according to claim 6, wherein, The second polymerizable compound includes compounds represented by chemical formula 4: [Chemical Formula 4] In chemical formula 4, L 4 It 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 Each is 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 6, wherein, The second polymerizable compound includes a compound represented by chemical formula 5: [Chemical Formula 5] In chemical formula 5, L 7 It is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and R 5 It is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

9. The curable composition according to claim 6, wherein, The second polymerizable compound has a refractive index of less than 1.5 or a viscosity of less than 10 cps.

10. The curable composition according to claim 6, wherein, The first polymerizable compound and the second polymerizable compound are contained in a weight ratio of 1:9 to 9:

1.

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

12. The curable composition according to claim 11, wherein, Based on the total amount of the solvent-free curable composition, the solvent-free curable composition comprises: The quantum dots, comprising 5 wt% to 60 wt%, and The polymerizable compound is 40 wt% to 95 wt%.

13. The curable composition according to claim 1, wherein, The curable composition further comprises a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

14. The curable composition according to claim 13, wherein, The light diffusing agent includes barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

15. The curable composition according to claim 1, wherein, The curable composition also contains a solvent.

16. The curable composition according to claim 15, wherein, Based on the total weight of the curable composition, the curable composition comprises 1 wt% to 40 wt% of the quantum dots, 1 wt% to 20 wt% of the polymerizable compound, and 40 wt% to 80 wt% of the solvent.

17. The curable composition according to claim 1, wherein, The curable composition further comprises malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorinated surfactants, or combinations thereof.

18. A cured layer, produced using any one of the curable compositions according to claims 1 to 17.

19. A display device comprising the cured layer of claim 18.

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