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

Abstract

(A) a quantum dot; and (B) a polymerizable compound comprising a compound represented by the following chemical formula 1, a curable composition, a cured film prepared using the curable composition, a color filter comprising the cured film, and a display device comprising the color filter are provided. [Chemical Formula 1] (In the above Chemical Formula 1, each substituent is as defined in the specification.)

Description

Technology Field

[0001] The present invention relates to a curable composition, a cured film manufactured using the said composition, a color filter comprising the said cured film, and a display device comprising the said color filter. Background Technology

[0003] In the case of conventional quantum dots, the solvents in which they can be dispersed are limited due to their hydrophobic surface characteristics, and consequently, it is true that there are significant difficulties in introducing them into polar systems such as binders or curable monomers.

[0004] For example, even in the case of quantum dot ink compositions that are being actively researched, in the initial stages, they were only dispersed to a degree that could be used in solvents for curable compositions with relatively low polarity and high hydrophobicity. Because of this, it was difficult to include more than 20 weight percent of quantum dots relative to the total amount of the composition, so the light efficiency of the ink could not be increased beyond a certain level. Even if quantum dots were forcibly added and dispersed to increase light efficiency, the viscosity exceeded the range where ink-jetting is possible, and thus processability could not be satisfied.

[0005] In addition, to achieve a viscosity range suitable for ink-jetting, a method has been used to lower the ink solid content by including more than 50% by weight of solvent relative to the total amount of the composition. Although this method also provides somewhat satisfactory results in terms of viscosity, it has the disadvantage of being difficult to apply to actual processes due to problems such as nozzle drying and clogging caused by solvent volatilization during ink-jetting, and a decrease in film thickness over time after ink-jetting, as well as severe thickness variation after curing.

[0006] Therefore, a solvent-free type of quantum dot ink is the most desirable form for actual process application, and it is assessed that the current technology of applying quantum dots themselves to solvent-based compositions has now reached its limits.

[0007] In the case of solvent-free curable compositions (quantum dot ink compositions), problems arise due to the excessive inclusion of polymerizable compounds, such as clogging and poor ejection caused by nozzle drying due to volatility, and a reduction in film thickness due to the volatilization of the jetted ink composition within the pattern barrier pixels. Therefore, various efforts are being made to improve the optical properties of solvent-free curable compositions. Generally, the method of increasing the content of inorganic materials is used to improve the optical properties of solvent-free curable compositions; however, the problem is that reflectivity increases as the content of inorganic materials increases. In other words, the improvement of optical properties and the reduction of reflectivity of solvent-free curable compositions are in a trade-off relationship, and there is a growing need for technology that can simultaneously improve both of these properties (improvement of optical properties and reduction of reflectivity). The problem to be solved

[0009] One embodiment is intended to provide a curable composition capable of simultaneously achieving improved optical properties and reduced reflectance.

[0010] Another embodiment is to provide a cured film manufactured using the above-mentioned curable composition.

[0011] Another embodiment is to provide a color filter comprising the above-mentioned curing film.

[0012] Another embodiment is to provide a display device including the above-mentioned color filter. means of solving the problem

[0014] One embodiment provides a curable composition comprising (A) quantum dots; and (B) a polymerizable compound comprising a compound represented by the following chemical formula 1.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] L 1 It is a divalent linker containing a sulfur atom, but does not include a disulfide (*-SS-*) linkage structure,

[0019] L 2 and L 3 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and

[0020] R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0021] The above L 1 It can be represented by any one of the following chemical formulas L-1 to L-4.

[0022] [Chemical Formula L-1]

[0023]

[0024] [Chemical Formula L-2]

[0025]

[0026] [Chemical Formula L-3]

[0027]

[0028] [Chemical Formula L-4]

[0029]

[0030] In the above chemical formulas L-1 to L-4,

[0031] L 4 to L 8Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0032] The compound represented by the above chemical formula 1 may have a refractive index greater than 1.455.

[0033] The compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3.

[0034] [Chemical Formula 1-1]

[0035]

[0036] [Chemical Formula 1-2]

[0037]

[0038] [Chemical Formula 1-3]

[0039]

[0040] The above polymerizable compound may further include a compound having a structure different from the compound represented by Chemical Formula 1.

[0041] A compound having a structure different from that of the compound represented by the above chemical formula 1 can be represented by the following chemical formula 2.

[0042] [Chemical Formula 2]

[0043]

[0044] In the above chemical formula 2,

[0045] L 9 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*), and

[0046] L 10 and L 11 Each is independently a single-bonded, substituted, or unsubstituted C1 to C10 alkylene group, and

[0047] R 3 and R 4Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0048] The compound represented by the above chemical formula 2 may have a refractive index of 1.455 or less.

[0049] The compound represented by the above chemical formula 1 and the compound having a structure different from the compound represented by the above chemical formula 1 may be included in a weight ratio of 1:9 to 9:1.

[0050] The above curable composition may be a solvent-free curable composition.

[0051] The solvent-free curable composition may comprise 5% to 60% by weight of the quantum dots and 40% to 95% by weight of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0052] The above curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0053] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0054] The above curable composition may further include a solvent.

[0055] The above curable composition may comprise, based on the total weight of the above curable composition, 1% to 40% by weight of the quantum dots; 1% to 20% by weight of the polymerizable compound; and 40% to 80% by weight of the solvent.

[0056] The above curable composition may further include malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0057] Another embodiment provides a cured film manufactured using the above-mentioned curable composition.

[0058] The above-mentioned hardened film may have a diffuse reflectance of 50% to 55%.

[0059] Another embodiment provides a color filter including the above-mentioned curing film.

[0060] Another embodiment provides a display device including the color filter.

[0061] Specific details regarding other aspects of the present invention are included in the following detailed description. Effects of the invention

[0063] By including a sulfur-containing di(meth)acrylate compound in the quantum dot-containing curable composition, the optical properties of the quantum dot-containing curable composition can be improved while simultaneously reducing the reflectance. Specific details for implementing the invention

[0065] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0066] Unless otherwise specifically stated in this specification, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, "heteroarylene group" means a C3 to C20 heteroarylene group, and "alkoxylene group" means a C1 to C20 alkoxylene group It means.

[0067] Unless specifically stated in this specification, "substitution" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl 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 or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 It means substituted with a heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0068] Additionally, unless otherwise specifically stated in this specification, "hetero" means that the chemical formula contains at least one heteroatom among N, O, S, and P.

[0069] Additionally, unless otherwise specifically stated in this specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means that both "acrylic acid" and "methacrylic acid" are possible.

[0070] Unless otherwise specifically stated in this specification, "combination" means mixing or copolymerization.

[0071] Unless otherwise defined in the chemical formulas within this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at said position.

[0072] Additionally, unless otherwise specifically stated in this specification, "*" signifies a part connected to the same or different atoms or chemical formulas.

[0073] Each component constituting the curable composition according to one embodiment will be described in detail below.

[0075] polymerizable compounds

[0076] A curable composition containing quantum dots according to one embodiment includes a sulfur-containing di(meth)acrylate compound having a high refractive index as a polymerizable compound, so that the high refractive properties of the sulfur-containing di(meth)acrylate compound lead to an effect of improving the optical properties of the curable composition, and furthermore, a thiol-ene addition reaction is induced during the thermal curing of the curable composition, thereby promoting the surface curing of the curable film of the curable composition and simultaneously satisfying the effect of reducing reflectance.

[0077] The above sulfur-containing di(meth)acrylate compound can be represented by the following chemical formula 1.

[0078] [Chemical Formula 1]

[0079]

[0080] In the above chemical formula 1,

[0081] L 1It is a divalent linker containing a sulfur atom, but does not include a disulfide (*-SS-*) linkage structure,

[0082] L 2 and L 3 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and

[0083] R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0084] Green quantum dot-containing curable compositions have the disadvantage of having relatively lower absorption (abs.) and luminous efficiency (EQE) and nearly twice as high reflectance compared to red quantum dot-containing curable compositions. Therefore, the technical challenge of improving the brightness of green quantum dot pixels in panels and reducing external light reflection to further improve front-side brightness has not yet been resolved.

[0085] The inventors clearly recognized the above-mentioned problems and, after conducting related research for a long time and undergoing hundreds of trials and errors to improve the optical properties and reduce the reflectance of a curable composition containing green quantum dots, they came to solve the technical problem by applying a compound represented by Chemical Formula 1 as a polymerizable compound.

[0086] Generally, the primary method used to improve optical properties in green quantum dot-containing curable compositions has been to increase the inorganic content, while conversely, the primary method used to reduce the reflectance of said green quantum dot-containing curable compositions has been to decrease the inorganic content. Since the improvement of optical properties and the reduction of reflectance are mutually opposing, or trade-off, properties, it has been very difficult to achieve both characteristics simultaneously.

[0087] According to one embodiment, by applying a sulfur-containing di(meth)acrylate compound represented by the above chemical formula 1 as a polymerizable compound to the composition of a curable composition, the effects of improving optical properties and reducing reflectance can be simultaneously achieved in a curable composition containing green quantum dots in addition to a curable composition containing red quantum dots.

[0088] Specifically, the improvement in optical properties is due to the high refractive index of the compound represented by Chemical Formula 1. For example, the compound represented by Chemical Formula 1 may have a refractive index greater than 1.455, for example, greater than 1.455 and less than or equal to 1.7. Since the compound represented by Chemical Formula 1 has a high refractive index within this range, the optical properties of a curable composition containing quantum dots that includes it as a polymerizable compound can be significantly improved.

[0089] Furthermore, the above-mentioned reflectance reduction effect is achieved when the compound represented by Formula 1, used as the polymerizable compound, is thermally decomposed during the thermal curing of the curable composition according to one embodiment, thereby exposing the thiol group. This thiol group facilitates a thiol-ene reaction between the carbon-carbon double bond of the (meth)acrylate group and the thiol group (see reaction scheme below), which promotes the surface curing of the thermally curable film of the curable composition according to one embodiment, ultimately allowing for a significant reduction in the reflectance of the cured film, particularly the diffuse reflectance. For example, the diffuse reflectance of the cured film can be reduced to 55% or less, for instance, from 50% to 55%.

[0090] [Reaction Equation]

[0091]

[0092] In the above chemical formula 1, L 1 This includes a disulfide (*-SS-*) linkage structure, or L 2 or L 3If this arylene group is included as a linker, the refractive index of the compound is lowered, which is disadvantageous in terms of improving optical properties, and furthermore, the thiol-ene reaction does not proceed smoothly, so the reflectance reduction effect is also halved, which is undesirable.

[0093] For example, the above L 1 It can be represented by any one of the following chemical formulas L-1 to L-4.

[0094] [Chemical Formula L-1]

[0095]

[0096] [Chemical Formula L-2]

[0097]

[0098] [Chemical Formula L-3]

[0099]

[0100] [Chemical Formula L-4]

[0101]

[0102] In the above chemical formulas L-1 to L-4,

[0103] L 4 to L 8 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0104] L of the above chemical formula 1 1 When the connector has the above structure, it may be very advantageous to simultaneously achieve the effect of improving the optical properties and reducing the reflectance (diffuse reflectance) of the curable composition according to one embodiment.

[0105] For example, the compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3, but is not necessarily limited thereto.

[0106] [Chemical Formula 1-1]

[0107]

[0108] [Chemical Formula 1-2]

[0109]

[0110] [Chemical Formula 1-3]

[0111]

[0112] For example, the polymerizable compound may further include a compound having a structure different from that of the compound represented by Chemical Formula 1. That is, the polymerizable compound may include the compound represented by Chemical Formula 1 and other compounds having a structure different from it.

[0113] For example, a compound having a structure different from that of the compound represented by the above chemical formula 1 can be represented by the following chemical formula 2.

[0114] [Chemical Formula 2]

[0115]

[0116] In the above chemical formula 2,

[0117] L 9 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*), and

[0118] L 10 and L 11 Each is independently a single-bonded, substituted, or unsubstituted C1 to C10 alkylene group, and

[0119] R 3 and R 4 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0120] A curable composition according to one embodiment can simultaneously achieve the effects of improving optical properties and reducing reflectance of the curable composition, just as when the compound represented by Formula 1 is used alone, even if the compound represented by Formula 1 is used together with the compound represented by Formula 1 having a high refractive index and additionally includes the compound represented by Formula 2 as a polymerizable compound.

[0121] For example, the compound represented by the above chemical formula 2 may have a refractive index of 1.455 or less. If the compound represented by the above chemical formula 2 has a refractive index greater than 1.455, it is advantageous for improving optical properties, but it may be disadvantageous in terms of reducing reflectance.

[0122] For example, the compound represented by the above chemical formula 1 and the compound having a structure different from that of the compound represented by the above chemical formula 1 (e.g., the compound represented by the above chemical formula 2, etc.) may be included in a weight ratio of 1:9 to 9:1, for example, a weight ratio of 5:5 to 9:1.

[0123] For example, the compound represented by the above chemical formula 1 may be included in a larger amount than a compound having a structure different from the compound represented by the above chemical formula 1 (e.g., a compound represented by the above chemical formula 2, etc.).

[0124] For example, a compound represented by the above chemical formula 1 and a compound having a structure different from that of the compound represented by the above chemical formula 1 (e.g., a compound represented by the above chemical formula 2, etc.) may be included in a weight ratio of 6:4 to 9:1.

[0125] When the compound represented by the above chemical formula 1 is included in a larger amount than the compound having a different structure from the compound represented by the above chemical formula 1 (e.g., the compound represented by the above chemical formula 2, etc.), for example in a weight ratio of 6:4 to 9:1, the curing rate of the curable composition according to one embodiment is increased, thereby maximizing the simultaneous improvement of two effects, namely improvement of optical properties and reduction of reflectance.

[0126] For example, the compound represented by the above chemical formula 2 may be represented by the following chemical formula 2-1 or 2-2, but is not necessarily limited thereto.

[0127] [Chemical Formula 2-1]

[0128]

[0129] [Chemical Formula 2-2]

[0130]

[0131] For example, compounds having a structure different from the compound represented by Chemical Formula 1 include, in addition to the compounds represented by Chemical Formulas 2-1 and 2-2, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, It may further include 1,6-hexanediol dimethacrylate or a combination thereof.

[0132] In addition, monomers commonly used in conventional thermosetting or photocurable compositions may be used in addition to the polymerizable compound above, and, for example, the monomer may further include oxetane-based compounds such as bis[1-ethyl(3-oxetanyl)]methyl ether.

[0133] The above polymerizable compound may be included in an amount of 40% to 95% by weight, for example, 50% to 90% by weight, based on the total amount of the solvent-free curable composition. The content of the above polymerizable compound must be within the above range to enable the production of a solvent-free curable composition having a viscosity suitable for ink jetting, and also allow the quantum dots in the produced solvent-free curable composition to have excellent dispersibility, thereby improving optical properties.

[0134] For example, the polymerizable compound may have a molecular weight of 170 g / mol to 1,000 g / mol. When the molecular weight of the polymerizable compound is within this range, it may be advantageous for ink-jetting as it does not impair the optical properties of the quantum dots and does not increase the viscosity of the composition.

[0135] In addition, if the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1% to 20% by weight, 1% to 15% by weight, for example, 5% to 15% by weight, relative to 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.

[0137] quantum dots

[0138] For example, the above quantum dots may have a maximum fluorescence emission wavelength at 500 nm to 680 nm.

[0139] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots may be included in an amount of 5% to 60% by weight, for example, 10% to 60% by weight, for example, 20% to 60% by weight, for example, 30% to 50% by weight. When the quantum dots are included within the above range, high light retention rate and light efficiency can be achieved even after curing.

[0140] For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the quantum dots may be included in an amount of 1% to 40% by weight, for example, 3% to 30% by weight, relative to the total amount of the curable composition. When the quantum dots are included within the above range, the photoconversion rate is excellent, and excellent processability can be achieved without impairing pattern characteristics and development characteristics.

[0141] For example, the above quantum dot absorbs light in a wavelength range of 360 nm to 780 nm, e.g., a wavelength range of 400 nm to 780 nm, and can emit fluorescence in a wavelength range of 500 nm to 700 nm, e.g., 500 nm to 580 nm, or emit fluorescence at 600 nm to 680 nm. That is, the above quantum dot has a maximum fluorescence emission wavelength (fluorescence λ) at 500 nm to 680 nm. em Can have ).

[0142] Each of the above quantum dots can independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum within the above range, the color purity is high, so when used as a color material in a color filter, there is an effect of increasing the color reproduction rate.

[0143] Each of the above quantum dots may independently be an organic material, an inorganic material, or a hybrid of an organic and an inorganic material.

[0144] The above quantum dots may each independently be composed of a core and a shell surrounding the core, and the core and shell may each independently have structures such as a core, core / shell, core / first shell / second shell, alloy, alloy / shell, etc., composed of Group II-IV, Group III-V, etc., but are not limited thereto.

[0145] For example, the core may comprise at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell surrounding the core may comprise at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

[0146] In one embodiment, as global interest in the environment has recently increased significantly and regulations on toxic substances are being strengthened, an environmentally friendly non-cadmium light-emitting material (InP / ZnS, InP / ZeSe / ZnS, etc.) with a somewhat lower quantum yield was used instead of a light-emitting material having a cadmium-based core, but it is not necessarily limited to this.

[0147] In the case of the above-mentioned core / shell structured quantum dots, the size (average particle size) of each of the total quantum dots including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

[0148] For example, the above quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. Each of the above red quantum dots may each independently have an average particle size of 10 nm to 15 nm. Each of the above green quantum dots may each independently have an average particle size of 5 nm to 8 nm.

[0149] Meanwhile, to ensure dispersion stability of the quantum dots, the curable composition according to one embodiment may further include a dispersant. The dispersant helps to uniformly disperse a photoconversion material, such as quantum dots, within the curable composition, and may be a nonionic, anionic, or cationic dispersant. Specifically, polyalkylene glycol or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkylamide alkylene oxide adduct, alkyl amine, etc., may be used, and these may be used alone or in a mixture of two or more. The dispersant may be used in an amount of 0.1% to 100% by weight, for example, 10% to 20% by weight, relative to the solid content of the photoconversion material, such as quantum dots.

[0150] For example, the quantum dots may be surface-modified quantum dots with a ligand having a polar group, such as a ligand having high affinity for the polymerizable compound. In the case of quantum dots surface-modified as described above, it is very easy to prepare a high-concentration or highly concentrated quantum dot dispersion (improving the dispersibility of quantum dots with respect to the polymerizable compound), which can have a significant impact on improving light efficiency and, in particular, may be advantageous for realizing a solvent-free curable composition.

[0151] For example, the ligand having the above polar group may have a structure that has high affinity with the chemical structure of the above polymerizable compound.

[0152] For example, the ligand having the above polar group may be represented by any one of the compounds represented by the following chemical formulas A to Q, but is not necessarily limited thereto.

[0153] [Chemical Formula A]

[0154]

[0155] [Chemical Formula B]

[0156]

[0157] [Chemical Formula C]

[0158]

[0159] [Chemical Formula D]

[0160]

[0161] (In the above chemical formula D, m1 is an integer from 0 to 10.)

[0162] [Chemical Formula E]

[0163]

[0164] [Chemical Formula F]

[0165]

[0166] [Chemical Formula G]

[0167]

[0168] [Chemical Formula H]

[0169]

[0171] [Chemical Formula I]

[0172]

[0173] [Chemical Formula J]

[0174]

[0175] [Chemical Formula K]

[0176]

[0177] [Chemical Formula L]

[0178]

[0179] [Chemical Formula M]

[0180]

[0181] [Chemical Formula N]

[0182]

[0183] [Chemical Formula O]

[0184]

[0185] [Chemical Formula P]

[0186]

[0187] [Chemical Formula Q]

[0188]

[0189] When the above ligand is used, surface modification of the quantum dots is made easier, and when quantum dots surface-modified with the above ligand are added to the aforementioned polymerizable compound and stirred, a very transparent dispersion can be obtained, which serves as a measure confirming that the surface modification of the quantum dots is very well done.

[0191] light diffuser

[0192] A curable composition according to one embodiment may further include a light diffusing agent.

[0193] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0194] The light diffusing agent above reflects light that is not absorbed by the aforementioned quantum dots and enables the quantum dots to reabsorb the reflected light. That is, the light diffusing agent increases the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

[0195] The above light diffusing agent has an average particle size (D 50 The average particle size of the light diffusing agent may be 150 nm to 250 nm, and specifically, 180 nm to 230 nm. When the average particle size of the light diffusing agent is within the above range, it may have a superior light diffusing effect and increase light conversion efficiency.

[0196] The light diffusing agent may be included in an amount of 1% to 20% by weight, for example, 2% to 15% by weight, for example, 3% to 10% by weight, relative to the total amount of the curable composition. If the light diffusing agent is included in an amount of less than 1% by weight relative to the total amount of the curable composition, it is difficult to expect an improvement in light conversion efficiency due to the use of the light diffusing agent, and if it is included in an amount exceeding 20% ​​by weight, there is a risk that a problem of quantum dot sedimentation may occur.

[0198] Polymerization initiator

[0199] A curable composition according to one embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0200] The above photopolymerization initiator is an initiator generally used in photosensitive resin compositions, and examples include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, aminoketone-based compounds, etc., but are not necessarily limited thereto.

[0201] Examples of the above acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0202] Examples of the above benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0203] Examples of the above thioxanthonic compounds include thioxanthon, 2-methylthioxanthon, isopropylthioxanthon, 2,4-diethylthioxanthon, 2,4-diisopropylthioxanthon, 2-chlorothioxanthon, etc.

[0204] Examples of the above-mentioned benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0205] Examples of the above 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, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, and bis(trichloromethyl)-6-styryl-s-triazine. Examples include 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0206] Examples of the above 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]ethanolone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the above O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one-oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one-oxime-O-acetate.

[0207] Examples of the above aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1).

[0208] In addition to the above compounds, the above photopolymerization initiator may use carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, etc.

[0209] The above photopolymerization initiator may also be used in combination with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring that energy.

[0210] Examples of the above-mentioned photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc.

[0211] Examples of the above-mentioned thermal polymerization initiators include peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, di-lauryl 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), t-butyl perbenzoate, etc., and 2,2'-azobis-2-methylpropionitrile, etc., but are not necessarily limited thereto, and any that is widely known in the art may be used.

[0212] The polymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 1% to 4% by weight, relative to the total amount of the curable composition. When the polymerization initiator is included within the above range, sufficient curing occurs during photolithography or thermal curing, thereby obtaining excellent reliability, and the decrease in transmittance caused by unreacted initiator can be prevented, thereby preventing the deterioration of the optical properties of the quantum dots.

[0214] Binder resin

[0215] A curable composition according to one embodiment may further include a binder resin.

[0216] The above binder resin may include acrylic resin, cardo resin, epoxy resin, or a combination thereof.

[0217] The above acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable thereto, and may be a resin comprising one or more acrylic repeating units.

[0218] Specific examples of the above-mentioned acrylic binder resins include polybenzyl methacrylate, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and these may be used alone or in combination of two or more types.

[0219] The weight-average molecular weight of the above acrylic resin may be 5,000 g / mol to 15,000 g / mol. 　 When the weight-average molecular weight of the above acrylic resin is within the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

[0220] The acid value of the above acrylic resin may be 80 mgKOH / g to 130 mgKOH / g. When the acid value of the above acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

[0221] The above cardo-based resin may be one used in conventional curable resin (or photosensitive resin) compositions, for example, one disclosed in Korean Patent Publication No. 10-2018-0067243, but is not limited thereto.

[0222] The above cardo-based resin comprises, for example, fluorene-containing compounds such as 9,9-bis(4-oxyranylmethoxyphenyl)fluorene; anhydride compounds such as benzenetetracarboxylic acid dihydride, naphthalenetetracarboxylic acid dihydride, biphenyltetracarboxylic acid dihydride, benzophenonetetracarboxylic acid dihydride, pyromellitic dihydride, cyclobutanetetracarboxylic acid dihydride, perylenetetracarboxylic acid dihydride, tetrahydrofurantetracarboxylic acid dihydride, tetrahydrophthalic anhydride; glycol 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; and phosphorus compounds such as triphenylphosphine. It can be prepared by mixing two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyl diethylamine, triethylamine, tributylamine, and benzyl triethylammonium chloride.

[0223] The weight-average molecular weight of the above cardo-based resin may be 500 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 30,000 g / mol. When the weight-average molecular weight of the above cardo-based resin is within the above range, pattern formation is good without residue when manufacturing a cured film, there is no loss of film thickness when developing the curable composition, and a good pattern can be obtained.

[0224] When the above binder resin is a cardo-based resin, the curable composition containing it, particularly the photosensitive resin composition, has excellent developability and good sensitivity during photocuring, resulting in excellent fine pattern formation ability.

[0225] The above epoxy resin may include monomers or oligomers that can be polymerized by heat, and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0226] The above epoxy resins may include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether, but are not necessarily limited thereto.

[0227] Commercial products of these compounds include, for bisphenyl epoxy resins, YX4000, YX4000H, YL6121H, YL6640, and YL6677 of Yukka Shell Epoxy Co., Ltd.; for cresol novolak type epoxy resins, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 of Nippon Kayaku Co., Ltd. and Epicoat 180S75 of Yukka Shell Epoxy Co., Ltd.; for bisphenol A type epoxy resins, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 of Yukka Shell Epoxy Co., Ltd.; Bisphenol F type epoxy resins include Epicoat 807 and 834 of Yukka Shell Epoxy Co., Ltd.; phenol novolac type epoxy resins include Epicoat 152, 154, and 157H65 of Yukka Shell Epoxy Co., Ltd. and EPPN 201 and 202 of Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CIBA-GEIGY AG's CY175, CY177, and CY179; UCC's ERL-4234, ERL-4299, ERL-4221, and ERL-4206; Showa Denko Co., Ltd.'s Shodine 509; CIBA-GEIGY AG's Araldite CY-182, CY-192, and CY-184; Dainippon Ink Kogyo Co., Ltd.'s Epichron 200 and 400; Yukka Shell Epoxy Co., Ltd.'s Epicoat 871, 872, and EP1032H60; and Celanese Coating Co., Ltd.'s ED-5661 and ED-5662; Examples of aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yuka Shell Epoxy Co., Ltd., Epolite 100MF from Kyoesha Yushi Kagaku Kogyo Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd.

[0228] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5% to 10% by weight, for example, 1% to 5% by weight, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

[0229] For example, if the curable composition according to one embodiment is a curable composition containing a solvent, the binder resin may be included in an amount of 1% to 30% by weight, for example, 3% to 20% by weight, based on the total amount of the curable composition. In this case, excellent pattern characteristics, heat resistance, and chemical resistance can be improved.

[0231] Other additives

[0232] To improve the stability and dispersibility of the above quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0233] The polymerization inhibitor may include hydroquinone-based compounds, catechol-based compounds, or combinations thereof, but is not necessarily limited thereto. As the curable composition according to one embodiment further includes the hydroquinone-based compounds, catechol-based compounds, or combinations thereof, room temperature crosslinking can be prevented during exposure after printing (coating) the curable composition.

[0234] For example, the above hydroquinone-based compound, catechol-based compound, or combination thereof is hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -Butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyrogallol, 2,6-di- t- It may include butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium, or a combination thereof, but is not necessarily limited thereto.

[0235] The above hydroquinone-based compound, catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the form of the dispersion may be included in an amount of 0.001% to 3% by weight, for example, 0.01% to 2% by weight, based on the total amount of the curable composition. When the polymerization inhibitor is included within the above range, the problem of deterioration over time at room temperature can be solved, while simultaneously preventing a decrease in sensitivity and surface peeling.

[0236] In addition, the curable composition according to one embodiment may further include malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof to improve heat resistance and reliability.

[0237] For example, a curable composition according to one embodiment may further include a silane-based coupling agent having reactive substituents such as vinyl groups, carboxyl groups, methacrylate groups, isocyanate groups, and epoxy groups to improve adhesion to a substrate.

[0238] Examples of the above-mentioned silane coupling agents include trimethoxysilyl benzoic acid, γ-methacrylate oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, β-epoxycyclohexyl ethyl trimethoxysilane, etc., and these may be used alone or in a mixture of two or more types.

[0239] The above silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the above curable composition. When the silane-based coupling agent is included within the above range, adhesion, storage stability, etc. are excellent.

[0240] In addition, the above-mentioned curable composition may further include a surfactant, such as a fluorine-based surfactant, as needed to improve coating properties and prevent defect formation, that is, to improve leveling performance.

[0241] The above-mentioned fluorine-based surfactant may have a low weight-average molecular weight of 4,000 g / mol to 10,000 g / mol, specifically 6,000 g / mol to 10,000 g / mol. Additionally, the above-mentioned fluorine-based surfactant may have a surface tension of 18 mN / m to 23 mN / m (measured in a 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). When the weight-average molecular weight and surface tension of the above-mentioned fluorine-based surfactant are within the above ranges, leveling performance can be further improved, staining can be prevented during high-speed coating, and since there is less bubble generation and fewer film defects, it provides excellent characteristics for slit coating, a high-speed coating method.

[0242] The above-mentioned fluorine-based surfactant is BM-1000 of BM Chemie. ® , BM-1100 ® Etc.; Mecha Pack F 142D of Dai Nippon Inki Gagaku High School Co., Ltd. ® , East F 172 ® , East F 173 ® , East F 183 ® Etc.; Sumitomo 3M Corporation’s Prorad FC-135 ® , same FC-170C ® , East FC-430 ® , East FC-431 ®Etc.; Asahi Glass Co., Ltd.'s Saffron S-112 ® , East S-113 ® , East S-131 ® , East S-141 ® , same S-145 ® Etc.; SH-28PA of Toray Silicon Co., Ltd. ® , Dong-190 ® , Dong-193 ® , SZ-6032 ® , SF-8428 ® Fluorine-based surfactants marketed under names such as F-482, F-484, F-478, F-554, etc. by DIC Co., Ltd. may be used.

[0243] In addition, the curable composition according to one embodiment may use a silicone-based surfactant together with the aforementioned fluorine-based surfactant. Specific examples of the silicone-based surfactant include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 of Toshiba Silicon.

[0244] The surfactant, including the above-mentioned fluorine-based surfactant, etc., may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, per 100 parts by weight of the above-mentioned curable composition. When the above-mentioned surfactant is included within the above range, the phenomenon of foreign matter occurring in the sprayed composition is reduced.

[0245] In addition, the curable composition according to one embodiment may further include a certain amount of other additives, such as antioxidants, within a range that does not impair physical properties.

[0247] menstruum

[0248] Meanwhile, the curable composition according to one embodiment may further include a solvent.

[0249] The above solvent is, 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; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate. Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate; lactic acid alkyl esters such as methyl lactate, ethyl lactate; hydroxyacetate alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate; acetate alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; Alkyl esters of 3-hydroxypropionates such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; alkyl esters of 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; alkyl esters of 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; alkyl esters of 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate;Alkyl esters of 2-hydroxy-2-methylpropionate such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; alkyl esters of 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Alternatively, there are compounds of ketone acid esters such as ethyl pyruvate, and examples include, but are not limited to, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc.;

[0250] For example, the above solvent preferably uses glycol ethers such as ethylene glycol monoethyl ether and ethylene diglycol methyl ethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; alcohols such as ethanol or a combination thereof.

[0251] For example, the solvent may be a polar solvent comprising propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0252] The above solvent may be included in an amount of 40% to 80% by weight, for example, 45% to 80% by weight, relative to the total amount of the curable composition. When the solvent is included within the above range, the solvent-type curable composition has an appropriate viscosity, so it can have excellent coating properties when performing large-area coating using spin coating and slits.

[0254] Another embodiment provides the above-described curable composition, for example, a cured film manufactured using the above-described curable composition, a color filter comprising the cured film, and a display device comprising the color filter. In this case, the cured film may have a diffuse reflectance of 50% to 55% as described above.

[0255] One of the methods for manufacturing the above-mentioned curable film comprises the step of forming a pattern by applying the above-mentioned curable composition onto a substrate using an inkjet spraying method (S1); and the step of curing the pattern (S2).

[0256] (S1) Step of forming a pattern

[0257] It is preferable to apply the above-mentioned curable composition onto a substrate with a thickness of 0.5 to 20 μm using an inkjet dispersion method. The inkjet spraying can form a pattern by spraying only a single color per nozzle and spraying repeatedly according to the required number of colors, or the pattern can be formed by spraying the required number of colors simultaneously through each inkjet nozzle to reduce the process.

[0258] (S2) Curing step

[0259] Pixels can be obtained by curing the pattern obtained above. At this time, both a thermal curing process and a photocuring process can be applied as the curing method. In the thermal curing process, it is preferable to cure by heating to a temperature of 100°C or higher, more preferably by heating to 100°C to 300°C, and slightly more preferably by heating to 160°C to 250°C. In the photocuring process, active rays such as UV rays of 190 nm to 450 nm, for example 200 nm to 500 nm, are irradiated. As light sources used for irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., may be used, and in some cases, X-rays, electron beams, etc., may also be used.

[0260] Another method for manufacturing the above-mentioned cured film is to manufacture the cured film using a lithography method with the above-mentioned curable composition, and the manufacturing method is as follows.

[0261] (1) Coating and film formation step

[0262] The above curable composition is applied to a substrate that has undergone a predetermined pretreatment using a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, etc., to a desired thickness, for example, 2㎛ to 10㎛, and then a coating film is formed by removing the solvent by heating at a temperature of 70℃ to 90℃ for 1 minute to 10 minutes.

[0263] (2) Exposure step

[0264] After interposing a mask of a predetermined shape to form a pattern required on the above-mentioned coating film, active rays such as UV light of 190 nm to 450 nm, for example 200 nm to 500 nm, are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc., may be used, and in some cases, X-rays, electron beams, etc., may also be used.

[0265] The exposure amount varies depending on the type, mixing amount, and dry film thickness of each component of the above-mentioned curable composition, but, for example, when using a high-pressure mercury lamp, it is 500 mJ / cm² 2 It is less than (based on a 365 nm sensor).

[0266] (3) Phenomenon stage

[0267] Following the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, thereby leaving only the exposed areas to form an image pattern. That is, when developed with an alkaline developer, the unexposed areas are dissolved, and an image color filter pattern is formed.

[0268] (4) Post-processing step

[0269] The image pattern obtained by the above phenomenon can be cured by reheating or irradiating with active rays to obtain a pattern that is excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc.

[0271] Preferred embodiments of the present invention are described below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited by the following embodiments.

[0273] Preparation of polymerizable compounds

[0274] Preparation Example 1

[0275] 20g of 2,2-thiodiethanol is placed in a flask and thoroughly dissolved in 400mL of dichloromethane. 32.6g of acryloyl chloride is added to this, and the mixture is stirred under a nitrogen atmosphere. At 0°C, 36.4g of trimethylamine is added dropwise over 1 hour, followed by stirring for 2 hours to terminate the reaction. 200mL of dichloromethane and 500mL of water are added for extraction; the dichloromethane layer is separated, and dilute hydrochloric acid is added to it to repeat the extraction 3 times. The dichloromethane layer is separated, MgSO4 is added, and the mixture is stirred for 5 minutes. After filtration, the filtrate is concentrated. After column purification, the solution is concentrated and vacuum dried to prepare the compound represented by the chemical formula 1-1 below (refractive index: 1.495).

[0276] [Chemical Formula 1-1]

[0277]

[0279] Preparation Example 2

[0280] 20g of 3,6-dithia-1,8-octanediol is placed in a flask and thoroughly dissolved in 200mL of dichloromethane and 200mL of ethanol. 21.8g of acryloyl chloride is added to this mixture and stirred under a nitrogen atmosphere. At 0°C, 24.4g of trimethylamine is added dropwise over 1 hour, followed by stirring for 2 hours to terminate the reaction. 200mL of dichloromethane and 500mL of water are added for extraction; the dichloromethane layer is separated, and dilute hydrochloric acid is added to it to repeat the extraction three times. The dichloromethane layer is separated, MgSO4 is added, and the mixture is stirred for 5 minutes. After filtration, the filtrate is concentrated. After column purification, the solution is concentrated and vacuum dried to prepare the compound represented by Chemical Formula 1-2 below (refractive index: 1.529).

[0281] [Chemical Formula 1-2]

[0282]

[0284] Preparation Example 3

[0285] 20g of 1,4-dithiane-2,5-diol is mixed with 300mL of ethanol and 200mL of dichloromethane and stirred. 26g of acryloyl chloride is added and stirred under a nitrogen atmosphere. 29.2g of trimethylamine is added dropwise over 1 hour at 0°C, followed by stirring for 2 hours to terminate the reaction. 200mL of dichloromethane and 500mL of water are added for extraction; the dichloromethane layer is separated, and dilute hydrochloric acid is added to repeat the extraction process 3 times. The dichloromethane layer is separated, MgSO4 is added, and the mixture is stirred for 5 minutes. After filtration, the filtrate is concentrated. After column purification, the solution is concentrated and vacuum dried to prepare the compound represented by the chemical formula 1-3 below (refractive index: 1.680).

[0286] [Chemical Formula 1-3]

[0287]

[0289] Preparation Example 4

[0290] 100g of 1,6-hexanediol is dissolved in 100ml of toluene and reacted with 135g of acrylic acid and 8.2g of methanesulfonic acid at 120℃ for 5 hours to prepare a compound represented by the following chemical formula 2-2 (refractive index: 1.455).

[0291] [Chemical Formula 2-2]

[0292]

[0294] Comparative Manufacturing Example 1

[0295] 20g of Bis(2-hydroxyethyl) disulfide is sufficiently dissolved in 300mL of ethanol and 150mL of methylene chloride. 25.7g of acryloyl chloride is added to this mixture and stirred for 10 minutes. At 0°C, 28.8g of triethylamine is slowly added dropwise, and after stirring for 5 hours, the reaction is terminated. Then, 250mL of methylene chloride and 300mL of water are added for extraction. The organic layer is separated and extracted three more times with a diluted aqueous hydrochloric acid solution. The dichloromethane layer is separated, MgSO4 is added, and the mixture is stirred for 5 minutes. After filtering, the filtrate is concentrated. After column purification, the solution is concentrated and vacuum dried to prepare the compound represented by the chemical formula C-1 below (refractive index: 1.517).

[0296] [Chemical Formula C-1]

[0297]

[0299] Comparative Manufacturing Example 2

[0300] 20g of 1,4-benzene dithiol is sufficiently dissolved in 200mL of methylene chloride. 22.5g of 2-chloroethyl acrylate is added to this and stirred for 10 minutes. Then, 17g of triethylamine is slowly added dropwise at 0°C, and the reaction is terminated after stirring for 12 hours. 300mL of methylene chloride and 300mL of water are added for extraction, the organic layer is separated, a dilute hydrochloric acid solution is added, and the extraction is repeated 3 times. The dichloromethane layer is separated, MgSO4 is added, and the mixture is stirred for 5 minutes. After filtering, the filtrate is concentrated. After column purification, the solution is concentrated and vacuum dried to prepare the compound represented by the chemical formula C-2 below (refractive index: 1.556).

[0301] [Chemical Formula C-2]

[0302]

[0304] Preparation of surface-modified quantum dot dispersion

[0305] Preparation Example 5

[0306] A magnetic bar is placed in a three-necked round-bottom flask, and a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical; quantum dot solid content 23 wt%) is added to each. A compound (ligand) represented by the chemical formula Q below is added to this, and the mixture is stirred at 80°C under a nitrogen atmosphere. After the reaction is finished, the mixture is cooled to room temperature (23°C), and then the quantum dot reaction solution is added to cyclohexane to form a precipitate. The precipitate and cyclohexane are separated by centrifugation, and the precipitate is sufficiently dried in a vacuum oven for 24 hours to obtain surface-modified quantum dots.

[0307] The surface-modified green quantum dots were stirred in a polymerizable compound for 12 hours to obtain a surface-modified quantum dot dispersion (QD solid content: 23 wt%).

[0308] (*Synthesis of the compound represented by chemical formula Q: Place 100g of pH-4 (Hannong Chemical) into a two-necked round-bottom flask and dissolve thoroughly in 300mL of THF. Add 15.4g of NaOH and 100mL of water at 0°C and dissolve thoroughly until a clear solution is obtained. Slowly inject a solution of 73g of para-toluene sulfonic chloride dissolved in 100mL of THF at 0°C. The injection was carried out for 1 hour, followed by stirring at room temperature for 12 hours. After the reaction is complete, add an excess amount of methylene chloride and stir; then add a saturated NaHCO3 solution and proceed with extraction, titration, and water removal. After removing the solvent, dry in a dry oven for 24 hours. Place 50g of the obtained dried product into a two-necked round-bottom flask and stir thoroughly in 300mL of ethanol. Then, add 27g of Thiourea, disperse, and reflux at 80°C for 12 hours. Afterward, NaOH An aqueous solution prepared by dissolving 4.4g in 20mL of water is injected, and while stirring for another 5 hours, an excess amount of methylene chloride is added and, after stirring, an aqueous hydrochloric acid solution is added, followed by extraction, titration, water removal, and solvent removal in sequence. The mixture is dried in a vacuum oven for 24 hours to obtain a compound represented by the following chemical formula Q.

[0309] [Chemical Formula Q]

[0310]

[0312] (Preparation of curable composition)

[0313] Examples 1 to 7 and Comparative Examples 1 to 3

[0314] Curable compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were prepared using the components mentioned below and with the compositions shown in Tables 1 and 2 below.

[0315] Specifically, the above quantum dot dispersion is weighed, mixed with a polymerizable compound to dilute it, a polymerization inhibitor is added, and the mixture is stirred for 5 minutes. Then, a photoinitiator is added, followed by the addition of a light diffusing agent. Afterward, the mixture is stirred for 1 hour to prepare a curable composition.

[0317] (A) Quantum Dot

[0318] Surface-modified green quantum dot dispersion prepared from Preparation Example 5

[0319] (B) Polymerizable compounds

[0320] (B-1) Compound of Preparation Example 1

[0321] (B-2) Compound of Preparation Example 2

[0322] (B-3) Compound of Preparation Example 3

[0323] (B-4) Compound of Preparation Example 4

[0324] (B-5) Compound of Comparative Preparation Example 1

[0325] (B-6) Compound of Comparative Preparation Example 2

[0326] (C) Photopolymerization initiator

[0327] TPO-L (Polynetron)

[0328] (D) Light diffusing agent

[0329] Titanium dioxide dispersion (TiO2 solid content 20 wt%, average particle size: 200 nm, Ditto Technology Co., Ltd.)

[0330] (E) Polymerization inhibitor

[0331] Methylhydroquinone (TOKYO CHEMICAL)

[0333] (Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A) Quantum dot dispersion 42 42 42 42 42 42 42 (B) Polymerizable compounds (B-1) 10.58 20.7 31.28 41.4 46 - - (B-2) - - - - - 41.4 - (B-3) - - - - - - 41.4 (B-4) 35.42 25.3 14.72 4.6 - 4.6 4.6 (B-5) - - - - - - - (B-6) - - - - - - - (B-7) - - - - - - - (C) Photopolymerization initiator 3 3 3 3 3 3 3 (D) Light diffusing agent 8 8 8 8 8 8 8 (E) Polymerization inhibitor 1 1 1 1 1 1 1 total 100 100 100 100 100 100 100

[0336] (Unit: weight%) Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Quantum dot dispersion 42 42 42 (B) Polymerizable compounds (B-1) - - - (B-2) - - - (B-3) - - - (B-4) 4.6 4.6 46 (B-5) - - - (B-6) 41.4 - - (B-7) - 41.4 - (C) Photopolymerization initiator 3 3 3 (D) Light diffusing agent 8 8 8 (E) Polymerization inhibitor 1 1 1 total 100 100 100

[0338] Evaluation: Evaluation of optical properties and diffuse reflectance of curable compositions

[0339] For each of the curable compositions according to Examples 1 to 7 and Comparative Examples 1 to 3, the quantum efficiency (EQE) after exposure and the diffuse reflectance (SCE) after curing were measured using a spectrophotometer (Konica Minolta, CM-3600A), and the results are shown in Table 3 below.

[0342] Quantum efficiency (%) after exposure Diffuse reflection after curing (%) Example 1 32.2 54.7 Example 2 32.9 53.6 Example 3 33.1 53.6 Example 4 33.6 52.5 Example 5 31.9 55.8 Example 6 33.5 52.5 Example 7 34.0 52.1 Comparative Example 1 31.5 56.1 Comparative Example 2 30.8 57.3 Comparative Example 3 31.7 56.1

[0344] From Table 3 above, it can be confirmed that the curable compositions according to Examples 1 to 7, compared with the curable compositions according to Comparative Examples 1 to 3, have improved optical properties with higher quantum efficiency after exposure, and at the same time have a reflectance reduction effect with lower diffuse reflectance after curing.

[0346] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the invention can be implemented in other specific forms without changing the technical concept or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

Claim 1 (A) quantum dots; and (B) a curable composition comprising a polymerizable compound comprising a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2: [Chemical Formula 1] In the above chemical formula 1, L 1 It is a divalent linker containing a sulfur atom, but does not include a disulfide (*-SS-*) linkage structure, and L 2 and L 3 Each is independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, [Chemical Formula 2] In the above chemical formula 2, L 9 is an unsubstituted C1 to C10 alkylene group, an unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*), and L 10 and L 11 Each is independently a single-bonded or unsubstituted C1 to C10 alkylene group, and R 3 and R 4 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group. Claim 2 In paragraph 1, the above L 1 A curable composition represented by any one of the following chemical formulas L-1 to L-4: [Chemical Formula L-1] [Chemical Formula L-2] [Chemical Formula L-3] [Chemical Formula L-4] In the above chemical formulas L-1 to L-4, L 4 to L 8 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group. Claim 3 In claim 1, the compound represented by the above chemical formula 1 is a curable composition having a refractive index greater than 1.

455. Claim 4 In claim 1, the compound represented by Chemical Formula 1 is a curable composition represented by any one of the following Chemical Formulas 1-1 to 1-3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] Claim 5 A curable composition according to claim 1, wherein the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are included in a weight ratio of 5:5 to 9:

1. Claim 6 A curable composition according to claim 1, wherein the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are included in a weight ratio of 6:4 to 9:

1. Claim 7 In claim 1, the compound represented by Chemical Formula 2 is a curable composition having a refractive index of 1.455 or less. Claim 8 A curable composition according to claim 1, wherein the compound represented by Chemical Formula 1 and the compound having a structure different from the compound represented by Chemical Formula 1 are included in a weight ratio of 1:9 to 9:

1. Claim 9 In claim 1, the curable composition is a solvent-free curable composition. Claim 10 In claim 9, the solvent-free curable composition comprises, with respect to the total amount of the solvent-free curable composition, 5% to 60% by weight of the quantum dots; and 40% to 95% by weight of the polymerizable compound. Claim 11 In claim 1, the curable composition further comprises a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof. Claim 12 In claim 11, the light diffusing agent is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof. Claim 13 In claim 1, the curable composition further comprises a solvent. Claim 14 In claim 13, the curable composition comprises, based on the total weight of the curable composition, 1% to 40% by weight of the quantum dots; 1% to 20% by weight of the polymerizable compound; and 40% to 80% by weight of the solvent. Claim 15 The curable composition of claim 1 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. Claim 16 A cured film manufactured using a curable composition according to any one of claims 1 to 15. Claim 17 In claim 16, the above-mentioned hardened film is a hardened film having a diffuse reflectance of 50% to 55%. Claim 18 A color filter comprising the cured film of Clause 16. Claim 19 A display device including the color filter of claim 18. Claim 20 In claim 1, the compound represented by Chemical Formula 2 is a curable composition represented by the following Chemical Formula 2-1 or 2-2. [Chemical Formula 2-1] [Chemical Formula 2-2]

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