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

Abstract

The present invention provides: a curable composition comprising (A) quantum dots surfaced-modified with two or more different surface modification materials and (B) a polymeric compound; a cured layer prepared using the curable composition; a color filter including the cured layer; and a display device including the color filter.

Description

A curable composition, a cured film manufactured using the composition, a color filter including the cured film, and a display device including the color filter

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

[0002]

[0003] In the case of general quantum dots, the solvents in which they can be dispersed are limited due to their hydrophobic surface properties, and as a result, there are many 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 relatively low in polarity and could only be dispersed in solvents used in highly hydrophobic curable compositions. For this reason, it was difficult to include quantum dots in an amount exceeding 20 wt% of the total composition, making it impossible to increase the ink's luminous efficiency beyond a certain level. In addition, even if quantum dots were added and dispersed to increase luminous efficiency, the viscosity exceeded the range for ink-jetting, making it impossible to satisfy the processability.

[0005] In addition, in order to implement a viscosity range that allows ink-jetting, a method of lowering the ink solids content by including a solvent of 50 wt% or more relative to the total composition has been used. This method also provides somewhat satisfactory results in terms of viscosity, but it has the disadvantage of being difficult to apply to actual processes due to problems such as nozzle drying due to solvent volatilization during ink-jetting, nozzle clogging, and a decrease in film thickness over time after ink-jetting, as well as a severe thickness deviation after curing.

[0006] Therefore, the solvent-free type of quantum dot ink that does not contain a solvent is the most desirable form for application to actual processes, and the current technology for applying quantum dots themselves to solvent-based compositions is now considered to have reached a certain limit.

[0007]

[0008] One embodiment is to provide a curable composition having excellent optical properties by improving the heat resistance and light resistance of quantum dots through surface modification of quantum dots.

[0009] Another embodiment is to provide a cured film manufactured using the curable composition.

[0010] Another embodiment is to provide a color filter comprising the above cured film.

[0011] Another embodiment is to provide a display device including the color filter.

[0012]

[0013] One embodiment provides a curable composition comprising (A) quantum dots surface-modified with different first surface-modifying materials and second surface-modifying materials; and (B) a polymerizable compound, wherein the first surface-modifying material comprises at each of its two terminals at least one selected from the group consisting of an unsaturated double bond and a carboxyl group, and a compound comprising a sulfide linkage, an ester linkage, or a combination thereof between the two terminals, or a compound in which the unsaturated double bond and the carboxyl group are directly bonded to each other.

[0014] The above first surface modification material can be represented by the following chemical formula 1.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] A is a cyclic compound substituted with a carbon-carbon unsaturated double bond or a cyclic compound in which a carbon-carbon unsaturated double bond is included within the ring structure,

[0019] L 1 Inland L 4 are each independently a single bond, an ester group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

[0020] The above ring compound may be a fused ring compound.

[0021] The above A can be represented by the following chemical formula A-1 or chemical formula A-2.

[0022] [Chemical Formula A-1]

[0023]

[0024] [Chemical Formula A-2]

[0025]

[0026] In the above chemical formula A-1 or chemical formula A-2,

[0027] R 1 is a substituted or unsubstituted vinyl group,

[0028] L 5 is a substituted or unsubstituted C1 to C20 alkylene group.

[0029] The above first surface modification material can be represented by the following chemical formula 2.

[0030] [Chemical Formula 2]

[0031]

[0032] In the above chemical formula 2,

[0033] R 1 is a substituted or unsubstituted vinyl group,

[0034] L 7 Inland L 10are each independently a single bond, an ester group, or a substituted or unsubstituted C1 to C20 alkylene group, provided that L 7 Inland L 10 At the same time, this is not a single bond.

[0035] The above first surface modification material can be represented by the following chemical formula 3.

[0036] [Chemical Formula 3]

[0037]

[0038] The above first surface modification material may be represented by any one of the following chemical formulas 1-1 to 1-4, chemical formula 2-1, chemical formula 2-2, and chemical formula 3.

[0039] [Chemical Formula 1-1]

[0040]

[0041] [Chemical Formula 1-2]

[0042]

[0043] [Chemical Formula 1-3]

[0044]

[0045] (In the above chemical formula 1-3, n is an integer from 1 to 20)

[0046] [Chemical Formula 1-4]

[0047]

[0048] [Chemical Formula 2-1]

[0049]

[0050] [Chemical Formula 2-2]

[0051]

[0052] The above second surface modifying material may include a thiol group, a phosphate group, or a phosphonic acid group at the terminal.

[0053] The above second surface modification material can be represented by the following chemical formula 4.

[0054] [Chemical Formula 4]

[0055]

[0056] In the above chemical formula 4,

[0057] R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cyclic group, or a substituted or unsubstituted C6 to C20 arylene group,

[0058] L 11 and L 12 are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 oxyalkylene group.

[0059] The above second surface modification material may be represented by any one of the following chemical formulas 4-1 to 4-3.

[0060] [Chemical Formula 4-1]

[0061]

[0062] [Chemical Formula 4-2]

[0063]

[0064] [Chemical Formula 4-3]

[0065]

[0066] The above polymerizable compound may include a compound represented by the following chemical formula 5.

[0067] [Chemical Formula 5]

[0068]

[0069] In the above chemical formula 5,

[0070] L 13 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0071] L 14 and L 15are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0072] R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0073] The above curable composition may be a solvent-free curable composition.

[0074] The solvent-free curable composition may include 5 to 60 wt% of the quantum dot and 40 to 95 wt% of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0075] The above curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0076] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0077] The above curable composition may further comprise a solvent.

[0078] The curable composition may include, based on the total weight of the curable composition, 1 wt% to 40 wt% of the quantum dot; 1 wt% to 20 wt% of the polymerizable compound; and 40 wt% to 80 wt% of the solvent.

[0079] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof.

[0080] Another embodiment provides a cured film manufactured using the curable composition.

[0081] Another embodiment provides a color filter including the cured film.

[0082] Another embodiment provides a display device including the color filter.

[0083] The display device may include a micro LED (μ-LED) light source.

[0084] Specific details of other aspects of the present invention are included in the detailed description below.

[0085]

[0086] When applying a high-power μ-LED as a light source for a display device, it is essential to improve the heat resistance and light resistance of the quantum dot. By introducing a ligand with a structure having excellent light resistance onto the surface of the quantum dot, stability can be improved, ultimately obtaining a curable composition with excellent optical properties.

[0087]

[0088] 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. The present invention is defined solely by the scope of the claims set forth below.

[0089] Unless otherwise specified herein, "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 It refers to an alkoxylene group.

[0090] Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is substituted with a halogen atom (F, Cl, Br, I), a hydroxy 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 C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0091] Additionally, unless otherwise specified herein, “hetero” means that the chemical formula contains at least one heteroatom of at least one of N, O, S, and P.

[0092] Additionally, unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0093] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0094] Unless otherwise defined in the chemical formulas in 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 that position.

[0095] Additionally, unless otherwise specified herein, “*” means a portion connected to the same or different atoms or chemical formulas.

[0096] Quantum dots, due to their superior color purity and other properties, have recently been widely used as display materials. However, when applying high-power μ-LEDs as light sources in display devices, improved heat and light resistance of quantum dots is absolutely necessary. For this purpose, thermoplastic or thermosetting resins, commonly used as encapsulation materials, can be used. However, as LED output increases, there is a growing demand for materials with superior heat and light resistance compared to conventional materials.

[0097] Accordingly, encapsulation using alicyclic epoxy resins or siloxane compounds is being developed, but its application is limited because the stability of quantum dots is not guaranteed at the high temperatures required during the manufacturing process.

[0098] Therefore, under this background, the inventors of the present invention have developed a novel quantum dot surface modification material capable of improving heat resistance and light resistance in order to improve the stability of quantum dots, and a display device including a cured film manufactured using a curable composition containing quantum dots surface-modified with such a surface modification material can ensure the stability of quantum dots even when μ-LED is applied as a light source, ultimately ensuring excellent optical properties. Furthermore, the curable composition according to one embodiment can be applied to a solvent-based curable composition, and in this case, not only excellent optical properties but also patterning properties can be improved.

[0099] Ultimately, the curable composition according to one embodiment can improve the stability of quantum dots by introducing a surface modifying material having a structure with superior light resistance compared to conventional materials into the quantum dots.

[0100] A curable composition according to one embodiment comprises (A) a quantum dot surface-modified with a first surface-modifying material and a second surface-modifying material different therefrom; and (B) a polymerizable compound, wherein the first surface-modifying material comprises an unsaturated double bond and a carboxyl group at one terminal, and further comprises i) a sulfide linkage, or ii) an ester linkage, or iii) the unsaturated double bond and the carboxyl group are directly bonded to each other.

[0101] That is, the quantum dot surface modifying material in the curable composition according to one embodiment may include an unsaturated double bond and a carboxyl group at one terminal, and may have a structural characteristic expressed as i) above, or a structural characteristic expressed as ii) above, or a structural characteristic expressed as iii) above.

[0102] Below, each component constituting the curable composition according to one embodiment is specifically described.

[0103]

[0104] quantum dots

[0105] According to one embodiment, the quantum dot in the curable composition includes two different functional groups (a functional group derived from a first surface-modifying material and a functional group derived from a second surface-modifying material), thereby improving the stability of the quantum dot, thereby improving both the optical properties of the solvent-free curable composition and the optical properties and patternability of the solvent-based curable composition.

[0106] For example, the first surface modification material may include a compound comprising one selected from the group consisting of an unsaturated double bond and a carboxyl group at each of the two terminals, and a sulfide linkage group, an ester linkage group, or a combination thereof between the two terminals, or a compound in which the unsaturated double bond and the carboxyl group are directly bonded to each other.

[0107] Specifically, the first surface modification material can be represented by the following chemical formula 1.

[0108] [Chemical Formula 1]

[0109]

[0110] In the above chemical formula 1,

[0111] A is a cyclic compound substituted with a carbon-carbon unsaturated double bond or a cyclic compound in which a carbon-carbon unsaturated double bond is included within the ring structure,

[0112] L 1 Inland L 4 are each independently a single bond, an ester group (*-C(=O)O-* or *-O(C=O)-*), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

[0113] The above substituted or unsubstituted C1 to C20 oxyalkylene group can be represented by the following chemical formula R-1.

[0114] [Chemical formula R-1]

[0115]

[0116] In the above chemical formula R-1,

[0117] L 6 is a substituted or unsubstituted C1 to C20 alkylene group,

[0118] m is an integer from 1 to 20.

[0119] For example, the ring compound may be a fused ring compound.

[0120] For example, in the above chemical formula 1, A can be represented by the following chemical formula A-1 or chemical formula A-2.

[0121] [Chemical Formula A-1]

[0122]

[0123] [Chemical Formula A-2]

[0124]

[0125] In the above chemical formula A-1 or chemical formula A-2,

[0126] R 1 is a substituted or unsubstituted vinyl group,

[0127] L 5 is a substituted or unsubstituted C1 to C20 alkylene group.

[0128] Specifically, the first surface modification material may be represented by the following chemical formula 2.

[0129] [Chemical Formula 2]

[0130]

[0131] In the above chemical formula 2,

[0132] R 1 is a substituted or unsubstituted vinyl group,

[0133] L 7 Inland L 10 are each independently a single bond, an ester group, or a substituted or unsubstituted C1 to C20 alkylene group, provided that L 7 Inland L 10 At the same time, this is not a single bond.

[0134] Specifically, the first surface modification material may be represented by the following chemical formula 3.

[0135] [Chemical Formula 3]

[0136]

[0137] For example, the first surface modification material may be represented by any one of the following chemical formulas 1-1 to 1-4, chemical formula 2-1, chemical formula 2-2, and chemical formula 3, but is not necessarily limited thereto.

[0138] [Chemical Formula 1-1]

[0139]

[0140] [Chemical Formula 1-2]

[0141]

[0142] [Chemical Formula 1-3]

[0143]

[0144] (In the above chemical formula 1-3, n is an integer from 1 to 20)

[0145] [Chemical Formula 1-4]

[0146]

[0147] [Chemical Formula 2-1]

[0148]

[0149] [Chemical Formula 2-2]

[0150]

[0151] Meanwhile, the second surface modification material may include a thiol group at the terminal.

[0152] For example, the second surface modification material may be represented by the following chemical formula 4.

[0153] [Chemical Formula 4]

[0154]

[0155] In the above chemical formula 4,

[0156] R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cyclic group, or a substituted or unsubstituted C6 to C20 arylene group,

[0157] L 11 and L 12 are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 oxyalkylene group.

[0158] The above or substituted or unsubstituted C1 to C20 oxyalkylene group can be represented by the chemical formula R-1 described above.

[0159] For example, the second surface modification material may be represented by any one of the following chemical formulas 4-1 to 4-3, but is not necessarily limited thereto.

[0160] [Chemical Formula 4-1]

[0161]

[0162] [Chemical Formula 4-2]

[0163]

[0164] [Chemical Formula 4-3]

[0165]

[0166] For example, the first surface modification material and the second surface modification material may be included in a weight ratio of 1:9 to 9:1 and used for surface modification of quantum dots. In this case, the mismatch between the surface-modified quantum dot surface and the polymerizable compound described below is minimized, thereby further improving the dispersibility of the quantum dot in the polymerizable compound.

[0167] For example, the quantum dot may have a maximum fluorescence emission wavelength between 500 nm and 680 nm.

[0168] 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 wt% to 60 wt%, such as 10 wt% to 60 wt%, such as 20 wt% to 60 wt%, such as 30 wt% to 50 wt%. When the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0169] For example, when the curable composition according to one embodiment is a curable composition including a solvent, the quantum dots may 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 the quantum dots are included within the above range, the photoconversion rate is excellent and the pattern characteristics and development characteristics are not impaired, so that excellent processability can be achieved.

[0170] For example, the quantum dot may absorb light in a wavelength range of 360 nm to 780 nm, for example, a wavelength range of 400 nm to 780 nm, and emit fluorescence in a wavelength range of 500 nm to 700 nm, for example, 500 nm to 580 nm, or emit fluorescence in a wavelength range of 600 nm to 680 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ) in a wavelength range of 500 nm to 680 nm. em ) can have.

[0171] The above quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum (FWHM) within the above range, the color purity is high, thereby increasing the color reproducibility when used as a color material in a color filter.

[0172] The above quantum dots may each independently be organic, inorganic, or a hybrid (hybrid) of organic and inorganic materials.

[0173] The above quantum dots can each independently be composed of a core and a shell surrounding the core, and the core and shell can each independently have a structure such as a core, core / shell, core / first shell / second shell, alloy, alloy / shell, etc., made of group II-IV, group III-V, etc., but are not limited thereto.

[0174] For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

[0175] In one implementation example, since environmental concerns have been increasing significantly worldwide and regulations on toxic substances have been strengthened, environmentally friendly non-cadmium-based luminescent materials (such as InP / ZnS, InP / ZnSe / ZnS) with somewhat lower quantum yields were used instead of luminescent materials having cadmium-based cores, but the present invention is not limited thereto.

[0176] In the case of the quantum dot of the above core / shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

[0177] For example, the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may each independently have an average particle diameter of 10 nm to 15 nm. The green quantum dots may each independently have an average particle diameter of 5 nm to 8 nm.

[0178] Meanwhile, in order 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 the photoconversion material such as quantum dots within the curable composition, and any nonionic, anionic, or cationic dispersant may be used. Specifically, polyalkylene glycol or its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkyl amide alkylene oxide adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1 wt% to 100 wt%, for example, 10 wt% to 20 wt%, relative to the solid content of the photoconversion material such as quantum dots.

[0179] For example, the second surface modification material, which is one of the quantum dot surface modification materials, may be represented by any one of the following chemical formulas A to H0.

[0180] In addition, the quantum dots may be further surface-modified with one or more of the surface-modifying materials represented by the following chemical formulas I to P to greatly facilitate the production of a high-concentration or high-enriched quantum dot dispersion (to improve the dispersibility of the quantum dots in a polymerizable compound) and to improve light efficiency. In this case, the surface modification of the quantum dots is made easier, and when the quantum dots surface-modified with the surface-modifying materials are added to a polymerizable compound matrix described below and stirred, a very transparent dispersion can be obtained, which serves as a measure for confirming that the surface modification of the quantum dots is very well done. Furthermore, it may also be advantageous for implementing a solvent-free curable composition.

[0181] [Chemical Formula A]

[0182]

[0183] [Chemical Formula B]

[0184]

[0185] [Chemical Formula C]

[0186]

[0187] [Chemical Formula D]

[0188]

[0189] (In the above chemical formula D, m1 is an integer from 0 to 10.)

[0190] [Chemical Formula E]

[0191]

[0192] [Chemical formula F]

[0193]

[0194] [Chemical formula G]

[0195]

[0196] [Chemical formula H]

[0197]

[0198] [Chemical Formula I]

[0199]

[0200] [Chemical formula J]

[0201]

[0202] [Chemical formula K]

[0203]

[0204] [Chemical formula L]

[0205]

[0206] [Chemical formula M]

[0207]

[0208] [Chemical formula N]

[0209]

[0210] [chemical formula O]

[0211]

[0212] [chemical formula P]

[0213]

[0214]

[0215] polymeric compounds

[0216] A curable composition according to one embodiment comprises a polymerizable compound, wherein the polymerizable compound may have a carbon-carbon double bond at a terminal.

[0217] The polymerizable compound having a carbon-carbon double bond at the terminal may be included in an amount of 40 wt% to 95 wt%, for example, 50 wt% to 90 wt%, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, it is possible to produce a solvent-free curable composition having a viscosity that allows ink jetting, and further, since the quantum dots in the produced solvent-free curable composition can have excellent dispersibility, the optical properties can also be improved.

[0218] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may have a molecular weight of 170 g / mol to 1,000 g / mol. When the molecular weight of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, the viscosity of the composition may not be increased without impairing the optical properties of the quantum dot, which may be advantageous for ink-jetting.

[0219] For example, a polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 5, but is not necessarily limited thereto.

[0220] [Chemical Formula 5]

[0221]

[0222] In the above chemical formula 5,

[0223] L 13is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0224] L 14 and L 15 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0225] R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0226] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 5-1, 5-2 or 5-3, but is not necessarily limited thereto.

[0227] [Chemical Formula 5-1]

[0228]

[0229] [Chemical Formula 5-2]

[0230]

[0231] [Chemical Formula 5-3]

[0232]

[0233] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may, in addition to the compounds represented by the above chemical formulas 5-1 to 5-3, be ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate or a combination thereof may be further included.

[0234] In addition, the polymerizable compound having a carbon-carbon double bond at the terminal may further include a monomer generally used in a conventional thermosetting or photocurable composition, and for example, the monomer may further include an epoxy compound, an oxetane compound, a vinyl ether compound, etc.

[0235] For example, the epoxy compound may include an aliphatic epoxy compound such as a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolak type epoxy compound, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, an alicyclic epoxy compound such as 1,2-epoxy-4-vinyl cyclohexane, and 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane.

[0236] It is also possible to use commercially available products as the above epoxy compound. Examples of commercially available epoxy compounds include "Celloxide 2000," "Celloxide 3000," and "Celloxide 4000" manufactured by Daisei Chemical Co., Ltd.

[0237] For example, the oxetane compounds are bis[1-ethyl(3-oxetanyl)]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, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, It may include 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, 3-hydroxybutyl-3-methyloxetane, etc.

[0238] It is also possible to use commercially available products as the above oxetane compound. Commercially available products of the oxetane compound include, for example, the Alon Oxetane series ("OXT-101", "OXT-212", "OXT-121", "OXT-221", etc.) manufactured by Toagosei Co., Ltd.; "Celoxide 2021", "Celoxide 2021A", "Celoxide 2021P", "Celoxide 2080", "Celoxide 2081", "Celoxide 2083", "Celoxide 2085", "Eppolid GT300", "Eppolid GT301", "Eppolid GT302", "Eppolid GT400", "Eppolid GT401", and "Eppolid GT403" manufactured by Daisei Chemical Co., Ltd.; Dow Chemical Japan Co., Ltd.'s "Cyracure UVR-6105", "Cyracure UVR-6107", "Cyracure UVR-6110", "Cyracure UVR-6128", "ERL4289", and "ERL4299" can be used. In addition, a publicly known oxetane compound (e.g., an oxetane compound described in Japanese Patent Application Laid-Open No. 2009-40830, etc.) can also be used.

[0239] For example, as the vinyl ether compound, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, etc. can be used.

[0240] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1 wt% to 20 wt%, 1 wt% to 15 wt%, for example, 5 wt% to 15 wt%, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dot may be improved.

[0241]

[0242] light diffuser

[0243] The curable composition according to one embodiment may further comprise a light diffusing agent.

[0244] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0245] The above-described light diffusing agent reflects light not absorbed by the aforementioned quantum dots and allows the reflected light to be reabsorbed by the quantum dots. In other words, the above-described light diffusing agent can increase the amount of light absorbed by the quantum dots, thereby increasing the photoconversion efficiency of the curable composition.

[0246] The above light diffusing agent has an average particle diameter (D 50 ) may be 150 nm to 250 nm, and specifically, 180 nm to 230 nm. When the average particle diameter of the light diffusing agent is within the above range, it may have a better light diffusing effect and increase the light conversion efficiency.

[0247] The above light diffusing agent can act as a scatterer, and either the rutile type or the anatase type can be used. However, in terms of improving external quantum efficiency, the rutile type may be more advantageous than the anatase type.

[0248] The light diffusing agent may be included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 15 wt%, for example, 1 wt% to 10 wt%, based on the total amount of the curable composition. If the light diffusing agent is included in an amount of less than 1 wt% based on the total amount of the curable composition, it is difficult to expect an effect of improving the light conversion efficiency due to the use of the light diffusing agent, and if it is included in an amount exceeding 20 wt%, there is a concern that quantum dot sedimentation problems may occur.

[0249]

[0250] polymerization initiator

[0251] The curable composition according to one embodiment may further comprise a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0252] The above photopolymerization initiator is an initiator generally used in a photosensitive resin composition, and examples thereof include, but are not limited to, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and aminoketone-based compounds.

[0253] Examples of the above acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0254] Examples of the above benzophenone compounds include benzophenone, benzoyl benzoate, 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.

[0255] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0256] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0257] 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, bis(trichloromethyl)-6-styryl-s-triazine, Examples thereof 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, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0258] 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-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate.

[0259] Examples of the above aminoketone compounds include 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0260] In addition to the above compound, the photopolymerization initiator may also include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, etc.

[0261] The above photopolymerization initiator may also be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy.

[0262] Examples of the above photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like.

[0263] Examples of the above thermal polymerization initiator include 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-azo-bis(isobutyronitrile), t-butyl perbenzoate, etc., and 2,2'-azobis-2-methylpropionitrile, etc., but are not necessarily limited thereto, and any one widely known in the art can be used.

[0264] The above polymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.5 wt% to 4 wt%, based on the total amount of the curable composition. When the polymerization initiator is included within the above range, sufficient curing can occur upon exposure to light or thermal curing, thereby obtaining excellent reliability, and a decrease in transmittance due to unreacted initiator can be prevented, thereby preventing a decrease in the optical properties of the quantum dot.

[0265]

[0266] binder resin

[0267] The curable composition according to one embodiment may further comprise a binder resin.

[0268] The above binder resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0269] The above acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.

[0270] Specific examples of the above acrylic binder resin include, but are not limited to, 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, and the like. These may be used singly or in combination of two or more.

[0271] 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 acrylic resin has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

[0272] 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.

[0273] The above-mentioned cardo resin may be one used in a conventional curable resin (or photosensitive resin) composition, and may be, for example, one presented in Korean Patent Publication No. 10-2018-0067243, but is not limited thereto.

[0274] The above cardo resin may be, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds such as benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; a glycol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate, and N-methylpyrrolidone; a phosphorus compound such as triphenylphosphine; And it can be manufactured by mixing two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, etc., but it is not necessarily limited thereto, and any known cardo resin can be used.

[0275] The weight average molecular weight of the above cardo 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 resin is within the above range, pattern formation is good without residue when producing a cured film, and there is no loss of film thickness when developing the curable composition, and a good pattern can be obtained.

[0276] When the above binder resin is a cardo-based resin, the developability of a curable composition containing the same, particularly a photosensitive resin composition, is excellent, and the sensitivity during photocuring is good, resulting in excellent fine pattern formation ability.

[0277] The above epoxy resin is a monomer or oligomer that can be polymerized by heat, and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0278] The above epoxy resin may include, but is not necessarily limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.

[0279] Commercially available products of these compounds include bisphenyl epoxy resins, YX4000, YX4000H, YL6121H, YL6640, YL6677 from Yukashell Epoxy Co., Ltd.; cresol novolac type epoxy resins, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Epicoat 180S75 from Yukashell Epoxy Co., Ltd.; bisphenol A type epoxy resins, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 from Yukashell Epoxy Co., Ltd.; Bisphenol F type epoxy resins include Epicoat 807 and 834 from Yukashell Epoxy Co., Ltd.; Phenol novolak type epoxy resins include Epicoat 152, 154, 157H65 from Yukashell Epoxy Co., Ltd. and EPPN 201, 202 from Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CY175, CY177 and CY179 from CIBA-GEIGY AG, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from UCC, Shodyne 509 from Showa Denko Co., Ltd., Araldite CY-182, CY-192 and CY-184 from CIBA-GEIGY AG, Epichron 200 and 400 from Dainippon Ink & Kogyo Co., Ltd., Epicoat 871, 872 and EP1032H60 from Yukashell Epoxy Co., Ltd., and ED-5661 and ED-5662 from Celanese Coating Co., Ltd.; Examples of aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yukashell Epoxy Co., Ltd., Epolite 100MF from Kyoeisha Yushi Chemical Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd.

[0280] 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 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.

[0281] For example, when the curable composition according to one embodiment is a curable composition including a solvent, the binder resin may be included in an amount 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, pattern characteristics, heat resistance, and chemical resistance can be improved.

[0282]

[0283] Other additives

[0284] To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0285] The polymerization inhibitor may include, but is not necessarily limited to, a hydroquinone-based compound, a catechol-based compound, or a combination thereof. According to one embodiment, since the curable composition further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, crosslinking at room temperature can be prevented during exposure after printing (coating) the curable composition.

[0286] For example, the hydroquinone-based compound, catechol-based compound, or combinations thereof may include, but are not necessarily limited to, 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-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium, or combinations thereof.

[0287] 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 wt% to 3 wt%, for example, 0.01 wt% to 2 wt%, based on the total amount of the curable composition. When the polymerization inhibitor is included within the above range, the problem of aging at room temperature can be solved, while at the same time preventing sensitivity degradation and surface peeling.

[0288] In addition, the curable composition according to one embodiment may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof to improve heat resistance and reliability.

[0289] For example, a curable composition according to one embodiment may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to a substrate, etc.

[0290] Examples of the above silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-(epoxycyclohexyl)ethyl trimethoxysilane, etc., and these may be used alone or in combination of two or more.

[0291] The above silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable composition. When the silane coupling agent is included within the above range, adhesion, storability, etc. are excellent.

[0292] In addition, the curable composition may further include a surfactant, such as a fluorinated surfactant, to improve coating properties and prevent defects, i.e., to improve leveling performance, as needed.

[0293] The above fluorinated surfactant may have a low weight average molecular weight of 4,000 g / mol to 10,000 g / mol, specifically, may have a weight average molecular weight of 6,000 g / mol to 10,000 g / mol. In addition, the fluorinated 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 fluorinated surfactant are within the above ranges, the leveling performance can be further improved, and the occurrence of spots can be prevented during high-speed coating, and since the occurrence of bubbles is small and the film defects are small, it provides excellent properties to slit coating, which is a high-speed coating method.

[0294] As the above fluorinated surfactant, BM Chemie's BM-1000 ® , BM-1100 ® Mecha Pack F 142D by Dai Nippon Inki Kagaku Kogyo Co., Ltd.® , East F 172 ® , East F 173 ® , East F 183 ® Back; Prorad FC-135 from Sumitomo 3M Co., Ltd. ® , East FC-170C ® , East FC-430 ® , East FC-431 ® Saffron S-112 from Asahi Glass Co., Ltd. ® , East S-113 ® , East S-131 ® , East S-141 ® , East S-145 ® SH-28PA from Toray Silicone Co., Ltd. ® , East-190 ® , East-193 ® , SZ-6032 ® , SF-8428 ® Fluorine-based surfactants sold under the names F-482, F-484, F-478, F-554, etc. by DIC Co., Ltd. can be used.

[0295] Additionally, the curable composition according to one embodiment may use a silicone-based surfactant together with the aforementioned fluorinated surfactant. Specific examples of the silicone-based surfactant include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 from Toshiba Silicone Co., Ltd.

[0296] The surfactant, including the fluorinated surfactant, may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant is included within the above range, the phenomenon of foreign substances occurring in the sprayed composition is reduced.

[0297] In addition, the curable composition according to one embodiment may further include a certain amount of other additives, such as an antioxidant, within a range that does not impair physical properties.

[0298]

[0299] menstruum

[0300] Meanwhile, the curable composition according to one embodiment may further include a solvent.

[0301] The solvent may be, 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 methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; 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, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-Hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate;2-Hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or there are compounds of ketone esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic 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., but are not limited thereto.;

[0302] For example, it is preferable to use a solvent such as a glycol ether such as ethylene glycol monoethyl ether or ethylene diglycol methyl ethyl ether; an ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; an ester such as 2-hydroxypropionate ethyl; a carbitol such as diethylene glycol monomethyl ether; a propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate or propylene glycol propyl ether acetate; an alcohol such as ethanol, or a combination thereof.

[0303] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0304] The solvent may be included in an amount of 40 wt% to 80 wt%, for example, 45 wt% to 80 wt%, based on 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, thereby providing excellent coating properties during large-area coating using spin coating and slitting.

[0305]

[0306] Another embodiment provides a curable composition, for example, a cured film manufactured using the curable composition, a color filter including the cured film, and a display device including the color filter. In this case, the display device may include a μ-LED as a light source.

[0307] One of the methods for manufacturing the above cured film includes a step (S1) of forming a pattern by applying the above curable composition onto a substrate using an inkjet spraying method; and a step (S2) of curing the pattern.

[0308] (S1) Pattern forming step

[0309] The above curable composition is preferably applied to 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 repeatedly spraying according to the required number of colors. To reduce the process, the pattern can also be formed by spraying the required number of colors simultaneously through each inkjet nozzle.

[0310] (S2) Hardening stage

[0311] The above-obtained pattern can be cured to obtain pixels. At this time, as a curing method, both a thermal curing process and a photocuring process can be applied. The thermal curing process is preferably cured by heating to a temperature of 100°C or higher, more preferably cured by heating to 100°C to 300°C, and even more preferably cured by heating to 160°C to 250°C. The photocuring process irradiates active rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm. 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. can be used, and in some cases, X-rays, electron beams, etc. can also be used.

[0312] Another method of manufacturing the above-mentioned cured film is to manufacture the cured film using the above-mentioned curable composition using a lithography method, and the manufacturing method is as follows.

[0313] (1) Application and film formation stage

[0314] 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, or the like to a desired thickness, for example, 2 μm to 10 μm, and then heated at a temperature of 70°C to 90°C for 1 to 10 minutes to remove the solvent, thereby forming a coating film.

[0315] (2) Exposure stage

[0316] In order to form a necessary pattern on the obtained film, a mask of a predetermined shape is interposed, and then an active ray such as UV light of 190 nm to 450 nm, for example, 200 nm to 500 nm, is irradiated. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., and in some cases, X-rays, electron beams, etc. can also be used.

[0317] The exposure dose 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 / cm 2 Below (based on 365 nm sensor).

[0318] (3) Phenomenon stage

[0319] Following the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, thereby leaving only the exposed portions to form an image pattern. That is, when developing with an alkaline developer, the unexposed portions are dissolved, and an image color filter pattern is formed.

[0320] (4) Post-processing stage

[0321] The image pattern obtained by the above phenomenon can be cured by reheating or irradiating with active rays, etc., to obtain a pattern superior in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc.

[0322]

[0323] Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0324]

[0325] (Manufacture of the first surface modification material)

[0326] Manufacturing Example 1

[0327] Synthesis of the compound (first surface modifying material) represented by chemical formula 1-1:

[0328] After adding 132.2 g of dicyclopentadiene, 92.12 g of mercaptoacetic acid, 0.3 g of AIBN, and 150 g of methanol to a round flask, the temperature is raised to 60°C and the mixture is reacted for 6 hours to obtain a compound represented by the following chemical formula 1-1.

[0329] [Chemical Formula 1-1]

[0330]

[0331]

[0332] Manufacturing Example 2

[0333] Synthesis of the compound (first surface modifying material) represented by chemical formula 1-2:

[0334] After adding 132.2 g of Dicyclopentadiene, 106.01 g of 3-Mercaptopropionic acid, 0.3 g of AIBN, and 150 g of Methanol to a round flask, the temperature is raised to 60°C and the reaction is carried out for 6 hours to obtain a compound represented by the following chemical formula 1-2.

[0335] [Chemical Formula 1-2]

[0336]

[0337]

[0338] Manufacturing Example 3

[0339] Synthesis of the compound (first surface modifying material) represented by chemical formula 1-3:

[0340] Dicyclopentadiene 132.2g, 2-Mercaptoethanol 78.1g, AIBN 0.3g, and Methanol 150g are added to a round flask, heated to 60℃, and reacted for 6 hours. The compound obtained here is transferred to an autoclave, 210g of the compound obtained above is placed in the autoclave, 0.1g of KOH is added, and the temperature is raised to 80℃ and maintained, while 132g of ethylene oxide is slowly added. After the addition is complete, maintain the temperature at 80℃ for 2 hours, and after confirming that the internal pressure of the reactor has decreased, cool it to obtain an intermediate compound. After adding 342 g of the compound obtained above, 150 g of succinic anhydride, 200 g of toluene, and 50 g of triethylamine, the mixture was reacted at 60°C for 8 hours, cooled to room temperature, and purified by washing with methylene chloride, distilled water, and 5% HCl aqueous solution to obtain a compound represented by the following chemical formula 1-3.

[0341] [Chemical Formula 1-3]

[0342]

[0343] (In the above chemical formula 1-3, n is an integer of 4.)

[0344]

[0345] Manufacturing Example 4

[0346] Synthesis of the compound (first surface modifying material) represented by chemical formula 1-4:

[0347] 120.0 g of 5-Vinyl-2-norbornene, 106.01 g of 3-Mercaptopropionic acid, 0.3 g of AIBN, and 150 g of methanol are added to a round flask, the temperature is raised to 60°C, and the reaction is performed for 6 hours to obtain a compound represented by the following chemical formula 1-4.

[0348] [Chemical Formula 1-4]

[0349]

[0350]

[0351] Manufacturing Example 5

[0352] The compound represented by Chemical Formula 2-2 (first surface modifying material) was purchased from Aldrich and used.

[0353] [Chemical Formula 2-2]

[0354]

[0355]

[0356] Manufacturing Example 6

[0357] The compound represented by chemical formula 3 (first surface modifying material) was purchased and used from Aldrich.

[0358] [Chemical Formula 3]

[0359]

[0360]

[0361] (Manufacture of second surface modification material)

[0362] Manufacturing Example 7

[0363] Synthesis of the compound (second surface-modifying material) represented by chemical formula 4-1:

[0364] Place 100 g of polyethylene glycol phenyl ether (Hanong Chemical, Ph-4) in a two-necked round-bottomed flask and sufficiently dissolve in 300 mL of THF. Add 15.4 g of NaOH and 100 mL of water at 0°C and sufficiently dissolve until a clear solution is obtained. Slowly inject a solution of 73 g of para-toluene sulfonyl chloride in 100 mL of THF at 0°C. The injection was carried out for 1 hour, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, an excess of methylene chloride was added and stirred. Then, a saturated NaHCO3 solution was added, followed by extraction, titration, and dewatering. After removing the solvent, the mixture was dried in a dry oven for 24 hours. Place 50 g of the obtained dried product in a two-necked round-bottomed flask and sufficiently stirred in 300 mL of ethanol. Afterwards, 27 g of thiourea was added, dispersed, and refluxed at 80°C for 12 hours. Afterwards, an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water is injected, and stirred for 5 more hours. An excess of methylene chloride is added, and after stirring, an aqueous hydrochloric acid solution is added, and extraction, titration, moisture removal, and solvent removal are performed in sequence. After drying in a vacuum oven for 24 hours, a compound represented by the following chemical formula 4-1 is obtained.

[0365] [Chemical Formula 4-1]

[0366]

[0367]

[0368] Manufacturing Example 8

[0369] Synthesis of the compound (second surface-modifying material) represented by chemical formula 4-2:

[0370] 150.22 g of hydroxydicyclopentadiene and 0.1 g of KOH are placed in a high-pressure reactor and the internal temperature is raised to 80°C. While controlling the internal pressure, 176 g of ethylene oxide is slowly added to synthesize HDCP-4. 326.22 g of HDCP-4 is placed in a two-necked round-bottom flask and sufficiently dissolved in 800 mL of THF. 44 g of NaOH and 100 mL of water are then added at 0°C and sufficiently dissolved until a clear solution is obtained. A solution of 210 g of para-toluene sulfonyl chloride in 300 mL of THF is slowly injected at 0°C. The injection is carried out for 2 hours, and the reactor is stirred at room temperature for 12 hours. After the reaction is complete, an excess of methylene chloride is added and stirred, followed by extraction, titration, and dewatering with a saturated NaHCO3 solution. After removing the solvent, the reactor is dried in a dry oven for 24 hours. The obtained dried product (481.2 g) is placed in a two-neck round bottom flask and thoroughly stirred in 500 mL of ethanol. Then, 91.2 g of Thiourea is added, dispersed, and refluxed at 80°C for 12 hours. Afterwards, an aqueous solution of 60 g of NaOH dissolved in 200 mL of water is injected, stirred for 5 more hours, an excess of methylene chloride is added, stirred, and then an aqueous hydrochloric acid solution is added, and extraction, titration, moisture removal, and solvent removal are sequentially performed. After drying in a vacuum oven for 24 hours, a compound represented by the following chemical formula 4-2 is obtained.

[0371] [Chemical Formula 4-2]

[0372]

[0373]

[0374] Manufacturing Example 9

[0375] Synthesis of the compound (second surface-modifying material) represented by chemical formula 4-3:

[0376] Place 234 g of polyethylene glycol allyl ether (Hanong Chemical, APEG-4) in a two-necked round-bottomed flask and sufficiently dissolve in 300 mL of THF. Add 44 g of NaOH and 100 mL of water at 0°C and sufficiently dissolve until a clear solution is obtained. Slowly inject a solution of 210 g of para-toluene sulfonyl chloride in 300 mL of THF at 0°C. The injection was carried out for 1 hour, and then stirred at room temperature for 12 hours. After the reaction was completed, add an excess of methylene chloride and stir, then add a saturated NaHCO3 solution, extract, titrate, and remove moisture. After removing the solvent, dry in a dry oven for 24 hours. Place 389 g of the obtained dried product in a two-necked round-bottomed flask and sufficiently stir in 500 mL of ethanol. Then, add 152 g of thiourea and reflux at 80°C for 12 hours. Afterwards, an aqueous solution of 60 g of NaOH dissolved in 200 mL of water is injected, and stirred for 5 more hours. An excess of methylene chloride is added, and after stirring, an aqueous hydrochloric acid solution is added, and extraction, titration, moisture removal, and solvent removal are performed in sequence. After drying in a vacuum oven for 24 hours, a compound represented by the following chemical formula 4-3 is obtained.

[0377] [Chemical Formula 4-3]

[0378]

[0379]

[0380] (Synthesis of surface-modified quantum dots)

[0381] Synthesis Example 1

[0382] 0.53 g of the surface-modifying agent of Manufacturing Example 1 and 0.26 g of the surface-modifying agent of Manufacturing Example 8 were added to 10 g of a cyclohexyl acetate (CHA) dispersion (InP / ZnSe / ZnS, Hansol Chemical; quantum dot solid content 23 wt%) containing green quantum dots, and stirred for 5 minutes. The temperature of the mixture was then increased to 80°C and refluxed for 10 hours. After cooling to room temperature, the mixture was precipitated in cyclohexane and centrifuged to remove the supernatant to obtain surface-modified quantum dot particles, which were then dried in a vacuum oven for 24 hours to obtain the final particles.

[0383] Synthesis Example 2

[0384] The same procedure as in Synthesis Example 1 was followed, except that the surface modification material of Manufacturing Example 2 was used instead of the surface modification material of Manufacturing Example 1.

[0385] Synthesis Example 3

[0386] The same procedure as in Synthesis Example 1 was followed, except that the surface modification material of Manufacturing Example 3 was used instead of the surface modification material of Manufacturing Example 1.

[0387] Synthesis Example 4

[0388] The same procedure as in Synthesis Example 1 was followed, except that the surface modification material of Manufacturing Example 4 was used instead of the surface modification material of Manufacturing Example 1.

[0389] Synthesis Example 5

[0390] Except that the surface modification material of Manufacturing Example 5 was used instead of the surface modification material of Manufacturing Example 1, the same procedure as Synthesis Example 1 was followed.

[0391] Synthesis Example 6

[0392] Except that the surface modification material of Manufacturing Example 6 was used instead of the surface modification material of Manufacturing Example 1, the same procedure as Synthesis Example 1 was followed.

[0393] Comparative synthesis example 1

[0394] The same procedure as in Synthesis Example 1 was followed, except that 0.79 g of the surface modifying material of Manufacturing Example 2 was used alone instead of the two types of surface modifying materials mentioned above.

[0395] Comparative synthesis example 2

[0396] The same procedure as in Synthesis Example 1 was followed, except that 0.79 g of the surface modifying material of Manufacturing Example 4 was used alone instead of the two types of surface modifying materials mentioned above.

[0397] Comparative synthesis example 3

[0398] Except that 0.79 g of the surface modifying material of Manufacturing Example 7 was used alone instead of the two types of surface modifying materials mentioned above, the same procedure as Synthesis Example 1 was followed.

[0399] Comparative synthesis example 4

[0400] The same procedure as in Synthesis Example 1 was followed, except that 0.79 g of the surface modifying material of Manufacturing Example 8 was used alone instead of the two types of surface modifying materials mentioned above.

[0401] Comparative synthesis example 5

[0402] The same procedure as in Synthesis Example 1 was followed, except that 0.79 g of the surface modifying material of Manufacturing Example 9 was used alone instead of the two types of surface modifying materials mentioned above.

[0403]

[0404] (Preparation of curable composition 1)

[0405] Based on the following respective components, curable compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were prepared.

[0406]

[0407] (A) Quantum dots

[0408] (A-1) Surface-modified green quantum dots prepared from the above synthesis example 1

[0409] (A-2) Surface-modified green quantum dots manufactured from the above synthesis example 2

[0410] (A-3) Surface-modified green quantum dots manufactured from the above synthesis example 3

[0411] (A-4) Surface-modified green quantum dots manufactured from the above synthesis example 4

[0412] (A-5) Surface-modified green quantum dots manufactured from the above synthesis example 5

[0413] (A-6) Surface-modified green quantum dots manufactured from the above synthesis example 6

[0414] (A-7) Surface-modified green quantum dots manufactured from the above comparative synthesis example 1

[0415] (A-8) Surface-modified green quantum dots manufactured from the above comparative synthesis example 2

[0416] (A-9) Surface-modified green quantum dots manufactured from the above comparative synthesis example 3

[0417] (A-10) Surface-modified green quantum dots manufactured from the above comparative synthesis example 4

[0418] (A-11) Surface-modified green quantum dots manufactured from the above comparative synthesis example 5

[0419] (B) polymeric compound

[0420] A compound represented by the following chemical formula 5-2 (M200, Miwon Chemical Co., Ltd.)

[0421] [Chemical Formula 5-2]

[0422]

[0423] (C) Photopolymerization initiator

[0424] TPO-L (Polynetron)

[0425] (D) Light diffuser

[0426] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0427]

[0428] Examples 1 to 6 and Comparative Examples 1 to 5

[0429] Specifically, the surface-modified green quantum dots and the polymerizable compound are mixed and stirred for 12 hours. A photopolymerization initiator is added, followed by a light diffusing agent.

[0430] (For example, in the case of Example 1, 41 g of surface-modified green quantum dots and 41 g of a polymerizable compound represented by Chemical Formula 5-2 are mixed and stirred to prepare a green quantum dot dispersion, and then 11 g of another curable monomer represented by Chemical Formula 5-2 is added thereto and stirred for 5 minutes, and then 3 g of a photopolymerization initiator and 4 g of a light diffusing agent are added and stirred to prepare a curable composition (ink).)

[0431] The specific composition is shown in Table 1 below.

[0432]

[0433] (Unit: wt%)Example 1Example 2Example 3Example 4Example 5Example 6Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Quantum dot (A-1)41----------(A-2)-41---------(A-3)--41--------(A-4)---41-------(A-5)----41------(A-6)-----41-----(A-7)------41----(A-8)-------41---(A-9)--------41--(A-10)---------41-(A-11)----------41Polymerizable compound52 ... Initiator 33333333333 Light diffuser 44444444444

[0434] Evaluation: Evaluation of optical properties of curable composition 1

[0435] The optical properties of each of the curable compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated, and the results are shown in Table 2 below.

[0436] Specifically, 2 mL of the above-mentioned curable composition was spin-coated on a glass substrate, and then exposed to 5 J for 9 seconds in a nitrogen UV exposure device to form a QD film (9 μm). The light efficiency and light resistance reliability were measured using a light efficiency meter (QE-2100, Otsuka). In addition, the viscosity was measured using a viscometer at 25°C.

[0437]

[0438] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Viscosity (cPs) 18.4 18.4 18.0 18.3 18.5 26.0 17 17.3 17.3 18.8 16.9 Luminous Efficiency (%) 33.2 33.1 33.2 33.2 33.2 33.2 2.7 32.5 32.6 31.9 32.1 Light Reliability (h@T90, 194K) 2000 h 2111 h 1998 h 1785 h 1642 h 1433 h 532 h 584 h 163 h 510 h 136 h

[0439] From the above Table 2, it can be confirmed that the curable compositions according to Examples 1 to 6 have superior optical properties and light resistance reliability compared to the curable compositions according to Comparative Examples 1 to 5. In addition, it can be confirmed that the curable compositions according to Examples 1 to 4 have superior light resistance reliability than the curable compositions according to Examples 5 and 6, and that the light resistance reliability can be further improved depending on the type of the first surface modification material.

[0440]

[0441] (Preparation of curable composition 2)

[0442] Based on the following respective components, curable compositions according to Examples 7 to 9 and Comparative Examples 6 to 9 were prepared.

[0443]

[0444] (A) Quantum dots

[0445] (A-2) Surface-modified green quantum dots manufactured from the above synthesis example 2

[0446] (A-4) Surface-modified green quantum dots manufactured from the above synthesis example 4

[0447] (A-5) Surface-modified green quantum dots manufactured from the above synthesis example 5

[0448] (A-7) Surface-modified green quantum dots manufactured from the above comparative synthesis example 1

[0449] (A-8) Surface-modified green quantum dots manufactured from the above comparative synthesis example 2

[0450] (A-9) Surface-modified green quantum dots manufactured from the above comparative synthesis example 3

[0451] (A-10) Surface-modified green quantum dots manufactured from the above comparative synthesis example 4

[0452] (B) polymeric compound

[0453] A compound represented by the following chemical formula 5-2 (M200, Miwon Chemical Co., Ltd.)

[0454] [Chemical Formula 5-2]

[0455]

[0456] (C) Photopolymerization initiator

[0457] TPO-L (Polynetron)

[0458] (D) Light diffuser

[0459] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0460] (E) Binder resin

[0461] Cardo resin (Tacoma, TA01) (weight average molecular weight: 4,000 g / mol)

[0462]

[0463] (F) solvent

[0464] Propylene glycol monomethyl ether acetate (PGMEA) (Sigma-Aldrich)

[0465] (G) Other additives

[0466] Fluorinated surfactant (F-554 (10%), DIC)

[0467]

[0468] Examples 7 to 9 and Comparative Examples 6 to 9

[0469] Using the above-mentioned components, curable compositions according to Examples 7 to 9 and Comparative Examples 6 to 9 were prepared with the compositions shown in Table 3 below.

[0470] Specifically, after dissolving the photopolymerization initiator in the solvent, the mixture was sufficiently stirred at room temperature for 2 hours. Subsequently, the polymerizable compound and binder resin were added, and the mixture was stirred at room temperature for another 1 hour. Thereafter, the quantum dot dispersion was mixed with the solvent in which the photopolymerization initiator was dissolved, and a light diffusing agent and a fluorinated surfactant were added thereto, and the mixture was stirred at room temperature for 1 hour. The product was filtered three times to remove impurities, thereby producing a curable composition.

[0471]

[0472] (Unit: wt%)Example 7Example 8Example 9Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Quantum dot (A-2)12.5------(A-4)-12.5-----(A-5)--12.5----(A-7)---12.5---(A-8)----12.5--(A-9)-----12.5-(A-10)------12.5Polymerizable compound10101010101010Binder resin4.84.84.84.84.84.84.84.8Photopolymerization initiator0.90.90.90.90.90.90.9Light diffusing agent1.21.21.21.21.21.21.21.2Solvent707070707070Other Additive0.60.60.60.60.60.60.60.6

[0473] Evaluation: Evaluation of optical properties and patternability of curable composition 2

[0474] The optical properties of each of the curable compositions according to Examples 7 to 9 and Comparative Examples 6 to 9 were evaluated, and the results are shown in Table 4 below.

[0475] Specifically, 2 mL of the above-mentioned curable composition was spin-coated on a glass substrate, and then soft-baked at 80° C. for 120 seconds using a hot plate, and exposed to UV light at 5 J for 9 seconds. The QD film (9 μm) formed was measured for its light efficiency and light resistance reliability using a light efficiency meter (QE-2100, Otsuka).

[0476] In addition, each of the curable compositions according to Examples 7 to 9 and Comparative Examples 6 to 9 was coated on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, and then soft-baked at 80°C for 120 seconds using a hot plate, and exposed at a power of 60 mJ using an exposure device (Ushio, ghi broadband). Subsequently, development was performed with a 0.2 wt% potassium hydroxide (KOH) aqueous solution using a developer (SVS, SSP-200). Thereafter, the cross-section of the pattern remaining after development was measured at a magnification of 20,000 times using a focused ion beam (FIB) scanning electron microscope (SEM), and the surface of the pattern remaining after development was measured at a magnification of 15,000 times, and the results are shown in Table 4 below. (The number of dark spots on the pattern cross-section and holes on the pattern surface were measured visually.)

[0477] * Pattern evaluation criteria

[0478] ○: No number of dark spots visible to the naked eye and less than 10 holes

[0479] X: 1 or more dark spots visible to the naked eye or 10 or more holes visible to the naked eye

[0480]

[0481] Example 7 Example 8 Example 9 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Pattern ○○○XXXX Light Efficiency (%) 32.5 32.4 32.5 32.0 32.1 32.3 32.2 Light Reliability (h@T90,194K) 486h 470h 423h 280h 257h 24h 30h

[0482] From the above Table 4, it can be confirmed that the curable compositions according to Examples 7 to 9 have superior patternability, optical properties, and light resistance reliability compared to the curable compositions according to Comparative Examples 6 to 9. In addition, it can be confirmed that the light resistance reliability can be further improved depending on the type of the first surface modification material, as the curable compositions according to Examples 7 and 8 have superior light resistance reliability than the curable composition according to Example 9.

[0483]

[0484] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. (A) Quantum dots surface-modified with different first surface-modifying materials and second surface-modifying materials; and (B) polymeric compound Including, A curable composition comprising a compound in which the first surface modifying material comprises at least one selected from the group consisting of an unsaturated double bond and a carboxyl group at each of the two terminals, and a sulfide linkage group, an ester linkage group, or a combination thereof between the two terminals, or a compound in which the unsaturated double bond and the carboxyl group are directly bonded to each other.

2. In paragraph 1, The first surface modification material is a curable composition represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, A is a cyclic compound substituted with a carbon-carbon unsaturated double bond or a cyclic compound in which a carbon-carbon unsaturated double bond is included within the ring structure, L 1 Inland L 4 are each independently a single bond, an ester group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

3. In paragraph 2, A curable composition wherein the above cyclic compound is a fused cyclic compound.

4. In paragraph 2, The above A is a curable composition represented by the following chemical formula A-1 or chemical formula A-2: [Chemical Formula A-1] [Chemical Formula A-2] In the above chemical formula A-1 or chemical formula A-2, R 1 is a substituted or unsubstituted vinyl group, L 5 is a substituted or unsubstituted C1 to C20 alkylene group.

5. In paragraph 1, The first surface modification material is a curable composition represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R 1 is a substituted or unsubstituted vinyl group, L 7 Inland L 10 are each independently a single bond, an ester group, or a substituted or unsubstituted C1 to C20 alkylene group, provided that L 7 Inland L 10 At the same time, this is not a single bond.

6. In paragraph 1, The above first surface modification material is a curable composition represented by the following chemical formula 3. [Chemical Formula 3] 7. In paragraph 1, The above first surface modification material is a curable composition represented by any one of the following chemical formulas 1-1 to 1-4, chemical formula 2-1, chemical formula 2-2, and chemical formula 3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] (In the above chemical formula 1-3, n is an integer from 1 to 20) [Chemical Formula 1-4] [Chemical Formula 2-1] [Chemical Formula 2-2] 8. In paragraph 1, The second surface modifying material is a curable composition comprising a thiol group, a phosphate group or a phosphonic acid group at a terminal.

9. In paragraph 8, The second surface modification material is a curable composition represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cyclic group, or a substituted or unsubstituted C6 to C20 arylene group, L 11 and L 12 are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C1 to C20 oxyalkylene group.

10. In paragraph 1, The second surface modification material is a curable composition represented by any one of the following chemical formulas 4-1 to 4-3. [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] 11. In paragraph 1, The above polymerizable compound is a curable composition comprising a compound represented by the following chemical formula 5: [Chemical Formula 5] In the above chemical formula 5, L 13 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 14 and L 15 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

12. In paragraph 1, The above curable composition is a curable composition that is a solvent-free curable composition.

13. In paragraph 12, The above solvent-free curable composition, with respect to the total amount of the above solvent-free curable composition, 5 to 60 wt% of the above quantum dots; and 40 to 95 wt% of the polymerizable compound A curable composition comprising:

14. In paragraph 1, The above curable composition further comprises a polymerization initiator, a light diffusing agent, a polymerization inhibitor or a combination thereof.

15. In paragraph 1, The above curable composition further comprises a solvent.

16. In paragraph 15, The curable composition comprises, based on the total weight of the curable composition, 1 wt% to 40 wt% of the quantum dot; 1 wt% to 20 wt% of the polymerizable compound; and 40 wt% to 80 wt% of the solvent.

17. In paragraph 1, The curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof.

18. A cured film manufactured using a curable composition according to any one of claims 1 to 17.

19. A color filter comprising the cured film of Article 18.

20. A display device including the color filter of Article 19.

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