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

Abstract

The invention provides a curable composition, a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter. A curable composition includes: (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound comprises a thiol alkene reaction product between a (meth) acrylate-based monomer and a thiol-based monomer.

Description

Technical Field

[0001] The present disclosure relates to a curable composition, a cured layer using the composition, a color filter including the cured layer, and a display device including the color filter. Background Art

[0002] In the case of ordinary quantum dots, due to having a hydrophobic surface feature, the solvent in which the quantum dots are dispersed is limited, and thus it is difficult to introduce into a polar system such as an adhesive or a curable monomer.

[0003] For example, even in the case of actively studying quantum dot ink compositions, the polarity is relatively low in the initial step and it can be dispersed in a solvent used in a curable composition having high hydrophobicity. Therefore, since it is difficult to include 20 wt % or more of quantum dots based on the total amount of the composition, it is impossible to improve the light efficiency of the ink beyond a certain level. Even if quantum dots are additionally added and dispersed in order to improve the light efficiency, the viscosity exceeds the range capable of inkjetting, and thus the processability may not be satisfied.

[0004] In order to achieve a viscosity range capable of inkjetting, a method of reducing the solid content of the ink by dissolving 50% by weight or more of a solvent based on the total amount of the composition has been used, which also provides slightly satisfactory results in terms of viscosity. However, it can be regarded as a satisfactory result in terms of viscosity, but nozzle drying and nozzle clogging due to solvent volatilization during inkjetting and a decrease in single film thickness over time after inkjetting may become worse, and it is difficult to control thickness deviation after curing. Therefore, it is difficult to apply it to an actual process.

[0005] Therefore, solvent-free quantum dot inks that do not contain solvents are the most ideal form to be applied to actual processes. The current technology of applying quantum dots themselves to solvent-based compositions is now limited to a certain extent.

[0006] It has been reported so far that since the solvent-based composition to be applied to the actual process contains 20 to 25 wt % of non-surface-modified quantum dots through ligand substitution and the like based on the total amount of the solvent-based composition and thus has viscosity limitations, it is difficult to increase the light efficiency and absorptivity. On the other hand, a method of reducing the content of quantum dots and increasing the content of light diffusers (scatterers) has been tried, but the deposition problem or low light efficiency has not been improved. Summary of the invention

[0007] Technical Challenges

[0008] One embodiment provides a quantum dot-containing curable composition having excellent stability due to excellent quantum dot barrier properties.

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

[0010] Another embodiment provides a color filter including a cured layer.

[0011] Another embodiment provides a display device including a color filter.

[0012] Means of solving the problem

[0013] One embodiment provides a curable composition comprising (A) quantum dots; and (B) a polymerizable compound, wherein the polymerizable compound comprises a product of a thiol-ene reaction between a (meth)acrylate monomer and a thiol monomer.

[0014] The thiol monomer may be a dithiol monomer.

[0015] The thiol-based monomer may be represented by Chemical Formula 1.

[0016] [Chemical formula 1]

[0017]

[0018] In Chemical Formula 1,

[0019] L 1 is an ether linkage group (*-O-*), a thioether linkage group (*-S-*), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0020] Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2.

[0021] [Chemical formula 1-1]

[0022]

[0023] In Chemical Formula 1-1,

[0024] L 2 is a substituted or unsubstituted C1 to C20 alkylene group,

[0025] [Chemical formula 1-2]

[0026]

[0027] In Chemical Formula 1-2,

[0028] L 3 and L 4 are each independently a substituted or unsubstituted C1 to C20 alkylene group, and

[0029] n is an integer of 0-10.

[0030] The (meth)acrylate-based monomer may include a monomer represented by Chemical Formula 2, a monomer represented by Chemical Formula 3, or a mixture thereof.

[0031] [Chemical formula 2]

[0032]

[0033] [Chemical formula 3]

[0034]

[0035] In Chemical Formula 2 and Chemical Formula 3,

[0036] R 1 To R 4 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and

[0037] L 5 To L 10 Each is independently a single bond, an ether linkage group (*-O-*), a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a divalent fluorene linkage group or a divalent bicyclic linkage group.

[0038] The monomer represented by Chemical Formula 2 may be represented by any one of Chemical Formula 2-1 to Chemical Formula 2-4.

[0039] [Chemical formula 2-1]

[0040]

[0041] [Chemical formula 2-2]

[0042]

[0043] [Chemical formula 2-3]

[0044]

[0045] [Chemical formula 2-4]

[0046]

[0047] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0048] R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0049] L 11 is a substituted or unsubstituted C1 to C20 alkylene group, and

[0050] L 12 and L 13 Each is independently an ether linkage group (*-O-*) or a substituted or unsubstituted C1 to C20 alkylene group.

[0051] In chemical formula 3, R 3 can be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 4 may be a substituted or unsubstituted C6 to C20 arylene group, and L 9 and L 10 Each may independently be an ether linking group (*—O—*) or a substituted or unsubstituted C1 to C20 alkylene group.

[0052] The polymerizable compound may include at least one selected from the monomer represented by Chemical Formula 4 to the monomer represented by Chemical Formula 7.

[0053] [Chemical formula 4]

[0054]

[0055] [Chemical formula 5]

[0056]

[0057] [Chemical formula 6]

[0058]

[0059] [Chemical formula 7]

[0060]

[0061] In Chemical Formulae 4 to 7,

[0062] Ac is a (meth)acrylate group,

[0063] L a To L d are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0064] R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0065] m is an integer from 0 to 10,

[0066] p is an integer from 1 to 100, and

[0067] q is an integer from 0 to 5.

[0068] The polymerizable compound may further include a monomer represented by Chemical Formula 8 in addition to a product of a thiol-ene reaction between a (meth)acrylate-based monomer and a thiol-based monomer.

[0069] [Chemical formula 8]

[0070]

[0071] In Chemical Formula 8,

[0072] R 5 and R 6 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0073] L 14 and L 16 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0074] L 15 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether linkage group (*-O-*).

[0075] The content of the monomer represented by Chemical Formula 8 is greater than the product of a thiol-ene reaction between the (meth)acrylate-based monomer and the thiol-based monomer.

[0076] The curable composition may have a viscosity of 500 centipoise to 1100 centipoise.

[0077] The curable composition may be a solvent-free curable composition.

[0078] The solvent-free curable composition may include 5 wt % to 60 wt % of the quantum dots and 40 wt % to 95 wt % of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0079] The curable composition may further include a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

[0080] The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0081] The curable composition may further include a solvent.

[0082] The curable composition may include, based on the total amount of the curable composition, 1 wt % to 40 wt % of quantum dots; 1 wt % to 20 wt % of the polymerizable compound; and 40 wt % to 80 wt % of the solvent.

[0083] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0084] Another embodiment provides a cured layer manufactured using the curable composition.

[0085] Another embodiment provides a color filter including a cured layer.

[0086] Another embodiment provides a display device including a color filter.

[0087] Other embodiments of the invention are included in the following detailed description.

[0088] Effects of the Invention

[0089] By introducing a novel oligomer using a thiol-ene reaction, a low-viscosity quantum-curable composition is provided that has excellent quantum dot dispersion and is capable of forming matrix wells due to high curing during UV curing. DETAILED DESCRIPTION

[0090] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are illustrative, and the present invention is not limited thereto and is defined by the scope of the claims.

[0091] In the present specification, when a specific definition is not otherwise provided, an “alkyl group” refers to a C1 to C20 alkyl group, an “alkenyl group” refers to a C2 to C20 alkenyl group, a “cycloalkenyl group” refers to a C3 to C20 cycloalkenyl group, a “heterocycloalkenyl group” refers to a C3 to C20 heterocycloalkenyl group, an “aryl group” refers to a C6 to C20 aryl group, an “arylalkyl group” refers to a C6 to C20 aralkyl group, an “alkylene group” refers to a C1 to C20 alkylene group, an “arylene group” refers to a C6 to C20 arylene group, an “alkylarylene group” refers to a C6 to C20 alkylarylene group, a “heteroarylene group” refers to a C3 to C20 heteroarylene group, and an “alkoxylene group” refers to a C1 to C20 alkyleneoxy group.

[0092] In the present specification, when a specific definition is not otherwise provided, “substituted” means that at least one hydrogen atom is replaced by a substituent selected from the group consisting of a halogen atom (F, Cl, Br or 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, a carbamimido group, a hydrazine group, a hydrazo group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group or a combination thereof.

[0093] In the present specification, when a specific definition is not otherwise provided, "hetero" means a heteroatom containing at least one of N, O, S and P in a chemical formula.

[0094] In the present specification, when a specific definition is not otherwise provided, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid".

[0095] In the present specification, when a specific definition is not otherwise provided, the term "combination" means mixing or copolymerization.

[0096] In the present specification, when a definition is not otherwise provided, when a chemical bond is not drawn at a position that should be given in a chemical formula, hydrogen is bonded at the position.

[0097] In addition, in the present specification, when a definition is not otherwise provided, "*" refers to a connection point with the same or different atom or chemical formula.

[0098] The quantum dot-containing curable composition according to the present invention includes a product of a thiol-ene reaction between a (meth)acrylate-based monomer and a thiol-based monomer as a polymerizable compound, and thus can disperse quantum dots in an amount equal to or greater than that of an existing polymerizable compound and also form a matrix well by UV. In addition, since the curable composition according to an embodiment has a low viscosity, it is not necessary to increase the temperature of the nozzle head during inkjet and thus there are no problems such as nozzle clogging, defective emission, or the like in the top nozzle according to the increase in temperature.

[0099] Hereinafter, each component constituting the curable composition according to one embodiment is described in detail.

[0100] quantum dots

[0101] The quantum dots contained in the curable composition according to one embodiment absorb light in the wavelength range of 360 nm to 780 nm (e.g., 400 nm to 780 nm), and emit fluorescence in the wavelength range of 500 nm to 700 nm (e.g., 500 nm to 580 nm), or emit fluorescence in the wavelength range of 600 nm to 680 nm. That is, the quantum dots may have a maximum fluorescence emission wavelength (fluorescence λ) of 500 nm to 680 nm. em ).

[0102] The quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm (eg, 20 nm to 50 nm). When the quantum dots have a full width at half maximum (FWHM) in the above range, color reproducibility is increased when used as a color material in a color filter due to high color purity.

[0103] The quantum dots may independently be organic materials, inorganic materials, or hybrids (mixtures) of organic and inorganic materials.

[0104] Quantum dots may independently consist of a core and a shell surrounding the core, and the core and the shell may independently have a structure of a core, core / shell, core / first shell / second shell, alloy, alloy / shell, or the like composed of Group II to Group IV, Group III to Group V, and the like, but are not limited thereto.

[0105] For example, the core may include at least one material selected from the following: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell layer surrounding the core may include at least one material selected from the following: CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

[0106] In one embodiment, since environmental concerns have greatly increased worldwide recently and restrictions on toxic materials have also been strengthened, cadmium-free luminescent materials (InP / ZnS, InP / ZeSe / ZnS, etc.) with slightly lower quantum efficiency (quantum yield) but environmentally friendly are used instead of luminescent materials with a cadmium-based core, but are not necessarily limited to this.

[0107] In the case of quantum dots of a core / shell structure, the overall size (average particle size) including the shell may be 1 nm to 15 nm, for example 5 nm to 15 nm.

[0108] For example, the quantum dots may independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may independently have an average particle size of 10 nanometers to 15 nanometers. The green quantum dots may independently have an average particle size of 5 nanometers to 8 nanometers.

[0109] On the other hand, for the dispersion stability of quantum dots, the solvent-free curable composition according to an embodiment may further include a dispersant to include quantum dots in the form of a quantum dot dispersion. The dispersant contributes to the uniform dispersibility of light conversion materials such as quantum dots in the solvent-free curable composition, and may include nonionic, anionic or cationic dispersants. Specifically, the dispersant may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, ethanol alkylene oxide addition product, sulfonate, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide addition product, alkylamine and the like, and it may be used alone or in a mixture of two or more than two. Based on the solid content of light conversion materials such as quantum dots, the dispersant can be used in an amount of 0.1% to 100% by weight (e.g., 10% to 20% by weight).

[0110] The quantum dots may be surface-modified using existing quantum dot surface modification materials (eg, thiol compounds, etc.) or may not be surface-modified.

[0111] The quantum dots may be present in an amount of 5 to 60 wt %, such as 10 to 60 wt %, such as 20 to 50 wt %, or such as 30 to 50 wt %, based on the total amount of the solvent-free curable composition. When the quantum dots (e.g., quantum dot dispersion) within the above range are included, high light retention and light efficiency may be achieved even after curing.

[0112] For example, when the curable composition according to an embodiment is a curable composition comprising 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 within the above range are included, the light conversion rate is increased without damaging the pattern characteristics and the development characteristics, and thus excellent processability can be obtained.

[0113] Polymerizable compounds

[0114] Currently, quantum dot-containing curable compositions (inks) have been developed in the direction of dedicated polymerizable compounds having good compatibility with quantum dots (eg, thiol-based binders or monomers), and some of them have been commercialized.

[0115] However, all thiol monomers developed so far only improve the dispersibility of quantum dots, but have a low degree of curing during UV curing, which leads to the disadvantage of forming a matrix. Therefore, in order to improve the dispersibility of the monomer, a technology of surface-modified quantum dots has been developed, but although the quantum dots are passivated with the surface-modified material, the dispersibility of the quantum dots is deteriorated, and the improvement of the photocurable rate and the film residue ratio has not been solved.

[0116] Therefore, the present inventors have solved the above-mentioned problems by using an oligomer, which is a product of a thiol-ene reaction between a (meth)acrylate-based monomer and a thiol-based monomer, as a polymerizable compound different from the existing monomers.

[0117] For example, the thiol monomer may be a dithiol monomer.

[0118] For example, the thiol monomer may be represented by Chemical Formula 1.

[0119] [Chemical formula 1]

[0120]

[0121] In Chemical Formula 1,

[0122] L 1 is an ether linkage group (*-O-*), a thioether linkage group (*-S-*), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0123] For example, Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2.

[0124] [Chemical formula 1-1]

[0125]

[0126] In Chemical Formula 1-1,

[0127] L 2 is a substituted or unsubstituted C1 to C20 alkylene group,

[0128] [Chemical formula 1-2]

[0129]

[0130] In Chemical Formula 1-2,

[0131] L 3 and L 4 are each independently a substituted or unsubstituted C1 to C20 alkylene group, and

[0132] n is an integer of 0-10.

[0133] For example, the (meth)acrylate-based monomer may include a monomer represented by Chemical Formula 2, a monomer represented by Chemical Formula 3, or a mixture thereof, but is not necessarily limited thereto.

[0134] [Chemical formula 2]

[0135]

[0136] [Chemical formula 3]

[0137]

[0138] In Chemical Formula 2 and Chemical Formula 3,

[0139] R 1 To R 4 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and

[0140] L 5 To L 10 Each is independently a single bond, an ether linkage group (*-O-*), a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a divalent fluorene linkage group or a divalent bicyclic linkage group.

[0141] The bivalent bicyclic structure may include all fused bicyclic structures, bridged bicyclic structures and spirocyclic structures.

[0142] For example, the monomer represented by Chemical Formula 2 may be represented by any one of Chemical Formula 2-1 to Chemical Formula 2-4, but is not necessarily limited thereto.

[0143] [Chemical formula 2-1]

[0144]

[0145] [Chemical formula 2-2]

[0146]

[0147] [Chemical formula 2-3]

[0148]

[0149] [Chemical formula 2-4]

[0150]

[0151] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0152] R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0153] L 11 is a substituted or unsubstituted C1 to C20 alkylene group, and

[0154] L 12 and L 13 Each is independently an ether linkage group (*-O-*) or a substituted or unsubstituted C1 to C20 alkylene group.

[0155] For example, in Chemical Formula 3, R 3 can be a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 4 may be a substituted or unsubstituted C6 to C20 arylene group, and L 9 and L 10 Each may independently be an ether linking group (*—O—*) or a substituted or unsubstituted C1 to C20 alkylene group.

[0156] For example, the polymerizable compound may include at least one selected from the monomer represented by Chemical Formula 4 to the monomer represented by Chemical Formula 7, but is not necessarily limited thereto.

[0157] [Chemical formula 4]

[0158]

[0159] [Chemical formula 5]

[0160]

[0161] [Chemical formula 6]

[0162]

[0163] [Chemical formula 7]

[0164]

[0165] In Chemical Formulae 4 to 7,

[0166] Ac is a (meth)acrylate group,

[0167] L a To L d are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0168] R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0169] m is an integer from 0 to 10,

[0170] p is an integer from 1 to 100, and

[0171] q is an integer from 0 to 5.

[0172] In the above chemical formula, Ac means a (meth)acrylate group, and can be represented by the chemical formula Ac.

[0173] [Chemical formula Ac]

[0174]

[0175] In the chemical formula Ac, R is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0176] The curable composition according to one embodiment does not use pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate and the like, which are used alone as polymerizable compounds for existing quantum dot-containing curable compositions, but includes a product of a thiol-ene reaction between a (meth)acrylate-based monomer and a thiol-based monomer as a polymerizable compound (or a part of a polymerizable compound), and thus can improve the high dispersibility of quantum dots and have a low viscosity, thereby forming a matrix well through UV and exhibiting excellent stability.

[0177] For example, when the curable composition according to an embodiment is a solvent-free curable composition, the content of the polymerizable compound may be 40 wt % to 95 wt %, such as 40 wt % to 90 wt %, such as 45 wt % to 85 wt %, or such as 45 wt % to 80 wt %, based on the total amount of the solvent-free curable composition. When the polymerizable compound within the above range is included, the solvent-free curable composition can be prepared to have inkjet viscosity, and in addition, the quantum dots in the solvent-free curable composition can have excellent dispersibility and also improve optical properties.

[0178] For example, the polymerizable compound may further include a monomer represented by Chemical Formula 8 in addition to a product of a thiol-ene reaction between a (meth)acrylate-based monomer and a thiol-based monomer.

[0179] [Chemical formula 8]

[0180]

[0181] In Chemical Formula 8,

[0182] R 5 and R6 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0183] L 14 and L 16 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0184] L 15 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether linkage group (*-O-*).

[0185] For example, the monomer represented by Chemical Formula 8 may have a molecular weight of 170 to 1000 g / mol. When the molecular weight of the monomer represented by Chemical Formula 8 is within the above range, inkjetting may be facilitated because the viscosity of the curable composition is not increased without reducing the optical properties of the quantum dots.

[0186] For example, the monomer represented by Chemical Formula 8 may be represented by Chemical Formula 8-1 or Chemical Formula 8-2, but is not limited thereto.

[0187] [Chemical formula 8-1]

[0188]

[0189] [Chemical formula 8-2]

[0190]

[0191] For example, the content of the monomer represented by Chemical Formula 8 may be greater than the product of the thiol-ene reaction between the (meth)acrylate-based monomer and the thiol-based monomer. In this case, the curable composition according to the embodiment may better form a matrix during UV curing.

[0192] For example, in addition to the product of the thiol-ene reaction between the (meth)acrylate monomer and the thiol monomer and the monomer represented by Chemical Formula 8, the polymerizable compound may further include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

[0193] In addition, in addition to the polymerizable compound, the curable composition according to an embodiment may further include monomers generally used in existing thermosetting or photocurable compositions, and for example, the monomers may further include cyclohexane compounds such as bis[1-ethyl(3-cyclohexane)]methyl ether.

[0194] For example, when the curable composition according to one embodiment includes a solvent, the content of the polymerizable compound may be 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 within the above range is included, the optical properties of the quantum dots may be improved.

[0195] Light Diffuser

[0196] The curable composition according to one embodiment may further include a light diffusing agent.

[0197] For example, the light diffuser may include barium sulfate (BaSO 4 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), zirconium oxide (ZrO 2 ), or a combination thereof.

[0198] The light diffuser can reflect the light not absorbed by the quantum dots and allow the quantum dots to absorb the reflected light again. That is, the light diffuser can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

[0199] The light diffusing agent may have an average particle size (D 50 ). When the average particle size of the light diffuser is within the above range, it can have a better light diffusion effect and improve the light conversion efficiency.

[0200] The content of the light diffuser may be 1 wt % to 20 wt %, such as 2 wt % to 15 wt %, such as 3 wt % to 10 wt %, based on the total amount of the curable composition. When less than 1 wt % of the light diffuser is included, it is difficult to expect the effect of improving the light conversion efficiency by using the light diffuser, and when more than 20 wt % of the light diffuser is included, the problem of quantum dot precipitation may occur.

[0201] Polymerization initiator

[0202] The curable composition according to an embodiment may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0203] The photopolymerization initiator may be a common initiator used in a photosensitive resin composition, such as acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, aminoketone compounds, and the like, but is not necessarily limited thereto.

[0204] Examples of the acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and the like.

[0205] Examples of the benzophenone compounds may be benzophenone, benzyl benzoate, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0206] Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0207] Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0208] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(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-methoxyphenylvinyl)-s-triazine and the like.

[0209] Examples of oxime compounds may be O-acyl oxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetoximo)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyl oxime compounds may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and the like.

[0210] Examples of amino ketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 and the like.

[0211] The photopolymerization initiator may further include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and the like other than the above compounds.

[0212] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transferring its energy.

[0213] Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0214] Examples of the thermal polymerization initiator may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauroyl peroxide, dilauroyl 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), tert-butyl perbenzoate, and the like, such as 2,2′-azobis-2-methylpropionitrile, but are not necessarily limited thereto, and any of the peroxides well known in the art may be used.

[0215] The content of the polymerization initiator may be 0.1 wt % to 5 wt %, for example 1 wt % to 4 wt %, based on the total amount of the curable composition. When the polymerization initiator within the range is included, it is possible to obtain excellent reliability due to sufficient curing during exposure or thermal curing, and it is possible to prevent the transmittance from being degraded due to the non-reactive initiator, thereby preventing the optical properties of the quantum dots from being degraded.

[0216] Binder resin

[0217] The curable composition according to an embodiment may further include a binder resin.

[0218] The binder resin may include an acryl-based resin, a cardo-based resin, an epoxy resin, or a combination thereof.

[0219] The acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including at least one acrylic repeating unit.

[0220] Specific examples of the acrylic binder resin may be polybenzyl methacrylate, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and may be used alone or in the form of a mixture of two or more.

[0221] The weight average molecular weight (Mw) of the acrylic binder resin may be 5,000 g / mol to 15,000 g / mol. When the acrylic binder resin has a weight average molecular weight within the range, close contact properties with a substrate, physical properties, and chemical properties are improved, and viscosity is appropriate.

[0222] The acrylic resin may have an acid value of 80 mgKOH / g to 130 mgKOH / g. When the acrylic resin has an acid value within the range, the pixel pattern may have excellent resolution.

[0223] The carbole-based resin may be used in an existing curable resin (or photosensitive resin) composition, and may be used, for example, as disclosed in Korean Patent Laid-Open Application No. 10-2018-0067243, but is not limited thereto.

[0224] The cardole-based resin can be prepared, for example, by mixing at least two of the following compounds: a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; an anhydride compound such as pyromellitic anhydride, naphthalenetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, benzophenonetetracarboxylic anhydride, pyromellitic anhydride, cyclobutanetetracarboxylic anhydride, perylenetetracarboxylic anhydride, tetrahydrofurantetracarboxylic anhydride, and tetrahydrophthalic anhydride; a diol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; a phosphorus-containing compound such as triphenylphosphine; and an amine or ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

[0225] The weight average molecular weight of the carbole-based binder 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 carbole-based binder resin is within the above range, a satisfactory pattern may be formed without residue during production of a cured layer and without loss of film thickness during development of a solvent-based curable composition.

[0226] When the binder resin is a carbole-based resin, the developability of a curable composition, particularly a photosensitive resin composition, containing the binder resin is improved, and the sensitivity during photocuring is good, so that fine pattern forming properties are improved.

[0227] The epoxy resin may be a monomer or an oligomer that can be polymerized by heat, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0228] The epoxy resin may include, but is not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cycloaliphatic epoxy resin, and aliphatic polyglycidyl ether.

[0229] Currently available products of the epoxy resin may include bisbenzene ring epoxy resins such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 from Yuka Shell Epoxy Co., Ltd.; cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 from Nippon Kayaku Co., Ltd. and EPIKOTE 180S75 from Yuka Shell Epoxy Co., Ltd.; bisphenol A epoxy resins such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1005, EPIKOTE 1006, EPIKOTE 1007, EPIKOTE 1008, EPIKOTE 1009, EPIKOTE 1100A from Yuka Shell Epoxy Co., Ltd. 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010 and EPIKOTE 828; bisphenol F type epoxy resins, such as EPIKOTE 807 and EPIKOTE 834 from Euka Shell Epoxy Resins Co., Ltd.; phenol novolac type epoxy resins, such as EPIKOTE 152, EPIKOTE 154 and EPIKOTE 157H65 from Euka Shell Epoxy Resins Co., Ltd. and EPPN 201, EPPN 202 from Nippon Kayaku Co., Ltd.; other cycloaliphatic epoxy resins, such as those from Ciba-Geigy Group (CIBA-GEIGY AG), ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from Union Carbide Corporation (UCC), Shodyne 509 from Showa Denko KK, ARALDITE CY-182, ARALDITE CY-192 and ARALDITE CY-184 from Ciba-Geigy, Epichron 200 and Epichron 400 from Dainippon Ink and Chemicals, Inc., EPIKOTE 871, EPIKOTE 872 and EPIKOTE EP1032H60 from Eukashell Epoxy Resins Co., Ltd., Celanese Coatings Co., Ltd.) ED-5661 and ED-5662 from Euka Shell Epoxy Resins Co., Ltd.; aliphatic polyglycidyl ethers such as EPIKOTE 190P and EPIKOTE 191P from Euka Shell Epoxy Resins Co., Ltd., Epolite 100MF from Kyoesha Yushi Co., Ltd., Epiol TMP from Nippon Yushi Co., Ltd., and the like. .

[0230] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the content of the binder resin may be 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 may be improved, and the storage stability of the composition may also be improved.

[0231] For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the content of the binder resin may be 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 may be improved.

[0232] Other additives

[0233] For improving the stability and dispersibility of quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0234] The polymerization inhibitor may include a hydroquinone-based compound, a catechol compound, or a combination thereof, but is not necessarily limited thereto. When the curable composition according to an embodiment further includes a hydroquinone-based compound, a catechol compound, or a combination thereof, room temperature crosslinking during exposure after printing (coating) the curable composition can be prevented.

[0235] For example, the hydroquinone compound, the catechol compound or a combination thereof may include hydroquinone, methyl hydroquinone, methoxy hydroquinone, tertiary butyl hydroquinone, 2,5-di-tertiary butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tertiary butyl catechol, 4-methoxyphenol, pyrogallol, 2,6-di-tertiary butyl-4-cresol, 2-naphthol, tris(N-hydroxy-N-nitrosoanilino-O,O')aluminum or a combination thereof, but are not necessarily limited thereto.

[0236] The hydroquinone compound, the catechol compound or the combination thereof can be used in the form of a dispersion, and the content of the polymerization inhibitor in the form of a dispersion can be 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, and at the same time, sensitivity reduction and surface peeling can be prevented.

[0237] In addition, the curable composition according to an embodiment may further include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, or a combination thereof, so as to improve heat resistance and reliability.

[0238] For example, the curable composition according to an embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, and the like, in order to improve close contact properties with a substrate.

[0239] Examples of the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these silane coupling agents may be used alone or in the form of a mixture of two or more.

[0240] The silane-based 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-based coupling agent is included within the above range, close contact properties, storage ability, and the like are improved.

[0241] In addition, the curable composition may further include a surfactant, such as a fluorine-based surfactant, as necessary, in order to improve coating properties and suppress the generation of spots, that is, to improve leveling performance.

[0242] The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g / mol to 10,000 g / mol, and specifically 6,000 g / mol to 10,000 g / mol. In addition, the fluorine-based surfactant may have a surface tension of 18 mN / m to 23 mN / m (measured using a 0.1% polyethylene glycol monomethyletheracetate (PGMEA) solution). When the fluorine-based surfactant has a weight average molecular weight and a surface tension within the range, the leveling performance may be further improved, and excellent characteristics may be provided when applied to slit coating as high-speed coating, because film defects may be less generated by preventing spot generation and suppressing vapor generation during high-speed coating.

[0243] Examples of fluorine-based surfactants include and (BM Chemie Inc.); MEGAFACE F MEGAFACE F MEGAFACE F and MEGAFACE F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FULORAD FULORAD and FULORAD (Sumitomo 3M Co., Ltd.); SURFLON SURFLON SURFLON SURFLON and SURFLON (ASAHI Glass Co., Ltd.); and as well as and the like (Toray Silicone Co., Ltd.); F-482, F-484, F-478, F-554 and the like from Dainippon Ink and Chemicals, Ltd. (DIC Co., Ltd.).

[0244] In addition to the fluorine-based surfactant, the curable composition according to one embodiment may also include a silicone-based surfactant. Specific examples of silicone-based surfactants may be TSF400, TSF401, TSF410, TSF4440 and the like from Toshiba Silicone Co., Ltd., but are not limited thereto.

[0245] The 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 range, less foreign matter is generated in the spray composition.

[0246] In addition, unless the properties are deteriorated, the curable composition according to an embodiment may further include a predetermined amount of other additives such as an antioxidant, a stabilizer, and the like.

[0247] Solvents

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

[0249] The solvent may, for example, include alcohols such as methanol, ethanol, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, and the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like; 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 and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and the like; lactic acid esters such as methyl lactate, ethyl lactate and the like; glycolic acid alkyl esters such as methyl glycolate, ethyl glycolate, butyl glycolate and the like; acetate alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate and the like; 3-hydroxypropionic acid alkyl esters such as 3-hydroxypropionic acid methyl ester, 3-hydroxypropionic acid ethyl ester and the like; 3-alkoxy propionic acid alkyl esters such as 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester and the like; 2-hydroxypropionic acid alkyl esters such as 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester, 2-hydroxypropionic acid propyl ester and the like; 2-alkoxy propionic acid alkyl esters such as 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-ethoxypropionic acid ethyl ester, 2 -ethoxypropionic acid methyl ester and the like; 2-hydroxy-2-methylpropionic acid alkyl esters, such as 2-hydroxy-2-methylpropionic acid methyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester and the like; 2-alkoxy-2-methylpropionic acid alkyl esters, such as 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester and the like; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methylbutyric acid methyl ester and the like;or ketoesters such as ethyl pyruvate and the like, and in addition, may be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celulose acetate, and the like, but are not limited thereto. ;

[0250] For example, the solvent may desirably be glycol ethers such as ethylene glycol monoethyl ether, ethylene diglycol methyl ethyl ether, and the like; ethylene glycol alkyl ether acetates such as ethyl celulose acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; alcohols such as ethanol and the like, or combinations thereof.

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

[0252] The content of the solvent may be 40% to 80% by weight, for example 45% to 80% by weight, based on the total amount of the curable composition. When the solvent is within the above range, the solvent-based curable composition has an appropriate viscosity and thus can have excellent coating properties when large-area coating is performed via spin coating and slit coating.

[0253] Another embodiment provides a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter.

[0254] One of the methods of manufacturing a cured layer may include coating a curable composition on a substrate using an inkjet spraying method to form a pattern (S1); and curing the pattern (S2).

[0255] (S1) Pattern formation

[0256] The curable composition can be ideally coated on the substrate by 0.5 micrometer to 20 micrometer using an inkjet spraying method. The inkjet spraying method can form a pattern by spraying a single color according to each nozzle and thus repeating the spraying multiple times according to the required number of colors, but the pattern can be formed by spraying the required number of colors simultaneously through each inkjet nozzle to reduce the process.

[0257] (S2) Solidification

[0258] The obtained pattern is cured to obtain pixels. In this article, the curing method may be a thermal curing process or a photocuring process. The thermal curing process may be performed at a temperature greater than or equal to 100°C, ideally in the range of 100°C to 300°C, and more ideally in the range of 160°C to 250°C. The photocuring process may include irradiating actinic rays, such as UV rays of 190 nanometers to 450 nanometers, for example 200 nanometers to 500 nanometers. Irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, and the like with low pressure, high pressure, or ultra-high pressure. X-rays, electron beams, and the like may also be used as needed.

[0259] Another method of manufacturing a cured layer may include manufacturing a cured layer using the aforementioned curable composition by the following lithography method.

[0260] (1) Coating and film formation

[0261] The curable composition is coated using a spin coating or slit coating method, a roll coating method, a screen printing method, a painting method, and the like to have a desired thickness, for example, a thickness ranging from about 2 microns to about 10 microns, on a substrate subjected to a predetermined pretreatment. Then, the coated substrate is heated at a temperature of about 70° C. to about 90° C. for about 1 minute to about 10 minutes to remove the solvent and to form a film.

[0262] (2) Exposure

[0263] After placing a mask having a predetermined shape, the resulting film is irradiated with actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, to form a desired pattern. Irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, and the like having low pressure, high pressure, or ultrahigh pressure. X-rays, electron beams, and the like may also be used as needed.

[0264] When a high pressure mercury lamp is used, the exposure process uses a light dose of, for example, 500 mJ / cm2 or less (using a 365 nm sensor). However, the light dose may vary depending on the type of each component of the curable composition, their combination ratio, and dry film thickness.

[0265] (3) Development

[0266] After the exposure process, the alkaline aqueous solution is used to develop the exposed film by dissolving and removing unnecessary portions other than the exposed portions, thereby forming an image pattern. In other words, when the alkaline developing solution is used for development, the non-exposed areas are dissolved and an image color filter pattern is formed.

[0267] (4) Post-processing

[0268] The developed image pattern may be heated again or irradiated by actinic rays and the like to be cured so as to achieve excellent quality in terms of heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, storage stability, and the like.

[0269] Mode for Carrying Out the Invention

[0270] Hereinafter, the present invention is described in more detail with reference to examples. However, these examples are not interpreted as limiting the scope of the present invention in any sense.

[0271] (Synthesis of polymerizable compound)

[0272] [Synthesis Example 1: Synthesis of a compound represented by Chemical Formula A]

[0273] (Reaction Scheme 1)

[0274]

[0275] 546 g of ethoxylated bisphenylfluorene diacrylate was dissolved in 500 ml of THF, and 2 g of triethylamine was added thereto. 45 g of 1,2-ethanedithiol was slowly added thereto, and then it was heated to 60° C. to obtain a compound represented by Chemical Formula A (Mw=1148).

[0276] [Synthesis Example 2: Synthesis of the compound represented by Chemical Formula B]

[0277] (Reaction Scheme 2)

[0278]

[0279] A compound represented by Chemical Formula (B) (Mw=887) was obtained in the same manner as in Synthesis Example 1, except that 304 g of tricyclodecane dimethanol diacrylate was used instead of ethoxylated bisphenylfluorene diacrylate.

[0280] [Synthesis Example 3: Synthesis of a compound represented by Chemical Formula C]

[0281] (Reaction Scheme 3)

[0282]

[0283] A compound represented by Chemical Formula (C) (Mw=1937) was obtained in the same manner as in Synthesis Example 1, except that 468 g of ethoxylated bisphenol A diacrylate was used instead of ethoxylated bisphenylfluorene diacrylate.

[0284] [Synthesis Example 4: Synthesis of a compound represented by Chemical Formula D]

[0285] (Reaction Scheme 4)

[0286]

[0287] A compound represented by Chemical Formula (D) (Mw=1102) was obtained in the same manner as in Synthesis Example 1, except that 226 g of 1,6-hexanediol diacrylate was used instead of ethoxylated bisphenylfluorene diacrylate.

[0288] (Preparation of curable composition)

[0289] Based on each of the following components, curable compositions according to Examples 1 to 6 and Comparative Examples 1 and 2 were prepared.

[0290] (A)Quantum dots

[0291] (A-1) Green quantum dots (InP / ZnSe / ZnS, Hansol Chemical)

[0292] (A-2) Red quantum dots (InP / ZnSe / ZnS, Hansong Chemical)

[0293] (B) Polymerizable compound

[0294] (B-1) Compound represented by Chemical Formula 8-2 (M200, Miwon Chemical)

[0295] [Chemical formula 8-2]

[0296]

[0297] (B-2)Neopenterythritol hexamethacrylate (DPHA, Nippon Kayaku Co., Ltd.)

[0298] (B-3) Polymerizable Compound of Synthesis Example 1

[0299] (B-4) Polymerizable Compound of Synthesis Example 2

[0300] (B-5) Polymerizable Compound of Synthesis Example 3

[0301] (B-6) Polymerizable Compound of Synthesis Example 4

[0302] (B-7) Acrylic binder resin (SM-CRB-400H, SMS Co., Ltd., Germany)

[0303] (B-8) Polysilsesquioxane (Arakawa, SQ506)

[0304] (C) Photopolymerization initiator

[0305] TPO-L(Polynetron)

[0306] (D) Light Diffuser

[0307] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0308] Examples 1 to 6 and Comparative Examples 1 and 2

[0309] Specifically, the quantum dots and the polymerizable compound are mixed and then stirred for 12 hours. Subsequently, a photopolymerization initiator is added thereto, and then a light diffusing agent is added thereto.

[0310] The specific compositions are shown in Table 1.

[0311] [Table 1]

[0312] (Unit: weight %)

[0313]

[0314] Evaluate

[0315] 2 ml of the curable composition according to Examples 1 to 6 and Comparative Examples 1 and 2 were taken respectively, and then spin-coated on a glass substrate at 1,500 rpm, exposed at 5 joules for 9 seconds by using a nitrogen UV exposure device to form a QD film, and then the QD film was measured with respect to the initial blue light conversion rate by using a light efficiency measurement instrument (QE-2100, Otsuka Electronics Co., Ltd.), and each substrate on which the QD film was formed was baked on a hot plate at 180° C. for 30 minutes under a nitrogen atmosphere and cooled to room temperature (23° C.) for 3 hours. Subsequently, the blue light conversion rate was re-measured using the light efficiency measurement instrument to calculate the thermal process retention rate (%) according to the following equation.

[0316] Thermal process retention rate (%) = [light conversion rate (after baking) / initial light conversion rate] × 100

[0317] In addition, the viscosity of the curable composition at 25° C. was measured by using a viscometer (RV-2 spins, 23 rpm, DV-II, Brookfield Engineering Laboratories, Inc.), and the results are shown in Table 2.

[0318] [Table 2]

[0319] Thermal process retention rate (%) Viscosity (cps) Example 1 95 314 Example 2 95 158 Example 3 97 160 Example 4 95 134 Example 5 97 400 Example 6 99 338 Comparative Example 1 87 370 Comparative Example 2 88 315

[0320] Referring to Table 2, the curable compositions according to Examples 1 to 6 minimized the deterioration of the thermal process retention rate after the heat resistance process, and thus exhibited an excellent thermal process retention rate (%) compared to the curable compositions according to Comparative Examples 1 and 2, and further, did not have a high viscosity, and thus smoothly ejected the ink even at room temperature.

[0321] Although the present invention has been described in conjunction with what are presently considered to be practical exemplary embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the above embodiments should be understood to be illustrative but not limiting of the present invention in any way.

Claims

1. A curable composition comprising: (A) Quantum dots; as well as (B) Polymerizable compound The polymerizable compound comprises a product of a thiol-ene reaction between a (meth)acrylate monomer and a thiol monomer.

2. The curable composition according to claim 1, wherein The thiol monomer is a dithiol monomer.

3. The curable composition according to claim 1, wherein The thiol monomer is represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, L 1 is an ether linkage group (*-O-*), a thioether linkage group (*-S-*), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

4. The curable composition according to claim 3, wherein Chemical formula 1 is represented by Chemical formula 1-1 or Chemical formula 1-2: [Chemical formula 1-1] in, In Chemical Formula 1-1, L 2 is a substituted or unsubstituted C1 to C20 alkylene group, [Chemical formula 1-2] Wherein, in Chemical Formula 1-2, L 3 and L 4 are each independently a substituted or unsubstituted C1 to C20 alkylene group, and n is an integer of 0-10.

5. The curable composition according to claim 1, wherein The (meth)acrylate monomer includes a monomer represented by Chemical Formula 2, a monomer represented by Chemical Formula 3, or a mixture thereof: [Chemical formula 2] [Chemical formula 3] in, In Chemical Formula 2 and Chemical Formula 3, R 1 To R 4 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and L 5 To L 10 Each is independently a single bond, an ether linkage group (*-O-*), a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, a divalent fluorene linkage group or a divalent bicyclic linkage group.

6. The curable composition according to claim 5, wherein The monomer represented by Chemical Formula 2 is represented by any one of Chemical Formula 2-1 to Chemical Formula 2-4: [Chemical formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] in, In Chemical Formula 2-1 to Chemical Formula 2-4, R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, L 11 is a substituted or unsubstituted C1 to C20 alkylene group, and L 12 and L 13 Each is independently an ether linkage group (*-O-*) or a substituted or unsubstituted C1 to C20 alkylene group.

7. The curable composition according to claim 5, wherein In chemical formula 3, R 3 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 4 is a substituted or unsubstituted C6 to C20 arylene group, and L 9 and L 10 Each is independently an ether linkage group (*-O-*) or a substituted or unsubstituted C1 to C20 alkylene group.

8. The curable composition according to claim 1, wherein The polymerizable compound includes at least one selected from the monomers represented by Chemical Formula 4 to the monomers represented by Chemical Formula 7: [Chemical formula 4] [Chemical formula 5] [Chemical formula 6] [Chemical formula 7] in, In Chemical Formulae 4 to 7, Ac is a (meth)acrylate group, L a To L d are each independently a substituted or unsubstituted C1 to C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, m is an integer from 0 to 10, p is an integer from 1 to 100, and q is an integer from 0 to 5.

9. The curable composition according to claim 1, wherein The polymerizable compound further includes a monomer represented by Chemical Formula 8 in addition to the product of the thiol-ene reaction between the (meth)acrylate-based monomer and the thiol-based monomer: [Chemical formula 8] in, In Chemical Formula 8, R 5 and R 6 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L 14 and L 16 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and L 15 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether linkage group (*-O-*).

10. The curable composition according to claim 9, wherein The content of the monomer represented by Chemical Formula 8 is greater than the product of the thiol-ene reaction between the (meth)acrylate-based monomer and the thiol-based monomer.

11. The curable composition according to claim 1, wherein The curable composition has a viscosity of 500 centipoise to 1100 centipoise.

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

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

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

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

16. The curable composition according to claim 1, wherein The curable composition further comprises a solvent.

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

18. The curable composition according to claim 1, wherein The curable composition further comprises malonic acid; 3-amino-1,2-propylene glycol; a silane coupling agent; a leveling agent; a fluorine surfactant; or a combination thereof.

19. A cured layer produced using the curable composition according to any one of claims 1 to 18.

20. A color filter comprising the cured layer according to claim 19.

21. A display device comprising the color filter according to claim 20.

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