Curable composition, composition cured layer, color filter, and display device

Abstract

A hardenable composition, a hardened layer manufactured using the hardenable composition, a color filter including the hardened layer, and a display device including the color filter are disclosed. The hardenable composition includes: (A) a quantum dot; and (B) a hardenable monomer having a viscosity of less than 6.2 centipoise and a vapor pressure of 1 x 10 ‑6 tor to 3 x 10 ‑3 tor.

Description

Technical Field

[0001] This disclosure relates to a curable composition, a curable layer manufactured using the composition, a color filter including the curable layer, and a display device including the color filter. Background Technology

[0002] In the case of general quantum dots, the solvent in which the quantum dots are dispersed is limited due to their hydrophobic surface properties, and therefore it is difficult to introduce them into polar systems (such as adhesives or curable monomers).

[0003] For example, even in cases where quantum dot ink compositions are actively studied, the polarity remains relatively low in the initial steps, and it can be dispersed in solvents used in curable compositions with high hydrophobicity. Therefore, since it is difficult to include 20% by weight or more of quantum dots in the total composition, it is impossible to increase the light efficiency of the ink beyond a certain level. Even if additional quantum dots are added and dispersed to increase light efficiency, the viscosity will still exceed the range suitable for inkjet printing, and therefore the processability may be unsatisfactory.

[0004] To achieve a viscosity range suitable for inkjet printing, a method of reducing ink solids content by dissolving 50% by weight or more of a solvent based on the total composition provides somewhat satisfactory results in terms of viscosity. However, while the viscosity may be considered satisfactory, nozzle drying can worsen due to solvent evaporation, nozzle clogging during inkjet printing, and the reduction in monolayer thickness over time after inkjet printing, making it difficult to control thickness deviations after curing. Therefore, it is difficult to apply this method to practical processes.

[0005] Therefore, solvent-free quantum dot inks are the most desirable form for practical applications. Current techniques for applying quantum dots themselves to solvent-based compositions are now subject to certain limitations.

[0006] In the case of solvent-free curable compositions (quantum dot ink compositions), the presence of excessive polymerizable compounds can lead to clogging and jetting failures. These clogging and failures are caused by nozzle drying due to volatility and by a reduction in single-film thickness due to the evaporation of the ink composition jetted into the patterned separator pixels. Therefore, it is desirable to reduce the viscosity of solvent-free curable compositions as much as possible. Efforts have been made to reduce the viscosity of solvent-free curable compositions by modifying the structure of the polymerizable compounds (e.g., increasing the molecular weight of the polymerizable monomers, introducing chemical structures including hydroxyl groups, etc.). However, since solvent-free curable compositions with the desired low viscosity have not yet been developed, one of the problems to date has been the lack of alternatives to providing curable compositions with insufficient inkjet properties. Summary of the Invention

[0007] Technical issues

[0008] The embodiment provides a curable composition with low viscosity and low volatility, resulting in a high film residue rate after inkjet printing on pixels.

[0009] Another embodiment provides a hardened layer manufactured using a hardenable composition.

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

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

[0012] Technical solution

[0013] An example provides a curable composition comprising: (A) quantum dots; and (B) a curable monomer having a viscosity of less than 6.2 centipoise (cps) and a vapor pressure of 1 × 10⁻⁶. -6 Torr up to 3×10 -3 Entrust.

[0014] The viscosity of the hardenable monomer can be greater than or equal to 3 centipoise and less than 6.2 centipoise.

[0015] The hardenable monomer may have an asymmetric structure.

[0016] The hardenable monomer can be represented by chemical formula 1.

[0017] [Chemical Formula 1]

[0018]

[0019] In chemical formula 1,

[0020] R a It is a substituted or unsubstituted C1 to C20 alkyl group, and

[0021] L a It is an unsubstituted C1 to C8 alkylene group, a substituted or unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by chemical formula 2.

[0022] [Chemical Formula 2]

[0023]

[0024] In chemical formula 2,

[0025] L b and L c Each is independently a substituted or unsubstituted C1 to C8 alkylene group, and

[0026] n is an integer from 1 to 3.

[0027] In chemical formula 1, L a It may be an unsubstituted C1 to C8 alkylene group, an unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by chemical formula 2.

[0028] In chemical formula 2, L b and L c Each can be an unsubstituted C1 to C6 alkylene group.

[0029] The hardenable monomer may be represented by any one of chemical formulas 1-1 to 1-9.

[0030] [Chemical Formula 1-1]

[0031]

[0032] [Chemical Formula 1-2]

[0033]

[0034] [Chemical Formulas 1-3]

[0035]

[0036] [Chemical Formulas 1-4]

[0037]

[0038] [Chemical Formulas 1-5]

[0039]

[0040] [Chemical Formulas 1-6]

[0041]

[0042] [Chemical Formulas 1-7]

[0043]

[0044] [Chemical Formulas 1-8]

[0045]

[0046] [Chemical Formulas 1-9]

[0047]

[0048] The quantum dots may be quantum dots whose surfaces have been modified with ligands having polar groups.

[0049] The ligand having the polar group can be represented by any of chemical formulas 3 to 16.

[0050] [Chemical Formula 3]

[0051]

[0052] [Chemical Formula 4]

[0053]

[0054] [Chemical Formula 5]

[0055]

[0056] [Chemical Formula 6]

[0057]

[0058] [Chemical Formula 7]

[0059]

[0060] [Chemical Formula 8]

[0061]

[0062] In chemical formulas 3 to 8

[0063] R 1 To R 7 Each is independently a substituted or unsubstituted C1 to C10 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0064] L 1 To L 16 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0065] n1 to n7 are each an independent integer from 0 to 10.

[0066] [Chemical Formula 9]

[0067]

[0068] [Chemical Formula 10]

[0069]

[0070] [Chemical Formula 11]

[0071]

[0072] Among them, in chemical formulas 9 to 11,

[0073] R 8 and R 9 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0074] L 17 To L 23 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0075] n8 to n10 are each an independent integer from 0 to 10.

[0076] [Chemical Formula 12]

[0077]

[0078] [Chemical Formula 13]

[0079]

[0080] [Chemical Formula 14]

[0081]

[0082] [Chemical Formula 15]

[0083]

[0084] Among them, in chemical formulas 12 to 15,

[0085] R 10 To R 15 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0086] L 24 To L 29 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0087] n11 to n16 are each an independent integer from 0 to 10.

[0088] [Chemical Formula 16]

[0089]

[0090] In chemical formula 16,

[0091] R 16 To R 18 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0092] L 30 To L 32 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0093] n17 to n19 are each an independent integer from 0 to 10.

[0094] The curable composition may be a solvent-free curable composition.

[0095] Based on the total amount of the solvent-free curable composition, the solvent-free curable composition may contain: 5% to 60% by weight of the quantum dots; and 40% to 95% by weight of the curable monomers.

[0096] The curable composition may further comprise a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0097] The light diffusing agent may contain barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0098] The curable composition may also contain a solvent.

[0099] Based on the total weight of the curable composition, the curable composition containing the solvent may contain 1% to 40% by weight of the quantum dots; 1% to 20% by weight of the curable monomer; and 40% to 80% by weight of the solvent.

[0100] The curable composition may further comprise malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorinated surfactant; or a combination thereof.

[0101] Another embodiment provides a hardening layer manufactured using the hardenable composition.

[0102] Another embodiment provides a color filter including the hardened layer.

[0103] Another embodiment provides a display device including the color filter.

[0104] Other embodiments of the present invention are included in the following detailed description.

[0105] Beneficial effects

[0106] To effectively reduce the viscosity of a curable composition containing monomers, a curable composition with low viscosity and low volatility can be provided by controlling the viscosity and vapor pressure of the curable monomers within a specific range, and specifically by using curable monomers with asymmetric structures. Detailed Implementation

[0107] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto, and is defined by the scope of the claims.

[0108] As used herein, unless otherwise defined, “alkyl” refers to C1 to C20 alkyl, “alkenyl” refers to C2 to C20 alkenyl, “cycloalkenyl” refers to C3 to C20 cycloalkenyl, “heterocyclic alkenyl” refers to C3 to C20 heterocyclic alkenyl, “aryl” refers to C6 to C20 aryl, “arylalkyl” refers to C6 to C20 arylalkyl, “alkylene” refers to C1 to C20 alkylene, “arylene” refers to C6 to C20 arylene, “alkylarylene” refers to C6 to C20 alkylarylene, “heteroarylene” refers to C3 to C20 heteroarylene, and “alkoxide” refers to C1 to C20 alkoxide.

[0109] As used herein, unless otherwise specifically defined, “substituted” means that at least one hydrogen atom is replaced by a substituent selected from the following: halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, imino, azido, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol, ester, ether, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocyclic alkyl, C2 to C20 heterocyclic alkenyl, C2 to C20 heterocyclic alkynyl, C3 to C20 heterocyclic aryl, or combinations thereof.

[0110] As used herein, unless otherwise specifically defined, “heterogeneous” means a chemical formula containing at least one heteroatom of N, O, S and P.

[0111] As used herein, unless otherwise specifically defined, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0112] As used herein, unless otherwise specifically defined, the term "combination" refers to a mixture or copolymer.

[0113] In this specification, unless otherwise defined, hydrogen bonds are located at the positions indicated in the chemical formula when chemical bonds are not drawn where they should be.

[0114] Furthermore, in this specification, unless otherwise defined, "*" refers to a point connected to the same or different atoms or chemical formulas.

[0115] This invention transforms the symmetrical structure of a conventional diacrylate-based curable monomer into an asymmetrical structure by replacing one functional group with a methacrylate group. This asymmetrical structure allows the curable monomer to have low viscosity and low vapor pressure, effectively reducing the viscosity of the curable composition containing the monomer. Consequently, the curable composition containing the monomer has low viscosity compared to other compositions and low volatility compared to other compositions with similar viscosity. As a result, after inkjet printing in pixels, it does not exhibit significant film residue degradation over time, thus achieving excellent color filters and display devices.

[0116] Generally speaking, diacrylate curable monomers have the advantage of reducing viscosity by adjusting molecular weight, but the disadvantage is that even if their chemical structure is modified, they cannot quickly reduce vapor pressure.

[0117] Furthermore, while the curing properties of dimethacrylate curable monomers are slightly inferior to those of diacrylate-based curable monomers, their vapor pressures are lower. Therefore, attempts have been made to prepare curable compositions containing sub-dots by mixing diacrylate-based and dimethacrylate curable monomers. However, since the two curable monomers do not interact or exhibit an azeotropic effect after inkjet printing in the pixel, each curable monomer volatilizes separately according to its own vapor pressure.

[0118] Therefore, the inventors have repeatedly demonstrated through research that the viscosity and vapor pressure of the curable monomer can be controlled to a specific range by configuring acrylate groups and methacrylate groups to coexist asymmetrically in a single chemical monomer structure (a host). Furthermore, it has been demonstrated that curable compositions containing this curable monomer have lower viscosity and volatility than conventional compositions, thus completing the present invention.

[0119] Each component constituting the curable composition according to the embodiments is described in detail below.

[0120] Hardenable monomers

[0121] To improve inkjet properties and thus ensure a smooth inkjet process, curable monomers with low vapor pressure and low viscosity are required. However, curable monomers generally have a structure with carbon-carbon double bonds at at least one of their two ends, which leads to a trade-off between vapor pressure and viscosity, and thus imposes many limitations.

[0122] Therefore, traditional research and development focuses on finding the optimal combination of curable monomers with different viscosities and vapor pressures. However, the inventors of this invention have taken a different approach, using a single curable monomer but modifying its structure to have an asymmetric structure. This results in a single curable monomer with low viscosity and low vapor pressure, specifically a viscosity of less than about 6.2 centipoise and a vapor pressure of about 1 × 10⁻⁶. -6 To about 3×10 -3 The curable monomers of the material allow curable compositions to have low viscosity and low volatility compared to other compositions with similar viscosity, and do not exhibit significantly degraded film residue after inkjet printing in pixels, thus providing a cured film with excellent patternability, etc.

[0123] Specifically, the embodiment provides a curable composition comprising: (A) quantum dots; and (B) a curable monomer having a viscosity of less than 6.2 centipoise and a vapor pressure of 1 × 10⁻⁶. -6 Up to 3×10 -3 Entrust.

[0124] For example, a curable monomer may have a viscosity greater than or equal to 3 centipoise and less than 6.2 centipoise.

[0125] Curable monomers can have asymmetric structures, and therefore individual curable monomers can have low viscosity and low vapor pressure. For example, diacrylate-based or dimethacrylate-based curable monomers with symmetric rather than asymmetric structures have high vapor pressures at low viscosity, or high viscosity at low vapor pressure, and therefore cannot be used as curable monomers in compositions.

[0126] Specifically, a hardenable monomer, and more specifically a hardenable monomer with an asymmetric structure, can be represented by chemical formula 1.

[0127] [Chemical Formula 1]

[0128]

[0129] In chemical formula 1,

[0130] R a It is a substituted or unsubstituted C1 to C20 alkyl group, and

[0131] L a It is an unsubstituted C1 to C8 alkylene group, a substituted or unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by chemical formula 2.

[0132] [Chemical Formula 2]

[0133]

[0134] In chemical formula 2,

[0135] L b and L c Each is independently a substituted or unsubstituted C1 to C8 alkylene group, and

[0136] n is an integer from 1 to 3.

[0137] Because curable monomers with asymmetric structures have an unsubstituted or short-length intermediate linking group between an acrylate group at one end and a methacrylate group at the other end, the viscosity and vapor pressure of the curable monomer can be reduced simultaneously. That is, to obtain both low viscosity and low vapor pressure (specifically, a viscosity less than 6.2 centipoise and a vapor pressure of 1 × 10⁻⁶), -4 Up to 3×10 -3 The curable monomers with a vapor pressure of 1000 ppm, structures with intermediate linking groups (such as the presence and length of substituents) and asymmetric structures should also be considered important.

[0138] For example, in chemical formula 1, L a It may be an unsubstituted C1 to C8 alkylene group, an unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by chemical formula 2.

[0139] For example, in chemical formula 2, L b and L c Each can independently represent an unsubstituted C1 to C6 alkylene group.

[0140] For example, a curable monomer can be represented by any of the chemical formulas 1-1 to 1-9, but is not necessarily limited to these.

[0141] [Chemical Formula 1-1]

[0142]

[0143] [Chemical Formula 1-2]

[0144]

[0145] [Chemical Formulas 1-3]

[0146]

[0147] [Chemical Formulas 1-4]

[0148]

[0149] [Chemical Formulas 1-5]

[0150]

[0151] [Chemical Formulas 1-6]

[0152]

[0153] [Chemical Formulas 1-7]

[0154]

[0155] [Chemical Formulas 1-8]

[0156]

[0157] [Chemical Formulas 1-9]

[0158]

[0159] When the curable composition according to the embodiments is a solvent-free curable composition, the content of the curable monomer, based on the total amount of the solvent-free curable composition, can be from 40% to 95% by weight, for example, from 40% to 85% by weight, for example, from 40% to 80% by weight. When the amount of curable monomer is within the above range, a solvent-free curable composition with a low viscosity (e.g., viscosity of 10 centipoise to 30 centipoise) capable of inkjet printing can be prepared, and the solvent-free curable composition has lower volatility than other curable compositions with the same viscosity and quantum dots content. Furthermore, the quantum dots in the prepared solvent-free curable composition can have excellent dispersibility, and the optical properties can also be improved.

[0160] Furthermore, when the curable composition includes a solvent, the content of the curable monomer, based on the total amount of the curable composition, can be from 1% to 15% by weight, for example, from 5% to 15% by weight. When the content of the curable monomer is within the above range, the optical properties of the quantum dots can be improved.

[0161] For example, curable monomers can have a molecular weight of 100 g / mol to 800 g / mol. When the molecular weight of the curable monomer is within the above range, it may be advantageous for inkjet printing because it does not increase the viscosity of the composition without impairing the optical properties of the quantum dots.

[0162] Furthermore, the curable composition according to the embodiments may also include monomers commonly used in conventional thermosetting or photocurable compositions (e.g., bis[1-ethyl(3-oxetane)] methyl ether and similar oxetane compounds, etc.) and curable monomers.

[0163] quantum dots

[0164] The quantum dots in the curable composition according to the embodiments can be surface-modified quantum dots with ligands having polar groups (e.g., ligands with high affinity for polymerizable compounds). In the case of surface-modified quantum dots as described above, it is very easy to prepare high-concentration or highly concentrated quantum dot dispersions (improving the dispersibility of quantum dots in polymerizable monomers), which can be very effective in improving light efficiency, and in particular, solvent-free curable compositions can be advantageously implemented.

[0165] For example, ligands with polar groups can have structures that have a high affinity for the chemical structure of polymerizable compounds.

[0166] For example, a ligand with a polar group can be represented by any of the chemical formulas 3 to 16, but is not necessarily limited to these.

[0167] [Chemical Formula 3]

[0168]

[0169] [Chemical Formula 4]

[0170]

[0171] [Chemical Formula 5]

[0172]

[0173] [Chemical Formula 6]

[0174]

[0175] [Chemical Formula 7]

[0176]

[0177] [Chemical Formula 8]

[0178]

[0179] In chemical formulas 3 to 8

[0180] R 1 To R 7 Each is independently a substituted or unsubstituted C1 to C10 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0181] L 1 To L 16 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0182] n1 to n7 are each an independent integer from 0 to 10.

[0183] [Chemical Formula 9]

[0184]

[0185] [Chemical Formula 10]

[0186]

[0187] [Chemical Formula 11]

[0188]

[0189] In chemical formulas 9 to 11,

[0190] R 8 and R 9 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0191] L 17 To L 23 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0192] n8 to n10 are each an independent integer from 0 to 10.

[0193] [Chemical Formula 12]

[0194]

[0195] [Chemical Formula 13]

[0196]

[0197] [Chemical Formula 14]

[0198]

[0199] [Chemical Formula 15]

[0200]

[0201] In chemical formulas 12 to 15,

[0202] R 10 To R 15 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0203] L 24 To L 29 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0204] n11 to n16 are each an independent integer from 0 to 10.

[0205] [Chemical Formula 16]

[0206]

[0207] In chemical formula 16,

[0208] R 16 To R 18 Each is independently a substituted or unsubstituted C1 to C10 alkyl group.

[0209] L 30 To L 32 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and

[0210] n17 to n19 are each an independent integer from 0 to 10.

[0211] For example, a compound represented by chemical formula 3 to chemical formula 16 can be any of the compounds represented by chemical formula A to chemical formula Q, but is not necessarily limited to these.

[0212] [Chemical Formula A]

[0213]

[0214] [Chemical Formula B]

[0215]

[0216] [Chemical formula C]

[0217]

[0218] [Chemical formula D]

[0219]

[0220] (In chemical formula D, m1 is an integer from 0 to 10.)

[0221] [Chemical Formula E]

[0222]

[0223] [Chemical formula F]

[0224]

[0225] [Chemical formula G]

[0226]

[0227] [Chemical formula H]

[0228]

[0229] [Chemical Formula I]

[0230]

[0231] [Chemical Formula J]

[0232]

[0233] [Chemical formula K]

[0234]

[0235] [Chemical formula L]

[0236]

[0237] [Chemical formula M]

[0238]

[0239] [Chemical formula N]

[0240]

[0241] [Chemical formula O]

[0242]

[0243] [Chemical formula P]

[0244]

[0245] [Chemical Formula Q]

[0246]

[0247] When ligands are used, the surface modification of quantum dots is easier, and when ligand-modified quantum dots are added to the above polymerizable compounds and stirred, an extremely transparent dispersion can be obtained, which indicates that the surface modification of quantum dots is excellent.

[0248] For example, quantum dots can have the largest fluorescence emission wavelength in the range of 500 nanometers to 680 nanometers.

[0249] For example, when the curable composition according to the embodiments is a solvent-free curable composition, the content of quantum dots can be from 5% to 60% by weight, for example, from 10% to 60% by weight, for example, from 20% to 60% by weight, for example, from 30% to 50% by weight. When the content of quantum dots is within the above range, high light retention rate and light efficiency can be achieved even after curing.

[0250] For example, when the curable composition according to the embodiment is a curable composition containing a solvent, the content of quantum dots may be from 1% to 40% by weight, for example, from 3% to 30% by weight, based on the total amount of the curable composition. When the content of quantum dots is within the above range, the light conversion efficiency is improved, and the patterning characteristics and developing characteristics are not impaired, thus improving processability is obtained.

[0251] To date, curable compositions (inks) including quantum dots have been developed specifically for thiol-based adhesives or monomers that are well compatible with quantum dots, and they are being commercialized.

[0252] For example, quantum dots absorb light in the wavelength range of 360 nm to 780 nm, such as 400 nm to 780 nm, and emit fluorescence in the wavelength range of 500 nm to 700 nm, such as 500 nm to 580 nm, or in the wavelength range of 600 nm to 680 nm. That is, quantum dots can exhibit the maximum fluorescence emission wavelength (fluorescence λ) in the 500 nm to 680 nm range. em ).

[0253] Quantum dots can independently have a full width at half maximum (FWHM) of 20 to 100 nanometers, for example, 20 to 50 nanometers. When quantum dots have a FWHM within this range, color reproducibility is increased due to high color purity when used as color materials in color filters.

[0254] Quantum dots can be organic materials, inorganic materials, or mixtures of organic and inorganic materials independently.

[0255] Quantum dots can be independently composed of a core and a shell surrounding the core, and the core and shell can independently have structures such as cores of groups II-IV, III-V, etc., cores / shells, cores / first shells / second shells, alloys, alloys / shells, etc., but are not limited to these.

[0256] For example, the core may contain at least one material selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not limited thereto. The shell surrounding the core may contain at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not limited thereto.

[0257] In this embodiment, since global environmental concerns have increased significantly recently and restrictions on toxic materials have been strengthened, cadmium-free luminescent materials (InP / ZnS, InP / ZnSe / ZnS, etc.) with slightly lower quantum efficiency (quantum yield) but no harm to the environment are used to replace luminescent materials with cadmium-based cores, but this is not necessarily the only option.

[0258] In the case of quantum dots with a core / shell structure, the overall size (average particle size), including the shell, can be 1 nanometer to 15 nanometers, for example, 5 nanometers to 15 nanometers.

[0259] For example, quantum dots can independently include red quantum dots, green quantum dots, or combinations thereof. Red quantum dots can independently have an average particle size of 10 nanometers to 15 nanometers. Green quantum dots can independently have an average particle size of 5 nanometers to 8 nanometers.

[0260] On the other hand, to achieve dispersion stability of quantum dots, the curable composition according to the embodiments may further include a dispersant. The dispersant contributes to the uniform dispersion of light-converting materials, such as quantum dots, in the curable composition and may include nonionic, anionic, or cationic dispersants. Specifically, the dispersant may be a polyalkylene glycol or its ester, polyoxyolefin, polyol ester epoxide addition product, alcohol epoxide addition product, sulfonate, sulfonate, carboxylic acid ester, carboxylate, alkylamide epoxide addition product, alkylamine, etc., and may be used alone or in mixtures of two or more. The amount of dispersant may be from 0.1% to 100% by weight, for example, from 10% to 20% by weight, based on the solids content of the light-converting material (e.g., quantum dots).

[0261] Light diffusing agent

[0262] The curable composition according to the embodiments may further comprise a light diffusing agent.

[0263] For example, light diffusing agents may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0264] The light diffusing agent can reflect light that has not been absorbed by the quantum dots and allow the quantum dots to reabsorb the reflected light. That is, the light diffusing agent can increase the amount of light absorbed by the quantum dots and increase the light conversion efficiency of the curable composition.

[0265] Light diffusing agents can have an average particle size (D) of 150 nm to 250 nm, specifically 180 nm to 230 nm. 50 When the average particle size of the light diffusing agent is within the specified range, it can have a better light diffusion effect and increase the light conversion efficiency.

[0266] The content of the light diffusing agent can be from 1% to 20% by weight, for example, from 2% to 15% by weight, or for example, from 3% to 10% by weight, based on the total amount of the curable composition. When the content of the light diffusing agent is less than 1% by weight, it is difficult to expect to improve the light conversion efficiency by using the light diffusing agent, and when its content is greater than 20% by weight, quantum dot deposition problems may occur.

[0267] Polymerization initiator

[0268] The curable composition according to the embodiments may further comprise a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0269] Photopolymerization initiators are commonly used initiators in photosensitive resin compositions, such as acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and aminoketone-based compounds, but are not limited to these.

[0270] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-but-1-one, etc.

[0271] Examples of benzophenone compounds include benzoyl benzoate, benzoyl benzoate, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, benzoyl acrylate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0272] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0273] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0274] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)- s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0275] Examples of oxime compounds include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethyl ketone, O-ethoxycarbonyl-α-oxyamino-1-phenylprop-1-one, etc. Specific examples of O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-but-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1-one-oxime-O-acetate, and 1-(4-phenylthiophenyl)-but-1-one-oxime-O-acetate.

[0276] Examples of amino ketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc.

[0277] In addition to the compounds mentioned above, photopolymerization initiators may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, etc.

[0278] Photopolymerization initiators can be used with photosensitizers that can induce a chemical reaction by absorbing light and become excited and then transfer their energy.

[0279] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0280] Examples of thermal polymerization initiators may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl percarbonate, 2,2-azobis(isobutyronitrile), tributyl perbenzoate, etc., such as 2,2'-azobis-2-methylpropionitrile, but not limited to these, and any of those currently available in this technology may be used.

[0281] The content of the polymerization initiator can be from 0.1% to 5% by weight, for example, from 1% to 4% by weight, based on the total amount of the curable composition. When the content of the polymerization initiator is within the range described above, excellent reliability can be obtained due to sufficient curing during exposure or heat curing, and transmittance degradation due to non-reactive initiators is prevented, thereby preventing the deterioration of the optical properties of the quantum dots.

[0282] Adhesive resin

[0283] The curable composition according to the embodiments may further comprise an adhesive resin.

[0284] Adhesive resins may include acrylic resins, calo resins, epoxy resins, or combinations thereof.

[0285] Acrylic resins can be copolymers of a first olefinically unsaturated monomer and a second olefinically unsaturated monomer that can be copolymerized therewith, and can be resins comprising at least one acrylic repeating unit.

[0286] Specific examples of acrylic adhesive resins may include polymethyl methacrylate, (meth)acrylic acid / phenyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene copolymer, (meth)acrylic acid / phenyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / phenyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but are not limited to these, and these may be used alone or in mixtures of two or more.

[0287] The weight-average molecular weight of acrylic adhesive resins can range from 5,000 g / mol to 15,000 g / mol. When the weight-average molecular weight of the acrylic adhesive resin is within this range, the adhesion properties to the substrate, physical and chemical properties are improved, and the viscosity is suitable.

[0288] Acrylic resins can have an acid value ranging from 80 mg KOH / g to 130 mg KOH / g. When the acid value of the acrylic resin is within this range, the pixel pattern can have excellent resolution.

[0289] Caldo resins can be used in conventional curable resin (or photosensitive resin) compositions, and can be used, for example as disclosed in Korean Patent Application Publication No. 10-2018-0067243, but are not limited thereto.

[0290] Calotype resins can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds, such as 9,9-bis(4-epoxyethylene methoxyphenyl)fluorene; acid anhydride compounds, such as phenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride; diol compounds, such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds, such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds, such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds, such as triphenylphosphine; and amine or ammonium salt compounds, such as tetramethylammonium chloride, tetraethylammonium bromide, benzyl diethylamine, triethylamine, tributylamine, or benzyl triethylammonium chloride.

[0291] The weight-average molecular weight of the caloric adhesive resin can be from 500 g / mol to 50,000 g / mol, for example from 1,000 g / mol to 30,000 g / mol. When the weight-average molecular weight of the caloric adhesive resin is within the range described, satisfactory patterns can be formed without residues during the production of the cured layer and without loss of film thickness during the development of the solvent-based curable composition.

[0292] When the adhesive resin is a caloric resin, the developability of curable compositions containing the adhesive resin, especially photosensitive resin compositions, is improved, and the sensitivity during photocuring is good, thereby improving the fine patterning properties.

[0293] Epoxy resins can be monomers or oligomers that can be polymerized by heating, and can contain compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0294] Epoxy resins may include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cyclic aliphatic epoxy resin and aliphatic polyglycidyl ether.

[0295] Its currently available products may include: bisphenol epoxy resins, such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 from YukaShell Epoxy Co., Ltd.; cresol varnish-type epoxy resins, such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 from Nippon Kayaku Co., Ltd., and EPIKOTE 180S75 from YukaShell Epoxy Co., Ltd.; and bisphenol A epoxy resins, such as EPIKOTE from YukaShell Epoxy Co., Ltd. 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828; bisphenol F type epoxy resins, such as EPIKOTE 807 and 834 from Yuxiang Shell Epoxy Co., Ltd.; phenolic varnish type epoxy resins, such as EPIKOTE 152, 154 and 157H65 from Yuxiang Shell Epoxy Co., Ltd. and EPPN 201 and 202 from Nippon Kayaku Co., Ltd.; other cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 from Ciba-Geigy AG, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from UCC, and from Showa Denko Co., Ltd. Shodyne 509 from DenkoK.K., ARALDITE CY-182, CY-192 and CY-184 from Ciba-Geigy AG, Epichron 200 and 400 from Dainippon Ink and Chemicals Inc., EPIKOTE 871, 872 and EP1032H60 from Yuka Shell Epoxy Co., Ltd., ED-5661 and ED-5662 from Celanese Coatings Co., Ltd.; aliphatic polyglycidyl ethers, such as EPIKOTE 190P and 191P from Yuka Shell Epoxy Co., Ltd., Epolite 100MF from Kyoesha Yushi Co., Ltd., and Nippon Yushi Co., Ltd. Epiol TMP, etc. of Co., Ltd.

[0296] For example, when the curable composition according to the embodiments is a solvent-free curable composition, the content of the adhesive resin may be from 0.5% to 10% by weight, for example, from 1% to 5% by weight, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

[0297] For example, when the curable composition according to the embodiments is a curable composition containing a solvent, the content of the adhesive resin may be from 1% to 30% by weight, for example, from 3% to 20% by weight, based on the total amount of the curable composition. In this case, pattern properties, heat resistance, and chemical resistance can be improved.

[0298] Other additives

[0299] To achieve improved stability and dispersion of quantum dots, the hardenable composition according to the embodiments may further include a polymerization inhibitor.

[0300] Polymerization inhibitors may include, but are not limited to, hydroquinone compounds, catechol compounds, or combinations thereof. When the curable composition according to the embodiments further comprises hydroquinone compounds, catechol compounds, or combinations thereof, room-temperature crosslinking during exposure after printing (coating) the curable composition can be prevented.

[0301] For example, hydroquinone compounds, catechol compounds, or combinations thereof may include hydroquinone, methylhydroquinone, methoxyhydroquinone, tributylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, tributylcatechol, 4-methoxycatechol, gallnutol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamino-O,O')aluminum, or combinations thereof, but are not necessarily limited to these.

[0302] Hydroquinone compounds, catechol compounds, or combinations thereof can be used in the form of dispersions, and the content of the polymerization inhibitor in the dispersion form can be from 0.001% to 3% by weight, for example, from 0.1% to 2% by weight, based on the total amount of the curable composition. When the content of the polymerization inhibitor is within the above range, the aging problem at room temperature can be solved, while preventing the decrease in sensitivity and surface peeling.

[0303] In addition, the curable composition according to the embodiments may further comprise malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorinated surfactant; or combinations thereof to improve heat resistance and reliability.

[0304] For example, the curable composition according to the embodiments may further include a silane-based coupling agent having reactive substituents such as vinyl, carboxyl, methacryloyloxy, isocyanate, epoxy, etc., to improve the tight contact properties with the substrate.

[0305] Examples of silane-based coupling agents include trimethoxysilylbenzoic acid, γ-methacrylate oxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc., and these coupling agents can be used alone or in mixtures of two or more.

[0306] The content of the silane coupling agent can be from 0.01 parts by weight to 10 parts by weight per 100 parts by weight of the curable composition. When the content of the silane coupling agent is within the said range, the close contact properties, storage capacity, etc., are improved.

[0307] In addition, the curable composition may, as needed, contain surfactants (e.g., fluorinated surfactants) to improve coating properties and inhibit spot formation, i.e., improve leveling performance.

[0308] Fluorinated surfactants can have a low weight-average molecular weight of 4,000 g / mol to 10,000 g / mol, and more specifically 6,000 g / mol to 10,000 g / mol. Furthermore, fluorinated surfactants can have a surface tension of 18 mN / m to 23 mN / m (measured in a 0.1% solution of polyethylene glycol monomethyl ether acetate (PGMEA)). When fluorinated surfactants have a weight-average molecular weight and surface tension within the aforementioned range, leveling performance can be further improved, and excellent properties can be provided when applying slit coating as a high-speed coating process, as fewer film defects are generated by preventing spot formation and suppressing vapor generation during high-speed coating.

[0309] Examples of fluorinated surfactants include and (BM Chemie Inc.); MEGAFACE and (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD Florard Florard and Florard (Sumitomo 3M Co., Ltd.) ; SURFLON Shafulong Shafulong Shafulong and Shafulong (ASAHI Glass Co., Ltd.); and and Examples include (Toray Silicone Co., Ltd.); and F-482, F-484, F-478, and F-554 from DICCo., Ltd.

[0310] In addition to fluorinated surfactants, the curable compositions according to the embodiments may contain silicone surfactants. Specific examples of silicone surfactants include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 from Toshiba Silicone Co., Ltd.

[0311] The surfactant content can be from 0.01 parts by weight to 5 parts by weight, for example, from 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant content is within the said range, less foreign matter is generated in the sprayed composition.

[0312] In addition, unless the properties deteriorate, the curable composition according to the embodiments may further contain predetermined amounts of other additives, such as antioxidants, stabilizers, etc.

[0313] solvent

[0314] Additionally, the curable composition according to the embodiments may further contain a solvent.

[0315] Solvents may include, for example, alcohols, such as methanol and ethanol; glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; cellosol acetates, such as methyl cellosol acetate, ethyl cellosol acetate, and diethyl cellosol acetate; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, and methyl-n-butyl ketone. methyl-n-pentyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters, such as methyl lactate, ethyl lactate, etc.; alkyl glycolic acid esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkyl acetate alkoxy esters, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; alkyl 3-hydroxypropionic acid esters, such as methyl 3-hydroxypropionic acid, ethyl 3-hydroxypropionic acid, etc.; alkyl 3-alkoxypropionic acid esters, such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid... Ethyl esters, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, propionic acid... 2-Hydroxy-2-methylethyl ester, hydroxyethyl acetate, 2-hydroxy-3-methylmethyl butyrate, etc.; or keto esters, such as ethyl pyruvate, etc., and in addition, may be N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., but not limited to these.

[0316] For example, the solvent may be a glycol ether, such as ethylene glycol monoethyl ether, ethylene glycol methyl ethyl ether, etc.; ethylene glycol alkyl ether acetate, such as ethyl cellosolve acetate, etc.; ester, such as 2-hydroxyethyl propionate, etc.; carbitol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; alcohol, such as ethanol, etc., or combinations thereof.

[0317] For example, the solvent may be a polar solvent, including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, propylene carbonate, γ-butyrolactone, or combinations thereof.

[0318] The solvent content can be from 40% to 80% by weight, for example, from 45% to 80% by weight, based on the total amount of the curable composition. When the solvent is within the range described, the solvent-based curable composition has a suitable viscosity and therefore exhibits excellent coating properties when coated over large areas by spin coating and slot coating.

[0319] Another embodiment provides a hardened layer manufactured using the said hardenable composition, a color filter including the hardened layer, and a display device including the color filter.

[0320] One of the methods for manufacturing a hardened layer may include: applying a hardenable composition onto a substrate using an inkjet printing method to form a pattern (S1); and hardening the pattern (S2).

[0321] (S1) Forming a pattern

[0322] It is desirable to coat a curable composition onto a substrate in the range of 0.5 to 20 micrometers using an inkjet printing method. While inkjet printing can form patterns by spraying a single color from each nozzle and thus repeating the spraying an equal number of times as desired, patterns can also be formed by simultaneously spraying the desired number of colors from each inkjet nozzle, thus reducing the processing complexity.

[0323] (S2) Hardening

[0324] The obtained pattern is hardened to obtain pixels. In this paper, the hardening method can be thermal curing or photocuring. Thermal curing can be performed at 100°C or higher, preferably in the range of 100°C to 300°C, and more preferably in the range of 160°C to 250°C. Photocuring may involve irradiation with photochemical rays, such as ultraviolet light at 190 nm to 450 nm, or for example, 200 nm to 500 nm. Irradiation is performed using a light source such as a mercury lamp, metal halide lamp, or argon laser with low pressure, high pressure, or ultra-high pressure. X-rays, electron beams, etc., may also be used as needed.

[0325] Other methods for manufacturing a hardened layer may include using the aforementioned hardenable composition to manufacture the hardened layer by the following photolithography method.

[0326] (1) Coating and film formation

[0327] A curable composition is coated onto a pre-treated substrate to a desired thickness, for example, between 2 and 10 micrometers, using methods such as spin coating, slot coating, roller coating, screen printing, or coating applicator. The coated substrate is then heated at 70°C to 90°C for 1 to 10 minutes to remove the solvent and form a film.

[0328] (2) Exposure

[0329] After placing a mask of a predetermined shape, the resulting film is irradiated with photochemical rays, such as UV rays of 190 nm to 450 nm or 200 nm to 500 nm, to form the desired pattern. Irradiation is performed using light sources such as mercury lamps, metal halide lamps, or argon lasers with low, high, or ultra-high pressure. X-rays, electron beams, etc., may also be used as needed.

[0330] When using a high-pressure mercury lamp, the exposure process uses a light dose of, for example, 500 mJ / cm² or less (using a 365 nm sensor). However, the light dose can vary depending on the type of each component of the curable composition, their combination ratio, and the dry film thickness.

[0331] (3) Development

[0332] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing the excess areas other than the exposed parts, thus forming an image pattern. In other words, when an alkaline developing solution is used, the unexposed areas are dissolved, forming an image color filter pattern.

[0333] (4) Post-processing

[0334] The developed image pattern can be hardened by reheating or irradiation with photochemical rays to achieve excellent qualities in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, and storage stability.

[0335] The invention is described in more detail below with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.

[0336] (Preparation of surface-modified quantum dots)

[0337] Preparation Example

[0338] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical; quantum dot solid content 23 wt%) was added. A compound (ligand) represented by the chemical formula Q was then added, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the temperature was lowered to room temperature (23°C), and the quantum dot reaction solution was added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and then thoroughly dried in a vacuum oven for one day, thereby obtaining surface-modified quantum dots.

[0339] *Synthesis of the compound represented by chemical formula Q: 100 g of PH-4 (Hannong Chemical Inc.) was placed in a two-necked round-bottom flask and then completely dissolved in 300 mL of THF. 15.4 g of NaOH and 100 mL of water were added at 0 °C and then completely dissolved until a clear solution was obtained. A solution obtained by dissolving 73 g of p-toluenesulfonyl chloride in 100 mL of THF was slowly added at 0 °C. The addition was carried out for 1 hour, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was complete, excess dichloromethane was added and then stirred, followed by the addition of a saturated solution of NaHCO3, then extraction, titration, and water removal. After solvent removal, the residue was... The product was dried in a drying oven for 24 hours. 50 g of the dried product was placed in a two-necked round-bottom flask and stirred thoroughly in 300 mL of ethanol. Then, 27 g of thiourea was added and dispersed, and the mixture was refluxed at 80 °C for 12 hours. Next, an aqueous solution prepared by dissolving 4.4 g of NaOH in 20 mL of water was added, and the mixture was stirred for another 5 hours. Excess dichloromethane was then added, followed by an aqueous solution of hydrochloric acid. Extraction, titration, water removal, and solvent removal were then performed sequentially. The resulting product was dried in a vacuum oven for 24 hours to obtain the compound represented by the chemical formula Q.

[0340] [Chemical Formula Q]

[0341]

[0342] (Preparation of curable compositions)

[0343] Hardenable compositions according to Examples 1 to 9 and Comparative Examples 1 to 6 were prepared based on each of the following components.

[0344] (A)Quantum dots

[0345] Surface-modified green quantum dots prepared according to the above preparation examples

[0346] (B) Polymerizable compounds

[0347] (B-1) The compound represented by chemical formula 1-1 (viscosity: 4.3 centipoise, vapor pressure: 2.9 × 10⁻⁶). -3 (to)

[0348] [Chemical Formula 1-1]

[0349]

[0350] (B-2) The compound represented by chemical formula 1-2 (viscosity: 5.5 centipoise, vapor pressure: 1 × 10⁻⁶). -3 (to)

[0351] [Chemical Formula 1-2]

[0352]

[0353] (B-3) A compound represented by chemical formula 1-3 (viscosity: 6.15 centipoise, vapor pressure: 3.6 × 10⁻⁶). -4 Torr (chemical formula 1-3)

[0354]

[0355] (B-4) Compounds represented by chemical formulas 1-4 (viscosity: 3.9 centipoise, vapor pressure: 3 × 10⁻⁶) -3 (to)

[0356] [Chemical Formulas 1-4]

[0357]

[0358] (B-5) Compounds represented by chemical formulas 1-5 (viscosity: 4.5 centipoise, vapor pressure: 1.9 × 10⁻⁶) -3 Torr (chemical formula 1-5)

[0359]

[0360] (B-6) A compound represented by chemical formula 1-6 (viscosity: 5.3 centipoise, vapor pressure: 1.2 × 10⁻⁶). -3 Torr (chemical formula 1-6)

[0361]

[0362] (B-7) Compound represented by chemical formula 1-7 (viscosity: 4.1 centipoise, vapor pressure: 7.8 × 10⁻⁶) -4 Torr (Chemical Formula 1-7)

[0363]

[0364] (B-8) A compound represented by chemical formula 1-8 (viscosity: 5.4 centipoise, vapor pressure: 9.5 × 10⁻⁶). -5 Torr (Chemical Formula 1-8)

[0365]

[0366] (B-9) Compounds represented by chemical formulas 1-9 (viscosity: 6.1 centipoise, vapor pressure: 5 × 10⁻⁶). -6 (to)

[0367] [Chemical Formulas 1-9]

[0368]

[0369] (B-10) A compound represented by the chemical formula C-1 (viscosity: 6.2 centipoise, vapor pressure: 1 × 10⁻⁶). -3 (to)

[0370] [Chemical formula C-1]

[0371]

[0372] (B-11) A compound represented by the chemical formula C-2 (viscosity: 4.5 centipoise, vapor pressure: 8 × 10⁻⁶). -3 (to)

[0373] [Chemical formula C-2]

[0374]

[0375] (B-12) A compound represented by the chemical formula C-3 (viscosity: 5.4 centipoise, vapor pressure: 2.85 × 10⁻⁶). -3 (to)

[0376] [Chemical formula C-3]

[0377]

[0378] (B-13) A compound represented by the chemical formula C-4 (viscosity: 4.45 centipoise, vapor pressure: 1.85 × 10⁻⁶). -3 (to)

[0379] [Chemical formula C-4]

[0380]

[0381] (B-14) A compound represented by the chemical formula C-5 (viscosity: 5.27 centipoise, vapor pressure: 3.7 × 10⁻⁶). -4 (to)

[0382] [Chemical formula C-5]

[0383]

[0384] (B-15) A compound represented by the chemical formula C-6 (viscosity: 6.4 centipoise, vapor pressure: 1.3 × 10⁻⁶). -4 (to)

[0385] [Chemical formula C-6]

[0386]

[0387] (C) Photopolymerization initiator

[0388] TPO-L (Polynetron)

[0389] (D) Light diffusing agent

[0390] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm))

[0391] (E) Polymerization inhibitors

[0392] Methylhydroquinone (Tokyo Chemical Co., Ltd.)

[0393] Examples 1 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3

[0394] Specifically, the surface-modified quantum dots prepared in the preparation example were mixed with a hardenable monomer at the same weight ratio and then stirred for 12 hours. In this paper, a polymerization inhibitor was added and then stirred for 5 minutes. Subsequently, a photoinitiator was added, followed by a light diffusing agent.

[0395] (Taking Example 1 as an example, 40 grams of surface-modified green quantum dots and 40 grams of a compound represented by chemical formula 1-1 as a curable monomer were mixed and stirred to prepare a quantum dot dispersion. 12.5 grams of another curable monomer represented by chemical formula 1-1 and 0.5 grams of polymerization inhibitor were added to it, and then it was stirred for 5 minutes. Subsequently, 3 grams of photoinitiator and 4 grams of light diffusing agent were added to it, and then it was stirred to prepare a curable composition.)

[0396] Specific compositions are shown in Tables 1 and 2.

[0397] (Table 1)

[0398] (Unit: % by weight)

[0399]

[0400] (Table 2)

[0401] (Unit: % by weight)

[0402]

[0403] Assessment 1: Evaluation of ink viscosity and volatility

[0404] The viscosity of each curable composition according to Examples 1 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 at 25°C was measured using a viscometer (RV-2 spins, 23 rpm, DV-II, manufactured by Brookfield Engineering Laboratories, Inc.), and the results are shown in Table 3. Furthermore, after inkjet printing each curable composition into pixels with barrier ribs, the thickness reduction rate of each individual film was measured using a 3D optical microscope (VK-9710 color 3D laser microscope, Keyence Corp., Japan) to calculate the film residue rate, and the results are shown in Table 3. In Table 3, a higher film residue rate indicates lower volatility.

[0405] (Table 3)

[0406]

[0407] Referring to Table 3, the curable compositions according to Examples 1 to 9, Reference Examples 1 to 3, and Comparative Examples 1 to 3 all have low viscosity. However, when compared with curable compositions having similar viscosity, the curable compositions according to Examples 1 to 9 exhibit a higher film residue rate than the curable compositions according to Reference Examples 1 to 3 and Comparative Examples 1 to 3, and therefore exhibit significantly improved volatility. In other words, the curable compositions according to the examples have low viscosity and simultaneously exhibit improved volatility.

[0408] Although the invention has been described in conjunction with exemplary embodiments now regarded as practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements contained within the spirit and scope of the appended claims. Therefore, the above embodiments should be understood as exemplary and not as limiting the invention in any way.

Claims

1. A curable composition comprising Quantum dots; and Curable monomer with a viscosity less than 6.2 centipoise and a vapor pressure of 1 × 10⁻⁶. -6 Up to 3×10 -3 Tuo, The curable monomer is represented by chemical formula 1: [Chemical Formula 1] In chemical formula 1, R a It is an unsubstituted methyl group, and L a It is an unsubstituted C1 to C8 alkylene group, a substituted or unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by chemical formula 2. [Chemical Formula 2] In chemical formula 2, L b and L c Each is independently a substituted or unsubstituted C1 to C8 alkylene group, and n is an integer from 1 to 3.

2. The curable composition according to claim 1, wherein the viscosity of the curable monomer is greater than or equal to 3 centipoise and less than 6.2 centipoise.

3. The curable composition according to claim 1, wherein... In chemical formula 1, L a It is an unsubstituted C1 to C8 alkylene group, an unsubstituted C3 to C6 cycloalkylene group, or a linking group represented by Formula 2, and In chemical formula 2, L b and L c Each is an unsubstituted C1 to C6 alkylene group.

4. The curable composition according to claim 1, wherein the curable monomer is represented by any one of chemical formulas 1-1 to 1-9: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formulas 1-3] [Chemical Formulas 1-4] [Chemical Formulas 1-5] [Chemical Formulas 1-6] [Chemical Formulas 1-7] [Chemical Formulas 1-8] [Chemical Formulas 1-9] 5. The hardenable composition according to claim 1, wherein the quantum dots are quantum dots whose surfaces are modified with ligands having polar groups.

6. The curable composition according to claim 5, wherein the ligand having the polar group is represented by any one of chemical formulas 3 to 16: [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] Among them, in chemical formulas 3 to 8, R 1 To R 7 Each is independently a substituted or unsubstituted C1 to C10 alkyl or a substituted or unsubstituted C6 to C20 aryl. L 1 To L 16 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and n1 to n7 are each an independent integer from 0 to 10. [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] Among them, in chemical formulas 9 to 11, R 8 and R 9 Each is independently a substituted or unsubstituted C1 to C10 alkyl group, L 17 To L 23 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and n8 to n10 are each independently an integer from 0 to 10. [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] Among them, in chemical formulas 12 to 15, R 10 To R 15 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. L 24 To L 29 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and n11 to n16 are each an independent integer from 0 to 10. [Chemical Formula 16] In chemical formula 16, R 16 To R 18 Each is independently a substituted or unsubstituted C1 to C10 alkyl group. L 30 To L 32 Each is independently a substituted or unsubstituted C1 to C10 alkylene group, and n17 to n19 are each an independent integer from 0 to 10.

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

8. The curable composition according to claim 7, wherein Based on the total amount of the solvent-free curable composition, the solvent-free curable composition comprises: 5% to 60% by weight of the quantum dots; and 40% to 95% by weight of the curable monomer.

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

10. The curable composition of claim 9, wherein the light diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

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

12. The curable composition of claim 11, wherein, based on the total weight of the curable composition, the curable composition comprises 1% to 40% by weight of the quantum dots; 1% to 20% by weight of the curable monomer; and 40% to 80% by weight of the solvent.

13. The curable composition of claim 1, wherein 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.

14. A hardening layer, manufactured using a hardenable composition as described in any one of claims 1 to 13.

15. A color filter comprising the hardened layer as described in claim 14.

16. A display device comprising the color filter as claimed in claim 15.

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