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

Abstract

The present invention provides a curable composition, a cured layer manufactured using the curable composition, a color filter comprising the cured layer, and a display device comprising the color filter, the curable composition comprising: (A) quantum dots; and (B) a polymerizable compound including a compound represented by a specific chemical formula.

Description

Technical Field

[0001] The present disclosure relates to a curable composition, a cured layer manufactured 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 general quantum dots, due to the hydrophobic surface characteristics, the solvent in which the quantum dots are dispersed is limited. Therefore, 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, 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, because the quantum dots are 20% by weight or more based on the total amount of the composition, the light efficiency of the ink cannot be improved to a certain level. Although quantum dots are additionally added and dispersed in order to improve light efficiency, the viscosity is beyond the range capable of inkjetting, and 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 a solvent of 50 wt % or more based on the total amount of the composition is also provided, which provides slightly satisfactory results in terms of viscosity. However, it can be regarded as a satisfactory result in terms of viscosity, but nozzle drying, nozzle clogging, and a decrease in the thickness of a single film over time after inkjetting due to solvent volatilization during inkjetting may become worse, and it is difficult to control the thickness deviation after curing. Therefore, it is difficult to apply it to an actual process.

[0005] Therefore, non-solvent quantum dot inks that do not contain solvents are the best form for practical applications. The current technology for applying quantum dots themselves to solvent-based compositions is now somewhat limited.

[0006] In the case of a solvent-free curable composition (quantum dot ink composition), since an excessive amount of polymerizable compounds is contained, blockage and ejection failure caused by nozzle drying due to volatility and a reduction in the thickness of the monolayer film due to the volatilization of the ink composition ejected in the patterned partition wall pixels may occur. Therefore, efforts have been made from different angles to improve the optical properties of solvent-free curable compositions. In order to improve the optical properties of solvent-free curable compositions, a method of increasing the content of inorganic materials is generally used, but there is a problem that the more inorganic materials, the higher the reflectivity. In other words, since there is a trade-off between the improvement of the optical properties of solvent-free curable compositions and the problem of reducing the reflectivity, the demand for technologies that can simultaneously improve the above-mentioned two properties (improvement of optical properties and reduction of reflectivity) is gradually increasing. Summary of the invention

[0007] Technical issues

[0008] The embodiment provides a curable composition capable of simultaneously improving optical properties and reducing reflectivity.

[0009] Another embodiment provides a cured layer produced 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] Technical Solutions

[0013] The embodiment provides a curable composition, the curable composition comprising: (A) quantum dots; and (B) a polymerizable compound, comprising a compound represented by Chemical Formula 1.

[0014] [Chemical formula 1]

[0015]

[0016] In Chemical Formula 1,

[0017] L 1 is a divalent linking group containing a sulfur atom, but does not contain a disulfide bond (*-SS-*) bonding structure,

[0018] L 2 and L 3 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group, and

[0019] R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0020] L 1 It can be represented by any one of Chemical Formula L-1 to Chemical Formula L-4.

[0021] [Chemical formula L-1]

[0022]

[0023] [Chemical formula L-2]

[0024]

[0025] [Chemical formula L-3]

[0026]

[0027] [Chemical formula L-4]

[0028]

[0029] In Chemical Formula L-1 to Chemical Formula L-4,

[0030] L 4 To L 8 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0031] The compound represented by Chemical Formula 1 may have a refractive index greater than 1.455.

[0032] The compound represented by Chemical Formula 1 may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3.

[0033] [Chemical formula 1-1]

[0034]

[0035] [Chemical formula 1-2]

[0036]

[0037] [Chemical formula 1-3]

[0038]

[0039] The polymerizable compound may further include a compound having a structure different from that of the compound represented by Chemical Formula 1.

[0040] A compound having a structure different from that of the compound represented by Chemical Formula 1 may be represented by Chemical Formula 2.

[0041] [Chemical formula 2]

[0042]

[0043] In chemical formula 2,

[0044] L 9 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0045] L 10 and L 11 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0046] R 3 and R4 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0047] The compound represented by Chemical Formula 2 may have a refractive index less than or equal to 1.455.

[0048] The compound represented by Chemical Formula 1 and a compound having a structure different from that of the compound represented by Chemical Formula 1 may be included in a weight ratio of 1:9 to 9:1.

[0049] The curable composition may be a solvent-free curable composition.

[0050] 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.

[0051] The curable composition may further include a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

[0052] The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0053] The curable composition may further include a solvent.

[0054] The curable composition may include 1 wt % to 40 wt % of quantum dots, 1 wt % to 20 wt % of a polymerizable compound, and 40 wt % to 80 wt % of a solvent, based on the total weight of the curable composition.

[0055] The curable composition may further include malonic acid, 3-amino 1,2-propylene glycol, a silane coupling agent, a fluorine-based surfactant, or a combination thereof.

[0056] Another embodiment provides a cured layer produced using the curable composition.

[0057] The cured layer may have a diffuse reflectivity of 50% to 55%.

[0058] Another embodiment provides a color filter including a cured layer.

[0059] Another embodiment provides a display device including a color filter.

[0060] Other embodiments of the present invention are included in the following detailed description.

[0061] Effects of the Invention

[0062] The sulfur-containing di(meth)acrylate compound is contained in the curable composition containing quantum dots, and thereby the optical characteristics of the curable composition containing quantum dots can be improved, and the reflectivity can be reduced at the same time. DETAILED DESCRIPTION

[0063] Embodiments of the present invention are described in detail below. However, these embodiments are illustrative and the present invention is not limited thereto and is defined by the scope of the claims.

[0064] In the present specification, when a specific definition is not otherwise provided, “alkyl” refers to a C1 to C20 alkyl group, “alkenyl” refers to a C2 to C20 alkenyl group, “cycloalkenyl” refers to a C3 to C20 cycloalkenyl group, “heterocycloalkenyl” refers to a C3 to C20 heterocycloalkenyl group, “aryl” refers to a C6 to C20 aryl group, “aralkyl” refers to a C6 to C20 aralkyl group, “alkylene” refers to a C1 to C20 alkylene group, “arylene” refers to a C6 to C20 arylene group, “alkylarylene” refers to a C6 to C20 alkylarylene group, “heteroarylene” refers to a C3 to C20 heteroarylene group, and “alkyleneoxy” refers to a C1 to C20 alkyleneoxy group.

[0065] 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 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.

[0066] 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.

[0067] 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”.

[0068] In the present specification, when a specific definition is not otherwise provided, the term "combination" means mixing or copolymerization.

[0069] 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.

[0070] In addition, in the present specification, when a definition is not otherwise provided, "*" means a connection point with the same atom or chemical formula or a different atom or chemical formula.

[0071] Hereinafter, each component constituting the curable composition according to the embodiment is described in detail.

[0072] Polymerizable compounds

[0073] The quantum dot-containing curable composition according to the embodiment includes a sulfur-containing di(meth)acrylate compound having a high refractive index as a polymerizable compound, so that the high refractive property of the sulfur-containing di(meth)acrylate compound can cause improvement in the optical properties of the curable composition, and further, when the curable composition is thermally cured, a thiol-ene addition reaction is induced to promote surface curing of a cured layer of the curable composition, thereby simultaneously satisfying a reflectivity reduction effect.

[0074] The sulfur-containing di(meth)acrylate compound may be represented by Chemical Formula 1.

[0075] [Chemical formula 1]

[0076]

[0077] In Chemical Formula 1,

[0078] L 1 is a divalent linking group containing a sulfur atom, but does not contain a disulfide bond (*-SS-*) bonding structure,

[0079] L 2 and L 3 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group, and

[0080] R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0081] The curable composition containing green quantum dots has a relatively low absorption rate (abs.) and light efficiency (EQE), and a reflectivity approximately twice that of the curable composition containing red quantum dots. Therefore, there are unresolved technical challenges for improving the brightness of green quantum dot pixels in panels, but reducing the reflection of external light requires further improvement of the brightness of the front side.

[0082] The present inventors have clearly identified the above problems and conducted long-term relevant research to improve the optical properties of a curable composition containing green quantum dots but reduce its reflectivity, through hundreds of trials and errors and finally successfully solved the technical challenges by applying the compound represented by Chemical Formula 1 as a polymerizable compound.

[0083] Generally speaking, in order to improve the optical properties of a curable composition containing green quantum dots, a method of increasing the content of inorganic materials is mainly used, but conversely, in order to reduce the reflectivity of a curable composition containing green quantum dots, a method of reducing the content of inorganic materials is used, wherein the improvement in optical properties and the reduction in reflectivity are relative to each other, that is, there is a trade-off relationship, which may make it difficult to achieve both properties at the same time.

[0084] According to the embodiment, the sulfur-containing di(meth)acrylate compound represented by Chemical Formula 1 as a polymerizable compound is applied to the curable composition, thereby simultaneously achieving optical property improvement and reduced reflection effect in a curable composition containing green quantum dots in addition to a curable composition containing red quantum dots.

[0085] Specifically, optical properties can be improved due to the high refractive index of the compound represented by Chemical Formula 1. For example, the compound represented by Chemical Formula 1 may have a refractive index greater than 1.455, for example greater than 1.455 and less than or equal to 1.7, wherein since the compound represented by Chemical Formula 1 has a high refractive index within the range, the optical properties of the curable composition containing this compound as a content quantum dot of the polymerizable compound can be greatly improved.

[0086] In addition, since the compound represented by Chemical Formula 1 used as a polymerizable compound is thermally decomposed during the thermal curing of the curable composition of the embodiment to expose a thiol group, and this thiol group is easy to induce a thiol-ene reaction (refer to the following reaction scheme) with the carbon-carbon double bond of the (meth)acrylate group, and thus promotes the surface curing of the thermally cured single film, and finally significantly reduces the reflectivity of the cured layer, especially the diffuse reflectance, so that the reflectivity reduction can be obtained. For example, the diffuse reflectance of the cured layer can be reduced to less than or equal to 55%, for example, 50% to 55%.

[0087] [Reaction scheme]

[0088]

[0089] In chemical formula 1, when L 1 Contains a disulfide bond (*-SS-*) linking structure, or L 2 or L 3When an arylene group is included as a linking group, the compound may have a lower refractive index and disadvantages in optical characteristics, and in addition, a thiol-ene reaction does not smoothly occur, thereby reducing the reflectivity-reducing effect to half.

[0090] For example, L 1 It can be represented by any one of Chemical Formula L-1 to Chemical Formula L-4.

[0091] [Chemical formula L-1]

[0092]

[0093] [Chemical formula L-2]

[0094]

[0095] [Chemical formula L-3]

[0096]

[0097] [Chemical formula L-4]

[0098]

[0099] In Chemical Formula L-1 to Chemical Formula L-4,

[0100] L 4 To L 8 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0101] When L in chemical formula 1 1 When the linking group has the above structure, it may be extremely advantageous to simultaneously achieve the effects of improving the optical characteristics of the curable composition according to the embodiment and reducing the reflectivity (diffuse reflectivity) thereof.

[0102] For example, the compound represented by Chemical Formula 1 may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-3, but is not necessarily limited thereto.

[0103] [Chemical formula 1-1]

[0104]

[0105] [Chemical formula 1-2]

[0106]

[0107] [Chemical formula 1-3]

[0108]

[0109] For example, the polymerizable compound may further include a compound having a structure different from that of the compound represented by Chemical Formula 1. That is, the polymerizable compound may include the compound represented by Chemical Formula 1 and another compound having a different structure.

[0110] For example, a compound having a structure different from that of the compound represented by Chemical Formula 1 may be represented by Chemical Formula 2.

[0111] [Chemical formula 2]

[0112]

[0113] In chemical formula 2,

[0114] L 9 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0115] L 10 and L 11 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and

[0116] R 3 and R 4 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0117] Even if the curable composition according to the embodiment further includes the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 1 having a high refractive index as polymerizable compounds, the effects of improving the optical properties of the curable composition and reducing the reflectivity can be simultaneously achieved, as in the case of using the compound represented by Chemical Formula 1 alone.

[0118] For example, the compound represented by Chemical Formula 2 may have a refractive index less than or equal to 1.455. When the compound represented by Chemical Formula 2 has a refractive index greater than 1.455, it is advantageous in improving optical characteristics, but may be disadvantageous in terms of reducing reflectivity.

[0119] For example, the compound represented by Chemical Formula 1 and a compound having a structure different from that of the compound represented by Chemical Formula 1 (eg, a compound represented by Chemical Formula 2, etc.) have a weight ratio of 1:9 to 9:1, eg, a weight ratio of 5:5 to 9:1.

[0120] For example, the compound represented by Chemical Formula 1 may be included in a higher amount than a compound having a structure different from that of the compound represented by Chemical Formula 1 (eg, a compound represented by Chemical Formula 2, etc.).

[0121] For example, the compound represented by Chemical Formula 1 and a compound having a structure different from that of the compound represented by Chemical Formula 1 (eg, a compound represented by Chemical Formula 2, etc.) may be included at a weight ratio of 6:4 to 9:1.

[0122] When the compound represented by Chemical Formula 1 is included in a higher amount than a compound having a structure different from the compound represented by Chemical Formula 1 (e.g., a compound represented by Chemical Formula 2, etc.), for example, at a weight ratio of 6:4 to 9:1, the curing rate of the curable composition according to the embodiment is increased, and the simultaneous improvement of the two effects of improving optical characteristics and reducing reflectivity can be maximized.

[0123] For example, the compound represented by Chemical Formula 2 may be represented by Chemical Formula 2-1 or Chemical Formula 2-2, but is not necessarily limited thereto.

[0124] [Chemical formula 2-1]

[0125]

[0126] [Chemical formula 2-2]

[0127]

[0128] For example, in addition to the compounds represented by Chemical Formula 2-1 and Chemical Formula 2-2, the compound having a structure different from that of the compound represented by Chemical Formula 1 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.

[0129] In addition to the polymerizable compound, a monomer generally used in an existing thermosetting or photocurable composition may be further used, and for example, the monomer may further contain an oxetane-based compound such as bis[1-ethyl(3-oxetanyl)]methyl ether.

[0130] The polymerizable compound may be included in an amount of 40 wt % to 95 wt %, for example, 50 wt % to 90 wt %, based on the total amount of the solvent-free curable composition. When the polymerizable compound is included within the range, a solvent-free curable composition having a viscosity capable of inkjetting may be prepared, and quantum dots in the prepared solvent-free curable composition may have improved dispersibility, thereby improving optical properties.

[0131] For example, the polymerizable compound may have a molecular weight of 170 to 1,000 g / mol. When the polymerizable compound has a molecular weight within the range, it may be advantageous for inkjetting because it does not increase the viscosity of the composition without interfering with the optical properties of the quantum dots.

[0132] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1 wt % to 20 wt %, 1 wt % to 15 wt %, for example, 5 wt % to 15 wt %, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dots may be improved.

[0133] quantum dots

[0134] For example, quantum dots may have a maximum fluorescence emission wavelength at 500 nm to 680 nm.

[0135] For example, when the curable composition according to an embodiment is a solvent-free curable composition, the quantum dots may be included in an amount of 5 wt % to 60 wt %, such as 10 wt % to 60 wt %, such as 20 wt % to 60 wt %, such as 30 wt % to 50 wt %. When the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0136] For example, when the curable composition according to the embodiment is a curable composition containing a solvent, the quantum dots may be included in an amount of 1 wt % to 40 wt %, for example, 3 wt % to 30 wt %, based on the total amount of the curable composition. When the quantum dots are included within the above range, the light conversion rate is improved without weakening the pattern characteristics and the development characteristics, so that excellent processability can be obtained.

[0137] For example, quantum dots absorb light in the wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emit fluorescence in the wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm, or emit fluorescence in the wavelength region of 600 nm to 680 nm. That is, the quantum dots may have a maximum fluorescence emission wavelength (λ) at 500 nm to 680 nm. em ).

[0138] The quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum (FWHM) in the above range, color reproducibility is increased when used as a color material in a color filter due to high color purity.

[0139] The quantum dots may be independently organic materials or inorganic materials, or a hybrid of organic materials and inorganic materials.

[0140] The quantum dots may each independently consist of a core and a shell surrounding the core, and the core and the shell may each independently have a structure of a core composed of Group II to Group IV, Group III to Group V, etc., core / shell, core / first shell / second shell, alloy, alloy / shell or the like, but is not limited thereto.

[0141] 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 not necessarily limited thereto. The shell surrounding the core may include at least one material selected from the following: CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but not necessarily limited thereto.

[0142] In an embodiment, since environmental concerns have greatly increased worldwide recently and restrictions on toxic materials have also been strengthened, non-cadmium-based light-emitting materials (InP / ZnS, InP / ZeSe / ZnS, etc.) with slightly lower quantum efficiency (quantum yield) but environmentally friendly are used instead of light-emitting materials with a cadmium-based core, but are not necessarily limited to this.

[0143] In the case of core / shell structured quantum dots, the overall size (average particle size) including the shell may be 1 nm to 15 nm, for example 5 nm to 15 nm.

[0144] For example, the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots each independently have an average particle size of 10 nanometers to 15 nanometers. The green quantum dots each independently have an average particle size of 5 nanometers to 8 nanometers.

[0145] On the other hand, for the dispersion stability of quantum dots, the curable composition according to the embodiment may further include a dispersant. The dispersant contributes to the uniform dispersibility of the light conversion material such as the quantum dots in the curable composition, and may include a nonionic, anionic or cationic dispersant. Specifically, the dispersant may be a polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide addition product, alkylamine, etc., and it may be used alone or in the form of a mixture of two or more than two. Relative to the solid content of the light conversion material such as quantum dots, the dispersant may be used in an amount of 0.1% by weight to 100% by weight, for example, 10% by weight to 20% by weight.

[0146] For example, the quantum dots may be quantum dots that have been surface-modified with a ligand having a polar group, such as a ligand having a high affinity for the polymerizable compound. In the case of surface-modified quantum dots as described above, it is very easy to prepare a highly concentrated or highly concentrated quantum dot dispersion (improving the dispersibility of the quantum dots relative to the polymerizable compound), which can have a huge impact on improving light efficiency and, in particular, can be advantageous for implementing a solvent-free curable composition.

[0147] For example, the ligand having a polar group may have a structure having a high affinity with the chemical structure of the polymerizable compound.

[0148] For example, the ligand having a polar group may be represented by any one of Chemical Formulae A to Q, but is not necessarily limited thereto.

[0149] [Chemical formula A]

[0150]

[0151] [Chemical formula B]

[0152]

[0153] [Chemical formula C]

[0154]

[0155] [Chemical formula D]

[0156]

[0157] In Chemical Formula D, m1 is an integer of 0 to 10.

[0158] [Chemical formula E]

[0159]

[0160] [Chemical formula F]

[0161]

[0162] [Chemical formula G]

[0163]

[0164] [Chemical formula H]

[0165]

[0166] [Chemical Formula I]

[0167]

[0168] [Chemical formula J]

[0169]

[0170] [Chemical formula K]

[0171]

[0172] [Chemical formula L]

[0173]

[0174] [Chemical formula M]

[0175]

[0176] [Chemical formula N]

[0177]

[0178] [Chemical formula O]

[0179]

[0180] [Chemical formula P]

[0181]

[0182] [Chemical formula Q]

[0183]

[0184] When a ligand is used, surface modification of quantum dots may become easier, and when quantum dots surface-modified with a ligand are added to the aforementioned polymerizable compound and then stirred, an extremely transparent dispersion liquid may be obtained, which confirms that surface modification of quantum dots is extremely sufficiently performed.

[0185] Light Diffuser

[0186] The curable composition according to an embodiment may further include a light diffusing agent.

[0187] 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.

[0188] 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.

[0189] The light diffusing agent may have an average particle size (D 50 ). When the average particle size of the light diffusing agent is within the above range, it can have a better light diffusing effect and improve the light conversion efficiency.

[0190] The light diffuser may be included in an amount of 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, a quantum dot precipitation problem may occur.

[0191] Polymerization initiator

[0192] The curable composition according to an embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0193] 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, etc., but is not necessarily limited thereto.

[0194] Examples of acetophenone compounds may include 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.

[0195] Examples of benzophenone compounds include 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.

[0196] Examples of the thioxanthone compounds may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0197] Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0198] 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, methyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxyphenylvinyl)-s-triazine, etc.

[0199] Examples of oxime compounds may be O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)9H-carbazole-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of 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.

[0200] Examples of aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 and the like.

[0201] In addition to the above compounds, the photopolymerization initiator may further include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and the like.

[0202] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming an excited state and then transferring its energy.

[0203] Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0204] Examples of the thermal polymerization initiator may be peroxides, specifically, benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydrogen peroxide (e.g., tert-butyl hydroperoxide, isopropylbenzene hydroperoxide), dicyclohexylperoxydicarbonate, 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 peroxide well known in the art may be used.

[0205] The polymerization initiator may be included in an amount of 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 is included within the range, 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.

[0206] Binder resin

[0207] The curable composition according to an embodiment may further include a binder resin.

[0208] The binder resin may include acrylic resin, cardo resin, epoxy resin or a combination thereof.

[0209] 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.

[0210] 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, etc., but are not limited thereto, and may be used alone or in the form of a mixture of two or more.

[0211] The weight average molecular weight 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.

[0212] The acid value of the acrylic resin may be 80 mg KOH / g to 130 mg KOH / g. When the acrylic resin has an acid value within the range, excellent pixel resolution may be obtained.

[0213] Cardo-based resins may be used in existing curable resin (or photosensitive resin) compositions, and may be used, for example, as disclosed in Korean Patent Publication No. 10-2018-0067243, but are not limited thereto.

[0214] The cardo-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 acid 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 compound such as triphenylphosphine; and an amine or ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

[0215] The weight average molecular weight of the cardo-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 cardo-based binder resin is within the above range, a satisfactory pattern can be formed without residue during the production of the cured layer and without loss of film thickness during the development of the curable composition.

[0216] When the binder resin is a cardo-based resin, the developability of a curable composition including the binder resin, particularly a photosensitive resin composition, is improved, and the sensitivity during photocuring is good, so that fine pattern forming properties are improved.

[0217] The epoxy resin may be a thermally polymerizable monomer or oligomer, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0218] The epoxy resin may include, but is not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cycloaliphatic epoxy resin, and aliphatic polyglycidyl ether, but is not necessarily limited thereto.

[0219] Commercially available products of the compound may be: bisphenyl epoxy resins such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co.; cresol novolac epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 of Nippon Kayaku Co., Ltd., and EPIKOTE 180S75 and the like of Yuka Shell Epoxy Co., Ltd.; bisphenol A epoxy resins such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004 and the like of Yuka Shell Epoxy Co., Ltd. 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010 and EPIKOTE 828; bisphenol F epoxy resins such as EPIKOTE 807 and EPIKOTE 834 from Eukaryotic Epoxy Resins Co., Ltd.; phenol novolac epoxy resins such as EPIKOTE 152, EPIKOTE 154 and EPIKOTE 157H65 from Eukaryotic Epoxy Resins Co., Ltd., and EPPN 201, EPPN 202 from Nippon Kayaku Co., Ltd., and EPPN 201, EPPN 202 from Nippon Kayaku Co., Ltd. 202; cycloaliphatic epoxy resins such as CY175, CY177 and CY179 of Ciba-Geigy Group, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 of Union Carbide Corporation (UCC), Shodyne 509 of Showa Denko KK, Araldite CY-182 of Ciba-Geigy Group, CY-192 and CY-184 of Dainippon Ink & Chemicals, Inc., EPICLON 200 and EPICLON 400 of Eukashell Epoxy Resins Co., Ltd., EPIKOTE 871, EPIKOTE 872 and Celanese Coatings Corporation), and the aliphatic polyglycidyl ether can be EPIKOTE 190P and EPIKOTE 191P of Euka Shell Epoxy Resin Co., Ltd., Kyoesha Yushi Co., Ltd.)'s Epolite 100MF, Nippon Yushi Co., Ltd.'s Epiol TMP, etc.

[0220] For example, when the curable composition according to the embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5 wt % to 10 wt %, for example, 1 wt % to 5 wt %, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition may be improved, and the storage stability of the composition may also be improved.

[0221] For example, when the curable composition according to the embodiment is a curable composition containing a solvent, the binder resin may be contained in an amount of 1 wt % to 30 wt %, for example, 3 wt % to 20 wt %, based on the total amount of the curable composition. In this case, pattern characteristics, heat resistance, and chemical resistance may be improved.

[0222] Other additives

[0223] In order to improve the stability and dispersion of quantum dots, the curable composition according to the embodiment may further include a polymerization inhibitor.

[0224] The polymerization inhibitor may include a hydroquinone 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 compound, a catechol compound, or a combination thereof, room temperature crosslinking during exposure after coating the curable composition may be prevented.

[0225] For example, the hydroquinone compound, the catechol compound or a combination thereof may be hydroquinone, methyl hydroquinone, methoxy hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tert-butyl catechol, 4-methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosoanilino-O,O')aluminum or a combination thereof, but are not necessarily limited thereto.

[0226] The hydroquinone compound, the catechol compound or the combination thereof may be used in the form of a dispersion. The polymerization inhibitor in the form of a dispersion may be included in an amount of 0.001 wt % to 3 wt %, for example, 0.01 wt % to 2 wt %, based on the total amount of the curable composition. When the polymerization inhibitor is included in the range, the time lapse at room temperature can be solved, and at the same time, the sensitivity reduction and the surface delamination phenomenon can be prevented.

[0227] In addition, the curable composition according to the 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.

[0228] For example, the curable composition according to the 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, etc., in order to improve close contact properties with a substrate.

[0229] Examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these silane coupling agents can be used alone or in the form of a mixture of two or more.

[0230] The silane-based coupling agent may be used in an amount of 0.01 parts by weight 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 range, close contact properties, storage ability, and the like are improved.

[0231] 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.

[0232] 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 as a 0.1% polyethylene glycol monomethylether acetate (PGMEA) solution). When the fluorine-based surfactant has a weight average molecular weight and a surface tension within the above 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.

[0233] Examples of fluorine-based surfactants include and (BM Chemie Inc.); MEGAFACE Magaface F Magaface F And Magafeisi F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD Fowlerard Fowlerard and Fowlerard (Sumitomo 3M Co., Ltd.); SURFLON Thrawn Thrawn Thrawn Thrawn (ASAHI Glass Co., Ltd.); and as well as etc. (Toray Silicone Co., Ltd.); F-482, F-484, F-478, F-554, etc. from Dainippon Ink and Chemicals Co., Ltd. (DIC Co., Ltd.).

[0234] In addition to the fluorine-based surfactant, the curable composition according to the embodiment may also include a silicone-based surfactant. Specific examples of the silicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba Silicone Co., Ltd., but are not limited thereto.

[0235] 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 coating composition.

[0236] In addition, unless the properties are deteriorated, the curable composition according to the embodiment may further include a predetermined amount of other additives such as an antioxidant, a stabilizer, and the like.

[0237] Solvents

[0238] Meanwhile, the curable composition according to an embodiment may further include a solvent.

[0239] The solvent may include, for example, alcohols such as methanol, ethanol, etc.; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; 2-ethoxyethyl acetate (cellosolve acetate), such as 2-methoxyethyl acetate (methylcellosolve acetate), 2-ethoxyethyl acetate (ethyl cellosolve acetate), 2-ethoxydiethyl acetate (diethyl cellosolve acetate), etc. 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, etc.; alkyl glycolate, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetate, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; alkyl 3-alkoxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionate, such as methyl 2-hydroxypropionate; esters, 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, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate Ester, methyl 2-hydroxy-3-methylbutyrate, etc.; 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, 2-phenoxyethyl acetate, etc., but are not limited thereto.

[0240] 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 2-ethoxyethyl 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.

[0241] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0242] The solvent may be included in an amount of 40 wt % to 80 wt %, for example, 45 wt % to 80 wt %, based on the total amount of the curable composition. When the solvent is 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.

[0243] 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. In this case, the cured layer may have a diffuse reflectivity of 50% to 55% as described above.

[0244] One of the methods of manufacturing the cured layer may include coating the aforementioned curable composition and the solvent-based curable composition on a substrate using an inkjet spraying method to form a pattern ( S1 ) and curing the pattern ( S2 ).

[0245] (S1) Patterning

[0246] The curable composition can be applied to the substrate to a thickness of about 0.5 micrometers to about 20 micrometers by 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 desired number of colors, but can form a pattern by spraying the desired number of colors simultaneously through each inkjet nozzle to reduce the process.

[0247] (S2) Solidification

[0248] 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 higher than or equal to about 100°C, ideally in the range of about 100°C to about 300°C, and more ideally in the range of about 160°C to about 250°C. The photocuring process may include radiating actinic rays, such as 190 nanometers to 450 nanometers, for example, UV rays of 200 nanometers to 500 nanometers. Radiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, etc. having a low pressure, a high pressure, or an ultra-high pressure. X-rays, electron beams, etc. may also be used as needed.

[0249] Another method of manufacturing a cured layer may include manufacturing a cured layer using the aforementioned curable composition by the following lithography method.

[0250] (1) Coating and film formation

[0251] The curable resin composition is coated to have a desired thickness, for example, a thickness in the range of about 2 micrometers to about 10 micrometers, on a substrate subjected to a predetermined pretreatment using a spin coating or slit coating method, a roll coating method, a screen printing method, a painting method, etc. 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 form a film.

[0252] (2) Exposure

[0253] 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 400 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, etc. having a low pressure, a high pressure, or an ultra-high pressure. X-rays, electron beams, etc. may also be used as needed.

[0254] When a high pressure mercury lamp is used, the exposure process uses, for example, a light dose of 500 mJ / cm2 or less (using a 365 nm sensor). However, the light dose may vary depending on the types of the components of the curable composition, their combination ratios, and the dry film thickness.

[0255] (3) Development

[0256] After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unnecessary parts except for the exposed parts, thereby forming an image pattern. In other words, when an alkaline developing solution is used for development, the non-exposed area is dissolved and an image color filter pattern is formed.

[0257] (4) Post-processing

[0258] The developed image pattern may be heated again or irradiated by actinic rays and the like for curing, 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.

[0259] Embodiments of the present disclosure

[0260] Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are not to be construed as limiting the scope of the present invention in any sense.

[0261] Preparation of polymerizable compounds

[0262] Preparation Example 1

[0263] 20 g of 2,2-thiodiethanol was placed in a flask and fully dissolved in 400 ml of dichloromethane. 32.6 g of acryloyl chloride was added thereto, and then stirred under a nitrogen atmosphere. 36.4 g of trimethylamine was injected dropwise at 0°C for 1 hour, and then stirred for 2 hours to complete the reaction. 200 ml of dichloromethane and 500 ml of water were added thereto for extraction, and after separating the dichloromethane layer therefrom, dilute hydrochloric acid was added thereto to repeat the extraction three times. MgSO was added to the separated dichloromethane layer. 4 , and then stirred for 5 minutes. After filtration, the filtrate therefrom was concentrated. The obtained product was subjected to column chromatography and then concentrated and vacuum dried to prepare a compound represented by Chemical Formula 1-1 (refractive index: 1.495).

[0264] [Chemical formula 1-1]

[0265]

[0266] Preparation Example 2

[0267] 20 g of 3,6-dithia-1,8-octanediol was placed in a flask and fully dissolved in 200 ml of dichloromethane and 200 ml of ethanol. 21.8 g of acryloyl chloride was added thereto, and then stirred under a nitrogen atmosphere. 24.4 g of trimethylamine was dropwise injected thereinto at 0°C for 1 hour and stirred for 2 hours to complete the reaction. 200 ml of dichloromethane and 500 ml of water were added thereto for extraction, and after separating the dichloromethane layer therefrom, dilute hydrochloric acid was added thereto to repeat the extraction three times. MgSO was added to the separated dichloromethane layer. 4, and then stirred for 5 minutes. After filtration, the filtrate therefrom was concentrated. The obtained product was subjected to column chromatography and then concentrated and vacuum dried to prepare a compound represented by Chemical Formula 1-2 (refractive index: 1.529).

[0268] [Chemical formula 1-2]

[0269]

[0270] Preparation Example 3

[0271] 20 g of 1,4-dithiane-2,5-diol was added to 300 ml of ethanol and 200 ml of dichloromethane, and then stirred. 26 g of acryloyl chloride was added thereto, and then stirred under a nitrogen atmosphere. 29.2 g of trimethylamine was dropwise injected thereto at 0° C. for 1 hour and stirred for 2 hours to complete the reaction. 200 ml of dichloromethane and 500 ml of water were added thereto for extraction, and after separating the dichloromethane layer therefrom, dilute hydrochloric acid was added thereto to repeat the extraction three times. The separated dichloromethane layer was separated, and MgSO was added thereto. 4 , and then stirred for 5 minutes. After filtration, the filtrate therefrom was concentrated. The resulting product was subjected to column chromatography and then concentrated and vacuum dried to prepare a compound represented by Chemical Formula 1-3 (refractive index: 1.680).

[0272] [Chemical formula 1-3]

[0273]

[0274] Preparation Example 4

[0275] 100 g of 1,6-hexanediol was dissolved in 100 ml of toluene, and 135 g of acrylic acid and 8.2 g of methanesulfonic acid were added thereto, and then reacted at 120° C. for 5 hours, thereby preparing a compound represented by Chemical Formula 2-2 (refractive index: 1.455).

[0276] [Chemical formula 2-2]

[0277]

[0278] Comparative Preparation Example 1

[0279] 20 g of bis(2-hydroxyethyl)disulfide was fully dissolved in 300 ml of ethanol and 150 ml of dichloromethane. 25.7 g of acryloyl chloride was added thereto, and then stirred for 10 minutes. 28.8 g of triethylamine was slowly injected dropwise thereto, and then stirred at 0°C for 5 hours to complete the reaction, and 250 ml of dichloromethane and 300 ml of water were added thereto for extraction. The organic layer was separated, and extracted three times with a dilute aqueous hydrochloric acid solution. The dichloromethane layer was separated therefrom, and MgSO was added 4 , and then stirred for 5 minutes. After filtration, the filtrate therefrom was concentrated. The obtained product was subjected to column chromatography and then concentrated and vacuum dried to prepare a compound represented by Chemical Formula C-1 (refractive index: 1.517).

[0280] [Chemical formula C-1]

[0281]

[0282] Comparative Preparation Example 2

[0283] 20 g of 1,4-benzenedithiol was fully dissolved in 200 ml of dichloromethane. 22.5 g of 2-chloroethyl acrylate was added thereto, and then stirred for 10 minutes, and 17 g of triethylamine was slowly injected dropwise thereto at 0°C, and then stirred for 12 hours to complete the reaction. 300 ml of dichloromethane and 300 ml of water were added thereto for extraction, and after separating the organic layer, a dilute hydrochloric acid solution was added thereto to repeat the extraction three times. The dichloromethane layer was separated therefrom, and MgSO was added thereto. 4 , and then stirred for 5 minutes. After filtration, the filtrate therefrom was concentrated. The obtained product was subjected to column chromatography and then concentrated and vacuum dried to prepare a compound represented by Chemical Formula C-2 (refractive index: 1.556).

[0284] [Chemical formula C-2]

[0285]

[0286] Preparation of surface-modified quantum dot dispersions

[0287] Preparation Example 5

[0288] After placing the magnetic bar in a 3-neck round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23% by weight, Hansol Chemical) was placed therein. A compound (ligand) represented by the chemical formula Q was added thereto, and then stirred at 80°C under a nitrogen atmosphere. After the reaction was completed and then cooled to room temperature (23°C), the quantum dot reaction solution was added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane via centrifugation and fully dried in a vacuum oven for 24 hours to obtain surface-modified quantum dots.

[0289] The surface-modified green quantum dots were stirred in the polymerizable compound for 12 hours to obtain a surface-modified quantum dot dispersion (QD solids: 23 wt%).

[0290] (*Synthesis of the compound represented by the chemical formula Q: 100 g of PH-4 (Hannong Chemical Inc.) was placed in a 2-necked round-bottom flask, and then fully dissolved in 300 ml of tetrahydrofuran (THF). 15.4 g of sodium hydroxide (NaOH) and 100 ml of water were injected therein at 0° C., and then fully dissolved until a clear solution was obtained.

[0291] A solution obtained by dissolving 73 g of p-toluenesulfonic acid chloride in 100 ml of THF was slowly injected thereinto at 0° C. The injection was performed for 1 hour, and the resulting mixture was stirred at room temperature for 12 hours. When the reaction was completed, an excess of dichloromethane was added thereto and then stirred, and NaHCO was added thereto 3 Saturated solution, followed by extraction, titration and dehydration. After removing the solvent, the residue was dried in a drying oven for 24 hours. 50 grams of the dried product was placed in a 2-necked round-bottom flask and fully stirred in 300 milliliters of ethanol. Subsequently, 27 grams of thiourea were added thereto and dispersed therein, and then refluxed at 80° C. for 12 hours. Then, an aqueous solution prepared by dissolving 4.4 grams of NaOH in 20 milliliters of water was injected therein, while stirring for another 5 hours, an excess of dichloromethane was added thereto, and then an aqueous hydrochloric acid solution was added thereto, followed by extraction, titration, dehydration and solvent removal in sequence. The resulting product was dried in a vacuum oven for 24 hours to obtain a compound represented by chemical formula Q. )

[0292] [Chemical formula Q]

[0293]

[0294] (Preparation of curable composition)

[0295] Examples 1 to 7 and Comparative Examples 1 to 3

[0296] Each curable composition according to Examples 1 to 7 and Comparative Examples 1 to 3 was prepared by using the composition shown in Tables 1 and 2.

[0297] Specifically, after weighing the quantum dot dispersion, it was diluted by mixing with the polymerizable compound, and a polymerization inhibitor was added and stirred for 5 minutes. Subsequently, a photoinitiator was added thereto, and a light diffuser was added thereto. Then, the corresponding crude liquid was stirred for 1 hour to prepare a curable composition.

[0298] (A)Quantum dots

[0299] Surface modified green quantum dot dispersion prepared by Preparation Example 5

[0300] (B) Polymerizable compound

[0301] (B-1) Preparation of the compound of Example 1

[0302] (B-2) Preparation of the compound of Example 2

[0303] (B-3) Preparation of the compound of Example 3

[0304] (B-4) Preparation of the compound of Example 4

[0305] (B-5) Comparative Preparation of Compounds of Example 1

[0306] (B-6) Comparative Preparation of Compounds of Example 2

[0307] (C) Photopolymerization initiator

[0308] TPO-L(Polynetron Co.)

[0309] (D) Light Diffuser

[0310] Titanium dioxide dispersion (TiO 2 Solid content: 20% by weight, average particle size: 200 nm, Ditto Technology)

[0311] (E) Polymerization inhibitor

[0312] Methylhydroquinone(TOKYO CHEMICAL)

[0313] (Table 1)

[0314] (Unit: weight %)

[0315]

[0316] (Table 2)

[0317] (Unit: weight %)

[0318]

[0319] Evaluation: Evaluation of optical properties and diffuse reflectance of curable compositions

[0320] The post-exposure quantum efficiency (EQE) and the post-curing diffuse reflectance (SCE) of each curable composition according to Examples 1 to 7 and Comparative Examples 1 to 3 were measured by using a spectrophotometer (CM-3600A, Konica Minolta Sensing Inc.), and the results are shown in Table 3.

[0321] (Table 3)

[0322] Quantum efficiency after exposure (%) Diffuse reflectivity after curing (%) Example 1 32.2 54.7 Example 2 32.9 53.6 Example 3 33.1 53.6 Example 4 33.6 52.5 Example 5 31.9 55.8 Example 6 33.5 52.5 Example 7 34.0 52.1 Comparative Example 1 31.5 56.1 Comparative Example 2 30.8 57.3 Comparative Example 3 31.7 56.1

[0323] Referring to Table 3, compared with the curable compositions according to Comparative Examples 1 to 3, the curable compositions according to Examples 1 to 7 exhibited higher post-exposure quantum efficiency and thus improved optical properties, and simultaneously exhibited lower post-curing diffuse reflectivity and thus a reflectivity reducing effect.

[0324] 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, the present invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood to be illustrative, but not limiting in any way the present invention.

Claims

1. A curable composition comprising: (A) Quantum dots; as well as (B) a polymerizable compound comprising a compound represented by Chemical Formula 1: [Chemical formula 1] Wherein, in Chemical Formula 1, L 1 is a divalent linking group containing a sulfur atom, but does not contain a disulfide bond (*-SS-*) bonding structure, L 2 and L 3 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C20 cycloalkylene group, and R 1 and R 2 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

2. The curable composition according to claim 1, wherein L 1 Represented by any one of Chemical Formula L-1 to Chemical Formula L-4: [Chemical formula L-1] [Chemical formula L-2] [Chemical formula L-3] [Chemical formula L-4] in, In Chemical Formula L-1 to Chemical Formula L-4, L 4 To L 8 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

3. The curable composition according to claim 1, wherein The compound represented by the Chemical Formula 1 has a refractive index less than or equal to 1.

455.

4. The curable composition according to claim 1, wherein The compound represented by the Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-3: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] 5. The curable composition according to claim 1, wherein The polymerizable compound further includes a compound having a structure different from that of the compound represented by Chemical Formula 1.

6. The curable composition according to claim 5, wherein The compound having a structure different from that of the compound represented by the Chemical Formula 1 is represented by the Chemical Formula 2: [Chemical formula 2] in, In the chemical formula 2, L 9 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*), L 10 and L 11 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, and R 3 and R 4 Each is independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

7. The curable composition according to claim 6, wherein The compound represented by the Chemical Formula 2 has a refractive index less than or equal to 1.

455.

8. The curable composition according to claim 5, wherein The compound represented by the Chemical Formula 1 and the compound having a structure different from that of the compound represented by the Chemical Formula 1 are included in a weight ratio of 1:9 to 9:

1.

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

10. The curable composition according to claim 9, 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.

11. 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.

12. The curable composition according to claim 11, wherein The light diffuser includes barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide or a combination thereof.

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

14. The curable composition according to claim 13, wherein The curable composition includes 1 wt % to 40 wt % of the quantum dots, 1 wt % to 20 wt % of the polymerizable compound, and 40 wt % to 80 wt % of the solvent, based on the total weight of the curable composition.

15. 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-based surfactant or a combination thereof.

16. A cured layer produced using the curable composition according to any one of claims 1 to 15.

17. The solidified layer according to claim 16, wherein The solidified layer has a diffuse reflectivity of 50% to 55%.

18. A color filter comprising the cured layer according to claim 16.

19. A display device comprising the color filter according to claim 18.

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