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

Abstract

A curable composition, a cured layer manufactured using the curable composition, a color filter including the cured layer, and a display device including the color filter are provided. The curable composition includes (A) quantum dots surface-modified with a surface-modification material represented by Chemical Formula 1; and (B) a polymerizable compound.

Description

Technical Field

[0001] This 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 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 more than 20% by weight 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 that reduces the ink solids content by dissolving a solvent of 50% or more by weight of the total composition provides somewhat satisfactory results in terms of viscosity. However, while this is considered a satisfactory result in terms of viscosity, it can worsen due to nozzle drying and clogging caused by solvent evaporation during inkjet printing, as well as the reduction in single-layer thickness over time after inkjet printing, and makes it difficult to control thickness deviation after curing. Therefore, it is difficult to apply this method to practical processes.

[0005] Therefore, solvent-free quantum dot inks are the most preferable form for practical applications. Current technology for applying quantum dots themselves to solvent-based compositions is somewhat limited.

[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] One embodiment provides a curable composition that has excellent out-gas properties while maintaining low viscosity.

[0009] Another embodiment provides a cured layer manufactured using a 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] Problem-solving methods

[0013] One embodiment provides a curable composition comprising (A) quantum dots surface-modified using a surface-modifying material represented by Formula 1; and (B) a polymerizable compound.

[0014] [Chemical Formula 1]

[0015]

[0016] In chemical formula 1,

[0017] R 1 It is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0018] L 1 To L 3 Each is independently a substituted or unsubstituted C1 to C20 alkylene group, with the limitation being L. 1 To L 3 Either of them must be a substituted C1 to C20 alkylene group, and

[0019] n1 is an integer from 0 to 20.

[0020] R 1 It can be a substituted or unsubstituted C1 to C3 alkyl group.

[0021] L 3 It can be a substituted C1 to C20 alkylene group. In this article, L 1 and L 2 Each can be an unsubstituted C1 to C20 alkylene group.

[0022] L 1 To L 3 Any of them can be a C2 to C20 branched alkylene group.

[0023] Surface-modified materials represented by chemical formula 1 can be represented by chemical formula 1-1 or chemical formula 1-2.

[0024] [Chemical Formula 1-1]

[0025]

[0026] [Chemical Formula 1-2]

[0027]

[0028] In chemical formulas 1-1 and 1-2,

[0029] n1 is an integer from 0 to 20.

[0030] The quantum dots may be quantum dots that have been further surface-modified using a surface-modifying material represented by chemical formula 2.

[0031] [Chemical Formula 2]

[0032]

[0033] In chemical formula 2,

[0034] R 2 It is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0035] L 4 To L 6 Each is independently an unsubstituted C1 to C20 alkylene group, and

[0036] n2 is an integer from 0 to 20.

[0037] The surface-modified material represented by chemical formula 2 can be represented by chemical formula 2-1.

[0038] [Chemical Formula 2-1]

[0039]

[0040] In chemical formula 2-1,

[0041] n2 is an integer from 0 to 20.

[0042] The surface modifier can be composed of a surface modifier represented by chemical formula 1 and a surface modifier represented by chemical formula 2 in a weight ratio of 9:1 to 1:9.

[0043] The curable component may be a solvent-free curable component.

[0044] The solvent-free curable composition may include 5% to 60% by weight of quantum dots and 40% to 95% by weight of polymerizable compounds, based on the total amount of solvent-free curable composition.

[0045] The curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0046] Light diffusing agents may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or combinations thereof.

[0047] The curable composition may also include a solvent.

[0048] The curable composition may contain 1% to 40% by weight of quantum dots; 1% to 20% by weight of polymerizable compound; and 40% to 80% by weight of solvent, based on the total weight of the curable composition.

[0049] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorinated surfactant; or combinations thereof.

[0050] Another embodiment provides a cured layer manufactured using the said curable composition.

[0051] Another embodiment provides a color filter including the cured layer.

[0052] Another embodiment provides a display device including the color filter.

[0053] Other embodiments of the invention are included in the following detailed description.

[0054] Invention Effects

[0055] The present invention can maintain the low viscosity of curable compositions containing quantum dots, and at the same time achieve low degassing and reduced properties by changing the structure of the surface modifier material used to surface modify the quantum dots in the curable compositions containing quantum dots. Detailed Implementation

[0056] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto, but is defined by the scope of the claims.

[0057] Unless otherwise defined, “alkyl” as used herein refers to C1 to C20 alkyl, “alkenyl” as refers to C2 to C20 alkenyl, “cycloalkenyl” as refers to C3 to C20 cycloalkenyl, “heterocyclic alkenyl” as refers to C3 to C20 heterocyclic alkenyl, “aryl” as refers to C6 to C20 aryl, “arylalkyl” as refers to C6 to C20 arylalkyl, “alkylene” as refers to C1 to C20 alkylene, “arylene” as refers to C6 to C20 arylene, “alkylarylene” as refers to C6 to C20 alkylarylene, “heteroarylene” as refers to C3 to C20 heteroarylene, and “alkoxide” as refers to C1 to C20 alkoxide.

[0058] Unless otherwise specifically defined, “substituted” as used herein 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.

[0059] Unless otherwise defined, “heterogeneous” as used herein refers to a chemical formula containing at least one heteroatom of N, O, S and P.

[0060] Unless otherwise defined, “(meth)acrylate” as used herein refers to both “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.

[0061] Unless otherwise defined, the term “combination” as used herein refers to a mixture or copolymer.

[0062] 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.

[0063] Furthermore, in this specification, unless otherwise defined, "*" refers to a point connected to the same or different atoms or chemical formulas.

[0064] The curable composition containing quantum dots according to the present invention can be prepared by surface modification of quantum dots using a surface modifier having a branched structure (wherein a conventional surface modifier having a linear structure is changed to have more substituents), thereby achieving lower degassing properties and effectively reducing viscosity compared to conventional curable compositions containing quantum dots.

[0065] To develop solvent-free curable compositions containing quantum dots, it is essential to develop compositions that can achieve both dispersion control and inkjet processing performance through surface modification of hydrophobic quantum dots. Therefore, to reduce conventional nozzle drying and film thickness variations over time due to solvent evaporation, solvent-free curable compositions with high quantum dot content have been designed. The structural selection of the surface modifier material used for surface modification of the quantum dots and the polymerizable compound used as the curing matrix are crucial factors determining the dispersibility, thermosetting power, and photocurability of the composition (ink). Quantum dots are hydrophobic due to their inorganic core and shell components and surface modification using organic materials, and they exhibit different emission wavelengths depending on the inorganic components and their size. Typically, because quantum dots are only a few nanometers in size and therefore have high curvature per unit area, the structure of the quantum dot surface modifier material can only be limited to relatively small low-molecular-weight materials. Furthermore, since green quantum dots degrade the absorption efficiency at blue wavelengths compared to red quantum dots, research is underway to improve luminescence efficiency by controlling the excitation wavelength. However, quantum dots designed according to this research direction lead to a deterioration in surface modification and high viscosity due to differences in organic / inorganic composition.

[0066] Therefore, the inventors of this invention focused on the structure of the surface modifier during the development of solvent-free curable compositions containing quantum dots, thus limiting surface modifiers with linear structures to those with epoxide structures, but making various modifications to the structure of the surface modifiers to keep them generally in a low molecular weight state. However, the high viscosity problem of the composition containing quantum dots has not been completely solved, and in addition, when the composition is exposed to the intensity of light, heat, etc. used to form a cured film, there is another serious problem of degassing due to the thermal decomposition of the surface modifier. The inventors conducted further research, and the results confirmed that degassing is mainly caused by phenoxyethyl ethanol chains, methoxyethyl ethanol chains, and similar structures, which are actually decomposed from the surface modifier, especially from the thermal decomposition of the epoxide structure in surface modifiers with relatively low molecular weight epoxide structures.

[0067] Based on the research results to date, the inventors of this invention have shifted their research focus from reducing viscosity to reducing degassing and have begun new research and development. As a result, by structurally changing a portion of the epoxide structure to ensure that the surface-modified material, which includes a low-molecular-weight epoxide structure, has substituents, the low viscosity properties of the composition and the degassing reduction effect are ultimately ensured, thus completing this invention.

[0068] Hereinafter, each component constituting the curable composition according to the embodiments is described in detail.

[0069] quantum dots

[0070] The quantum dots in the curable composition according to the embodiments are surface modified using a surface modifier material represented by chemical formula 1.

[0071] [Chemical Formula 1]

[0072]

[0073] In chemical formula 1,

[0074] R 1 It is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0075] L 1 To L 3 Each is independently a substituted or unsubstituted C1 to C20 alkylene group, with the limitation being L. 1 To L 3 Either of them must be a substituted C1 to C20 alkylene group, and

[0076] n1 is an integer from 0 to 20.

[0077] For example, in Equation 1, n1 can be an integer from 1 to 20.

[0078] Quantum dots that have been surface-modified using surface-modifying materials represented by Chemical Formula 1 can be readily prepared into highly dense or highly concentrated quantum dot dispersions (improving the dispersibility of quantum dots relative to polymerizable monomers described later), and thus have significant effects on low viscosity and reduced degassing, particularly advantageously achieving solvent-free curable compositions.

[0079] However, in chemical formula 1, L 1 To L 3 They may not be simultaneously substituted C1 to C20 alkylene groups. In Formula 1, when using L... 1 To L 3Simultaneously, when quantum dots are surface-modified with substituted C1 to C20 alkylene surface-modified materials, the surface-modified quantum dots may exhibit poor dispersibility in polymerizable monomers, which will be described later.

[0080] For example, in chemical formula 1, R 1 It can be a substituted or unsubstituted C1 to C3 alkyl group. In this case, the degassing reduction effect can be maximized.

[0081] For example, in chemical formula 1, L 3 It can be a substituted C1 to C20 alkylene group, and L 1 and L 2 Each can be an unsubstituted C1 to C20 alkylene group.

[0082] For example, in chemical formula 1, L 1 To L 3 Any of them can be a C2 to C20 branched alkylene group.

[0083] For example, a surface-modified material represented by chemical formula 1 can be represented by chemical formula 1-1 or chemical formula 1-2, but is not necessarily limited to these.

[0084] [Chemical Formula 1-1]

[0085]

[0086] [Chemical Formula 1-2]

[0087]

[0088] In chemical formulas 1-1 and 1-2,

[0089] n1 is an integer from 0 to 20.

[0090] For example, n1 can be an integer from 1 to 20.

[0091] For example, quantum dots can be quantum dots that have undergone surface modification using surface modifiers represented by chemical formula 1 and surface modifiers represented by chemical formula 2.

[0092] [Chemical Formula 2]

[0093]

[0094] In chemical formula 2,

[0095] R 2 It is a substituted or unsubstituted C1 to C20 alkyl or a substituted or unsubstituted C6 to C20 aryl.

[0096] L 4To L 6 Each is independently an unsubstituted C1 to C20 alkylene group, and

[0097] n2 is an integer from 0 to 20.

[0098] For example, n2 can be an integer from 1 to 20.

[0099] For example, a surface-modified material represented by chemical formula 2 can be represented by chemical formula 2-1, but is not necessarily limited to this.

[0100] [Chemical Formula 2-1]

[0101]

[0102] In chemical formula 2-1,

[0103] n2 is an integer from 0 to 20.

[0104] For example, n2 can be an integer from 1 to 20.

[0105] For example, a weight ratio of 9:1 to 1:9, such as 9:1 to 5:5, can include a surface modifier represented by Chemical Formula 1 and a surface modifier represented by Chemical Formula 2. Specifically, when the weight ratio of the two types of quantum dot surface modifiers is within the above range, it is more advantageous to further reduce the viscosity of the composition and to implement the low degassing characteristics of the curable composition according to the embodiments.

[0106] Furthermore, when using the two types of surface modifiers mentioned above, surface modification of quantum dots may be easier compared to using surface modifiers with different structures. When quantum dots surface-modified using surface modifiers are added to a polymerizable compound, which will be described later, and stirred, an extremely transparent dispersion is obtained, which is a measure to confirm that the surface modification of quantum dots is carried out very well.

[0107] For example, quantum dots can have the largest fluorescence emission wavelength in the range of 500 nanometers to 680 nanometers.

[0108] For example, when the curable composition according to the embodiment is a solvent-free curable composition, the quantum dot content 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 quantum dot content is within the above range, high light retention and light efficiency can be achieved even after curing.

[0109] 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 can be obtained.

[0110] To date, curable components (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.

[0111] 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 ).

[0112] 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 full width at half maximum (FWHM) within this range, color reproducibility is increased due to high color purity when used as color materials in color filters.

[0113] Quantum dots can be organic materials, inorganic materials, or mixtures of organic and inorganic materials independently.

[0114] Quantum dots can each 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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 conversion 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, a polyoxyolefin, a polyol ester epoxy alkylation product, an alcohol epoxy alkylation product, a sulfonate, a sulfonate salt, a carboxylic acid ester, a carboxylate, an alkylamide epoxy alkylation product, an alkylamine, etc., and may be used alone or in mixtures of two or more. The amount of dispersant used 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 conversion material (e.g., quantum dots).

[0120] polymerizable compounds

[0121] The curable composition according to the embodiments comprises a polymerizable compound, and the polymerizable compound may have carbon-carbon double bonds at its ends.

[0122] The content of polymerizable compounds with carbon-carbon double bonds at the ends can be from 40% to 95% by weight, for example, from 50% to 90% by weight, based on the total amount of solvent-free curable composition. When polymerizable compounds with carbon-carbon double bonds at the ends are included within the range described above, solvent-free curable compositions with viscosities suitable for inkjet printing can be prepared, and the quantum dots in the prepared solvent-free curable compositions can have improved dispersibility, thereby improving optical properties.

[0123] For example, polymerizable compounds with carbon-carbon double bonds at the ends can have molecular weights ranging from 170 g / mol to 1000 g / mol. When the molecular weight of polymerizable compounds with carbon-carbon double bonds at the ends is within the above range, it can be advantageous for inkjet printing because the viscosity of the composition does not increase without impairing the optical properties of the quantum dots.

[0124] For example, polymerizable compounds with carbon-carbon double bonds at the ends can be represented by chemical formula 6, but are not necessarily limited to this.

[0125] [Chemical Formula 6]

[0126]

[0127] In chemical formula 6,

[0128] R 6 and R 7 Each is independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

[0129] L 6 and L 8 Each is independently a single-bonded or substituted or unsubstituted C1 to C10 alkylene group, and

[0130] L 7 It is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*).

[0131] For example, polymerizable compounds with carbon-carbon double bonds at the ends can be represented by chemical formula 6-1 or chemical formula 6-2, but are not necessarily limited to these.

[0132] [Chemical Formula 6-1]

[0133]

[0134] [Chemical Formula 6-2]

[0135]

[0136] For example, in addition to the compounds represented by chemical formula 6-1 or chemical formula 6-2, polymerizable compounds having carbon-carbon double bonds at the ends may also 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, phenolic epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or combinations thereof.

[0137] Furthermore, polymerizable compounds having carbon-carbon double bonds at the ends may also include monomers commonly used in conventional thermosetting or photocurable compositions, and, for example, the monomers may also include oxetane compounds, such as bis[1-ethyl(3-oxetane)]methyl ether.

[0138] Furthermore, when the curable composition contains a solvent, the content of the polymerizable compound, based on the total amount of the curable composition, can be from 1 wt% to 20 wt%, from 1 wt% to 15 wt%, or for example, from 5 wt% to 15 wt%. When the polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved.

[0139] Light diffusing agent

[0140] The curable composition according to the embodiments may further include a light diffusing agent.

[0141] For example, light diffusing agents may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0142] Light diffusing agents can reflect light that has not been absorbed by the quantum dots and allow the quantum dots to reabsorb the reflected light. In other words, light diffusing agents can increase the amount of light absorbed by the quantum dots and increase the light conversion efficiency of the curable components.

[0143] 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.

[0144] The content of the light diffusing agent can be from 1% to 20% by weight, for example, from 2% to 15% by weight, or from 3% to 10% by weight, based on the total amount of the curable components. 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.

[0145] Polymerization initiator

[0146] The curable composition according to the embodiments may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0147] Photopolymerization initiators are commonly used initiators for 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.

[0148] 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.

[0149] 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.

[0150] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0151] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0152] 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.

[0153] 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.

[0154] Examples of amino ketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc.

[0155] 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.

[0156] Photopolymerization initiators can be used with photosensitizers that can induce a chemical reaction by absorbing light and become excited and subsequently transfer their energy.

[0157] Examples of photosensitizers include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol tetra-3-mercaptopropionate.

[0158] 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 known in this art may be used.

[0159] 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 curable components. When the content of the polymerization initiator is within the range described, excellent reliability can be obtained due to sufficient curing during exposure or thermal curing, and transmittance degradation due to non-reactive initiators is prevented, thereby preventing the deterioration of the optical properties of the quantum dots.

[0160] Adhesive resin

[0161] The curable composition according to the embodiments may further include an adhesive resin.

[0162] Adhesive resins may include acrylic resins, calo resins, epoxy resins, or combinations thereof.

[0163] 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.

[0164] 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.

[0165] 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 appropriate.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] When the adhesive resin is a caloric resin, the developability of the curable component containing the adhesive resin, specifically the photosensitive resin component, is improved, and the sensitivity during photocuring is good, thereby improving the fine patterning properties.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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 solvent-free 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.

[0175] For example, when the curable composition according to the embodiment 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 characteristics, heat resistance, and chemical resistance can be improved.

[0176] Other additives

[0177] To improve the stability and dispersibility of quantum dots, the curable composition according to the embodiments may further include a polymerization inhibitor.

[0178] 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.

[0179] 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.

[0180] 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% by weight to 3% by weight, for example, from 0.01% by weight to 2% by weight, based on the total amount of the curable components. When the content of the polymerization inhibitor is within the above range, the aging problem at room temperature can be solved, while preventing the reduction of sensitivity and surface peeling.

[0181] In addition, the curable composition according to the embodiments may also include malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorinated surfactant; or combinations thereof to improve heat resistance and reliability.

[0182] 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.

[0183] Examples of silane-based coupling agents include trimethoxysilylbenzoic acid, γ-methacrylate oxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(epoxycyclohexyl)ethyltrimethoxysilane, etc., and these coupling agents can be used alone or in mixtures of two or more.

[0184] 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 curable composition. When the content of the silane coupling agent is within the said range, the close contact properties, storage capacity, etc., are improved.

[0185] In addition, the curable composition may also include surfactants (such as fluorinated surfactants) as needed to improve coating properties and suppress spot formation, i.e. improve leveling performance.

[0186] 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 applied as a high-speed slit coating, as this reduces film defects by preventing spot formation and suppressing vapor generation during high-speed coating.

[0187] Examples of fluorinated surfactants include and (BM Chemie Inc.); MEGAFACE F F F and F (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 DIC Co., Ltd.

[0188] In addition to fluorinated surfactants, the curable composition according to the embodiments may include silicone surfactants. Specific examples of silicone surfactants include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 from Toshiba Silicone Co., Ltd.

[0189] 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.

[0190] In addition, unless it would degrade the properties, the curable composition according to the embodiments may also contain a predetermined amount of other additives, such as antioxidants, stabilizers, etc.

[0191] solvent

[0192] Additionally, the curable composition according to the embodiments may further include a solvent.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] One of the methods for manufacturing a cured layer may include: applying a curable component onto a substrate using an inkjet printing method to form a pattern (S1); and curing the pattern (S2).

[0199] (S1) Forming a pattern

[0200] It is desirable to coat curable components onto a substrate in the range of 0.5 micrometers to 20 micrometers using an inkjet printing method. The inkjet printing method can form patterns by having each nozzle spray a single color and thus repeating the spraying an equal number of times as desired, but the patterns can also be formed by having each inkjet nozzle simultaneously spray the desired number of colors, thereby reducing the number of processes.

[0201] (S2) Curing

[0202] The obtained pattern is cured to obtain pixels. In this document, the curing method can be a thermosetting or photopolymerization process. Thermosetting processes can be performed at temperatures greater than or equal to 100°C, preferably in the range of 100°C to 300°C, and more preferably in the range of 160°C to 250°C. Photopolymerization processes may involve irradiation with photochemical rays, such as ultraviolet light at 190 nm to 450 nm, or for example, 200 nm to 400 nm. 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.

[0203] Other methods for manufacturing a cured layer may include using the aforementioned curable components to manufacture the cured layer via the following photolithography method.

[0204] (1) Coating and film formation

[0205] A curable composition is coated onto a pre-treated substrate to a desired thickness, such as between 2 and 10 micrometers, using methods such as spin coating, slot coating, roller coating, screen printing, or a coater. 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.

[0206] (2) Exposure

[0207] After placing a mask of a predetermined shape, the resulting film is irradiated with photochemical rays, such as ultraviolet (UV) rays of 190 nm to 450 nm or 200 nm to 400 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.

[0208] 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.

[0209] (3) Development

[0210] 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, thereby 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.

[0211] (4) Post-processing

[0212] The developed image pattern can be heated again or irradiated with photochemical rays to cure it, so as to achieve excellent qualities in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, and storage stability.

[0213] Forms of implementing the invention

[0214] 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.

[0215] (Preparation of surface-modified quantum dots)

[0216] Synthesis example 1

[0217] 100 g of the compound represented by chemical formula A-1 (Hannong Chemicals Inc.) was placed in a two-necked round-bottom flask and then thoroughly dissolved in 300 mL of tetrahydrofuran (THF). 36.6 g of NaOH and 100 mL of water were added at 0 °C and dissolved thoroughly until a clear solution was obtained. Subsequently, a solution obtained by dissolving 127 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 stirred, followed by the addition of a saturated solution of NaHCO3 for extraction and titration, and then the water and solvent were removed. The product was then dried in a drying oven for 24 hours. 50 g of the dried product was placed in a two-necked round-bottom flask and thoroughly stirred in 300 mL of ethanol. Subsequently, 58 g of thiourea was added and dispersed, and then refluxed at 80 °C for 12 hours. Then, an aqueous solution prepared by dissolving 18.5 g of NaOH in 20 mL of water was injected, and the mixture was stirred for another 5 hours. Excess dichloromethane was added, followed by the addition of an aqueous hydrochloric acid solution. Extraction, titration, and removal of water and solvent were then performed sequentially. The resulting product was dried in a vacuum oven for 24 hours to obtain the compound represented by chemical formula 1-1-1.

[0218] [Chemical Formula A-1]

[0219]

[0220] [Chemical Formula 1-1-1]

[0221]

[0222] Synthesis example 2

[0223] Except that the compound represented by chemical formula B-1 (Hannong Chemical Company) was used instead of the compound represented by chemical formula A-1, the compound represented by chemical formula 1-2-1 was obtained in the same manner as in Synthesis Example 1.

[0224] [Chemical Formula B-1]

[0225]

[0226] [Chemical Formula 1-2-1]

[0227]

[0228] Synthesis example 3

[0229] Except that triethylene glycol monomethyl ether was used instead of the compound represented by chemical formula A-1, the compound represented by chemical formula C-1 was obtained in the same manner as in Synthesis Example 1.

[0230] [Chemical formula C-1]

[0231]

[0232] Preparation Example 1

[0233] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23 wt%, Hansol Chemical) was added. A compound represented by formula 1-1-1 was then added, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the quantum dot reaction solution was cooled to room temperature (23°C) and then added to cyclohexane to collect the precipitate. The precipitate was separated from the cyclohexane by centrifugation and thoroughly dried in a vacuum oven for one day, thereby obtaining surface-modified green quantum dots.

[0234] Preparation Example 2

[0235] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23 wt%, Hanssol Chemical Company) was added. Subsequently, a compound represented by chemical formula 1-2-1 was added, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the quantum dot reaction solution was cooled to room temperature (23°C) and added to cyclohexane, thereby capturing the precipitate. The precipitate was separated from the cyclohexane by centrifugation and thoroughly dried in a vacuum oven, thus obtaining surface-modified green quantum dots.

[0236] Preparation Example 3

[0237] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23 wt%, Hanssol Chemical Company) was added. Subsequently, a surface modifier represented by chemical formula 1-1-1 and a surface modifier represented by C-1 were added in a weight ratio of 50:50, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the quantum dot reaction solution was cooled to room temperature (23°C) and added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and thoroughly dried in a vacuum oven, thereby obtaining surface-modified green quantum dots.

[0238] Preparation Example 4

[0239] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23 wt%, Hanssol Chemical Company) was added. Subsequently, a surface modifier represented by chemical formula 1-2-1 and a surface modifier represented by C-1 were added in a weight ratio of 50:50, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the quantum dot reaction solution was cooled to room temperature (23°C) and added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and thoroughly dried in a vacuum oven, thereby obtaining surface-modified green quantum dots.

[0240] Comparative Preparation Example 1

[0241] After placing a magnetic rod into a three-necked round-bottom flask, a green quantum dot dispersion solution (InP / ZnSe / ZnS, quantum dot solid: 23 wt%, Hansol Chemical Company) was added. Subsequently, a surface-modifying material, indicated by C-1, was added, and the mixture was stirred at 80°C under a nitrogen atmosphere. When the reaction was complete, the quantum dot reaction solution was cooled to room temperature (23°C) and added to cyclohexane to capture the precipitate. The precipitate was separated from the cyclohexane by centrifugation and thoroughly dried in a vacuum oven, thereby obtaining surface-modified green quantum dots.

[0242] (Preparation of curable components)

[0243] The curable compositions according to Examples 1 to 4 and Comparative Example 1 were prepared based on the following components.

[0244] (A)Quantum dots

[0245] (A-1) Surface-modified green quantum dots prepared in Preparation Example 1

[0246] (A-2) Surface-modified green quantum dots prepared in Preparation Example 2

[0247] (A-3) Surface-modified green quantum dots prepared in Preparation Example 3

[0248] (A-4) Surface-modified green quantum dots prepared in Preparation Example 4

[0249] (A-5) Surface-modified green quantum dots prepared in Comparative Preparation Example 1

[0250] (B) Polymerizable compounds

[0251] The compound represented by chemical formula 6-2 (1,6-hexanediol diacrylate, Meiyuan Specialty Chemicals Co., Ltd.)

[0252] [Chemical Formula 6-2]

[0253]

[0254] (C) Photopolymerization initiator

[0255] TPO-L (Polynetron)

[0256] (D) Light diffusing agent

[0257] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solids content 50% by weight), Iridos Co., Ltd.

[0258] (E) Polymerization inhibitor

[0259] Methylhydroquinone (Tokyo Chemical Co., Ltd.)

[0260] Examples 1 to 4 and Comparative Example 1

[0261] Specifically, surface-modified green quantum dots were mixed with a polymerizable compound and stirred for 12 hours. In this study, a polymerization inhibitor was added, followed by stirring for 5 minutes. Then, if necessary, a photoinitiator was added, followed by a light diffusing agent.

[0262] (Taking Example 1 as an example, 41 grams of surface-modified green quantum dots were mixed with 41 grams of a polymerizable compound represented by chemical formula 6-2 and stirred to prepare a green quantum dot dispersion. 10.95 grams of another polymerizable compound represented by chemical formula 6-2 and 0.05 grams of polymerization inhibitor were added to the dispersion, and the mixture was stirred for 5 minutes. Subsequently, 3 grams of photoinitiator and 4 grams of light diffusing agent were added to the dispersion, and the mixture was stirred again to prepare a curable composition.)

[0263] The specific components are shown in Table 1.

[0264] [Table 1]

[0265] (Unit: % by weight)

[0266]

[0267] Assessment: Evaluation of the viscosity and degassing of the curable component.

[0268] The viscosity and degassing characteristics of the curable compositions according to Examples 1 to 4 and Comparative Example 1 were evaluated respectively, and the results are shown in Table 2.

[0269] (Methods for evaluating viscosity)

[0270] The viscosity of the curable components according to Examples 1 to 4 and Comparative Example 1 at 25°C was measured using a viscometer (90 rpm, HAAKE Rheostress 6000, Thermo Scientific). The results are shown in Table 2.

[0271] (Methods for assessing degassing output)

[0272] Single-film samples formed from the curable compositions according to Examples 1 to 4 and Comparative Example 1 were weighed and placed in HS vials, which were then sealed with caps. The samples were collected and degassed for 30 minutes at 180°C using headspace gas chromatography (GC2010 Plus series, Shimdzu Corp., Japan) to measure their quantity, and the results are shown in Table 2.

[0273] [Table 2]

[0274] Viscosity (cps) Degassing (area, %) Example 1 24.6 <![CDATA[6.80×10 6 ]]> Example 2 24.5 <![CDATA[7.13×10 6 ]]> Example 3 24.3 <![CDATA[7.01×10 6 ]]> Example 4 24.2 <![CDATA[7.21×10 6 ]]> Comparative Example 1 26.2 <![CDATA[7.56×10 6 ]]>

[0275] Referring to Table 2, compared with the curable composition according to Comparative Example 1, the curable compositions according to Examples 1 to 4 exhibited relatively low degassing while maintaining low viscosity.

[0276] Although the invention has been described in conjunction with exemplary embodiments now considered 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 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 modified using surface-modifying materials represented by chemical formula 1-1 or chemical formula 1-2 and surface-modifying materials represented by chemical formula 2-1; and Polymerizable compounds; [Chemical Formula 1-1] [Chemical Formula 1-2] in, In chemical formulas 1-1 and 1-2, n1 is an integer from 0 to 20. [Chemical Formula 2-1] In chemical formula 2-1, n2 is an integer from 0 to 20. The surface modifier represented by chemical formula 1-1 or chemical formula 1-2 and the surface modifier represented by chemical formula 2-1 are contained in a weight ratio of 9:1 to 1:

9.

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

3. The curable composition according to claim 2, wherein... Based on the total amount of the solvent-free curable components, The solvent-free curable composition comprises: 5% to 60% by weight of the quantum dots; and 40% to 95% by weight of the polymerizable compound.

4. 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.

5. The curable composition according to claim 4, wherein the light diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

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

7. The curable composition according to claim 6, wherein The curable composition comprises, in total quantity, the curable composition including: From 1 wt% to 40 wt% of the quantum dots; 1% to 20% by weight of the polymerizable compound; and 40% to 80% by weight of the solvent.

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

9. A curable layer, manufactured using a curable composition as described in any one of claims 1 to 8.

10. A color filter comprising the cured layer as described in claim 9.

11. A display device comprising the color filter as claimed in claim 10.

Images