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

Abstract

Disclosed are a curable composition, a cured layer using the curable composition, and a display device including the cured layer. The curable composition includes: (A) a quantum dot including a first functional group represented by Chemical Formula 1 and a second functional group including a *-OC (= O) group at a terminal; and (B) a polymerizable compound.

Description

Technical Field

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

[0002] In the case of general quantum dots, due to the presence of hydrophobic surface properties, the solvents in which the quantum dots are dispersed are limited, and thus it is difficult to introduce them into a polar system (such as an adhesive or a curable monomer).

[0003] Like traditional photoresist compositions, the quantum dot photoresist composition applied to quantum dot displays is composed of a photosensitive monomer, an adhesive, an initiator, a solvent, additives, etc., and also contains quantum dots and a light diffusing agent instead of pigments / dyes to ensure color characteristics, wherein the quantum dots have the function of converting incident blue light into red light and green light after forming a single film.

[0004] Since quantum dots represented by CdSe, InP, etc. have made rapid progress in terms of luminous efficiency (quantum yield), a synthesis method for quantum dots capable of achieving a luminous efficiency close to 100% is currently being introduced. Currently, quantum dot-OLED TVs (QD-OLED TVs) using a quantum dot ink composition based on an organic light emitting diode (OLED) blue backlight have been successfully commercialized. As a subsequent version, quantum dot displays made by using a blue micro light emitting diode (μ-light emitting diode, μ-LED) as a backlight are being developed. Since this μ-LED light source has much stronger intensity than traditional OLEDs, developing a quantum dot photoresist composition capable of withstanding the strong light intensity of the μ-LED light source is one of the key technologies. Summary of the Invention

[0005] Technical Challenges

[0006] One embodiment provides a curable composition containing quantum dots, and the curable composition containing quantum dots ensures light resistance reliability, that is, the ability to withstand strong light.

[0007] Another embodiment provides a cured layer produced using the curable composition.

[0008] Another embodiment provides a display device including the cured layer.

[0009] Means for Solving the Problem

[0010] One embodiment provides a curable composition, the curable composition comprising: (A) a quantum dot, including a first functional group represented by Chemical Formula 1 and a second functional group including a *-OC(=O) group at the terminal end; and (B) a polymerizable compound.

[0011] [Chemical Formula 1]

[0012]

[0013] In Chemical Formula 1,

[0014] R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a fused ring group thereof,

[0015] L 1 to L 4 each independently is a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0016] n is an integer from 1 to 20.

[0017] The second functional group may be represented by Chemical Formula 2.

[0018] [Chemical Formula 2]

[0019]

[0020] In Chemical Formula 2,

[0021] R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or *-C(=O)R 3 , where R 3 is a C1 to C10 alkyl group or (where R a to R c each independently is a hydrogen atom or a C1 to C10 alkyl group),

[0022] L 5 to L 7 each independently is a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0023] m is an integer from 1 to 20.

[0024] The first functional group and the second functional group may be included in a molar ratio of 1:0.5 to 1:1.5.

[0025] The first functional group may be represented by at least one selected from Chemical Formula 1-1 to Chemical Formula 1-3.

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 1-2]

[0029]

[0030] [Chemical Formula 1-3]

[0031]

[0032] The second functional group may be represented by at least one selected from Chemical Formula 2-1 to Chemical Formula 2-4.

[0033] [Chemical Formula 2-1]

[0034]

[0035] [Chemical Formula 2-2]

[0036]

[0037] [Chemical Formula 2-3]

[0038]

[0039] [Chemical Formula 2-4]

[0040]

[0041] The first functional group may be derived from a compound represented by Chemical Formula 3.

[0042] [Chemical Formula 3]

[0043]

[0044] In Chemical Formula 3,

[0045] R 1 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a fused ring group thereof.

[0046] L 1 to L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0047] n is an integer from 1 to 20.

[0048] The compound represented by Chemical Formula 3 can be represented by at least one selected from Chemical Formulas 3-1 to 3-3.

[0049] [Chemical Formula 3-1]

[0050]

[0051] [Chemical Formula 3-2]

[0052]

[0053] [Chemical Formula 3-3]

[0054]

[0055] The second functional group can be derived from a compound represented by Chemical Formula 4.

[0056] [Chemical Formula 4]

[0057]

[0058] In Chemical Formula 4,

[0059] R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or *-C(=O)R 3 , where R 3 is a C1 to C10 alkyl group or (where R a to R c are each independently a hydrogen atom or a C1 to C10 alkyl group),

[0060] L 5 to L 7 are each independently a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0061] m is an integer from 1 to 20.

[0062] The compound represented by Chemical Formula 4 can be represented by at least one selected from Chemical Formulas 4-1 to 4-4.

[0063] [Chemical Formula 4-1]

[0064]

[0065] [Chemical Formula 4-2]

[0066]

[0067] [Chemical Formula 4-3]

[0068]

[0069] [Chemical Formula 4-4]

[0070]

[0071] The curable composition may further contain a polymerization initiator, an adhesive resin, a light diffusing agent, a solvent, or a combination thereof.

[0072] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

[0073] The curable composition may further contain: malonic acid; 3-amino-1,2-propanediol; a polymerization inhibitor; a silane coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0074] Based on the total weight of the curable composition, the curable composition may contain: 1 wt% to 40 wt% of quantum dots; 1 wt% to 20 wt% of a polymerizable compound; 0.1 wt% to 5 wt% of a polymerization initiator; 1 wt% to 30 wt% of an adhesive resin; 1 wt% to 20 wt% of a light diffusing agent; and 40 wt% to 80 wt% of a solvent.

[0075] Another embodiment provides a cured layer made using the curable composition.

[0076] Another embodiment provides a display device including the cured layer.

[0077] Other embodiments of the present invention are included in the following detailed description.

[0078] Advantages of the Invention

[0079] By surface-modifying the quantum dots in the curable composition containing quantum dots using a quantum dot surface modification material having a composition that did not exist previously, the light resistance reliability of the curable composition can be improved. Detailed Description of Specific Embodiments

[0080] Embodiments of the present invention are described in detail below. However, these embodiments are exemplary, and the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0081] When no additional definition is provided, as used herein, "alkyl" refers to C1-C20 alkyl, "alkenyl" refers to C2-C20 alkenyl, "cycloalkenyl" refers to C3-C20 cycloalkenyl, "heterocycloalkenyl" refers to C3-C20 heterocycloalkenyl, "aryl" refers to C6-C20 aryl, "arylalkyl" refers to C6-C20 arylalkyl, "alkylene" refers to C1-C20 alkylene, "arylene" refers to C6-C20 arylene, "alkylarylene" refers to C6-C20 alkylarylene, "heteroarylene" refers to C3-C20 heteroarylene, and "alkoxy" refers to C1-C20 alkoxy.

[0082] When no specific definition is provided otherwise, as used herein, "substituted" means that at least one hydrogen atom is replaced by a substituent selected from the following: a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1-C20 alkoxy group, a nitro group, a cyano group, an amino group, an imino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a mercapto group, an ester group, an ether group, a carboxyl group or its salt, a sulfonic acid group or its salt, a phosphoric acid group or its salt, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 cycloalkynyl group, a C2-C20 heterocycloalkyl group, a C2-C20 heterocycloalkenyl group, a C2-C20 heterocycloalkynyl group, a C3-C20 heteroaryl group or a combination thereof.

[0083] When no specific definition is provided otherwise, as used herein, "hetero" means containing at least one heteroatom of N, O, S and P in a chemical formula.

[0084] When no specific definition is provided otherwise, as used herein, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid".

[0085] When no specific definition is provided otherwise, as used herein, the term "combination" means mixing or copolymerizing.

[0086] In this specification, when no additional definition is provided, when a chemical bond is not drawn at the position where it should be given in a chemical formula, a hydrogen bond is formed at that position.

[0087] In addition, in this specification, when no additional definition is provided, "*" means a point linked to the same or different atoms or chemical formulas.

[0088] The light resistance reliability in this specification refers to the light resistance reliability under high light resistance conditions (placed in a backlight of 100,000 nits (nit) or more than 100,000 nits for more than 500 hours).

[0089] Compared with the conventional curable composition containing quantum dots, the curable composition containing quantum dots according to the present invention can surface-modify the quantum dots using a surface-modifying material with a new composition, thereby achieving high light resistance reliability.

[0090] According to the latest trend in the display field of replacing the light source from OLED with a micro LED, the light resistance of the film installed inside the display has become more important than ever. Therefore, the light resistance of the cured layer formed by curing the curable composition containing quantum dots also needs to be extremely improved. However, the conventional quantum dot surface-modifying materials cannot individually ensure excellent film light resistance, so they are not sufficient for micro LED light sources.

[0091] Generally, in order to improve the curing rate of the curable composition containing quantum dots, a highly sensitive initiator or a polyfunctional monomer is additionally used, and the above-mentioned conventional techniques with specific configurations can improve one of all the properties of the curable composition containing quantum dots (such as dispersibility, heat resistance, and curing rate), but will deteriorate other properties except the improved property. In other words, regarding the properties of the curable composition containing quantum dots, there is no known technique for a curable composition containing quantum dots that can maintain a low viscosity and achieve high light resistance.

[0092] Specifically, the techniques known so far include methods of encapsulating the surface of quantum dots using a polymer containing a heat-resistant functional group or a silicone (or an organic material such as tetraethoxysilane (TEOS)) system, or encapsulating the surface of quantum dots using aluminum, titanium, or their oxides. In addition, recently, attempts have been made to simultaneously improve the brightness and durability by doping a small amount of transition metal (Cu, Mg, etc.) components into the quantum dot synthesis.

[0093] However, the above methods are still in the stage of academic research and are still far from being actually applied to displays.

[0094] Therefore, the inventors of the present invention repeatedly conducted research and completed a curable composition that has excellent light resistance reliability even under high light resistance conditions by surface-modifying quantum dots using two different types of surface-modifying materials. For example, the curable composition according to the embodiment contains: (A) quantum dots, including a first functional group represented by Chemical Formula 1 and a second functional group including a *-OC(=O) group at the end; and (B) a polymerizable compound.

[0095] [Chemical Formula 1]

[0096]

[0097] In Chemical Formula 1,

[0098] R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a fused ring group thereof,

[0099] L 1 to L 4 each independently represents a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1-C20 alkylene group, and

[0100] n is an integer from 1 to 20.

[0101] Since the current display market is changing towards generating clear light with smaller pixels and thinner thickness (such as μ-LED and nano-LED), the curable composition according to the embodiment has extremely excellent light resistance reliability under high light resistance conditions and conforms to the current display market trend. On the contrary, compared with before surface modification, the conventional quantum dot photoresist composition generally using a thiol-based ligand as a quantum dot surface modification material can improve light resistance reliability, but the light retention rate (light resistance reliability) deteriorates under high light resistance conditions of blue LEDs, and thus there is a problem that it cannot be used as a backlight for emitting extremely strong light (such as μ-LED or nano-LED).

[0102] According to the embodiment, since the first functional group represented by Chemical Formula 1 and the second functional group including *-OC(=O) group at the end are simultaneously used as a quantum dot surface modification material, extremely excellent light resistance reliability can be achieved under high light resistance conditions. Since the first functional group is derived from a thiol-based ligand and the second functional group is derived from a carboxyl ligand, different from when the thiol-based ligand and the carboxyl ligand are used as quantum dot surface modification materials respectively, when the thiol-based ligand and the carboxyl ligand are simultaneously used as quantum dot surface modification materials, the light resistance reliability can be improved under high light resistance conditions. Even when two different types of thiol-based ligands are used as quantum dot surface modification materials, or when two different types of carboxyl ligands are used as quantum dot surface modification materials, it is difficult to improve the light resistance reliability under high light resistance conditions, and any combination of a thiol-based ligand and a carboxyl ligand as in the embodiment is also most favorable for improving the light resistance reliability under high light resistance conditions.

[0103] Hereinafter, each component constituting the curable composition according to the embodiment will be described in detail.

[0104] Quantum dots

[0105] As is well known, the most efficient ligand capable of passivating the surface of quantum dots as an organic material ligand is a ligand having a thiol group. Among them, the interaction between the carboxylic acid type ligand and the surface of the quantum dots is relatively weak, and the phosphoric acid type ligand has sufficient quantum dot dispersibility, but there is a problem of reduced efficiency (causing color change).

[0106] Since display technology has evolved from the past LCD to OLED, near-eye display (NED), and most recently micro-LED, which gradually increases the intensity of blue light, the durability (especially light resistance) of quantum dots needs to be significantly improved compared to the current level.

[0107] Therefore, in order to provide effective passivation of the quantum dot surface, a surface modification material is constructed by using a combination of a thiol-based ligand (first functional group) and a carboxyl ligand (second functional group). When the curable composition containing quantum dots with the ligand for surface modification is loaded as a single film on a display panel, even when exposed to strong blue light such as micro-LED for a long time, the curable composition containing quantum dots can maintain the initial light efficiency and has extremely excellent light resistance reliability.

[0108] For example, the second functional group can be represented by Chemical Formula 2.

[0109] [Chemical Formula 2]

[0110]

[0111] In Chemical Formula 2,

[0112] R 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or *-C(=O)R 3 , where R 3 is a C1-C10 alkyl group or (where R a to R c are each independently a hydrogen atom or a C1-C10 alkyl group),

[0113] L 5 to L 7Each is independently a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1 to C20 alkylene group, and

[0114] m is an integer from 1 to 20.

[0115] For example, Chemical Formula 2 can be represented by any one of Chemical Formulas 2A to 2C.

[0116] [Chemical Formula 2A]

[0117]

[0118] [Chemical Formula 2B]

[0119]

[0120] [Chemical Formula 2C]

[0121]

[0122] In Chemical Formulas 2A to 2C,

[0123] R 3 to R 5 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0124] L 8 to L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group, and

[0125] p is an integer from 1 to 20.

[0126] For example, the first functional group and the second functional group can be included in a molar ratio of 1:0.5 to 1:1.5. When the first functional group and the second functional group are included in the above molar ratio range, the light resistance reliability of the curable composition according to the examples can be maximized.

[0127] For example, the first functional group can be represented by at least one selected from Chemical Formulas 1-1 to 1-3, but is not necessarily limited thereto.

[0128] [Chemical Formula 1-1]

[0129]

[0130] [Chemical Formula 1-2]

[0131]

[0132] [Chemical Formula 1-3]

[0133]

[0134] For example, the second functional group may be represented by at least one selected from Chemical Formulas 2-1 to 2-4, but is not necessarily limited thereto.

[0135] [Chemical Formula 2-1]

[0136]

[0137] [Chemical Formula 2-2]

[0138]

[0139] [Chemical Formula 2-3]

[0140]

[0141] [Chemical Formula 2-4]

[0142]

[0143] For example, the first functional group may be derived from a compound represented by Chemical Formula 3.

[0144] [Chemical Formula 3]

[0145]

[0146] In Chemical Formula 3,

[0147] R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a fused ring group thereof,

[0148] L 1 to L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1-C20 alkylene group, and

[0149] n is an integer from 1 to 20.

[0150] For example, the compound represented by Chemical Formula 3 may be represented by at least one selected from Chemical Formulas 3-1 to 3-3, but is not necessarily limited thereto.

[0151] [Chemical Formula 3-1]

[0152]

[0153] [Chemical Formula 3-2]

[0154]

[0155] [Chemical Formula 3-3]

[0156]

[0157] For example, the second functional group can be derived from a compound represented by Chemical Formula 4.

[0158] [Chemical Formula 4]

[0159]

[0160] In Chemical Formula 4,

[0161] R 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or *-C(=O)R 3 , where R 3 is a C1-C10 alkyl group or (where R a to R c are each independently a hydrogen atom or a C1-C10 alkyl group),

[0162] L 5 to L 7 are each independently a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1-C20 alkylene group, and

[0163] m is an integer from 1 to 20.

[0164] For example, the compound represented by Chemical Formula 4 can be represented by at least one selected from Chemical Formulas 4-1 to 4-4, but is not necessarily limited thereto.

[0165] [Chemical Formula 4-1]

[0166]

[0167] [Chemical Formula 4-2]

[0168]

[0169] [Chemical Formula 4-3]

[0170]

[0171] [Chemical Formula 4-4]

[0172]

[0173] If quantum dots surface-modified with a surface-modifying material are added to a polymerizable compound described later and stirred, a highly transparent dispersion can be obtained, which is a criterion for confirming excellent surface modification of the quantum dots.

[0174] For example, the quantum dots may have a maximum fluorescence emission wavelength at 500 nm to 680 nm.

[0175] For example, the quantum dots may be included in an amount of 1 wt% to 40 wt%, such as 3 wt% to 30 wt%, based on the total amount of the curable composition. If the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0176] For example, the quantum dots absorb light in a wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emit fluorescence in a wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm or in a wavelength region of 600 nm to 680 nm. That is, the quantum dots may have a maximum fluorescence emission wavelength at 500 nm to 680 nm (fluorescence λ em ).

[0177] The quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, such as 20 nm to 50 nm. If the quantum dots have a FWHM within the above range, color reproducibility is increased due to high color purity when used as a color material in a color filter.

[0178] The quantum dots may each independently be an organic material, an inorganic material, or a hybrid (mixture) of an organic material and an inorganic material.

[0179] The quantum dots may each independently be composed of a core and a shell surrounding the core, and the core and the shell may each independently have a structure such as a core, a core / shell, a core / first shell / second shell, an alloy, an alloy / shell, etc. composed of Group II-IV, Group III-V, etc., but are not limited thereto.

[0180] For example, the core may include at least one material selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and their alloys, but is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and their alloys, but is not necessarily limited thereto.

[0181] In an embodiment, due to the fact that the worldwide concern for the environment has increased significantly recently and the restrictions on toxic materials have been strengthened, a cadmium-free luminescent material (InP / ZnS, InP / ZnSe / ZnS, etc.) with a slightly lower quantum efficiency (quantum yield) but environmentally harmless is used to replace the luminescent material with a cadmium-based core, but it is not necessarily limited thereto.

[0182] In the case of quantum dots in a core / shell structure, the overall size (average particle diameter) including the shell may be from 1 nanometer to 15 nanometers, for example, from 5 nanometers to 15 nanometers.

[0183] For example, the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may each independently have an average particle diameter of 10 nanometers to 15 nanometers. The green quantum dots may each independently have an average particle diameter of 5 nanometers to 8 nanometers.

[0184] On the other hand, to achieve the dispersion stability of the quantum dots, the curable composition according to the embodiment may further contain a dispersant. The dispersant helps the uniform dispersion of light conversion materials such as quantum dots in the curable composition and may include nonionic dispersants, anionic dispersants, or cationic dispersants. Specifically, the dispersant may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonate ester, sulfonate salt, carboxylate ester, carboxylate salt, alkylamide alkylene oxide adduct, alkylamine, etc., and it may be used alone or in the form of a mixture of two or more. Based on the solid content of the light conversion material (such as quantum dots), a 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.

[0185] Polymerizable compound

[0186] The curable composition according to the embodiment may contain a polymerizable compound, and the polymerizable compound may have a carbon-carbon double bond at its end.

[0187] For example, the polymerizable compound having a carbon-carbon double bond at its end may have a molecular weight of 170 g / mol to 1,000 g / mol. If the molecular weight of the polymerizable compound having a carbon-carbon double bond at its end is within the above range, it may be beneficial for inkjet printing because it does not increase the viscosity of the composition and does not interfere with the optical properties of the quantum dots.

[0188] For example, the polymerizable compound having a carbon-carbon double bond at its end may be represented by Chemical Formula 6, but it is not necessarily limited thereto.

[0189] [Chemical Formula 6]

[0190]

[0191] In Chemical Formula 6,

[0192] R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group,

[0193] L 14 and L 16 are each independently a single bond or a substituted or unsubstituted C1-C10 alkylene group, and

[0194] L 15 is a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, or an ether group (*-O-*).

[0195] For example, a polymerizable compound having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 6-1, Chemical Formula 6-2, or Chemical Formula 6-3, but is not necessarily limited thereto.

[0196] [Chemical Formula 6-1]

[0197]

[0198] [Chemical Formula 6-2]

[0199]

[0200] [Chemical Formula 6-3]

[0201]

[0202] For example, in addition to the above compounds of Chemical Formula 6-1, Chemical Formula 6-2, or Chemical Formula 6-3, polymerizable compounds having a carbon-carbon double bond at the terminal 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 epoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

[0203] In addition, together with the polymerizable compound having a carbon-carbon double bond at the end, common monomers of conventional thermosetting or photocurable compositions may also be included. For example, the monomers also include oxetane compounds such as bis[1-ethyl(3-oxetane)]methyl ether.

[0204] In addition, when the curable composition contains a solvent, the polymerizable compound may be included in an amount of 1 wt% to 20 wt%, 1 wt% to 15 wt%, for example 1 wt% to 10 wt% based on the total amount of the curable composition. If the polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved.

[0205] Light diffusing agent

[0206] The curable composition according to the embodiment may also include a light diffusing agent.

[0207] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or a combination thereof.

[0208] The light diffusing agent can reflect the light not absorbed in the aforementioned quantum dots and allow the quantum dots to absorb the reflected light again. That is, the light diffusing agent can increase the amount of light absorbed by the quantum dots and increase the light conversion efficiency of the curable composition.

[0209] The light diffusing agent may have an average particle size (D 50 ) of 150 nm to 250 nm, and specifically 180 nm to 230 nm. If the average particle size of the light diffusing agent is within the above range, it can have a better light diffusing effect and increase the light conversion efficiency.

[0210] Based on the total amount of the curable composition, the light diffusing agent may be included in an amount of 1 wt% to 20 wt%, for example 2 wt% to 15 wt%, for example 3 wt% to 10 wt%. If the light diffusing agent is included in an amount less than 1 wt% based on the total amount of the curable composition, it is difficult to expect the effect of improving the light conversion efficiency due to the use of the light diffusing agent, and if the light diffusing agent is included in an amount greater than 20 wt%, there is a possibility that the quantum dots may precipitate.

[0211] Polymerization initiator

[0212] The curable composition according to the embodiment may also include a polymerization initiator, such as a photoinitiator, a thermal initiator, or a combination thereof.

[0213] A photoinitiator is generally an initiator used in a photosensitive resin composition, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, an aminoketone-based compound, etc., but is not necessarily limited thereto.

[0214] Examples of acetophenone-based compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0215] Examples of benzophenone-based compounds may be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 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, etc.

[0216] Examples of thioxanthone-based compounds may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0217] Examples of benzoin-based compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0218] Examples of the triazine-based compounds may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 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-piperonyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0219] Examples of the oxime-based compounds may be O-acyl oxime-based compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyl oxime-based 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)-octan-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, etc.

[0220] Examples of the amino ketone-based compounds may be 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0221] In addition to the above-mentioned compounds, the photoinitiator may further include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, etc.

[0222] The photoinitiator can be used together with a photosensitizer that can cause a chemical reaction by absorbing light and become excited and then transfer its energy.

[0223] Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, etc.

[0224] Examples of the thermal polymerization initiator may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2'-azobis(isobutyronitrile), tert-butyl perbenzoate, etc., such as 2,2'-azobis-2-methylpropionitrile, but not necessarily limited thereto, and any one well-known in this art may be used.

[0225] Based on the total amount of the curable composition, the polymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt%. If the polymerization initiator is included within the above range, excellent reliability can be obtained due to sufficient curing during exposure or thermal curing, and deterioration of the transmittance can be prevented due to non-reactive initiators, thereby preventing deterioration of the optical properties of the quantum dots.

[0226] Binder resin

[0227] The curable composition according to the embodiment may further include an adhesive resin.

[0228] The adhesive resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0229] 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.

[0230] Specific examples of the acrylic resin may be polybenzyl methacrylate, (meth)acrylic acid / methyl methacrylate copolymer, (meth)acrylic acid / methyl methacrylate / styrene copolymer, (meth)acrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / methyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but not limited thereto, and these may be used alone or in the form of a mixture of two or more.

[0231] The weight average molecular weight of the acrylic resin may be 5,000 g / mol to 15,000 g / mol. If the weight average molecular weight of the acrylic resin is within the above range, the close contact property, physical and chemical properties with the substrate are improved, and the viscosity is appropriate.

[0232] The acid value of the acrylic resin may be 80 mg KOH / g to 130 mg KOH / g. If the acid value of the acrylic resin is within the above range, excellent pixel resolution can be obtained.

[0233] The cardo-based resin can be used in conventional curable resin (or photosensitive resin) compositions. For example, a composition as proposed in Korean Patent Publication No. 10-2018-0067243 can be used, but it is not limited thereto.

[0234] The cardo-based resin can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds such as 9,9-bis(4-glycidyloxymethoxyphenyl)fluorene; acid anhydride compounds such as pyromellitic 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-based compounds such as propylene glycol methyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

[0235] The weight-average molecular weight of the cardo-based binder resin can be 500 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 30,000 g / mol. If the weight-average molecular weight of the cardo-based binder resin is within the above range, a satisfactory pattern can be formed without residues during the production of the cured layer and without loss of film thickness during the development of the curable composition.

[0236] If the binder resin is a cardo-based resin, the curable composition containing the binder resin, specifically the photosensitive resin composition, has excellent developability and sensitivity during photocuring and thus has fine pattern-forming ability.

[0237] The epoxy resin can be a thermopolymerizable monomer or oligomer and can contain compounds having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

[0238] The epoxy resin may further include 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.

[0239] As commercially available products of these compounds, bisphenol epoxy resins may be YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co., Ltd.; cresol novolac epoxy resins may be EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 of Nippon Kayaku Co., Ltd., and EPIKOTE 180S75 etc. of Yuka Shell Epoxy Co., Ltd.; bisphenol A epoxy resins may be EPIKOTE 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 of Yuka Shell Epoxy Co., Ltd.; bisphenol F epoxy resins may be EPIKOTE807 and 834 of Yuka Shell Epoxy Co., Ltd.; phenol novolac epoxy resins may be EPIKOTE 152, 154 or 157H65 of Yuka Shell Epoxy Co., Ltd., and EPPN 201, 202 of Nippon Kayaku Co., Ltd., and EPPN 201, 202 of Nippon Kayaku Co., Ltd.; cycloaliphatic epoxy resins may be CY175, CY177 and CY179 of CIBA-GEIGY A.G Corp., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 of U.C.C., Shodyne 509 of Showa Denko K.K., Araldite CY-182, CY-192 and CY-184 of CIBA-GEIGY A.G Corp., EPICLON 200 and 400 of Dainippon Ink&Chemicals Inc., EPIKOTE 871 and 872 and EP1032H60 of Yuka Shell Epoxy Co., Ltd., ED-5661 and ED-5662 of Celanese Coating Corporation; aliphatic polyglycidyl ethers may be EPIKOTE 190P and 191P of Yuka Shell Epoxy Co., Ltd., EPOLITE 100MF of Kyoeisha YushiKagaku Kogyo Co., Ltd., EPIOL TMP of NihonYushi K.K., etc.

[0240] For example, based on the total amount of the curable composition, the binder resin may be included in an amount of 1 wt% to 30 wt%, such as 3 wt% to 20 wt%. In such a case, the pattern properties, heat resistance, and chemical resistance can be improved.

[0241] Other additives

[0242] To improve the stability and dispersibility of the quantum dots, the curable composition according to the embodiment may further include a polymerization inhibitor.

[0243] The polymerization inhibitor may include a hydroquinone-based compound, a catechol-based compound, or a combination thereof, but is not necessarily limited thereto. When the curable composition according to the embodiment further includes a hydroquinone-based compound, a catechol-based compound, or a combination thereof, room-temperature crosslinking during exposure can be prevented after the curable composition is coated.

[0244] For example, the hydroquinone-based compound, the catechol-based compound, or the combination thereof may be hydroquinone, methyl hydroquinone, methoxy hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tert-butyl catechol, 4-methoxy catechol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamino-O,O')aluminum, or a combination thereof, but is not necessarily limited thereto.

[0245] The hydroquinone-based compound, the catechol-based compound, or the combination thereof may be used in the form of a dispersion. Based on the total amount of the curable composition, the polymerization inhibitor in the form of a dispersion may be included in an amount of 0.001 wt% to 3 wt%, such as 0.01 wt% to 2 wt%. If the polymerization inhibitor is included within the above range, the aging problem at room temperature can be solved, and at the same time, sensitivity deterioration and surface delamination can be prevented.

[0246] In addition, the curable composition according to the embodiment may further include malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof to improve heat resistance and reliability.

[0247] For example, the curable composition according to the embodiment may further include a silane-based coupling agent having reactive substituents such as vinyl, carboxyl, methacryloxy, isocyanate, epoxy, etc. to improve the close contact property with the substrate.

[0248] Examples of the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., and these coupling agents may be used alone or in the form of a mixture of two or more kinds.

[0249] Based on 100 parts by weight of the curable composition, the silane coupling agent may be used in an amount of 0.01 part by weight to 10 parts by weight. If the silane coupling agent is included within the said range, properties such as close contact property and storage ability are improved.

[0250] In addition, the curable composition may further contain a surfactant (e.g., a fluorine-based surfactant) as needed to improve the coating property and suppress the generation of spots, that is, to improve the leveling performance.

[0251] 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 in a 0.1% polyethyleneglycolmonomethylether acetate (PGMEA) solution). If the fluorine-based surfactant has a weight average molecular weight and a surface tension within the said range, the leveling performance can be further improved, and when applied as a slot die coating for high-speed coating, excellent characteristics can be provided because film defects can be less generated by preventing the generation of spots and suppressing the generation of vapor during high-speed coating.

[0252] Examples of the fluorine-based surfactant may be and (BM Chemie Inc.); MEGAFACE F F F and F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FULORAD FULORAD and FULORAD (Sumitomo 3M Co., Ltd.); SURFLON SURFLON SURFLON Safron and Safron (Asahi Glass Co., Ltd.); and and etc. (Toray Silicone Co., Ltd.); F-482, F-484, F-478, F-554, etc. of DIC Co., Ltd.

[0253] In addition to fluorine-based surfactants, the curable composition according to the examples may contain silicone-based surfactants. Specific examples of the silicone-based surfactants may be TSF400, TSF401, TSF410, TSF4440, etc. of Toshiba Silicone Co., Ltd., but are not limited thereto.

[0254] Based on 100 parts by weight of the curable composition, the surfactant may be contained in an amount of 0.01 part by weight to 5 parts by weight, for example, 0.1 part by weight to 2 parts by weight. If the surfactant is contained within the above range, foreign substances will be less likely to be generated in the ejected composition.

[0255] In addition, unless the properties are deteriorated, the curable composition according to the examples may further contain other additives, such as antioxidants, stabilizers, etc. in a predetermined amount.

[0256] Solvent

[0257] Meanwhile, the curable composition according to the examples may further contain a solvent.

[0258] Solvents can include, for example: alcohols such as methanol, ethanol, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc.; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; 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, etc.; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, 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.; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, etc.; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; 2-alkoxy-2-methylpropionic acid alkyl esters 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, 2-hydroxy-3-methylmethyl butyrate, etc.; or keto acid esters such as ethyl pyruvate, etc. In addition, it can be N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate, etc., but not limited thereto.

[0259] For example, the solvent may desirably 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.; an 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.; an alcohol such as ethanol, etc. or a combination thereof.

[0260] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone or a combination thereof.

[0261] Based on the total amount of the curable composition, the solvent may be included in an amount of, for example, 40 wt% to 80 wt%, such as 45 wt% to 80 wt% of the balance. If the solvent is within the said range, the solvent-based curable composition has an appropriate viscosity and thus can have excellent coating properties when being coated over a large area by spin coating and slot coating.

[0262] Another embodiment provides a cured layer produced using the above curable composition and a display device including the cured layer. For example, the display device may include a micro LED light source.

[0263] One of the methods for manufacturing the cured layer is to use the curable composition to manufacture the cured layer by a lithography method, and the manufacturing method is as follows.

[0264] (1) Coating and film formation

[0265] The curable composition is coated on a substrate that has undergone a predetermined pretreatment to have a desired thickness, such as a thickness in the range of 2 μm to 10 μm, by a spin coating or slot coating method, a roll coating method, a screen printing method, a coater method, etc. Then, the coated substrate is heated at a temperature of 70°C to 90°C for 1 minute to 10 minutes to remove the solvent and form a film.

[0266] (2) Exposure

[0267] After placing a mask having a predetermined shape, the obtained film is irradiated with actinic rays such as UV rays of, for example, 190 nm to 450 nm, such as 200 nm to 400 nm, to form a desired pattern. As the light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, an i-line, a KrF, an ArF, an I-ArF, an EUV, an X-ray, an electron beam, etc. can be used as needed.

[0268] When using a high-pressure mercury lamp, the exposure process uses a light dose of, for example, 500 mJ / cm² or less than 500 mJ / cm² (using a 365 nm sensor). However, the light dose may vary depending on the type of each component of the curable composition, its combination ratio, and the dry film thickness.

[0269] (3) Development

[0270] After the exposure process, the exposed film is developed using an alkaline aqueous solution by dissolving and removing the excess portions except for the exposed portions to form an image pattern. In other words, when using an alkaline developing solution for development, the unexposed areas are dissolved, and an image color filter pattern is formed.

[0271] (4) Post-treatment

[0272] The developed image pattern can be cured by heating again or irradiating the developed image pattern with actinic rays, etc., to achieve excellent qualities in terms of heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, storage stability, etc.

[0273] Modes for implementing the present application

[0274] Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the present invention in any sense.

[0275] (Synthesis of surface modification material)

[0276] Synthesis Example 1

[0277] 100 g of PH-4 (Hannong Chemical Inc.) was added to a two-necked round-bottom flask and then fully dissolved in 300 mL of THF (tetrahydrofuran). Subsequently, 15.4 g of NaOH and 100 mL of water were added thereto at 0 °C and then fully dissolved until a clear solution was obtained. Then, a solution prepared by dissolving 73 g of p-toluenesulfonyl chloride in 100 mL of THF was slowly injected therein at 0 °C. The injection was carried out 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, a saturated NaHCO3 solution was added thereto and then extraction, titration and dehydration were carried out. After removing the solvent, the residue was dried under reduced pressure for 24 hours. 50 g of the dried product was added to a two-necked round-bottom flask and then fully stirred in 300 mL of ethanol. Subsequently, 27 g of thiourea was added thereto and dispersed therein, and then refluxed at 80 °C for 12 hours. After injecting an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water, an excess of dichloromethane was added thereto while further stirring for 5 minutes, and then the mixture was stirred, and an aqueous hydrochloric acid solution was added thereto to carry out extraction, titration, dehydration and solvent removal in sequence. The resulting product was dried under reduced pressure for 24 hours to obtain the compound represented by Chemical Formula 3-1.

[0278] [Chemical Formula 3-1]

[0279]

[0280] Synthesis Example 2

[0281] 100 g of THF-4 (Hannon Chemical Co., Ltd.) was added to a two-necked round-bottomed flask and then fully dissolved in THF. Subsequently, 43.1 g of NaOH and 100 mL of water were added thereto at 0 °C and then fully dissolved until a clear solution was obtained. Then, a solution prepared by dissolving 102.7 g of p-toluenesulfonyl chloride in 100 mL of THF was slowly added thereto at 0 °C. The injection was carried out for 1 hour, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, an excess of dichloromethane was added thereto, and then the mixture was stirred. A saturated NaHCO3 solution was added thereto, and then extraction, titration, and dehydration were carried out. After removing the solvent, the residue was dried under reduced pressure for 24 hours. 150 g of the dried product was added to a two-necked round-bottomed flask and then fully stirred in 1.5 L of ethanol. Subsequently, 47.5 g of thiourea was added thereto and dispersed therein, and then the mixture was refluxed at 80 °C for 12 hours. After injecting an aqueous solution of 13.2 g of NaOH dissolved in 60 mL of water thereto, an excess of dichloromethane was added thereto while further stirring for 5 hours, and then the mixture was stirred. An aqueous hydrochloric acid solution was added thereto, and then extraction, titration, dehydration, and solvent removal were carried out in sequence. The resulting product was dried under reduced pressure for 24 hours to obtain the compound represented by Chemical Formula 3-2.

[0282] [Chemical Formula 3-2]

[0283]

[0284] Synthesis Example 3

[0285] 100 g of HDCP-4 (Hannon Chemical Co., Ltd.) was added to a two-necked round-bottom flask and then completely dissolved in 300 mL of THF. Subsequently, 49.0 g of NaOH and 100 mL of water were added thereto at 0 °C and then completely dissolved until a clear solution was obtained. Then, a solution prepared by dissolving 116.8 g of p-toluenesulfonyl chloride in 100 mL of THF was slowly injected thereto at 0 °C. The injection was carried out for 1 hour, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, dichloromethane was added thereto, and then the mixture was stirred. A saturated NaHCO3 solution was added thereto and then extraction, titration, and dehydration were carried out. After removing the solvent, the residue was dried under reduced pressure for 12 hours. 140 g of the dried product was added to a two-necked round-bottom flask and sufficiently stirred in 1.5 L of ethanol. Subsequently, 41.9 g of thiourea was added thereto and dispersed therein, and then refluxed at 80 °C for 12 hours. After injecting an aqueous solution of 13.2 g of NaOH dissolved in 60 mL of water thereto, an excessive amount of dichloromethane was added thereto while further stirring for 5 hours, and then the mixture was stirred. An aqueous hydrochloric acid solution was added thereto and then extraction, titration, dehydration, and solvent removal were carried out in sequence. The resulting product was dried under reduced pressure for 24 hours to obtain the compound represented by Chemical Formula 3-3.

[0286] [Chemical Formula 3-3]

[0287]

[0288] Synthesis Example 4

[0289] 10 g of 2-hydroxyethyl acetate was added to a round-bottom flask and then completely dissolved in 150 mL of CH2Cl2. Subsequently, 9.6 g of succinic anhydride and 0.1 g of DMAP (4-dimethylaminopyridine) were added thereto, and then stirred at room temperature for 13 hours. The reaction product was washed with 100 mL of 1N aqueous HCl solution and additionally washed with 100 mL of water, and the resulting organic layer was dried under reduced pressure to obtain the compound represented by Chemical Formula 4-2.

[0290] [Chemical Formula 4-2]

[0291]

[0292] Synthesis Example 5

[0293] 12.5 g of 2 - hydroxyethyl methacrylate was added to a round - bottom flask and then completely dissolved in 150 mL of CH₂Cl₂. Subsequently, 9.6 g of succinic anhydride and 0.1 g of DMAP were added thereto, and then the mixture was stirred at room temperature for 13 hours. The reaction product was washed with 120 mL of 1N aqueous HCl solution and additionally washed with 120 mL of water, and the resulting organic layer was dried under reduced pressure to obtain the compound represented by Chemical Formula 4 - 3.

[0294] [Chemical Formula 4 - 3]

[0295]

[0296] Synthesis Example 6

[0297] 11.2 g of 2 - hydroxyethyl acrylate was added to a round - bottom flask and then completely dissolved in 150 mL of CH₂Cl₂. Subsequently, 9.6 g of succinic anhydride and 0.1 g of DMAP were added thereto and then the mixture was stirred at room temperature for 13 hours. The reaction product was washed with 110 mL of 1N aqueous HCl solution and additionally washed with 110 mL of water, and the resulting organic layer was dried under reduced pressure to obtain the compound represented by Chemical Formula 4 - 4.

[0298] [Chemical Formula 4 - 4]

[0299]

[0300] (Preparation of Surface - Modified Quantum Dots)

[0301] After placing a magnetic bar into a three - necked round - bottom flask, a green quantum dot dispersion solution (26 wt% of quantum dot solids; InP / ZnSe / ZnS, Hansol Chemical) was placed therein. Then, the surface - modifying materials according to Synthesis Examples 1 to 7 were added thereto, and then the mixture was stirred at 80 °C under a nitrogen atmosphere. When the reaction was completed, the quantum dot reaction solution was cooled to room temperature (23 °C) and added to cyclohexane to precipitate the product. The precipitate was separated from cyclohexane by centrifugation and thoroughly dried in a vacuum oven for one day to obtain surface - modified green quantum dots.

[0302] (Preparation of Curable Compositions)

[0303] Based on each of the following components, curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 were prepared.

[0304] (A) Quantum dots

[0305] (A-1) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-1 (M2963, TCI) (molar ratio = 1:1)

[0306] (A-2) Green quantum dots surface-modified with the compound of Chemical Formula 3-2 and the compound of Chemical Formula 4-1 (molar ratio = 1:1)

[0307] (A-3) Green quantum dots surface-modified with the compound of Chemical Formula 3-3 and the compound of Chemical Formula 4-1 (molar ratio = 1:1)

[0308] (A-4) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-1 (molar ratio = 1:0.5)

[0309] (A-5) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-1 (molar ratio = 1:1.5)

[0310] (A-6) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-1 (molar ratio = 1:0.3)

[0311] (A-7) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-1 (molar ratio = 1:1.2)

[0312] (A-8) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-2 (molar ratio = 1:1)

[0313] (A-9) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-3 (molar ratio = 1:1)

[0314] (A-10) Green quantum dots surface-modified with the compound of Chemical Formula 3-1 and the compound of Chemical Formula 4-4 (molar ratio = 1:1)

[0315] (A-11) Green quantum dots surface-modified with the compound of Chemical Formula 3-1

[0316] (A-12) Green quantum dots surface-modified with the compound of Chemical Formula 3-2

[0317] (A-13) Green quantum dots surface-modified with the compound of Chemical Formula 3-3

[0318] (A-14) Green quantum dots surface-modified with the compound of Chemical Formula 4-1

[0319] (A-15) Green quantum dots surface-modified with the compound of Chemical Formula 4-2

[0320] (A-16) Green quantum dots surface-modified with the compound of Chemical Formula 4-3

[0321] (A-17) Green quantum dots surface-modified with the compound of Chemical Formula 4-4

[0322] (A-18) Green quantum dots without surface modification

[0323] [Chemical Formula 4-1]

[0324]

[0325] (B) Polymerizable compound

[0326] Compound represented by Chemical Formula 6-2 (M200, Miwon Chemical Co., Ltd.)

[0327] [Chemical Formula 6-2]

[0328]

[0329] (C) Photoinitiator

[0330] TPO-L (Polynetron Co.)

[0331] (D) Light diffusing agent

[0332] Titanium dioxide dispersion (rutile TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0333] (E) Solvent

[0334] PGMEA (Sigma-Aldrich Corporation)

[0335] (F) Binder resin

[0336] Acrylic binder resin (SP-RY67-1, Showa Denko)

[0337] (G) Other additives

[0338] Fluorine-based surfactant (F-554, DIC Co., Ltd.)

[0339] Examples 1 to 10 and Comparative Examples 1 to 8

[0340] The curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 were prepared using the following components for each of the compositions shown in Tables 1 and 2.

[0341] [Table 1]

[0342] (Unit: wt%)

[0343]

[0344] [Table 2]

[0345] (Unit: wt%)

[0346]

[0347] Evaluation 1: Evaluation of the light efficiency of the curable composition

[0348] The light efficiency of each of the curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 was evaluated, and the results are shown in Table 3.

[0349] (Method for evaluating light efficiency)

[0350] Each of the curable compositions was coated, exposed, and baked to prepare a single-layer sample having a size of 2 cm × 2 cm, and then the light efficiency, pattern characteristics, and surface sensitivity were measured under a blue 20,000 nits light source condition using a self-made blue LED planar light source for illumination.

[0351] In addition, the light efficiency of the single-layer sample was measured using an integrating sphere device (QE-2100, Otsuka Electronics Co., Ltd.) and an in-line luminance meter (M7000, Mcscience Inc.).

[0352] Furthermore, the pattern characteristics and surface sensitivity of the single-layer sample were visually inspected using a scanning electron microscope (SEM) and evaluated as Good or Inferior.

[0353] [Table 3]

[0354] Light efficiency (%) Pattern characteristics Surface sensitivity Example 1 33.8 Good Good Example 2 33.7 Good Good Example 3 33.6 Good Good Example 4 33.6 Good Good Example 5 33.7 Good Good Example 6 33.5 Good Good Example 7 33.5 Good Good Example 8 33.7 Good Good Example 9 33.8 Good Good Example 10 33.7 Good Good Comparative Example 1 33.2 Good Good Comparative Example 2 33.5 Good Good Comparative Example 3 33.1 Good Good Comparative Example 4 33.2 Good Good Comparative Example 5 33.2 Good Good Comparative Example 6 33.1 Good Good Comparative Example 7 33.3 Good Good Comparative Example 8 33.0 Good Good

[0355] Referring to Table 3, all of the curable compositions of Examples 1 to 10 and Comparative Examples 1 to 8 exhibited excellent light efficiency, pattern characteristics, and surface sensitivity.

[0356] Evaluation 2: Evaluation of the light resistance reliability of the curable composition under high light resistance conditions

[0357] The light resistance reliability (light retention rate) of each of the curable compositions of Examples 1 to 10 and Comparative Examples 1 to 8 was evaluated under high light resistance conditions (when allowed to be placed under a blue backlight of 100,000 nits or more for 500 hours or more), and the results are shown in Table 4.

[0358] [Table 4]

[0359] Light resistance reliability (%) Example 1 67 Example 2 65 Example 3 62 Example 4 63 Example 5 64 Example 6 57 Example 7 58 Example 8 63 Example 9 64 Example 10 62 Comparative Example 1 45 Comparative Example 2 48 Comparative Example 3 42 Comparative Example 4 41 Comparative Example 5 44 Comparative Example 6 45 Comparative Example 7 43 Comparative Example 8 31

[0360] Referring to Table 4, the curable compositions of Examples 1 to 10 exhibited extremely excellent light resistance reliability under high light resistance conditions compared to the curable compositions of Comparative Examples 1 to 8. In addition, by controlling the molar ratio of the first functional group to the second functional group, the light resistance reliability was further improved.

[0361] Although the present invention has been described in connection with exemplary embodiments that are presently considered to be practical, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the claims. Accordingly, the above embodiments should be understood as illustrative and not as limiting the present invention in any way.

Claims

1. A curable composition, comprising: (A) Quantum dots, including a first functional group represented by Chemical Formula 1 and a second functional group including a *-OC(=O) group at the end; and (B) A polymerizable compound: [Chemical Formula 1] Among them, In Chemical Formula 1, R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a fused ring group thereof. L 1 to L 4 each independently represents a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and n is an integer from 1 to 20.

2. The curable composition according to claim 1, wherein the second functional group is represented by Chemical Formula 2: [Chemical Formula 2] Among them, In Chemical Formula 2, R 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or *-C(=O)R 3 , where R 3 is a C1-C10 alkyl group or (where R a to R c are each independently a hydrogen atom or a C1-C10 alkyl group), L 5 to L 7 each independently is a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1 to C20 alkylene group, and m is an integer from 1 to 20.

3. The curable composition according to claim 1, wherein the first functional group and the second functional group are included in a molar ratio of 1:0.5 to 1:1.

5.

4. The curable composition according to claim 1, wherein the first functional group is represented by at least one selected from 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 second functional group is represented by at least one selected from Chemical Formulas 2-1 to 2-4: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] 6. The curable composition according to claim 1, wherein the first functional group is derived from a compound represented by Chemical Formula 3: [Chemical Formula 3] Among them, In Chemical Formula 3, R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a fused ring group thereof. L 1 to L 4 each independently is a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, and n is an integer from 1 to 20.

7. The curable composition according to claim 6, wherein the compound represented by Chemical Formula 3 is represented by at least one selected from Chemical Formulas 3-1 to 3-3: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] 8. The curable composition according to claim 1, wherein the second functional group is derived from a compound represented by Chemical Formula 4: [Chemical Formula 4] Among them, In Chemical Formula 4, R 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or *-C(=O)R 3 , wherein R 3 is a C1-C10 alkyl group or (wherein R a to R c are each independently a hydrogen atom or a C1-C10 alkyl group), L 5 to L 7 each independently is a single bond, an ether group (*-O-*), an ester group (*-C(=O)O-* or *-OC(=O)-*), or a substituted or unsubstituted C1 to C20 alkylene group, and m is an integer from 1 to 20.

9. The curable composition according to claim 8, wherein the compound represented by Chemical Formula 4 is represented by at least one selected from Chemical Formulas 4-1 to 4-4: [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] [Chemical Formula 4-4] 10. The curable composition according to claim 1, wherein the curable composition further comprises a polymerization initiator, an adhesive resin, a light diffusing agent, a solvent, or a combination thereof.

11. The curable composition according to claim 10, wherein the light diffusing agent includes barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

12. The curable composition according to claim 10, wherein the curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a polymerization inhibitor; a silane coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

13. The curable composition according to claim 10, wherein based on the total weight of the curable composition, the curable composition comprises: 1 wt% to 40 wt% of the quantum dots; 1 wt% to 20 wt% of the polymerizable compound; 0.1 wt% to 5 wt% of the polymerization initiator; 1 wt% to 30 wt% of the adhesive resin; 1% to 20% by weight of the light diffusing agent; and 40% to 80% by weight of the solvent.

14. A cured layer, which is made of the curable composition according to any one of claims 1 to 13.

15. A display device, which includes the cured layer according to claim 14.

Images