Curable composition, cured layer produced using composition and display device including cured layer

Abstract

Provided are: a curable composition comprising (A) quantum dots comprising a first functional group represented by a specific chemical formula and a second functional group comprising a *-OC(=O) group at the terminal thereof, and (B) a polymerizable compound; a cured layer produced using the composition; and a display device including the cured layer.

Description

A curable composition, a cured film manufactured using the composition, and a display device comprising the cured film

[0001] The present invention relates to a curable composition, a cured film manufactured using the composition, and a display device including the cured film.

[0002]

[0003] In the case of general quantum dots, the solvents in which they can be dispersed are limited due to their hydrophobic surface characteristics, and as a result, there are many difficulties in introducing them into polar systems such as binders or curable monomers.

[0004] The quantum dot photoresist composition applied to the quantum dot display is composed of a photosensitive monomer, binder, initiator, solvent, and additives as basic components, like the existing photoresist composition, and contains quantum dots and a light diffusing agent instead of a pigment / dye to provide color characteristics, and the quantum dots have the function of converting incident blue light into red and green light after forming a single film.

[0005] Quantum dots, such as CdSe and InP, have rapidly developed in terms of luminous efficiency (Quantum Yield), and currently, synthesis methods with luminous efficiency close to 100% have been introduced, and a QD-OLED TV using a quantum dot ink composition based on an OLED blue backlight has been successfully commercialized. As a follow-up version, a quantum dot display using a blue μ-LED as a backlight is being developed. Since the intensity of this μ-LED light source is much stronger than that of conventional OLEDs, developing a quantum dot photoresist composition that can withstand the strong light of the μ-LED light source for a long time is currently one of the key technologies.

[0006]

[0007] One embodiment is to provide a quantum dot-containing curable composition that has secured light stability, which is the ability to withstand strong light.

[0008] Another embodiment is to provide a cured film manufactured using the curable composition.

[0009] Another embodiment is to provide a display device including the cured film.

[0010]

[0011] One embodiment provides a curable composition comprising (A) a quantum dot comprising a first functional group represented by the following chemical formula 1 and a second functional group comprising a *-OC(=O) group at a terminal, and (B) a polymerizable compound.

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1,

[0015] 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,

[0016] L 1 Inland L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group,

[0017] n is an integer from 1 to 20.

[0018] The above second functional group can be represented by the following chemical formula 2.

[0019] [Chemical Formula 2]

[0020]

[0021] In the above chemical formula 2,

[0022] 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group,

[0023] L 5 Inland 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,

[0024] m is an integer from 1 to 20.

[0025] The first functional group and the second functional group may be included in a molar ratio of 1:0.5 to 1:1.5.

[0026] The above first functional group may be represented by at least one selected from the group consisting of the following chemical formulas 1-1 to 1-3.

[0027] [Chemical Formula 1-1]

[0028]

[0029] [Chemical Formula 1-2]

[0030]

[0031] [Chemical Formula 1-3]

[0032]

[0033] The above second functional group may be represented by at least one selected from the group consisting of the following chemical formulas 2-1 to 2-4.

[0034] [Chemical Formula 2-1]

[0035]

[0036] [Chemical Formula 2-2]

[0037]

[0038] [Chemical Formula 2-3]

[0039]

[0040] [Chemical Formula 2-4]

[0041]

[0042] The above first functional group may be derived from a compound represented by the following chemical formula 3.

[0043] [Chemical Formula 3]

[0044]

[0045] In the above chemical formula 3,

[0046] 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,

[0047] L 1 Inland L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group,

[0048] n is an integer from 1 to 20.

[0049] The compound represented by the above chemical formula 3 can be represented by at least one selected from the group consisting of the following chemical formulas 3-1 to 3-3.

[0050] [Chemical Formula 3-1]

[0051]

[0052] [Chemical Formula 3-2]

[0053]

[0054] [Chemical Formula 3-3]

[0055]

[0056] The above second functional group may be derived from a compound represented by the following chemical formula 4.

[0057] [Chemical Formula 4]

[0058]

[0059] In the above chemical formula 4,

[0060] 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group,

[0061] L 5 Inland 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,

[0062] m is an integer from 1 to 20.

[0063] The compound represented by the above chemical formula 4 can be represented by at least one selected from the group consisting of the following chemical formulas 4-1 to 4-4.

[0064] [Chemical Formula 4-1]

[0065]

[0066] [Chemical Formula 4-2]

[0067]

[0068] [Chemical Formula 4-3]

[0069]

[0070] [Chemical Formula 4-4]

[0071]

[0072] The curable composition may further include a polymerization initiator, a binder resin, a light diffusing agent, a solvent, or a combination thereof.

[0073] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0074] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; a polymerization inhibitor; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof.

[0075] The curable composition may include, based on the total weight of the curable composition, 1 wt% to 40 wt% of the quantum dot; 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 binder resin; 1 wt% to 20 wt% of the light diffusing agent; and 40 wt% to 80 wt% of the solvent.

[0076] Another embodiment provides a cured film manufactured using the curable composition.

[0077] Another embodiment provides a display device including the cured film.

[0078] Specific details of other aspects of the present invention are included in the detailed description below.

[0079]

[0080] By surface-modifying the quantum dots in a quantum dot-containing curable composition with a quantum dot surface-modifying material having an unprecedented composition, the light resistance reliability of the curable composition can be improved.

[0081]

[0082] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0083] Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, "heteroarylene group" means a C3 to C20 heteroarylene group, and "alkoxylene group" means a C1 to C20 It refers to an alkoxylene group.

[0084] Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is substituted with a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 It means substituted with a C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0085] Additionally, unless otherwise specified herein, “hetero” means that the chemical formula contains at least one heteroatom of at least one of N, O, S, and P.

[0086] Additionally, unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0087] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0088] Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

[0089] Additionally, unless otherwise specified herein, “*” means a portion connected to the same or different atoms or chemical formulas.

[0090] The light stability mentioned in this specification means light stability under high light conditions (exposed to a backlight of 100,000 nits or more for 500 hours or more).

[0091]

[0092] The quantum dot-containing curable composition according to the present invention can achieve higher light resistance reliability compared to existing quantum dot-containing curable compositions by surface-modifying the quantum dots using a novel surface-modifying material.

[0093] With the recent trend in the display industry shifting from OLEDs to micro LEDs as light sources, the light resistance of films incorporated into displays is becoming more important than ever. Consequently, improving the light resistance of cured films manufactured by curing quantum dot-containing curable compositions has become crucial. However, existing quantum dot surface modifiers alone are insufficient to achieve the excellent film light resistance suitable for use as micro LED light sources.

[0094] In general, in order to improve the curing rate of a quantum dot-containing curable composition, a high-sensitivity initiator or a multifunctional monomer has been additionally used. However, all of these prior arts were able to improve one of the properties of the quantum dot-containing curable composition, such as dispersibility, heat resistance, and curing rate, by selectively selecting a specific configuration, but had a problem in that other properties than the properties improved by the selectively selected configuration were inferior. That is, to date, there has been no known technology for a quantum dot-containing curable composition that can implement high light resistance while maintaining low viscosity with respect to the properties of the quantum dot-containing curable composition.

[0095] Specifically, known techniques include wrapping the quantum dot surface with a polymer or organic material containing a heat-resistant functional group, such as siloxane (or TEOS, etc.), or inorganic encapsulation of the quantum dot surface with aluminum, titanium, or their oxides. In addition, there have been recent attempts to simultaneously increase brightness and durability by doping a small amount of a transition metal (Cu, Mg, etc.) during the quantum dot synthesis stage.

[0096] However, all of the above methods remain at the academic study level and are still difficult to apply to actual display applications.

[0097] Accordingly, the inventors of the present invention have conducted repeated research and have completed a curable composition having excellent light resistance reliability even under high light conditions by performing surface modification of quantum dots using two different types of surface modification materials. Specifically, the curable composition according to one embodiment comprises (A) a quantum dot including a first functional group represented by the following chemical formula 1 and a second functional group including a *-OC(=O) group at the terminal; and (B) a polymerizable compound.

[0098] [Chemical Formula 1]

[0099]

[0100] In the above chemical formula 1,

[0101] 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,

[0102] L 1 Inland L 4are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group,

[0103] n is an integer from 1 to 20.

[0104] The current display market is shifting toward emitting clear light with smaller pixels and thinner thicknesses, such as μ-LED and nano-LED, and the curable composition according to one embodiment has excellent light resistance reliability under high light conditions, thus conforming to the current display market trend. On the other hand, in conventional quantum dot photoresist compositions, thiol-based ligands are generally used as quantum dot surface modification materials. In this case, although light resistance reliability can be improved compared to before surface modification, there is a problem in that it cannot be applied to backlights that emit very strong light, such as μ-LED or nano-LED, because the light retention rate is greatly reduced (light resistance reliability is inferior) under high light resistance conditions of blue LED.

[0105] According to one embodiment, since the first functional group represented by the above chemical formula 1 and the second functional group including a *-OC(=O) group at the terminal are simultaneously used as a quantum dot surface modification material, excellent light resistance reliability can be achieved even under high light resistance conditions. The first functional group is derived from a thiol-based ligand, and the second functional group is derived from a carboxyl group ligand. When the thiol-based ligand and the carboxyl group ligand are simultaneously used as a quantum dot surface modification material, unlike when the thiol-based ligand and the carboxyl group ligand are each used as a quantum dot surface modification material, improved light resistance reliability under high light resistance conditions can be achieved. Even when two different types of thiol ligands are used as quantum dot surface modification materials or two different types of carboxyl ligands are used as quantum dot surface modification materials, it is difficult to improve light resistance reliability under high light resistance conditions. Even when different types of ligands are used as quantum dot surface modification materials, a combination of thiol ligands and carboxyl ligands, as in one embodiment, may be most advantageous for improving light resistance reliability under high light resistance conditions.

[0106] Below, each component constituting the curable composition according to one embodiment is specifically described.

[0107]

[0108] quantum dots

[0109] As is well known, the most efficient ligand structure currently available for passivating the quantum dot surface with an organic ligand is a ligand containing a thiol group. Carboxylic acid-type ligands have relatively weak interactions with the quantum dot surface, and phosphoric acid-type ligands have good quantum dot dispersibility, but have a weakness (inducing color change) that reduces efficiency.

[0110] Display technologies have been developed from LCDs in the past to OLEDs, NEDs, and most recently, micro LEDs. As the intensity of blue light continues to increase, the durability (especially light resistance) of quantum dots also needs to be significantly improved compared to the current level.

[0111] Accordingly, the present invention relates to a quantum dot-containing curable composition having excellent light resistance reliability, which maintains the initial luminous efficiency even when exposed to strong blue light such as micro LED for a long period of time when the quantum dot-containing curable composition surface-modified with the ligand is mounted on a display panel in a single-film state by configuring a surface-modifying material by combining a thiol-based ligand (first functional group) and a carboxyl-based ligand (second functional group) for effective passivation of the quantum dot surface.

[0112] For example, the second functional group may be represented by the following chemical formula 2.

[0113] [Chemical Formula 2]

[0114]

[0115] In the above chemical formula 2,

[0116] 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group,

[0117] L 5 Inland L 7are 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,

[0118] m is an integer from 1 to 20.

[0119] For example, the above chemical formula 2 can be represented by any one of the following chemical formulas 2A to 2C.

[0120] [Chemical Formula 2A]

[0121]

[0122] [Chemical Formula 2B]

[0123]

[0124] [Chemical Formula 2C]

[0125]

[0126] In the above chemical formulas 2A to 2C,

[0127] R 3 Inland R 5 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0128] L 8 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0129] p is an integer from 1 to 20.

[0130] For example, the first functional group and the second functional group may 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 molar ratio range, the light resistance reliability of the curable composition according to one embodiment can be maximized.

[0131] For example, the first functional group may be represented by at least one selected from the group consisting of the following chemical formulas 1-1 to 1-3, but is not necessarily limited thereto.

[0132] [Chemical Formula 1-1]

[0133]

[0134] [Chemical Formula 1-2]

[0135]

[0136] [Chemical Formula 1-3]

[0137]

[0138] For example, the second functional group may be represented by at least one selected from the group consisting of the following chemical formulas 2-1 to 2-4, but is not necessarily limited thereto.

[0139] [Chemical Formula 2-1]

[0140]

[0141] [Chemical Formula 2-2]

[0142]

[0143] [Chemical Formula 2-3]

[0144]

[0145] [Chemical Formula 2-4]

[0146]

[0147] For example, the first functional group may be derived from a compound represented by the following chemical formula 3.

[0148] [Chemical Formula 3]

[0149]

[0150] In the above chemical formula 3,

[0151] R 1is 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,

[0152] L 1 Inland L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group,

[0153] n is an integer from 1 to 20.

[0154] For example, the compound represented by the above chemical formula 3 may be represented by at least one selected from the group consisting of the following chemical formulas 3-1 to 3-3, but is not necessarily limited thereto.

[0155] [Chemical Formula 3-1]

[0156]

[0157] [Chemical Formula 3-2]

[0158]

[0159] [Chemical Formula 3-3]

[0160]

[0161] For example, the second functional group may be derived from a compound represented by the following chemical formula 4.

[0162] [Chemical Formula 4]

[0163]

[0164] In the above chemical formula 4,

[0165] R 2is 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group,

[0166] L 5 Inland 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,

[0167] m is an integer from 1 to 20.

[0168] For example, the compound represented by the above chemical formula 4 may be represented by at least one selected from the group consisting of the following chemical formulas 4-1 to 4-4, but is not necessarily limited thereto.

[0169] [Chemical Formula 4-1]

[0170]

[0171] [Chemical Formula 4-2]

[0172]

[0173] [Chemical Formula 4-3]

[0174]

[0175] [Chemical Formula 4-4]

[0176]

[0177] When the quantum dots surface-modified with the above surface-modifying material are added to the polymerizable compound described below and stirred, a very transparent dispersion can be obtained, which serves as a measure of confirming that the quantum dots have been surface-modified very well.

[0178] For example, the quantum dot may have a maximum fluorescence emission wavelength between 500 nm and 680 nm.

[0179] For example, the quantum dots may be included in an amount of 1 wt% to 40 wt%, for example, 3 wt% to 30 wt%, based on the total amount of the curable composition. When the quantum dots are included within the above range, the photoconversion rate is excellent and the pattern characteristics and development characteristics are not impaired, thereby enabling excellent processability.

[0180] For example, the quantum dot may absorb light in a wavelength range of 360 nm to 780 nm, for example, a wavelength range of 400 nm to 780 nm, and emit fluorescence in a wavelength range of 500 nm to 700 nm, for example, 500 nm to 580 nm, or emit fluorescence in a wavelength range of 600 nm to 680 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ) in a wavelength range of 500 nm to 680 nm. em ) can have.

[0181] The above quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum (FWHM) within the above range, the color purity is high, thereby increasing the color reproducibility when used as a color material in a color filter.

[0182] The above quantum dots may each independently be organic, inorganic, or a hybrid (hybrid) of organic and inorganic materials.

[0183] The above quantum dots can each independently be composed of a core and a shell surrounding the core, and the core and shell can each independently have a structure such as a core, core / shell, core / first shell / second shell, alloy, alloy / shell, etc., made of group II-IV, group III-V, etc., but are not limited thereto.

[0184] For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

[0185] In one implementation example, since environmental concerns have been increasing significantly worldwide and regulations on toxic substances have been strengthened, environmentally friendly non-cadmium-based luminescent materials (such as InP / ZnS, InP / ZnSe / ZnS) with somewhat lower quantum yields were used instead of luminescent materials having cadmium-based cores, but the present invention is not limited thereto.

[0186] In the case of the quantum dot of the above core / shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

[0187] 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 nm to 15 nm. The green quantum dots may each independently have an average particle diameter of 5 nm to 8 nm.

[0188] Meanwhile, in order to ensure dispersion stability of the quantum dots, the curable composition according to one embodiment may further include a dispersant. The dispersant helps to uniformly disperse the photoconversion material such as quantum dots within the curable composition, and any nonionic, anionic, or cationic dispersant may be used. Specifically, polyalkylene glycol or its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkyl amide alkylene oxide adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1 wt% to 100 wt%, for example, 10 wt% to 20 wt%, relative to the solid content of the photoconversion material such as quantum dots.

[0189]

[0190] polymeric compounds

[0191] A curable composition according to one embodiment comprises a polymerizable compound, wherein the polymerizable compound may have a carbon-carbon double bond at a terminal.

[0192] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may have a molecular weight of 170 g / mol to 1,000 g / mol. When the molecular weight of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, the viscosity of the composition may not be increased without impairing the optical properties of the quantum dot, which may be advantageous for ink-jetting.

[0193] For example, a polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 6, but is not necessarily limited thereto.

[0194] [Chemical Formula 6]

[0195]

[0196] In the above chemical formula 6,

[0197] R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0198] L 14 and L 16 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0199] L 15 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*).

[0200] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 6-1, chemical formula 6-2 or 6-3, but is not necessarily limited thereto.

[0201] [Chemical Formula 6-1]

[0202]

[0203] [Chemical Formula 6-2]

[0204]

[0205] [Chemical Formula 6-3]

[0206]

[0207] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may, in addition to the compound represented by the chemical formula 6-1, chemical formula 6-2 or chemical formula 6-3, include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, It may further include 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate or a combination thereof.

[0208] In addition, the polymerizable compound having a carbon-carbon double bond at the terminal may further include a monomer generally used in a conventional thermosetting or photocurable composition, and for example, the monomer may further include an oxetane-based compound such as bis[1-ethyl(3-oxetanyl)]methyl ether.

[0209] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1 wt% to 20 wt%, 1 wt% to 15 wt%, for example, 1 wt% to 10 wt%, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dot may be improved.

[0210]

[0211] light diffuser

[0212] The curable composition according to one embodiment may further comprise a light diffusing agent.

[0213] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0214] The above-described light diffusing agent reflects light not absorbed by the aforementioned quantum dots and allows the reflected light to be reabsorbed by the quantum dots. In other words, the above-described light diffusing agent can increase the amount of light absorbed by the quantum dots, thereby increasing the photoconversion efficiency of the curable composition.

[0215] The above light diffusing agent has an average particle diameter (D 50 ) may be 150 nm to 250 nm, and specifically, 180 nm to 230 nm. When the average particle diameter of the light diffusing agent is within the above range, it may have a better light diffusing effect and increase the light conversion efficiency.

[0216] 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%, based on the total amount of the curable composition. If the light diffusing agent is included in an amount of less than 1 wt% based on the total amount of the curable composition, it is difficult to expect an effect of improving the light conversion efficiency due to the use of the light diffusing agent, and if it is included in an amount exceeding 20 wt%, there is a concern that a quantum dot sedimentation problem may occur.

[0217]

[0218] polymerization initiator

[0219] The curable composition according to one embodiment may further comprise a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0220] The above photopolymerization initiator is an initiator generally used in a photosensitive resin composition, and examples thereof include, but are not limited to, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and aminoketone-based compounds.

[0221] Examples of the above acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0222] Examples of the above benzophenone compounds include benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, 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.

[0223] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0224] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0225] Examples of the above 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, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, Examples thereof include 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0226] Examples of the above 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-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyl oxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate.

[0227] Examples of the above aminoketone compounds include 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0228] In addition to the above compound, the photopolymerization initiator may also include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, etc.

[0229] The above photopolymerization initiator may also be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy.

[0230] Examples of the above photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like.

[0231] Examples of the above thermal polymerization initiator include 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 peroxydicarbonate, 2,2-azo-bis(isobutyronitrile), t-butyl perbenzoate, etc., and 2,2'-azobis-2-methylpropionitrile, etc., but are not necessarily limited thereto, and any one widely known in the art can be used.

[0232] The polymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt%, based on the total amount of the curable composition. When the polymerization initiator is included within the above range, sufficient curing can occur upon exposure to light or thermal curing, thereby obtaining excellent reliability, and a decrease in transmittance due to unreacted initiator can be prevented, thereby preventing a decrease in the optical properties of the quantum dot.

[0233]

[0234] binder resin

[0235] The curable composition according to one embodiment may further comprise a binder resin.

[0236] The above binder resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0237] The above 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 one or more acrylic repeating units.

[0238] Specific examples of the above acrylic binder resin include, but are not limited to, polybenzyl methacrylate, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like. These may be used singly or in combination of two or more.

[0239] The weight average molecular weight of the above acrylic resin may be 5,000 g / mol to 15,000 g / mol. When the weight average molecular weight of the above acrylic resin is within the above range, the adhesiveness with the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

[0240] The acid value of the above acrylic resin may be 80 mgKOH / g to 130 mgKOH / g. When the acid value of the above acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

[0241] The above-mentioned cardo resin may be one used in a conventional curable resin (or photosensitive resin) composition, and may be, for example, one presented in Korean Patent Publication No. 10-2018-0067243, but is not limited thereto.

[0242] The above cardo resin may be, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds such as benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; a glycol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate, and N-methylpyrrolidone; a phosphorus compound such as triphenylphosphine; And it can be prepared by mixing two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

[0243] The weight average molecular weight of the above cardo resin may be 500 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the above cardo resin is within the above range, pattern formation is good without residue when producing a cured film, and there is no loss of film thickness when developing the curable composition, and a good pattern can be obtained.

[0244] When the above binder resin is a cardo-based resin, the developability of a curable composition containing the same, particularly a photosensitive resin composition, is excellent, and the sensitivity during photocuring is good, resulting in excellent fine pattern formation ability.

[0245] The above epoxy resin is a monomer or oligomer that can be polymerized by heat, and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

[0246] The above epoxy resin may include, but is not necessarily limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.

[0247] Commercially available products of these compounds include bisphenyl epoxy resins, YX4000, YX4000H, YL6121H, YL6640, YL6677 from Yukashell Epoxy Co., Ltd.; cresol novolac type epoxy resins, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Epicoat 180S75 from Yukashell Epoxy Co., Ltd.; bisphenol A type epoxy resins, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 from Yukashell Epoxy Co., Ltd.; Bisphenol F type epoxy resins include Epicoat 807 and 834 from Yukashell Epoxy Co., Ltd.; Phenol novolak type epoxy resins include Epicoat 152, 154, 157H65 from Yukashell Epoxy Co., Ltd. and EPPN 201, 202 from Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CY175, CY177 and CY179 from CIBA-GEIGY AG, ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from UCC, Shodyne 509 from Showa Denko Co., Ltd., Araldite CY-182, CY-192 and CY-184 from CIBA-GEIGY AG, Epichron 200 and 400 from Dainippon Ink & Kogyo Co., Ltd., Epicoat 871, 872 and EP1032H60 from Yukashell Epoxy Co., Ltd., and ED-5661 and ED-5662 from Celanese Coating Co., Ltd.; Examples of aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yukashell Epoxy Co., Ltd., Epolite 100MF from Kyoeisha Yushi Chemical Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd.

[0248] For example, the binder resin may be included in an amount of 1 wt% to 30 wt%, for example 3 wt% to 20 wt%, based on the total amount of the curable composition. In this case, pattern characteristics, heat resistance, and chemical resistance can be improved.

[0249]

[0250] Other additives

[0251] To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0252] The polymerization inhibitor may include, but is not necessarily limited to, a hydroquinone-based compound, a catechol-based compound, or a combination thereof. According to one embodiment, since the curable composition further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, crosslinking at room temperature can be prevented during exposure after printing (coating) the curable composition.

[0253] For example, the hydroquinone-based compound, catechol-based compound, or combinations thereof may include, but are not necessarily limited to, hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium, or combinations thereof.

[0254] The above hydroquinone-based compound, catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the form of the dispersion may be included in an amount of 0.001 wt% to 3 wt%, for example, 0.01 wt% to 2 wt%, based on the total amount of the curable composition. When the polymerization inhibitor is included within the above range, the problem of aging at room temperature can be solved, while at the same time preventing sensitivity degradation and surface peeling.

[0255] In addition, the curable composition according to one embodiment may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof to improve heat resistance and reliability.

[0256] For example, a curable composition according to one embodiment may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to a substrate, etc.

[0257] Examples of the above silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-epoxycyclohexylethyl trimethoxysilane, etc., and these may be used alone or in combination of two or more.

[0258] The above silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the curable composition. When the silane coupling agent is included within the above range, adhesion, storability, etc. are excellent.

[0259] In addition, the curable composition may further include a surfactant, such as a fluorinated surfactant, to improve coating properties and prevent defects, i.e., to improve leveling performance, as needed.

[0260] The above fluorinated surfactant may have a low weight average molecular weight of 4,000 g / mol to 10,000 g / mol, specifically, may have a weight average molecular weight of 6,000 g / mol to 10,000 g / mol. In addition, the fluorinated surfactant may have a surface tension of 18 mN / m to 23 mN / m (measured in a 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). When the weight average molecular weight and surface tension of the fluorinated surfactant are within the above ranges, the leveling performance can be further improved, and the occurrence of spots can be prevented during high-speed coating, and since the occurrence of bubbles is small and the film defects are small, it provides excellent properties to slit coating, which is a high-speed coating method.

[0261] As the above fluorinated surfactant, BM Chemie's BM-1000 ® , BM-1100 ® Mecha Pack F 142D by Dai Nippon Inki Kagaku Kogyo Co., Ltd. ® , East F 172 ® , East F 173 ® , East F 183 ® Back; Prorad FC-135 from Sumitomo 3M Co., Ltd. ® , East FC-170C ® , East FC-430 ® , East FC-431 ® Saffron S-112 from Asahi Glass Co., Ltd. ® , East S-113 ® , East S-131 ® , East S-141 ® , East S-145 ® SH-28PA from Toray Silicone Co., Ltd. ® , East-190 ® , East-193 ® , SZ-6032 ® , SF-8428 ®Fluorine-based surfactants sold under the names F-482, F-484, F-478, F-554, etc. by DIC Co., Ltd. can be used.

[0262] Additionally, the curable composition according to one embodiment may use a silicone-based surfactant together with the aforementioned fluorinated surfactant. Specific examples of the silicone-based surfactant include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 from Toshiba Silicone Co., Ltd.

[0263] The surfactant, including the fluorinated surfactant, may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant is included within the above range, the phenomenon of foreign substances occurring in the sprayed composition is reduced.

[0264] In addition, the curable composition according to one embodiment may further include a certain amount of other additives, such as an antioxidant, within a range that does not impair physical properties.

[0265]

[0266] menstruum

[0267] Meanwhile, the curable composition according to one embodiment may further include a solvent.

[0268] The solvent may be, 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; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-Hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate;2-Hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or there are compounds of ketone esters such as ethyl pyruvate, and also 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, phenyl cellosolve acetate, etc., but are not limited thereto.;

[0269] For example, it is preferable to use a solvent such as a glycol ether such as ethylene glycol monoethyl ether or ethylene diglycol methyl ethyl ether; an ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; an ester such as 2-hydroxypropionate ethyl; a carbitol such as diethylene glycol monomethyl ether; a propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate or propylene glycol propyl ether acetate; an alcohol such as ethanol, or a combination thereof.

[0270] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0271] The solvent may be included as a remainder, for example, 40 wt% to 80 wt%, for example, 45 wt% to 80 wt%, based on the total amount of the curable composition. When the solvent is included within the above range, the solvent-type curable composition has an appropriate viscosity, and thus can have excellent coatability when spin-coating and slitting are used for large-area coating.

[0272]

[0273] Another embodiment provides a curable composition, such as a cured film manufactured using the curable composition, and a display device including the cured film. For example, the display device may include a micro LED light source.

[0274] One of the methods for manufacturing the above cured film is to manufacture the cured film using the above curable composition using a lithography method, and the manufacturing method is as follows.

[0275] (1) Application and film formation stage

[0276] The above curable composition is applied to a substrate that has undergone a predetermined pretreatment using a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like to a desired thickness, for example, 2 μm to 10 μm, and then heated at a temperature of 70°C to 90°C for 1 to 10 minutes to remove the solvent, thereby forming a coating film.

[0277] (2) Exposure stage

[0278] In order to form a necessary pattern on the obtained film, a mask of a predetermined shape is interposed, and then an active ray such as UV light of 190 nm to 450 nm, for example, 200 nm to 400 nm, is irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, i-line, KrF, ArF, I-ArF, EUV, X-ray, and electron beam may be used depending on the case.

[0279] The exposure dose varies depending on the type, mixing amount, and dry film thickness of each component of the above-mentioned curable composition, but for example, when using a high-pressure mercury lamp, it is 500 mJ / cm 2 Below (based on 365 nm sensor).

[0280] (3) Phenomenon stage

[0281] Following the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form an image pattern. That is, when developing with an alkaline developer, the unexposed portions are dissolved, and an image color filter pattern is formed.

[0282] (4) Post-processing stage

[0283] The image pattern obtained by the above phenomenon can be cured by reheating or irradiating with active rays, etc., to obtain a pattern superior in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc.

[0284]

[0285] Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0286]

[0287] (Synthesis of surface modification materials)

[0288] Synthesis Example 1

[0289] Place 100 g of PH-4 (Hanong Chemical) in a two-necked round-bottomed flask and sufficiently dissolve in 300 mL of THF (tetrahydrofuran). Add 15.4 g of NaOH and 100 mL of water at 0°C and sufficiently dissolve until a clear solution is obtained. Slowly inject a solution of 73 g of para-toluene sulfonic chloride in 100 mL of THF at 0°C. The injection was carried out for 1 hour, and then stirred at room temperature for 12 hours. After the reaction was completed, add an excess of methylene chloride and stir, then add a saturated NaHCO3 solution, extract, titrate, and remove moisture. After removing the solvent, dry under reduced pressure for 24 hours. Place 50 g of the obtained dried product in a two-necked round-bottomed flask and sufficiently stir in 300 mL of ethanol. Then, add 27 g of thiourea, disperse, and reflux at 80°C for 12 hours. Afterwards, an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water is injected, stirred for 5 more hours, excess methylene chloride is added, stirred, and then hydrochloric acid aqueous solution is added, followed by extraction, titration, moisture removal, and solvent removal in that order. Drying under reduced pressure for 24 hours obtains a compound represented by the following chemical formula 3-1.

[0290] [Chemical Formula 3-1]

[0291]

[0292]

[0293] Synthesis Example 2

[0294] Place 100 g of THF-4 (Hanong Chemical) in a two-necked round-bottomed flask and sufficiently dissolve in 300 mL of THF. Add 43.1 g of NaOH and 100 mL of water at 0 °C and sufficiently dissolve until a clear solution is obtained. Slowly inject a solution of 102.7 g of para-toluene sulfonic chloride in 100 mL of THF at 0 °C. The injection was carried out for 1 hour, and then stirred at room temperature for 12 hours. After the reaction was completed, add an excess of methylene chloride and stir, then add a saturated NaHCO3 solution, extract, titrate, and remove moisture. After removing the solvent, dry under reduced pressure for 24 hours. Place 150 g of the obtained dried product in a two-necked round-bottomed flask and sufficiently stir in 1.5 L of ethanol. Then, add 47.5 g of thiourea, disperse, and reflux at 80 °C for 12 hours. Afterwards, an aqueous solution of 13.2 g of NaOH dissolved in 60 mL of water is injected, stirred for 5 more hours, excess methylene chloride is added, stirred, and then hydrochloric acid aqueous solution is added, followed by extraction, titration, moisture removal, and solvent removal in that order. Drying under reduced pressure for 24 hours obtains a compound represented by the following chemical formula 3-2.

[0295] [Chemical Formula 3-2]

[0296]

[0297]

[0298] Synthesis Example 3

[0299] Place 100 g of HDCP-4 (Hanong Chemical) in a two-necked round-bottomed flask and sufficiently dissolve in 300 mL of THF. Add 49.0 g of NaOH and 100 mL of water at 0°C and sufficiently dissolve until a clear solution is obtained. Slowly inject a solution of 116.8 g of para-toluene sulfonic chloride in 100 mL of THF at 0°C. The injection was carried out for 1 hour, and then stirred at room temperature for 12 hours. After the reaction was completed, add an excess of methylene chloride and stir, then add a saturated NaHCO3 solution, extract, titrate, and remove moisture. After removing the solvent, dry under reduced pressure for 24 hours. Place 140 g of the obtained dried product in a two-necked round-bottomed flask and sufficiently stir in 1.5 L of ethanol. Then, add 41.9 g of thiourea, disperse, and reflux at 80°C for 12 hours. Afterwards, an aqueous solution of 13.2 g of NaOH dissolved in 60 mL of water is injected, stirred for 5 more hours, excess methylene chloride is added, stirred, and then hydrochloric acid aqueous solution is added, and extraction, titration, moisture removal, and solvent removal are performed in sequence. Drying under reduced pressure for 24 hours obtains a compound represented by the following chemical formula 3-3.

[0300] [Chemical Formula 3-3]

[0301]

[0302]

[0303] Synthesis Example 4

[0304] 10 g of 2-Hydroxyethyl acetate is placed in a round-bottomed flask and sufficiently dissolved in 150 mL of CH2Cl2. Then, 9.6 g of succinic anhydride and 0.1 g of DMAP (4-Dimethylaminopyridine) are added and stirred at room temperature for 13 hours. The reaction product is washed with 100 mL of a 1 N HCl aqueous solution and further washed with 100 mL of water, and the organic layer is dried under reduced pressure to obtain a compound represented by the following chemical formula 4-2.

[0305] [Chemical Formula 4-2]

[0306]

[0307]

[0308] Synthesis Example 5

[0309] 12.5 g of 2-Hydroxyethyl methacrylate is placed in a round-bottomed flask and sufficiently dissolved in 150 mL of CH2Cl2. Then, 9.6 g of succinic anhydride and 0.1 g of DMAP are added and stirred at room temperature for 13 hours. The reaction product is washed with 120 mL of a 1 N HCl aqueous solution and further washed with 120 mL of water, and the organic layer is dried under reduced pressure to obtain a compound represented by the following chemical formula 4-3.

[0310] [Chemical Formula 4-3]

[0311]

[0312]

[0313] Synthesis Example 6

[0314] 11.2 g of 2-Hydroxyethyl acrylate is placed in a round-bottomed flask and sufficiently dissolved in 150 mL of CH2Cl2. Then, 9.6 g of succinic anhydride and 0.1 g of DMAP are added and stirred at room temperature for 13 hours. The reaction product is washed with 110 mL of a 1 N HCl aqueous solution and further washed with 110 mL of water, and the organic layer is dried under reduced pressure to obtain a compound represented by the following chemical formula 4-4.

[0315] [Chemical Formula 4-4]

[0316]

[0317]

[0318] (Manufacture of surface-modified quantum dots)

[0319] A magnetic bar is placed in a three-necked round-bottomed flask, and a green quantum dot dispersion solution (InP / ZnSe / ZnS, Hansol Chemical; quantum dot solid content 26 wt%) is added. The surface-modifying materials according to Synthetic Examples 1 to 7 are added thereto, and the mixture is stirred at 80°C in a nitrogen atmosphere. After the reaction is complete, the mixture is cooled to room temperature (23°C), and the quantum dot reaction solution is added to cyclohexane to precipitate. The precipitate and cyclohexane are separated by centrifugation, and the precipitate is sufficiently dried in a vacuum oven for one day to obtain surface-modified green quantum dots.

[0320]

[0321] (Manufacture of curable composition)

[0322] Based on the following respective components, curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 were prepared.

[0323] (A) Quantum dots

[0324] (A-1) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the following chemical formula 4-1 (M2963, TCI) (molar ratio = 1:1)

[0325] (A-2) Green quantum dots surface-modified with the compound of the above chemical formula 3-2 and the compound of the following chemical formula 4-1 (molar ratio = 1:1)

[0326] (A-3) Green quantum dots surface-modified with the compound of the above chemical formula 3-3 and the compound of the following chemical formula 4-1 (molar ratio = 1:1)

[0327] (A-4) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the following chemical formula 4-1 (molar ratio = 1:0.5)

[0328] (A-5) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the following chemical formula 4-1 (molar ratio = 1:1.5)

[0329] (A-6) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the following chemical formula 4-1 (molar ratio = 1:0.3)

[0330] (A-7) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the following chemical formula 4-1 (molar ratio = 1:1.2)

[0331] (A-8) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the chemical formula 4-2 (molar ratio = 1:1)

[0332] (A-9) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the chemical formula 4-3 (molar ratio = 1:1)

[0333] (A-10) Green quantum dots surface-modified with the compound of the above chemical formula 3-1 and the compound of the chemical formula 4-4 (molar ratio = 1:1)

[0334] (A-11) Green quantum dots surface-modified with the compound of the above chemical formula 3-1

[0335] (A-12) Green quantum dots surface-modified with the compound of the above chemical formula 3-2

[0336] (A-13) Green quantum dots surface-modified with the compound of the above chemical formula 3-3

[0337] (A-14) Green quantum dots surface-modified with a compound of the following chemical formula 4-1

[0338] (A-15) Green quantum dots surface-modified with the compound of the above chemical formula 4-2

[0339] (A-16) Green quantum dots surface-modified with the compound of the above chemical formula 4-3

[0340] (A-17) Green quantum dots surface-modified with the compound of the above chemical formula 4-4

[0341] (A-18) Green quantum dots without surface modification

[0342] [Chemical Formula 4-1]

[0343]

[0344]

[0345] (B) polymeric compound

[0346] A compound represented by the following chemical formula 6-2 (M200, Miwon Chemical Co., Ltd.)

[0347] [Chemical Formula 6-2]

[0348]

[0349] (C) Photopolymerization initiator

[0350] TPO-L (Polynetron)

[0351] (D) Light diffuser

[0352] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0353] (E) solvent

[0354] PGMEA (Sigma-Aldrich)

[0355] (F) Binder resin

[0356] Acrylic binder resin (SP-RY67-1, SHOWA DENKO)

[0357] (G) Other additives

[0358] Fluorinated surfactant (F-554, DIC)

[0359]

[0360] Examples 1 to 10 and Comparative Examples 1 to 8

[0361] Using the components mentioned below, curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 were prepared with the compositions shown in Tables 1 and 2 below.

[0362]

[0363] (Unit: wt%)Example 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8Example 9Example 10Quantum dot (A-1)15---------(A-2)-15--------(A-3)--15-------(A-4)---15------(A-5)----15-----(A-6)-----15----(A-7)------15---(A-8)-------15--(A-9)--------15-(A-10)---------15Polymerizable compound4444444444Photopolymerization Initiator 0.50.50.50.50.50.50.50.50.50.5 Light Diffusing Agent 33333333333 Solvent 70707070707070707070 Binder Resin 5555555555 Other Additives 2.52.52.52.52.52.52.52.52.52.5

[0364] (Unit: wt%)Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Quantum dot (A-11)15-------(A-12)-15------(A-13)--15-----(A-14)---15----(A-15)----15---(A-16)-----15--(A-17)------15-(A-18)-------15Polymerizable compound44444444Photopolymerization initiator0.50.50.50.50.50.50.50.50.5Light diffusing agent3333333Solvent7070707070707070Binder resin5555555Other Additive2.52.52.52.52.52.52.52.52.5

[0365]

[0366] Evaluation 1: Evaluation of the luminous efficiency of the curable composition

[0367] The luminous 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 below.

[0368]

[0369] (Light efficiency evaluation method)

[0370] For each of the above-mentioned curable compositions, a 2 cm x 2 cm single-film specimen was manufactured through coating, exposure, and baking processes, and then the light efficiency, pattern characteristics, and surface sensitivity were measured under blue 20,000 nit light source conditions using a self-made blue LED surface light source.

[0371] The luminous efficacy of the single-film specimens was measured using an integrating sphere device (QE-2100, otsuka electronics) and an in-line luminance meter (M7000, Mcscience).

[0372] Pattern characteristics and surface sensitivity were visually observed using a scanning electron microscope (SEM) and evaluated as good or bad.

[0373]

[0374] Light Efficiency (%) Pattern Characteristic Surface Sensitivity Example 133.8 Good Good Example 233.7 Good Good Example 333.6 Good Good Example 433.6 Good Good Example 533.7 Good Good Example 633.5 Good Good Example 733.5 Good Good Example 833.7 Good Good Example 933.8 Good Good Example 1033.7 Good Good Comparative Example 133.2 Good Good Comparative Example 233.5 Good Good Comparative Example 333.1 Good Good Comparative Example 433.2 Good Good Comparative Example 533.2 Good Good Comparative Example 633.1 Good Good Comparative Example 733.3 Good Good Comparative Example 833.0 Good Good

[0375]

[0376] From Table 3 above, it can be confirmed that both the curable compositions according to Examples 1 to 10 and the curable compositions according to Comparative Examples 1 to 8 have excellent light efficiency, pattern characteristics, and surface sensitivity.

[0377]

[0378] Evaluation 2: Evaluation of light resistance reliability of curable compositions under high light conditions

[0379] For each of the curable compositions according to Examples 1 to 10 and Comparative Examples 1 to 8, the light resistance reliability (light retention rate) was evaluated under high light resistance conditions (exposed for 500 hours or more under a blue backlight of 100,000 nit or more), and the results are shown in Table 4 below.

[0380]

[0381] Light resistance reliability (%) Example 167 Example 265 Example 362 Example 463 Example 564 Example 657 Example 758 Example 863 Example 964 Example 1062 Comparative Example 145 Comparative Example 248 Comparative Example 342 Comparative Example 441 Comparative Example 544 Comparative Example 645 Comparative Example 743 Comparative Example 831

[0382]

[0383] From the above Table 4, it can be confirmed that the curable compositions according to Examples 1 to 10 have much better light resistance reliability under high light conditions than the curable compositions according to Comparative Examples 1 to 8. In addition, it can be confirmed that the light resistance reliability can be further improved by controlling the molar ratio of the first functional group and the second functional group.

[0384]

[0385] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. (A) A quantum dot comprising a first functional group represented by the following chemical formula 1 and a second functional group comprising a *-OC(=O) group at the terminal; and (B) polymeric compound A curable composition comprising: [Chemical Formula 1] In the above chemical formula 1, 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, L 1 Inland L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, n is an integer from 1 to 20.

2. In paragraph 1, The second functional group is a curable composition represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group, L 5 Inland 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, m is an integer from 1 to 20.

3. In paragraph 1, A curable composition in which the first functional group and the second functional group are included in a molar ratio of 1:0.5 to 1:1.

5.

4. In paragraph 1, A curable composition in which the first functional group is represented by at least one selected from the group consisting of the following chemical formulas 1-1 to 1-3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] 5. In paragraph 1, A curable composition in which the second functional group is represented by at least one selected from the group consisting of the following chemical formulas 2-1 to 2-4. [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] [Chemical Formula 2-4] 6. In paragraph 1, A curable composition wherein the first functional group is derived from a compound represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, 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, L 1 Inland L 4 are each independently a single bond, an ether group (*-O-*), or a substituted or unsubstituted C1 to C20 alkylene group, n is an integer from 1 to 20.

7. In paragraph 6, A curable composition represented by the compound represented by the above chemical formula 3, wherein the compound is at least one selected from the group consisting of the following chemical formulas 3-1 to 3-3. [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] 8. In paragraph 1, A curable composition wherein the second functional group is derived from a compound represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, 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 and the above R 3 is a C1 to C10 alkyl group or (Above R a Inland R c are each independently a hydrogen atom or a C1 to C10 alkyl group, L 5 Inland 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, m is an integer from 1 to 20.

9. In paragraph 8, A curable composition represented by the compound represented by the above chemical formula 4, wherein the compound is at least one selected from the group consisting of the following chemical formulas 4-1 to 4-4. [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] [Chemical Formula 4-4] 10. In paragraph 1, The curable composition further comprises a polymerization initiator, a binder resin, a light diffusing agent, a solvent or a combination thereof.

11. In paragraph 10, The above light diffusing agent is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.

12. In paragraph 10, The curable composition further comprises malonic acid; 3-amino-1,2-propanediol; a polymerization inhibitor; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof.

13. In paragraph 10, The above curable composition, with respect to the total weight of the above curable composition, 1 wt% to 40 wt% of the above quantum dots; 1 to 20 wt% of the polymerizable compound; 0.1 wt% to 5 wt% of the polymerization initiator; 1 to 30 wt% of the above binder resin; 1 to 20 wt% of the above light diffusing agent; and 40 to 80 wt% of the above solvent A curable composition comprising:

14. A cured film manufactured using a curable composition according to any one of claims 1 to 13.

15. A display device including the cured film of Article 14.

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