Curable composition, cured film produced using composition, and display device comprising cured film

Abstract

Provided are: a curable composition comprising (A) quantum dots which are surface-modified with a specific compound, and (B) a polymerizable compound; a cured film produced using the curable composition; and a display device comprising the cured film.

Description

Curable composition, cured film manufactured using the composition, display device including 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 properties, and as a result, there are many difficulties in introducing them into polar systems such as binders or curable monomers.

[0004] For example, even in the case of quantum dot ink compositions that are being actively researched, in the initial stages, they were relatively low in polarity and could only be dispersed in solvents used in highly hydrophobic curable compositions. For this reason, it was difficult to include quantum dots in an amount exceeding 20 wt% of the total composition, making it impossible to increase the ink's luminous efficiency beyond a certain level. In addition, even if quantum dots were added and dispersed to increase luminous efficiency, the viscosity exceeded the range for ink-jetting, making it impossible to satisfy the processability.

[0005] In addition, in order to implement a viscosity range that allows ink-jetting, a method of lowering the ink solids content by including a solvent of 50 wt% or more relative to the total composition has been used. This method also provides somewhat satisfactory results in terms of viscosity, but it has the disadvantage of being difficult to apply to actual processes due to problems such as nozzle drying due to solvent volatilization during ink-jetting, nozzle clogging, and a decrease in film thickness over time after ink-jetting, as well as a severe thickness deviation after curing.

[0006] Accordingly, a solvent-free curable composition (quantum dot ink composition) that does not use a solvent has been developed. However, in this case, due to the characteristic of containing an excessive amount of a polymerizable compound, problems arise such as clogging and poor ejection due to nozzle drying caused by volatility, and a decrease in single-film thickness due to volatilization of the ink composition jetted within the pattern partition pixel. Above all, the biggest problem is that it is difficult to improve the optical properties of the solvent-free curable composition.

[0007] That is, the reality is that neither solvent-curable nor solvent-free curable compositions have yet demonstrated satisfactory levels of light / heat resistance reliability.

[0008]

[0009] One embodiment is to provide a curable composition having high stability of quantum dots, excellent dispersibility of quantum dots, and thus excellent reliability and optical properties such as heat resistance and light resistance.

[0010] Another embodiment is to provide a cured film manufactured using the curable composition.

[0011] Another embodiment is to provide a display device including the cured film.

[0012]

[0013] One embodiment provides a curable composition comprising (A) a quantum dot surface-modified with a compound represented by the following chemical formula 1; and (B) a polymerizable compound.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*,

[0018] Y1 and Y 2 are each independently *-O-*, *-S-* or *-C(=O)NH-*,

[0019] R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0020] L 1 Inland L 8 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

[0021] The compound represented by the above chemical formula 1 may have a symmetrical structure.

[0022] The compound represented by the above chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-5.

[0023] [Chemical Formula 1-1]

[0024]

[0025] [Chemical Formula 1-2]

[0026]

[0027] [Chemical Formula 1-3]

[0028]

[0029] [Chemical Formula 1-4]

[0030]

[0031] [Chemical Formula 1-5]

[0032]

[0033] In the above chemical formulas 1-1 to 1-5,

[0034] X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*,

[0035] R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0036] L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0037] L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0038] n1 and n2 are each independently an integer from 1 to 10.

[0039] The compound represented by the above chemical formula 1 can be represented by any one of the following chemical formulas 2 to 17.

[0040] [Chemical Formula 2]

[0041]

[0042] [Chemical Formula 3]

[0043]

[0044] [Chemical Formula 4]

[0045]

[0046] [Chemical Formula 5]

[0047]

[0048] [Chemical Formula 6]

[0049]

[0050] [Chemical Formula 7]

[0051]

[0052] [Chemical Formula 8]

[0053]

[0054] [Chemical Formula 9]

[0055]

[0056] [Chemical Formula 10]

[0057]

[0058] [Chemical Formula 11]

[0059]

[0060] (In the above chemical formula 11,

[0061] R x Is am)

[0062] [Chemical Formula 12]

[0063]

[0064] [Chemical Formula 13]

[0065]

[0066] [Chemical Formula 14]

[0067]

[0068] [Chemical Formula 15]

[0069]

[0070] [Chemical Formula 16]

[0071]

[0072] [Chemical Formula 17]

[0073]

[0074] The above quantum dots may be further surface-modified with a compound represented by the following chemical formula 18.

[0075] [Chemical Formula 18]

[0076]

[0077] In the above chemical formula 18,

[0078] X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH,

[0079] Y 11 is *-O-*, *-S-* or *-C(=O)NH-*,

[0080] R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0081] L 31 Inland L 34 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

[0082] The compound represented by the above chemical formula 18 can be represented by any one of the following chemical formulas 18-1 to 18-5.

[0083] [Chemical Formula 18-1]

[0084]

[0085] [Chemical Formula 18-2]

[0086]

[0087] [Chemical Formula 18-3]

[0088]

[0089] [Chemical Formula 18-4]

[0090]

[0091] [Chemical Formula 18-5]

[0092]

[0093] In the above chemical formulas 18-1 to 18-5,

[0094] X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH,

[0095] R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0096] L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0097] L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0098] n1 and n2 are each independently an integer from 1 to 10.

[0099] The compound represented by the above chemical formula 18 can be represented by any one of the following chemical formulas 19 to 34.

[0100] [Chemical Formula 19]

[0101]

[0102] [Chemical Formula 20]

[0103]

[0104] [Chemical Formula 21]

[0105]

[0106] [Chemical Formula 22]

[0107]

[0108] [Chemical Formula 23]

[0109]

[0110] [Chemical Formula 24]

[0111]

[0112] [Chemical Formula 25]

[0113]

[0114] [Chemical Formula 26]

[0115]

[0116] [Chemical Formula 27]

[0117]

[0118] [Chemical Formula 28]

[0119]

[0120] [Chemical Formula 29]

[0121]

[0122] [Chemical Formula 30]

[0123]

[0124] [Chemical Formula 31]

[0125]

[0126] [Chemical Formula 32]

[0127]

[0128] [Chemical Formula 33]

[0129]

[0130] [Chemical Formula 34]

[0131]

[0132] The above curable composition may be a solvent-free curable composition.

[0133] The solvent-free curable composition may include 5 to 60 wt% of the quantum dot and 40 to 95 wt% of the polymerizable compound, based on the total amount of the solvent-free curable composition.

[0134] The above curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0135] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0136] The curable composition may further include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent; a leveling agent; a fluorinated surfactant; or a combination thereof.

[0137] The above curable composition may further comprise a solvent.

[0138] 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; and 40 wt% to 80 wt% of the solvent.

[0139] Another embodiment provides a cured film manufactured using the curable composition.

[0140] Another embodiment provides a display device including the cured film.

[0141] Specific details of other aspects of the present invention are included in the detailed description below.

[0142]

[0143] 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 reliability and optical properties of the quantum dot-containing curable composition can be improved.

[0144]

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] Additionally, unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0150] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0151] 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.

[0152] Additionally, unless otherwise specified herein, “*” means a portion connected to the same or different atoms or chemical formulas.

[0153]

[0154] The quantum dot-containing curable composition according to the present invention can achieve superior heat / light resistance properties compared to existing quantum dot-containing curable compositions by surface-modifying the quantum dots using a surface-modifying material having a novel structure.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] However, all of the above methods remain at the academic study level and are still difficult to apply to practical display applications. Typically, for displays using quantum dots, efforts are made to increase the intensity of the light source to improve brightness. However, increasing the intensity of the light source to improve brightness inevitably leads to a technological challenge: the stability of the quantum dot particles deteriorates, thereby improving panel reliability.

[0159] Accordingly, the inventors of the present invention conducted repeated research and completed a curable composition having excellent heat / light resistance reliability by increasing the dispersibility of quantum dots.

[0160] Specifically, in the case of existing quantum dot-containing curable compositions, reliability has been improved by protecting quantum dots through ligand modification on the quantum dot surface to improve light / heat resistance reliability, adding inorganic substances to supplement defect sites on the quantum dot surface, or forming an organic matrix on the quantum dot surface to block moisture and oxygen.

[0161] However, among the quantum dot-containing curable compositions, solvent-based curable compositions can experience aggregation due to residual inorganic salts used during ligand modification, making it impossible to manufacture single-layer compositions or adversely affecting storage stability. Furthermore, thiol-based ligands can undergo thiol-ene coupling reactions with double bonds, such as acrylate, which are curable substituents within the composition, resulting in increased viscosity when the composition is stored for extended periods.

[0162] Organic compound ligands that can bind to the surface of quantum dots include carboxylic acid, thiol, amine, and hydroxamic acid. Among these, thiol-based ligands have the disadvantage of causing a thiol-ene reaction with a double bond such as acrylate, which is a curing group in the composition, when the sulfur atom is converted to a radical or ionic state, and an issue of a thiol-based characteristic odor is occurring in the ligand raw material and the quantum dots and composition after the sulfur element is formed. Hydroxamic acid is a functional group that has the stability of binding to quantum dots at the level of thiol-based compounds while overcoming these disadvantages.

[0163] Hydroxamic acid is generally known to form a bidentate coordination bond with the zinc (Zn) dangling site that forms the shell portion of a quantum dot. In fact, it is known to react with zinc cations, not quantum dots, to form a metal complex as shown in the figure below, in which two equivalents of hydroxamic acid coordinate with one equivalent of zinc atom, while the zinc atom itself also binds to a monovalent water molecule. The fact that a water molecule is bound as a ligand of the zinc metal may mean that the metal complex is in a form that can also form a coordination bond with a sulfur atom that forms the shell portion of the quantum dot.

[0164]

[0165] The present invention relates to a hydroxamic acid-zinc (or carboxylic acid-zinc) complex that can bind to the sulfur (S) dangling site of the Zn-S shell of a quantum dot, along with a hydroxamic acid and a carboxylic acid substituted for the zinc dangling site. The purpose of preparing the zinc-ligand complex in advance is that when an inorganic zinc salt is used in the ligand substitution process, the zinc cation first binds to the sulfur dangling site and then binds to the ligand, but aggregation occurs in the subsequent process for producing a curable composition, making it impossible to produce a single film. Therefore, by first coordinating the zinc element and the ligand and then introducing them into the ligand substitution process to form a coordination bond with the sulfur dangling site of the quantum dot, an inorganic salt does not need to be used, and thus the purpose is to prevent the coagulation caused by this. In addition, by increasing the substitution rate of a ligand having excellent optical properties and other durability, the optical properties, heat resistance, and light resistance reliability of a curable composition, particularly a solvent-type curable composition, can be greatly improved.

[0166] A curable composition according to one embodiment comprises (A) a quantum dot surface-modified with a compound represented by the following chemical formula 1; and (B) a polymerizable compound.

[0167] [Chemical Formula 1]

[0168]

[0169] In the above chemical formula 1,

[0170] X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*,

[0171] Y 1 and Y 2 are each independently *-O-*, *-S-* or *-C(=O)NH-*,

[0172] R 1 and R 2are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0173] L 1 Inland L 8 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

[0174] Below, each component constituting the curable composition according to one embodiment is specifically described.

[0175]

[0176] quantum dots

[0177] 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. Phosphoric acid-type ligands have good quantum dot dispersibility, but have a weakness (inducing color change) that reduces efficiency.

[0178] 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 heat and light resistance) of quantum dots also needs to be significantly improved compared to the current level.

[0179] Accordingly, the present invention introduces a ligand having a structure different from that of a conventional ligand, specifically a compound represented by the chemical formula 1, for effective passivation of the quantum dot surface. In this case, unlike the conventional one, when a quantum dot-containing curable composition is mounted on a display panel in a single-film state, the initial luminous efficiency can be maintained even when exposed to strong blue light such as micro LED for a long period of time.

[0180] For example, the compound represented by the above chemical formula 1 may have a symmetrical structure.

[0181] For example, the compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-5, but is not necessarily limited thereto.

[0182] [Chemical Formula 1-1]

[0183]

[0184] [Chemical Formula 1-2]

[0185]

[0186] [Chemical Formula 1-3]

[0187]

[0188] [Chemical Formula 1-4]

[0189]

[0190] [Chemical Formula 1-5]

[0191]

[0192] In the above chemical formulas 1-1 to 1-5,

[0193] X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*,

[0194] R 1 and R 2are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0195] L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0196] L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0197] n1 and n2 are each independently an integer from 1 to 10.

[0198] For example, the compound represented by the above chemical formula 1 may be represented by any one of the following chemical formulas 2 to 17, but is not necessarily limited thereto.

[0199] [Chemical Formula 2]

[0200]

[0201] [Chemical Formula 3]

[0202]

[0203] [Chemical Formula 4]

[0204]

[0205] [Chemical Formula 5]

[0206]

[0207] [Chemical Formula 6]

[0208]

[0209] [Chemical Formula 7]

[0210]

[0211] [Chemical Formula 8]

[0212]

[0213] [Chemical Formula 9]

[0214]

[0215] [Chemical Formula 10]

[0216]

[0217] [Chemical Formula 11]

[0218]

[0219] (In the above chemical formula 11,

[0220] R x Is am)

[0221] [Chemical Formula 12]

[0222]

[0223] [Chemical Formula 13]

[0224]

[0225] [Chemical Formula 14]

[0226]

[0227] [Chemical Formula 15]

[0228]

[0229] [Chemical Formula 16]

[0230]

[0231] [Chemical Formula 17]

[0232]

[0233] For example, the quantum dot may be further surface-modified with a compound represented by the following chemical formula 15. In this case, the surface modification effect of the quantum dot is maximized, thereby maximizing the heat / light resistance reliability of the quantum dot-containing curable composition.

[0234] [Chemical Formula 18]

[0235]

[0236] In the above chemical formula 18,

[0237] X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH,

[0238] Y 11 is *-O-*, *-S-* or *-C(=O)NH-*,

[0239] R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0240] L 31 Inland L 34 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

[0241] For example, the compound represented by the above chemical formula 18 may be represented by any one of the following chemical formulas 18-1 to 18-5, but is not necessarily limited thereto.

[0242] [Chemical Formula 18-1]

[0243]

[0244] [Chemical Formula 18-2]

[0245]

[0246] [Chemical Formula 18-3]

[0247]

[0248] [Chemical Formula 18-4]

[0249]

[0250] [Chemical Formula 18-5]

[0251]

[0252] In the above chemical formulas 18-1 to 18-5,

[0253] X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH,

[0254] R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof,

[0255] L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0256] L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[0257] n1 and n2 are each independently an integer from 1 to 10.

[0258] For example, the compound represented by the above chemical formula 18 may be represented by any one of the following chemical formulas 19 to 34, but is not necessarily limited thereto.

[0259] [Chemical Formula 19]

[0260]

[0261] [Chemical Formula 20]

[0262]

[0263] [Chemical Formula 21]

[0264]

[0265] [Chemical Formula 22]

[0266]

[0267] [Chemical Formula 23]

[0268]

[0269] [Chemical Formula 24]

[0270]

[0271] [Chemical Formula 25]

[0272]

[0273] [Chemical Formula 26]

[0274]

[0275] [Chemical Formula 27]

[0276]

[0277] [Chemical Formula 28]

[0278]

[0279] [Chemical Formula 29]

[0280]

[0281] [Chemical Formula 30]

[0282]

[0283] [Chemical Formula 31]

[0284]

[0285] [Chemical Formula 32]

[0286]

[0287] [Chemical Formula 33]

[0288]

[0289] [Chemical Formula 34]

[0290]

[0291] 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.

[0292] For example, the quantum dot may have a maximum fluorescence emission wavelength between 500 nm and 680 nm.

[0293] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots may be included in an amount of 5 wt% to 60 wt%, such as 10 wt% to 60 wt%, such as 20 wt% to 60 wt%, such as 30 wt% to 50 wt%. When the quantum dots are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0294] For example, when the curable composition according to one embodiment is a curable composition including a solvent, the quantum dots may be included in an amount of 1 wt% to 40 wt%, for example, 3 wt% to 30 wt%, based on the total amount of the curable composition. When the quantum dots are included within the above range, the photoconversion rate is excellent and the pattern characteristics and development characteristics are not impaired, so that excellent processability can be achieved.

[0295] Up to now, quantum dot-containing curable compositions (inks) have been developed by specializing in thiol-based binders or monomers that have good compatibility with quantum dots, and are even being commercialized.

[0296] 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.

[0297] 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.

[0298] The above quantum dots may each independently be organic, inorganic, or a hybrid (hybrid) of organic and inorganic materials.

[0299] 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.

[0300] 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.

[0301] 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 / ZeSe / ZnS) with somewhat lower quantum yields were used instead of luminescent materials having cadmium-based cores, but the present invention is not limited thereto.

[0302] 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.

[0303] 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.

[0304] 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.

[0305]

[0306] polymeric compounds

[0307] 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.

[0308] The polymerizable compound having a carbon-carbon double bond at the terminal may be included in an amount of 40 wt% to 95 wt%, for example, 50 wt% to 90 wt%, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, it is possible to produce a solvent-free curable composition having a viscosity that allows ink jetting, and further, since the quantum dots in the produced solvent-free curable composition can have excellent dispersibility, the optical properties can also be improved.

[0309] 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.

[0310] For example, a polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 35, but is not necessarily limited thereto.

[0311] [Chemical Formula 35]

[0312]

[0313] In the above chemical formula 35,

[0314] R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0315] L 19 and L 21 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0316] L 20 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*).

[0317] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 35-1, chemical formula 35-2 or 35-3, but is not necessarily limited thereto.

[0318] [Chemical Formula 35-1]

[0319]

[0320] [Chemical Formula 35-2]

[0321]

[0322] [Chemical Formula 35-3]

[0323]

[0324] 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 35-1, chemical formula 35-2 or chemical formula 35-3, include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate or a combination thereof may be further included.

[0325] 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.

[0326] In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1 wt% to 20 wt%, 1 wt% to 15 wt%, for example, 5 wt% to 15 wt%, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, the optical properties of the quantum dot can be improved, and sufficient curing occurs upon exposure in the pattern forming process, resulting in excellent reliability. In addition, the heat resistance, light resistance, chemical resistance, resolution, and adhesion of the pattern are also excellent.

[0327] Meanwhile, when the curable composition contains a solvent, the polymerizable compound may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0328] Since the polymerizable compound has the ethylenically unsaturated double bond, sufficient polymerization occurs upon exposure in the pattern forming process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0329] Specific examples of the polymerizable compound used in the above solvent-type curable composition include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate. Examples thereof include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy (meth)acrylate.

[0330] Examples of commercially available products of the above polymerizable compounds are as follows. An example of the monofunctional ester of the above (meth)acrylic acid is Aronix M-101 from Toagosei Chemical Co., Ltd. ® , East M-111 ® , East M-114 ® KAYARAD TC-110S from Nihon Kayaku Co., Ltd. ® , Dong TC-120S ® Back; V-158 of Osaka Yuki Kagaku Kogyo Co., Ltd. ® , V-2311 ® Examples of the bifunctional ester of the above (meth)acrylic acid include Aronix M-210 from Toagosei Kagaku Kogyo Co., Ltd. ® , East M-240 ® , East M-6200 ® KAYARAD HDDA from Nihon Kayaku Co., Ltd. ® , Dong HX-220® , East R-604 ® Back; V-260 from Osaka Yuki Kagaku Kogyo Co., Ltd. ® , V-312 ® , V-335 HP ® Examples of the trifunctional ester of the above (meth)acrylic acid include Aronix M-309 from Toagosei Chemical Co., Ltd. ® , East M-400 ® , East M-405 ® , East M-450 ® , East M-7100 ® , East M-8030 ® , East M-8060 ® KAYARAD TMPTA from Nihon Kayaku Co., Ltd. ® , East DPCA-20 ® , East-30 ® , East-60 ® , East-120 ® Back; V-295 of Osaka Yuki Kayaku High School Co., Ltd. ® , East-300 ® , East-360 ® , Dong-GPT ® , Dong-3PA ® , East-400 ® The above products can be used alone or in combination of two or more.

[0331] The above polymerizable compound may be used by treating it with an acid anhydride to impart better developing properties.

[0332]

[0333] light diffuser

[0334] The curable composition according to one embodiment may further comprise a light diffusing agent.

[0335] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0336] 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.

[0337] 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.

[0338] 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, 2 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 quantum dot sedimentation problems may occur.

[0339]

[0340] polymerization initiator

[0341] 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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0346] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0347] 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.

[0348] 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.

[0349] Examples of the above aminoketone compounds include 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] The polymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, for example, 2 wt% to 8 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.

[0355]

[0356] binder resin

[0357] The curable composition according to one embodiment may further comprise a binder resin.

[0358] The above binder resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0359] 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.

[0360] 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.

[0361] 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 acrylic resin has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

[0362] 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.

[0363] 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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367] 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.

[0368] 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.

[0369] 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.

[0370] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5 wt% to 10 wt%, for example, 1 wt% to 5 wt%, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

[0371] For example, when the curable composition according to one embodiment is a curable composition including a solvent, 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, excellent pattern characteristics, heat resistance, and chemical resistance can be improved.

[0372]

[0373] Other additives

[0374] To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0375] 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.

[0376] 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.

[0377] 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.

[0378] 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.

[0379] 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.

[0380] Examples of the above silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β-epoxycyclohexyl)ethyl trimethoxysilane, etc., and these may be used alone or in combination of two or more.

[0381] 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.

[0382] 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.

[0383] 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.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] 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.

[0388]

[0389] menstruum

[0390] Meanwhile, the curable composition according to one embodiment may further include a solvent.

[0391] 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.;

[0392] 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 ethyl 2-hydroxypropionate; 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; cyclohexyl acetate, or a combination thereof.

[0393] For example, the solvent may be a high boiling point 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, cyclohexyl acetate, or a combination thereof.

[0394] The solvent may be included in an amount of 40 wt% to 80 wt%, for example, 45 wt% to 80 wt%, based on the total amount of the curable composition. When the solvent is included within the above range, the solvent-type curable composition has an appropriate viscosity, thereby providing excellent coating properties during large-area coating using spin coating and slitting.

[0395]

[0396] Another embodiment provides a curable composition, for example, a cured film manufactured using the curable composition, a color filter including the cured film, and a display device including the color filter. For example, the display device may include a micro LED light source.

[0397] One of the methods for manufacturing the above cured film includes a step (S1) of forming a pattern by applying the above curable composition onto a substrate using an inkjet spraying method; and a step (S2) of curing the pattern.

[0398] (S1) Pattern forming step

[0399] The above curable composition is preferably applied to a substrate with a thickness of 0.5 to 20 μm using an inkjet dispersion method. The inkjet spraying can form a pattern by spraying only a single color per nozzle and repeatedly spraying according to the required number of colors. To reduce the process, the pattern can also be formed by spraying the required number of colors simultaneously through each inkjet nozzle.

[0400] (S2) Hardening stage

[0401] The obtained pattern can be cured to obtain pixels. At this time, as a curing method, both a thermal curing process and a photocuring process can be applied. The thermal curing process is preferably cured by heating to a temperature of 100°C or higher, more preferably cured by heating to 100°C to 300°C, and even more preferably cured by heating to 160°C to 250°C. The photocuring process irradiates active rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 400 nm. 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, an i-line, a KrF, an ArF, an I-ArF, an EUV, an X-ray, and an electron beam can be used, depending on the case.

[0402] Another method of manufacturing the above-mentioned cured film is to manufacture the cured film using the above-mentioned curable composition using a lithography method, and the manufacturing method is as follows.

[0403] (1) Application and film formation stage

[0404] 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.

[0405] (2) Exposure stage

[0406] 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.

[0407] 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).

[0408] (3) Phenomenon stage

[0409] Following the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, thereby 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.

[0410] (4) Post-processing stage

[0411] 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.

[0412]

[0413] 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.

[0414]

[0415] (Synthesis of surface modification materials)

[0416] (first ligand)

[0417] Synthesis Example 1-1

[0418] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor, chemical formula 19, dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried to obtain a compound represented by the following chemical formula 2.

[0419] [Chemical Formula 2]

[0420]

[0421]

[0422] Synthesis Example 1-2

[0423] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 20 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 3.

[0424] [Chemical Formula 3]

[0425]

[0426]

[0427] Synthesis Example 1-3

[0428] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 21 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 4.

[0429] [Chemical Formula 4]

[0430]

[0431] Synthesis Example 1-4

[0432] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 22 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 5.

[0433] [Chemical Formula 5]

[0434]

[0435] Synthesis Example 1-5

[0436] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 23 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 6.

[0437] [Chemical Formula 6]

[0438]

[0439] Synthesis Example 1-6

[0440] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 24 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 7.

[0441] [Chemical Formula 7]

[0442]

[0443] Synthesis Example 1-7

[0444] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 25 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 8.

[0445] [Chemical Formula 8]

[0446]

[0447] Synthesis Example 1-8

[0448] An aqueous solution of 1 equivalent of zinc acetate dissolved in 50 times its weight of distilled water is rapidly added dropwise to a solution of 2.5 equivalents of the precursor chemical formula 26 dissolved in 10 times its weight of distilled water: methyl alcohol = 1:1 solvent. After stirring at room temperature, a 10% aqueous potassium hydroxide solution is added dropwise to adjust the pH from 4.5 to 6.4 to 7. The white precipitate formed at this time is filtered under reduced pressure while passing an excess of distilled water through it to remove water-soluble impurities, and then dried, thereby finally producing a compound represented by the following chemical formula 9.

[0449] [Chemical Formula 9]

[0450]

[0451] Synthesis Example 1-9

[0452] A suspension of the carboxylic acid precursor chemical formula 27 in dichloromethane was dropwise added 5 times the weight of thionyl chloride and 0.1 times the weight of dimethylformamide, then a reflux condenser was installed, heated for 1 hour, and the solvent was removed under reduced pressure. The remaining white solid was dissolved again in dichloromethane, and 1 equivalent each of 4-aminopyridine and triethylamine were added dropwise, and then a reflux condenser was installed again, heated for 24 hours. After removal of the solvent and drying, it was dissolved again in dichloromethane, washed with a saturated aqueous sodium bicarbonate solution, and dried. A methanol solution of the corresponding compound was added dropwise to a methanol solution of 1 equivalent of zinc chloride, and then heated for reaction, thereby producing a compound represented by chemical formula 10.

[0453] [Chemical Formula 10]

[0454]

[0455] Synthesis Example 1-10

[0456] 2.5 equivalents of the carboxylic acid precursor chemical formula 28 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 11.

[0457] [Chemical Formula 11]

[0458]

[0459] (In the above chemical formula 11,

[0460] R x Is am)

[0461] Synthesis Example 1-11

[0462] 2.5 equivalents of the carboxylic acid precursor chemical formula 29 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 12.

[0463] [Chemical Formula 12]

[0464]

[0465] Synthesis Example 1-12

[0466] Dissolve 2.5 equivalents of the carboxylic acid precursor chemical formula 30 and 1 equivalent of zinc oxide in ethanol and stir at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 13.

[0467] [Chemical Formula 13]

[0468]

[0469] Synthesis Example 1-13

[0470] 2.5 equivalents of the carboxylic acid precursor chemical formula 31 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 14.

[0471] [Chemical Formula 14]

[0472]

[0473] Synthesis Example 1-14

[0474] 2.5 equivalents of the carboxylic acid precursor chemical formula 32 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 15.

[0475] [Chemical Formula 15]

[0476]

[0477] Synthesis Example 1-15

[0478] 2.5 equivalents of the carboxylic acid precursor chemical formula 33 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 16.

[0479] [Chemical Formula 16]

[0480]

[0481] Synthesis Example 1-16

[0482] 2.5 equivalents of the carboxylic acid precursor chemical formula 34 and 1 equivalent of zinc oxide are dissolved in ethanol and stirred at 70°C for 60 minutes under an inert gas atmosphere. After cooling to room temperature, centrifuge at 6000 rpm for 3 minutes to remove the supernatant, and then pour the precipitate into ethanol twice and repeat centrifugation to prepare a compound represented by chemical formula 17.

[0483] [Chemical Formula 17]

[0484]

[0485] (second ligand)

[0486] Synthesis Example 2-1

[0487] Carboxylic acid precursor 27 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mass is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mass is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 19.

[0488] [Chemical Formula 19]

[0489]

[0490] Synthesis Example 2-2

[0491] Carboxylic acid precursor 28 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mass is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mass is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 20.

[0492] [Chemical Formula 20]

[0493]

[0494] Synthesis Example 2-3

[0495] Carboxylic acid precursor 29 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mixture is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mixture is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 21.

[0496] [Chemical Formula 21]

[0497]

[0498] Synthesis Example 2-4

[0499] After adding 5 equivalents of carboxylic acid precursor 30 and 1,1-carbonyldiimide to 5 times the volume of tetrahydrofuran, the mixture is stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added and the mixture is continued to be stirred at room temperature. After 24 hours, the reaction mixture is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mixture is extracted twice with ethyl acetate, the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter to finally produce a compound represented by the following chemical formula 22.

[0500] [Chemical Formula 22]

[0501]

[0502] Synthesis Example 2-5

[0503] Carboxylic acid precursor 31 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mass is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mass is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 23.

[0504] [Chemical Formula 23]

[0505]

[0506] Synthesis Example 2-6

[0507] Carboxylic acid precursor 32 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mass is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mass is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 24.

[0508] [Chemical Formula 24]

[0509]

[0510] Synthesis Example 2-7

[0511] After adding 5 equivalents of carboxylic acid precursor 33 and 1,1-carbonyldiimide to 5 times the volume of tetrahydrofuran, the mixture is stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added and the mixture is continued to be stirred at room temperature. After 24 hours, the reaction mixture is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mixture is extracted twice with ethyl acetate, the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter to finally produce a compound represented by the following chemical formula 25.

[0512] [Chemical Formula 25]

[0513]

[0514] Synthesis Example 2-8

[0515] Carboxylic acid precursor 34 and 5 equivalents of 1,1-carbonyldiimide are added to 5 times the volume of tetrahydrofuran, and stirred at room temperature under an inert nitrogen gas. After 1 hour, 2 equivalents of hydroxylamine hydrochloride are added, and stirring is continued at room temperature. After 24 hours, the reaction mass is poured into a 5% aqueous solution of sodium bisulfate and stirred. The reaction mass is extracted twice with ethyl acetate, and the organic layer is dried and filtered. The product is dissolved in ethyl acetate, an excess of charcoal is added, stirred, and filtered through a silica gel pad filter, to finally produce a compound represented by the following chemical formula 26.

[0516] [Chemical Formula 26]

[0517]

[0518] Synthesis Example 2-9

[0519] A 2-molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 27 and a terminal hydroxyl group (in Chemical Formula 27, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating to 70°C again. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 27 with a carboxylic acid substituted below.

[0520] [Chemical Formula 27]

[0521]

[0522] Synthesis Example 2-10

[0523] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 28 and having a terminal hydroxyl group substituted (in Chemical Formula 28, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% aqueous hydrochloric acid solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 28 having a carboxylic acid substituted below.

[0524] [Chemical Formula 28]

[0525]

[0526] Synthesis Example 2-11

[0527] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 29 and having a hydroxyl group substituted at the terminal (in Chemical Formula 29, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 29 having a carboxylic acid substituted below.

[0528] [Chemical Formula 29]

[0529]

[0530] Synthesis Example 2-12

[0531] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 30 with a substituted hydroxyl group at the terminal (in Chemical Formula 30, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 30 with a substituted carboxylic acid below.

[0532] [Chemical Formula 30]

[0533]

[0534] Synthesis Example 2-13

[0535] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 31 and having a hydroxyl group substituted at the terminal (in Chemical Formula 31, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 31 having a carboxylic acid substituted below.

[0536] [Chemical Formula 31]

[0537]

[0538] Synthesis Example 2-14

[0539] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 32 and having a terminal hydroxyl group substituted (in Chemical Formula 32, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 32 having a carboxylic acid substituted below.

[0540] [Chemical Formula 32]

[0541]

[0542] Synthesis Example 2-15

[0543] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 33 and having a terminal hydroxyl group substituted (in Chemical Formula 33, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 33 having the following carboxylic acid substituted therein.

[0544] [Chemical Formula 33]

[0545]

[0546] Synthesis Example 2-16

[0547] A 2 molar concentration m-xylene solution of a precursor having the same structure as Chemical Formula 34 and having a terminal hydroxyl group substituted (in Chemical Formula 34, the terminal is *-CH2OH instead of *-COOH) is stirred while mixing powders of 1.5 equivalents of sodium chloroacetate and 1.5 equivalents of sodium hydroxide, then slowly adding the powder using a powder adding glass sieve for 10 minutes, stirring at 70°C for 1 hour, cooling to room temperature, adding 1.5 equivalents of a 10% hydrochloric acid aqueous solution using a pipette, and then heating again to 70°C. After 30 minutes, the reactant cooled to room temperature is transferred to a separatory funnel, the aqueous layer is removed, and washed with an aqueous sodium chloride solution. The organic layer is dried, filtered, and concentrated by rotation to finally produce a compound represented by Chemical Formula 34 having a carboxylic acid substituted below.

[0548] [Chemical Formula 34]

[0549]

[0550]

[0551] (Manufacture of surface-modified quantum dots)

[0552] Manufacturing Example 1

[0553] 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 green quantum dots have oleic acid substituted on their surfaces. The first ligand (represented by the chemical formula 2) is added thereto and stirred at 60°C for 2 hours under a nitrogen atmosphere, followed by adding the second ligand (represented by the chemical formula 19) together with ZnCl2 and stirring at 25°C for 2 hours under 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 collect the 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.

[0554] Manufacturing Example 2

[0555] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 3 and a compound represented by Chemical Formula 20 were used as the first ligand and the second ligand, respectively.

[0556] Manufacturing Example 3

[0557] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 4 and a compound represented by Chemical Formula 21 were used as the first ligand and the second ligand, respectively.

[0558] Manufacturing Example 4

[0559] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 5 and a compound represented by Chemical Formula 22 were used as the first ligand and the second ligand, respectively.

[0560] Manufacturing Example 5

[0561] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 6 and a compound represented by Chemical Formula 23 were used as the first ligand and the second ligand, respectively.

[0562] Manufacturing Example 6

[0563] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 7 and a compound represented by Chemical Formula 24 were used as the first ligand and the second ligand, respectively.

[0564] Manufacturing Example 7

[0565] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 8 and a compound represented by Chemical Formula 25 were used as the first ligand and the second ligand, respectively.

[0566] Manufacturing Example 8

[0567] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 9 and a compound represented by Chemical Formula 26 were used as the first ligand and the second ligand, respectively.

[0568] Manufacturing Example 9

[0569] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 10 and a compound represented by Chemical Formula 27 were used as the first ligand and the second ligand, respectively.

[0570] Manufacturing Example 10

[0571] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 11 and a compound represented by Chemical Formula 28 were used as the first ligand and the second ligand, respectively.

[0572] Manufacturing Example 11

[0573] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 12 and a compound represented by Chemical Formula 29 were used as the first ligand and the second ligand, respectively.

[0574] Manufacturing Example 12

[0575] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 13 and a compound represented by Chemical Formula 30 were used as the first ligand and the second ligand, respectively.

[0576] Manufacturing Example 13

[0577] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 14 and a compound represented by Chemical Formula 31 were used as the first ligand and the second ligand, respectively.

[0578] Manufacturing Example 14

[0579] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 15 and a compound represented by Chemical Formula 32 were used as the first ligand and the second ligand, respectively.

[0580] Manufacturing Example 15

[0581] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 16 and a compound represented by Chemical Formula 33 were used as the first ligand and the second ligand, respectively.

[0582] Manufacturing Example 16

[0583] The same procedure as in Preparation Example 1 was followed, except that a compound represented by Chemical Formula 17 and a compound represented by Chemical Formula 34 were used as the first ligand and the second ligand, respectively.

[0584] Manufacturing Example 17

[0585] The same procedure as in Manufacturing Example 1 was followed except that the second ligand was not used.

[0586] Manufacturing Example 18

[0587] The same procedure as in Manufacturing Example 2 was followed except that the second ligand was not used.

[0588] Manufacturing Example 19

[0589] The same procedure as in Manufacturing Example 3 was followed except that the second ligand was not used.

[0590] Manufacturing Example 20

[0591] The same procedure as in Manufacturing Example 4 was followed except that the second ligand was not used.

[0592] Manufacturing Example 21

[0593] The same procedure as in Manufacturing Example 5 was followed except that the second ligand was not used.

[0594] Manufacturing Example 22

[0595] The same procedure as in Manufacturing Example 6 was followed except that the second ligand was not used.

[0596] Manufacturing Example 23

[0597] The same procedure as in Manufacturing Example 7 was followed except that the second ligand was not used.

[0598] Manufacturing Example 24

[0599] The same procedure as in Manufacturing Example 8 was followed except that the second ligand was not used.

[0600] Manufacturing Example 25

[0601] The same procedure as in Manufacturing Example 9 was followed except that the second ligand was not used.

[0602] Manufacturing Example 26

[0603] The same procedure as in Manufacturing Example 10 was followed except that the second ligand was not used.

[0604] Manufacturing Example 27

[0605] The same procedure as in Manufacturing Example 11 was followed except that the second ligand was not used.

[0606] Manufacturing Example 28

[0607] The same procedure as in Manufacturing Example 12 was followed except that the second ligand was not used.

[0608] Manufacturing Example 29

[0609] The same procedure as in Manufacturing Example 13 was followed except that the second ligand was not used.

[0610] Manufacturing Example 30

[0611] The same procedure as in Manufacturing Example 14 was followed except that the second ligand was not used.

[0612] Manufacturing Example 31

[0613] The same procedure as in Manufacturing Example 15 was followed except that the second ligand was not used.

[0614] Manufacturing Example 32

[0615] The same procedure as in Manufacturing Example 16 was followed except that the second ligand was not used.

[0616] Comparative Manufacturing Example 1

[0617] The same procedure as in Manufacturing Example 1 was followed except that the first ligand was not used.

[0618] Comparative Manufacturing Example 2

[0619] The same procedure as in Manufacturing Example 2 was followed except that the first ligand was not used.

[0620] Comparative manufacturing example 3

[0621] The same procedure as in Manufacturing Example 3 was followed except that the first ligand was not used.

[0622] Comparative Manufacturing Example 4

[0623] The same procedure as in Manufacturing Example 4 was followed except that the first ligand was not used.

[0624] Comparative Manufacturing Example 5

[0625] The same procedure as in Manufacturing Example 5 was followed except that the first ligand was not used.

[0626] Comparative Manufacturing Example 6

[0627] The same procedure as in Manufacturing Example 6 was followed except that the first ligand was not used.

[0628] Comparative Manufacturing Example 7

[0629] The same procedure as in Manufacturing Example 7 was followed except that the first ligand was not used.

[0630] Comparative Manufacturing Example 8

[0631] The same procedure as in Manufacturing Example 8 was followed except that the first ligand was not used.

[0632] Comparative Manufacturing Example 9

[0633] The same procedure as in Manufacturing Example 9 was followed except that the first ligand was not used.

[0634] Comparative Manufacturing Example 10

[0635] The same procedure as in Manufacturing Example 10 was followed except that the first ligand was not used.

[0636] Comparative Manufacturing Example 11

[0637] The same procedure as in Manufacturing Example 11 was followed except that the first ligand was not used.

[0638] Comparative Manufacturing Example 12

[0639] The same procedure as in Manufacturing Example 12 was followed except that the first ligand was not used.

[0640] Comparative Manufacturing Example 13

[0641] The same procedure as in Manufacturing Example 13 was followed except that the first ligand was not used.

[0642] Comparative Manufacturing Example 14

[0643] The same procedure as in Manufacturing Example 14 was followed except that the first ligand was not used.

[0644] Comparative Manufacturing Example 15

[0645] The same procedure as in Manufacturing Example 15 was followed except that the first ligand was not used.

[0646] Comparative Manufacturing Example 16

[0647] The same procedure as in Manufacturing Example 16 was followed except that the first ligand was not used.

[0648] Comparative Manufacturing Example 17

[0649] The same procedure as in Preparation Example 1 was followed, except that mono(2-acryloyloxyethyl) Succinate (TCI) and a compound represented by Chemical Formula 20 were used as the first ligand and the second ligand, respectively.

[0650]

[0651] (Preparation of solvent-based curable composition)

[0652] Based on the respective components below, curable compositions according to Examples 1 to 32 and Comparative Examples 1 to 17 were prepared according to the compositions in Table 1 below. Specifically, a photopolymerization initiator was dissolved in a solvent, and then sufficiently stirred at room temperature for 2 hours. Subsequently, a polymerizable compound, a binder resin, and a light diffusing agent were added, and sufficiently mixed for about 15 minutes, and then stirred at room temperature for another 1 hour. Meanwhile, quantum dots and a dispersant were added to a dispersion medium, and stirred at room temperature for 30 minutes to prepare a quantum dot solution. Thereafter, the quantum dot solution was mixed with a solution in which the photopolymerization initiator, etc. were dissolved, and then stirred at room temperature for 30 minutes, and the product was filtered three times to remove impurities, thereby preparing a solvent-type curable composition.

[0653]

[0654] (A) Quantum dots

[0655] (A-1) Quantum dot of manufacturing example 1

[0656] (A-2) Quantum dot of manufacturing example 2

[0657] (A-3) Quantum dot of manufacturing example 3

[0658] (A-4) Quantum dot of manufacturing example 4

[0659] (A-5) Quantum dot of manufacturing example 5

[0660] (A-6) Quantum dot of manufacturing example 6

[0661] (A-7) Quantum dot of manufacturing example 7

[0662] (A-8) Quantum dot of manufacturing example 8

[0663] (A-9) Quantum dot of manufacturing example 9

[0664] (A-10) Quantum dot of manufacturing example 10

[0665] (A-11) Quantum dot of manufacturing example 11

[0666] (A-12) Quantum dot of manufacturing example 12

[0667] (A-13) Quantum dot of manufacturing example 13

[0668] (A-14) Quantum dot of manufacturing example 14

[0669] (A-15) Quantum dot of manufacturing example 15

[0670] (A-16) Quantum dot of manufacturing example 16

[0671] (A-17) Quantum dot of manufacturing example 17

[0672] (A-18) Quantum dot of manufacturing example 18

[0673] (A-19) Quantum dot of manufacturing example 19

[0674] (A-20) Quantum dot of manufacturing example 20

[0675] (A-21) Quantum dot of manufacturing example 21

[0676] (A-22) Quantum dot of manufacturing example 22

[0677] (A-23) Quantum dot of manufacturing example 23

[0678] (A-24) Quantum dot of manufacturing example 24

[0679] (A-25) Quantum dot of manufacturing example 25

[0680] (A-26) Quantum dot of manufacturing example 26

[0681] (A-27) Quantum dot of manufacturing example 27

[0682] (A-28) Quantum dot of manufacturing example 28

[0683] (A-29) Quantum dot of manufacturing example 29

[0684] (A-30) Quantum dot of manufacturing example 30

[0685] (A-31) Quantum dot of manufacturing example 31

[0686] (A-32) Quantum dot of manufacturing example 32

[0687] (A-33) Quantum dot of comparative manufacturing example 1

[0688] (A-34) Quantum dot of comparative manufacturing example 2

[0689] (A-35) Quantum dot of comparative manufacturing example 3

[0690] (A-36) Quantum dot of comparative manufacturing example 4

[0691] (A-37) Quantum dot of comparative manufacturing example 5

[0692] (A-38) Quantum dot of comparative manufacturing example 6

[0693] (A-39) Quantum dot of comparative manufacturing example 7

[0694] (A-40) Quantum dot of comparative manufacturing example 8

[0695] (A-41) Quantum dot of comparative manufacturing example 9

[0696] (A-42) Quantum dot of comparative manufacturing example 10

[0697] (A-43) Quantum dot of comparative manufacturing example 11

[0698] (A-44) Quantum dot of comparative manufacturing example 12

[0699] (A-45) Quantum dot of comparative manufacturing example 13

[0700] (A-46) Quantum dot of comparative manufacturing example 14

[0701] (A-47) Quantum dot of comparative manufacturing example 15

[0702] (A-48) Quantum dot of comparative manufacturing example 16

[0703] (A-49) Quantum dot of comparative manufacturing example 17

[0704] (B) polymeric compound

[0705] Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku)

[0706] (C) Photopolymerization initiator

[0707] Oxime initiator (PBG-305, Tronyl)

[0708] (D) Light diffuser

[0709] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0710] (E) Binder resin

[0711] (E-1) RY67-1 (showa denko)

[0712] (E-2) TA-001 (Tacoma)

[0713] (F) solvent

[0714] Propylene glycol monomethyl ether acetate (PGMEA) (Sigma-Aldrich)

[0715] (G) Other additives

[0716] Leveling agent (F-554, DIC)

[0717]

[0718] (Unit: wt%)Example 1Example 2Example 3Example 4Example 5Example 6Example 7Example 8Example 9Example 10Quantum dot15 (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)Polymerizable compound3.53.53.53.53.53.53.53.53.53.5Photopolymerization initiator0.50.50.50.50.50.50.50.50.50.50.50.5Light diffusing agent3333333333Binder Resin (E-1) 4.5 ...

[0719] (Unit: wt%)Example 11Example 12Example 13Example 14Example 15Example 16Example 17Example 18Example 19Example 20Quantum dot15 (A-11)15 (A-12)15 (A-13)15 (A-14)15 (A-15)15 (A-16)15 (A-17)15 (A-18)15 (A-19)15 (A-20)Polymerizable compound3.53.53.53.53.53.53.53.53.53.5Photopolymerization initiator0.50.50.50.50.50.50.50.50.50.50.50.5Light diffusing agent3333333333Binder Resin (E-1) 4.5 ...

[0720] (Unit: wt%)Example 21Example 22Example 23Example 24Example 25Example 26Example 27Example 28Example 29Example 30Quantum dot15 (A-21)15 (A-22)15 (A-23)15 (A-24)15 (A-25)15 (A-26)15 (A-27)15 (A-28)15 (A-29)15 (A-30)Polymerizable compound3.53.53.53.53.53.53.53.53.53.5Photopolymerization initiator0.50.50.50.50.50.50.50.50.50.50.50.5Light diffusing agent3333333333Binder Resin (E-1) 4.5 ...

[0721] (Unit: wt%)Example 31Example 32Quantum dot 15 (A-31) 15 (A-32)Polymerizable compound 3.53.5Photopolymerization initiator 0.50.5Light diffusing agent 33Binder resin (E-1) 4.54.5(E-2) 1.51.5Solvent 7070Other additives 22

[0722] (Unit: wt%)Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Comparative Example 10Quantum Dot15 (A-33)15 (A-34)15 (A-35)15 (A-36)15 (A-37)15 (A-38)15 (A-39)15 (A-40)15 (A-41)15 (A-42)Polymerizable Compound3.53.53.53.53.53.53.53.53.53.5Photopolymerization Initiator0.50.50.50.50.50.50.50.50.50.50.50.5Light Diffusing Agent3333333333Binder Resin (E-1) 4.5 ...

[0723] (Unit: wt%)Comparative Example 11Comparative Example 12Comparative Example 13Comparative Example 14Comparative Example 15Comparative Example 16Comparative Example 17Quantum Dot 15 (A-43) 15 (A-44) 15 (A-45) 15 (A-46) 15 (A-47) 15 (A-48) 15 (A-49)Polymerizable Compound 3.53.53.53.53.53.53.5Photopolymerization Initiator 0.50.50.50.50.50.50.50.5Light Diffusing Agent 3333333Binder Resin (E-1) 4.54.54.54.54.54.54.5(E-2) 1.51.51.51.51.51.51.51.5Solvent 70707070707070Other Additive2222222

[0724] Evaluation: Evaluation of light resistance reliability of curable compositions

[0725] The light resistance reliability of each of the curable compositions according to Examples 1 to 32 and Comparative Examples 1 to 17 was evaluated, and the results are shown in Tables 7 and 8 below.

[0726]

[0727] (Light resistance reliability evaluation method)

[0728] The curable composition manufactured above was used to make a 2 cm x 2 cm single-film specimen, and the change in luminous efficiency over time was measured under blue 100,000 nit light source conditions using a self-made blue LED surface light source.

[0729] The single-film specimens were measured for luminous efficacy and temporal luminance using an integrating sphere device (QE-2100, otsuka electronics) and an in-line luminance meter (M7000, Mcscience).

[0730] The comparison was made based on the time to reach T90 (the time it takes for the initial luminous efficacy measurement value to drop to 90% when the initial luminous efficacy measurement value is 100%) with an initial measurement value of 100% as the standard.

[0731]

[0732] T90(hr)T90(hr)Example 11000Example 17800Example 21000Example 18800Example 31000Example 19800Example 41000Example 20800Example 51000Example 21800Example 61000Example 22800Example 71000Example 23800Example 81000Example 24800Example 91000Example 25800Example 101000Example 26800Example 111000Example 27800Example 121000Example 28800Example 131000 Example 29800 Example 141000 Example 30800 Example 151000 Example 31800 Example 161000 Example 32800

[0733] T90(hr)Comparative example 1230Comparative example 2220Comparative example 3150Comparative example 4150Comparative example 5180Comparative example 6250Comparative example 7230Comparative example 8180Comparative example 9190Comparative example 10180Comparative example 11240Comparative example 12240Comparative example 13200Comparative example 14190Comparative example 15180Comparative example 16220Comparative example 17220

[0734] From Tables 7 and 8 above, it can be seen that the curable composition according to one embodiment can significantly improve light resistance.

[0735] 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) Quantum dots surface-modified with a compound represented by the following chemical formula 1; and (B) polymeric compound A curable composition comprising: [Chemical Formula 1] In the above chemical formula 1, X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*, Y 1 and Y 2 are each independently *-O-*, *-S-* or *-C(=O)NH-*, R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, L 1 Inland L 8 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

2. In paragraph 1, The compound represented by the above chemical formula 1 is a curable composition having a symmetrical structure.

3. In paragraph 1, The compound represented by the above chemical formula 1 is a curable composition represented by any one of the following chemical formulas 1-1 to 1-5: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] In the above chemical formulas 1-1 to 1-5, X 1 and X 2 are each independently *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-O-* or *-O-*, R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group, n1 and n2 are each independently an integer from 1 to 10.

4. In paragraph 1, The compound represented by the above chemical formula 1 is a curable composition represented by any one of the following chemical formulas 2 to 17. [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] (In the above chemical formula 11, R x Is am) [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] 5. In paragraph 1, A curable composition wherein the quantum dot is further surface-modified with a compound represented by the following chemical formula 18: [Chemical Formula 18] In the above chemical formula 18, X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH, Y 11 is *-O-*, *-S-* or *-C(=O)NH-*, R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, L 31 Inland L 34 are each independently a single bond, an ester group (*-C(=O)O-* or *-OC(=O)-*), *-(L 9 -O) n -*(L 9 is a C1 to C10 alkylene group, and n is an integer from 1 to 20) or a substituted or unsubstituted C1 to C20 alkylene group.

6. In paragraph 5, The compound represented by the above chemical formula 18 is a curable composition represented by any one of the following chemical formulas 18-1 to 18-5: [Chemical Formula 18-1] [Chemical Formula 18-2] [Chemical Formula 18-3] [Chemical Formula 18-4] [Chemical Formula 18-5] In the above chemical formulas 18-1 to 18-5, X 3 is a hydroxy group or *-NR (R is a hydrogen atom or a C1 to C10 alkyl group)-OH, R 3 is a hydrogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, L 10 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, L 11 Inland L 13 are each independently a substituted or unsubstituted C1 to C20 alkylene group, n1 and n2 are each independently an integer from 1 to 10.

7. In paragraph 5, The compound represented by the above chemical formula 18 is a curable composition represented by any one of the following chemical formulas 19 to 34. [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34] 8. In paragraph 1, The above curable composition is a curable composition that is a solvent-free curable composition.

9. In paragraph 8, The above solvent-free curable composition, with respect to the total amount of the above solvent-free curable composition, 5 to 60 wt% of the above quantum dots; and 40 to 95 wt% of the polymerizable compound A solvent-free curable composition comprising:

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

13. In paragraph 1, The above curable composition further comprises a solvent.

14. In paragraph 13, 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; and 40 to 80 wt% of the above solvent A curable composition comprising:

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

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

Images