Curable composition, cured film manufactured using curable composition, and display device

Abstract

Provided are: a curable composition comprising (A) a first quantum dot having a core-shell structure including In and P components in the core and at least two components among Zn, Se, and S in the shell, (B) a second quantum dot having a core-shell structure including at least three components among Ag, In, Ga, and S in the core and at least two components among Ag, Ga, S, and Zn in the shell, and (C) a polymerizable compound, wherein the first quantum dot and the second quantum dot are included in a weight ratio of 50:50 to 5:95; a cured film manufactured using the curable composition; and a display device including the cured film.

Description

Curable composition, cured film and display device manufactured using the curable composition

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

[0002]

[0003] Nanostructures containing group I-III-VI semiconductors are promising candidates for non-toxic fluorescent materials. Uematsu et al. NPG Asia Materials 10:713-726 (2018) reported that AgInS-2 / GaS x Core / shell nanostructures were disclosed, where x ranges from 0.8 to 1.5. These core / shell nanostructures exhibited band-edge emission and broad red-shifted defect emission. A reduction in the defect emission was obtained by modifying the shelling procedure by using a temperature gradient reaction and by using 1,3-dimethylthiourea (as a sulfur source) and Ga(acac)3 to produce GaS. However, the band-edge emission was red-shifted, while the defect emission persisted.

[0004] Kameyama et al., ACS Appl. Mater. Interfaces 10:42844–42855 (2018) describe Ag-In-Ga-S (AIGS) nanostructures with significant defect emission. The defect emission was reduced by the application of a GaS shell. However, the defect emission remained at approximately 15% of the band-edge emission intensity, and the photoluminescence quantum yield was low (<30%).

[0005] There remains a need in the art for AIGS nanostructures with very high band-edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced redshift.

[0006]

[0007] One embodiment is to provide a curable composition having high absorbance and low viscosity while being economical.

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

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

[0010]

[0011] One embodiment provides a curable composition comprising: (A) a first quantum dot having a core-shell structure, comprising In and P components in the core and at least two components of Zn, Se, and S in the shell; (B) a second quantum dot having a core-shell structure, comprising at least three components of Ag, In, Ga, and S in the core and at least two components of Ag, Ga, S, and Zn in the shell; and (C) a polymerizable compound, wherein the first quantum dot and the second quantum dot are included in a weight ratio of 50:50 to 5:95.

[0012] The first quantum dot and the second quantum dot may be included in a weight ratio of 50:50 to 20:80.

[0013] Both the shell within the first quantum dot and the shell within the second quantum dot may include ZnS.

[0014] The first quantum dot and the second quantum dot may exist separately without being combined with each other.

[0015] The second quantum dot has a peak emission wavelength (PWL) in the range of 480-680 nm, more than 80% of the emission is band-edge emission, and can exhibit a quantum yield (QY) of 80% to 99.9%.

[0016] The second quantum dot may have a half-width of less than 40 nm.

[0017] The second quantum dot may have an average diameter of 5 nm to 10 nm.

[0018] The second quantum dot has a size of 4.00 x 10 at 450 nm. 5 M -1 cm -1 It can have a maximum absorption coefficient above.

[0019] The above polymerizable compound may include a compound represented by the following chemical formula 1.

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1,

[0023] L 6 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0024] L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0025] R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0026] The above curable composition may be a solvent-free curable composition.

[0027] 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.

[0028] The above curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0029] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0030] The above curable composition may further comprise a solvent.

[0031] 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.

[0032] 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.

[0033] Another embodiment provides a cured film manufactured using the curable composition.

[0034] Another embodiment provides a color filter including the cured film.

[0035] Another embodiment provides a display device including the color filter.

[0036] Specific details of other aspects of the present invention are included in the detailed description below.

[0037]

[0038] By employing quantum dots with a core / shell structure that is made of a completely different material from that of conventional InP-based quantum dots, the light absorption rate can be significantly increased, and furthermore, by controlling the mixing ratio when mixing quantum dots with a core-shell structure made of the new material with conventional InP-based quantum dots, the quantum dots can be prevented from agglomerating with each other, thereby ultimately obtaining a curable composition with excellent optical properties, low viscosity, and high economic efficiency.

[0039]

[0040] Figure 1 is a graph showing the maximum absorption coefficient according to the wavelength of each of the first quantum dot and the second quantum dot.

[0041] Figure 2 is a drawing comparing a picture in which quantum dots are present in a monodisperse form without being aggregated in a curable composition and a picture in which quantum dots are present in a aggregated form in a curable composition.

[0042]

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] Additionally, unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0048] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0049] 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.

[0050] Additionally, unless otherwise specified herein, “*” means a portion connected to the same or different atoms or chemical formulas.

[0051] InP quantum dots, developed as an alternative to Cd series quantum dots due to their toxicity, are currently being used in QD-Ink for QD-OLED, QD-ink for uLED, and photoresist sheets. However, due to the low extinction coefficient (ε) of InP quantum dots, the quantum dot content must be increased to achieve the desired amount of light when applied to displays, and the limitation of a high single-film thickness when applied to panels continues to appear.

[0052] Specifically, InP-based quantum dots have a very low absorption rate of green light due to the low proportion of the core within the core / shell quantum dot particle, and when applied to displays, the quantum dots must be used in excessive amounts, which is very disadvantageous in terms of fairness. In addition, when applied to panels, the thickness of the quantum dot-containing cured film must be thick, which inevitably reduces the freedom of panel design.

[0053] After clearly recognizing the above-mentioned shortcomings of the InP-based quantum dots in use in the past, the inventors developed a new material, namely, a new 4-component composition Ag-In-Ga-S-based quantum dot, to overcome the above-mentioned shortcomings.

[0054] The Ag-In-Ga-S quantum dots themselves have a high absorption coefficient, so they can drastically reduce the quantum dot content in a solvent-free or solvent-based curable composition, and also allow for a thinner single film thickness within the panel, which has the advantage of increasing the degree of freedom in panel design. By lowering the quantum dot content in the solvent-free or solvent-based curable composition, the content of inorganic substances is lowered, which also has the advantage of improving the processability of each material.

[0055] In addition, the absorption coefficient of the Ag-In-Ga-S quantum dots is 17 times that of the InP quantum dots, so that even with a low content of the Ag-In-Ga-S quantum dots, superior light absorption and external quantum efficiency (EQE) can be achieved compared to the InP quantum dots. This is because the Ag-In-Ga-S quantum dots have a high ratio of cores within the particles. In addition, the Ag-In-Ga-S quantum dots have the advantage of easy wavelength tuning due to their composition in addition to the quantum confinement effect.

[0056] In the case of the Ag-In-Ga-S quantum dots, the native ligand attached to the surface of the quantum dots during the synthesis process is oleylamine. Generally, a quantum dot dispersion is prepared by substituting the ligand of the Ag-In-Ga-S quantum dots with a polyethylene-amine or siloxane amine called Jeffamine for dispersion in a process solvent or monomer. Therefore, since the functional group substituted with the ligand is the same as an amine, the driving force of the reaction is characterized in that the reaction proceeds depending on the concentration of the newly introduced new ligand.

[0057] The problem is that these ligand substitution reactions are extremely inefficient due to extremely low substitution / purification yields. In other words, even if conventional InP quantum dots were replaced with Ag-In-Ga-S quantum dots, surface modification would not be effective, preventing engineers from fully exploiting the superior properties of the aforementioned Ag-In-Ga-S quantum dots. This is the current technological barrier facing engineers.

[0058] In addition, the production cost of the Ag-In-Ga-S quantum dots is too high considering their composition.

[0059] Above all, when manufacturing a curable composition using the quantum dots, the viscosity of the composition containing the quantum dots is high due to the aggregation phenomenon between the quantum dots in the composition, which poses a major problem in terms of economic feasibility and mass production.

[0060] Accordingly, the inventors of the present invention have made efforts to improve economic feasibility and mass productivity in various ways, and have confirmed that the problems of economic feasibility and mass productivity can be solved at once by mixing the InP-based quantum dots and the Ag-In-Ga-S-based quantum dots and controlling the mixing weight ratio thereof, thereby completing the present invention.

[0061] The components constituting the curable composition according to the following implementation example are described in detail.

[0062]

[0063] (A) First quantum dot and (B) Second quantum dot

[0064] That is, the quantum dots in the curable composition according to one embodiment include two different types of quantum dots.

[0065] The above two types of quantum dots are both core-shell structured quantum dots, for example, the first quantum dot is a core-shell structured quantum dot including In and P components in the core and at least two components of Zn, Se, and S in the shell, and the second quantum dot is a core-shell structured quantum dot including at least three components of Ag, In, Ga, and S in the core and at least two components of Ag, Ga, S, and Zn in the shell.

[0066] When quantum dots of the same content are applied to a curable composition, the optical properties may be superior when the second quantum dot is applied alone compared to when the first quantum dot is applied alone. However, as mentioned above, the price of the second quantum dot is much higher than that of the first quantum dot, making it impossible to apply it to actual products. Therefore, a method of mixing the two types of quantum dots may be considered, but in this case, since aggregation between the quantum dots occurs too easily, it rather increases the viscosity of the curable composition and causes the optical properties to deteriorate. This phenomenon may be more prominent when the first quantum dot and the second quantum dot of the core-shell structure have the same shell.

[0067] Accordingly, after extensive research, the present inventors have confirmed that even if the first and second quantum dots of the core-shell structure both have the same shell, by controlling the mixing weight ratio between the two types of quantum dots at a specific ratio, that is, controlling the weight ratio to a weight ratio of 50:50 to 5:95, the aggregation phenomenon between the quantum dots can be suppressed, the viscosity of the resulting composition can be lowered, and the optical properties can be improved. Furthermore, when the mixing weight ratio between the two types of quantum dots is controlled as described above, the content of the quantum dots used in the preparation of the curable composition can also be minimized, which ultimately makes it very easy to prepare a curable composition with very low viscosity.

[0068] Specifically, when the first quantum dot and the second quantum dot are mixed at the above weight ratio and used, it is possible to manufacture a curable composition at a lower cost while maintaining the excellent optical properties of the second quantum dot. In addition, since the core in the first quantum dot is sensitive to changes in wavelength according to size, it is difficult to mass-produce core-shell structured quantum dots with an appropriate wavelength, but by mixing the second quantum dot, which depends on the In / Ga ratio rather than the particle size, a curable composition with an appropriate wavelength can be mass-produced. In addition, compared to a composition using only the first quantum dot that can exhibit the same optical properties, a curable composition with a low total inorganic content can be manufactured by mixing the second quantum dot with an appropriate ratio, which has better optical properties, and thus a curable composition with a low viscosity can be manufactured.

[0069] If the first quantum dot is included in a greater weight than the second quantum dot, or if the first quantum dot is included in an amount less than 5 wt% based on the total weight (100 wt%) of the first and second quantum dots, simultaneous improvement of viscosity and optical properties cannot be achieved. In addition, if the first quantum dot is used alone, the optical properties become too inferior, and conversely, if the second quantum dot is used alone, the viscosity properties become too inferior. Therefore, it may be desirable to use the first quantum dot and the second quantum dot as a mixture.

[0070] For example, the first quantum dot and the second quantum dot may be included in a weight ratio of 50:50 to 20:80. In this case, it may be most effective in simultaneously improving the optical properties and viscosity properties of the curable composition.

[0071] For example, both the shell in the first quantum dot and the shell in the second quantum dot may include ZnS. In general, in the case of core-shell quantum dots, if the composition of the shells is the same, there is a tendency for them to aggregate well even if the compositions of the cores are different. This aggregation phenomenon between quantum dots tends to lengthen the central wavelength of emission and causes an increase in the viscosity of the composition, which ultimately inevitably leads to a decrease in luminous efficiency. However, according to one embodiment, by controlling the mixing weight ratio of two types of core-shell structured quantum dots having different cores but shells of the same composition as above, the aggregation phenomenon between the quantum dots can be suppressed, ultimately improving luminous efficiency. That is, the first quantum dot and the second quantum dot may not be combined with each other but may exist separately.

[0072] For example, the core of the second quantum dot may be selected from a ternary compound selected from the group consisting of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2CuGaO2, AgGaO2, AgAlO2 and mixtures thereof, or a quaternary compound such as AgInGaS2, CuInGaS2, etc.

[0073] For example, the second quantum dot may have a peak emission wavelength (PWL) in the range of 480 nm to 680 nm, more than 80% of the emission is band-edge emission, and may exhibit a quantum yield (QY) of 80% to 99.9%.

[0074] For example, the quantum yield may be from 82% to 96%, such as from 85% to 95%, such as from 86% to 94%.

[0075] For example, the second quantum dot may have a half-width of less than 40 nm, for example, 36 nm to 38 nm. When the second quantum dot has a half-width of the above range, the color purity is high, and thus, when used as a color material in a display device, the color reproducibility is increased.

[0076] For example, the second quantum dot may have an average diameter of 5 nm to 10 nm. In this case, 70% to 90% of the average diameter may be the average diameter of the core, and the remainder may be the average diameter of the shell.

[0077] For example, the second quantum dot has a size of 4.00 x 10 at 450 nm. 5 M -1 cm -1 Ideally, for example, 5.00 x 10 5 M -1 cm -1 The quantum dot can have a maximum absorption coefficient as described above. By having the above-described maximum absorption coefficient, the green light absorption rate can be greatly improved.

[0078] For example, the first 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 first quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ) in a wavelength range of 500 nm to 680 nm. em ) can have.

[0079] The first quantum dot may have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the first quantum dot has a full width at half maximum (FWHM) in the above range, the color purity is high, and thus, when used as a color material in a color filter, the color reproducibility is enhanced.

[0080] The above first quantum dots may each independently be organic, inorganic, or a hybrid (hybrid) of organic and inorganic materials.

[0081] The above first quantum dots may each independently be composed of a core and a shell surrounding the core, and the core and shell may 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.

[0082] 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.

[0083] In one implementation example, since environmental concerns have been increasing significantly worldwide and regulations on toxic substances have been strengthened, instead of a luminescent material having a cadmium core, an environmentally friendly non-cadmium luminescent material (such as InP / ZnS, InP / ZnSe / ZnS) with a somewhat lower quantum yield can be used as the first quantum dot, but is not necessarily limited thereto.

[0084] In the case of the first quantum dot of the above core / shell structure, the size (average particle diameter) of each of the entire first quantum dots including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

[0085] For example, the first quantum dot may include a red quantum dot, a green quantum dot, or a combination thereof. The red quantum dot may have an average particle diameter of 10 nm to 15 nm. The green quantum dot may have an average particle diameter of 5 nm to 8 nm.

[0086] 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.

[0087] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots (the first quantum dots and the second 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.

[0088] For example, when the curable composition according to one embodiment is a curable composition including a solvent, the quantum dots (first quantum dots and second 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.

[0089]

[0090] (C) polymeric compound

[0091] For example, the polymerizable compound may have a carbon-carbon double bond at the terminal.

[0092] 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.

[0093] 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.

[0094] For example, a polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 1, but is not necessarily limited thereto.

[0095] [Chemical Formula 1]

[0096]

[0097] In the above chemical formula 1,

[0098] L 6 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*),

[0099] L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0100] R 4and R 5 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0101] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following chemical formula 1-1, 1-2 or 1-3, but is not necessarily limited thereto.

[0102] [Chemical Formula 1-1]

[0103]

[0104] [Chemical Formula 1-2]

[0105]

[0106] [Chemical Formula 1-3]

[0107]

[0108] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be, in addition to the compounds represented by the chemical formulae 1-1 to 1-3, 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-hexanediol dimethacrylate or Combinations of these may be included further.

[0109] 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.

[0110] 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 may be improved.

[0111] Meanwhile, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond may be used as the polymerizable compound.

[0112] 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.

[0113] Specific examples of the above polymerizable compounds 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, dipentaerythritol Examples thereof include 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.

[0114] 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.

[0115] The above polymerizable compound may be used by treating it with an acid anhydride to provide better developing properties.

[0116]

[0117] light diffuser

[0118] The above curable composition may further include a light diffusing agent.

[0119] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0120] 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.

[0121] 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.

[0122] The above light diffusing agent can act as a scatterer, and either the rutile type or the anatase type can be used. However, in terms of improving external quantum efficiency, the rutile type may be more advantageous than the anatase type.

[0123] The light diffusing agent may be included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 15 wt%, for example, 1 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.

[0124]

[0125] polymerization initiator

[0126] The curable composition may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0131] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0132] 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.

[0133] 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.

[0134] Examples of the above aminoketone compounds include 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The above polymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.5 wt% to 4 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.

[0140]

[0141] binder resin

[0142] The above curable composition may further comprise a binder resin.

[0143] The above binder resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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 manufactured by mixing two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, etc., but it is not necessarily limited thereto, and any known cardo resin can be used.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] For example, when the curable composition 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.

[0156] For example, when the curable composition is a curable composition containing 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.

[0157]

[0158] Other additives

[0159] To improve the stability and dispersibility of the quantum dots, the curable composition may further include a polymerization inhibitor.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] In addition, 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 to improve heat resistance and reliability.

[0164] For example, the curable composition 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] Additionally, the curable composition may use a silicone-based surfactant together with the aforementioned fluorine-based surfactant. Specific examples of the silicone-based surfactant include, but are not limited to, TSF400, TSF401, TSF410, and TSF4440 from Toshiba Silicone Co., Ltd.

[0171] 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.

[0172] In addition, the above curable composition may further contain a certain amount of other additives, such as antioxidants, within a range that does not impair physical properties.

[0173]

[0174] menstruum

[0175] Meanwhile, the curable composition may further include a solvent.

[0176] 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.;

[0177] For example, it is preferable to use a solvent such as a glycol ether such as ethylene glycol monoethyl ether or ethylene diglycol methyl ethyl ether; an ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate; an ester such as 2-hydroxypropionate ethyl; a carbitol such as diethylene glycol monomethyl ether; a propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate or propylene glycol propyl ether acetate; an alcohol such as ethanol, or a combination thereof.

[0178] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, cyclohexyl acetate, or a combination thereof.

[0179] 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.

[0180]

[0181] 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.

[0182] 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.

[0183] (S1) Pattern forming step

[0184] 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.

[0185] (S2) Hardening stage

[0186] The above-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 500 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, etc. can be used, and in some cases, X-rays, electron beams, etc. can also be used.

[0187] 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.

[0188] (1) Application and film formation stage

[0189] 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.

[0190] (2) Exposure stage

[0191] 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 500 nm, is irradiated. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., and in some cases, X-rays, electron beams, etc. can also be used.

[0192] 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).

[0193] (3) Phenomenon stage

[0194] 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.

[0195] (4) Post-processing stage

[0196] 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.

[0197]

[0198] 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.

[0199]

[0200] (Manufacture of curable composition)

[0201] Based on the following respective components, curable compositions according to Examples 4 to 6 and Comparative Examples 5 to 8 were prepared.

[0202]

[0203] (A) Quantum dots

[0204] (A-1) InP / ZnS quantum dots

[0205] (A-2) InP / ZnSe / ZnS quantum dots

[0206] (A-3) AgGaS2 / ZnS quantum dots

[0207] (A-4) AgInGaS2 / ZnS quantum dots

[0208] (B) polymeric compound

[0209] A compound represented by the following chemical formula 1-2 (M200, Miwon Chemical Co., Ltd.)

[0210] [Chemical Formula 1-2]

[0211]

[0212] (C) Photopolymerization initiator

[0213] TPO-L (Polynetron)

[0214] (D) Light diffuser

[0215] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0216]

[0217] Examples 1 to 20 and Comparative Examples 1 to 32

[0218] Specifically, the above quantum dots and polymerizable compound are mixed and stirred for 12 hours. After adding a photopolymerization initiator, a light diffusing agent is added.

[0219] The specific compositions are shown in Tables 1 to 8 below.

[0220]

[0221] (Unit: wt%)Example 1Example 2Example 3Example 4Example 5Quantum dot(A-1)7.5532.50.75(A-2)-----(A-3)7.5101212.514.25(A-4)-----Polymerizable compound7878787878Photopolymerization initiator33333Light diffusing agent44444

[0222] (Unit: wt%)Comparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Quantum Dot (A-1)1514.2512.51087.70.7-(A-2)--------(A-3)-0.752.5577.314.315(A-4)--------Polymerizable Compound7878787878787878Photopolymerization Initiator33333333Light Diffusing Agent444444444

[0223] (Unit: wt%) Example 6 Example 7 Example 8 Example 9 Example 10 Quantum dot (A-1) 7.55 32.5 0.75 (A-2) ----- (A-3) ----- (A-4) 7.5 10 12 12.5 14.25 Polymerizable compound 78 78 78 78 78 Polymerization initiator 33 333 Light diffusing agent 44 44

[0224] (Unit: wt%) Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Quantum Dot (A-1) 15 14.25 12.5 10 8 7.7 0.7 - (A-2) -------- (A-3) -------- (A-4) - 0.75 2.5 5 7 7.3 14.3 15 Polymerizable Compound 7 8 7 8 7 8 7 8 7 8 7 8 7 8 Photopolymerization Initiator 3 3 3 3 3 3 3 Light Diffusing Agent 4 4 4 4 4 4

[0225] (Unit: wt%) Example 11 Example 12 Example 13 Example 14 Example 15 Quantum dot (A-1)-----(A-2)7.5532.50.75(A-3)7.5101212.514.25(A-4)-----Polymerizable compound7878787878Photopolymerization initiator33333Light diffusing agent44444

[0226] (Unit: wt%) Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Quantum Dot (A-1)--------(A-2)1514.2512.51087.70.7-(A-3)-0.752.5577.314.315(A-4)--------Polymerizable Compound7878787878787878 Photopolymerization Initiator33333333 Light Diffusing Agent444444444

[0227] (Unit: wt%) Example 16 Example 17 Example 18 Example 19 Example 20 Quantum dot (A-1)-----(A-2) 7.55 32.5 0.75 (A-3)-----(A-4) 7.5 10 12 12.5 14.25 Polymerizable compound 78 78 78 78 78 Photopolymerization initiator 33 333 Light diffusing agent 44 444

[0228] (Unit: wt%) Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 Quantum dot (A-1)--------(A-2)1514.2512.51087.70.7-(A-3)--------(A-4)-0.752.5577.314.315 Polymerizable compound7878787878787878 Photopolymerization initiator33333333 Light diffusing agent44444444

[0229] Evaluation: Viscosity and optical properties of curable compositions The viscosity and optical properties of each of the curable compositions according to Examples 1 to 20 and Comparative Examples 1 to 32 were evaluated, and the results are shown in Tables 9 to 16 below.

[0230] The viscosity of the curable composition was evaluated using HAAKE MARS IQ Air from Thermo Scientific (Shear rate 90 1 / s, t 200s, 25℃). If the measured viscosity of the curable composition is in the range of 16.5 cPs to 18.0 cPs, the viscosity characteristic can be evaluated as very excellent. If the viscosity is less than 16.5 cPs or more than 18.0 cPs and less than or equal to 20.0 cPs, the viscosity characteristic can be evaluated as average. If the viscosity is more than 20.0 cPs, the viscosity characteristic can be evaluated as poor.

[0231] In addition, 2 mL of the above-mentioned curable composition was spin-coated on a glass substrate, and then the QD film (9 μm) formed by exposing it to 5 J for 9 seconds in a nitrogen UV exposure device was subjected to thermal curing under a nitrogen atmosphere, and the external quantum efficiency was measured using a light efficiency meter (QE-2100, Otsuka).

[0232]

[0233] Example 1 Example 2 Example 3 Example 4 Example 5 External quantum efficiency (%) 27.5 27.6 27.6 26.9 27.0 Viscosity (cPs) 16.9 17.3 18.0 19.3 18.3

[0234] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 External Quantum Efficiency (%) 15.1 15.2 15.5 16.0 16.3 16.8 27.0 27.1 Viscosity (cPs) 15.1 15.5 15.3 15.6 16.3 16.4 22.3 20.1

[0235] Example 6 Example 7 Example 8 Example 9 Example 10 External quantum efficiency (%) 27.4 27.5 27.6 26.8 27.0 Viscosity (cPs) 16.8 17.2 17.9 19.2 19.7

[0236] Comparative Example 9Comparative Example 10Comparative Example 11Comparative Example 12Comparative Example 13Comparative Example 14Comparative Example 15Comparative Example 16External Quantum Efficiency (%)15.115.315.416.116.216.727.027.0Viscosity (cPs)15.315.415.715.816.116.222.120.8

[0237] Example 11 Example 12 Example 13 Example 14 Example 15 External quantum efficiency (%) 27.5 27.5 27.6 26.8 26.9 Viscosity (cPs) 16.6 17.0 17.8 18.8 18.1

[0238] Comparative Example 17Comparative Example 18Comparative Example 19Comparative Example 20Comparative Example 21Comparative Example 22Comparative Example 23Comparative Example 24External Quantum Efficiency (%)15.015.215.316.016.016.826.927.0Viscosity (cPs)15.215.515.816.016.116.422.020.5

[0239] Example 16 Example 17 Example 18 Example 19 Example 20 External quantum efficiency (%) 27.5 27.4 27.7 26.9 27.0 Viscosity (cPs) 16.9 17.4 17.9 19.2 19.7

[0240] Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 External Quantum Efficiency (%) 14.9 15.1 15.3 15.8 15.9 16.5 26.8 26.9 Viscosity (cPs) 15.5 15.7 15.9 16.2 16.4 16.4 22.5 20.3

[0241] From the above Tables 9 to 16, it can be confirmed that the curable compositions according to Examples 1 to 20 are superior in both optical properties and viscosity properties compared to the curable compositions according to Comparative Examples 1 to 32. In particular, it can be seen that no matter how high the content of the second quantum dots is, if they are not mixed with the first quantum dots, there is a limit to the improvement in optical efficiency due to the quantum dot aggregation phenomenon, and the viscosity of the composition also increases.

[0242] The present invention is not limited to the above-described embodiments, but can be manufactured in a variety of different forms. Those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. (A) A first quantum dot having a core-shell structure, comprising In and P components in the core and at least two components of Zn, Se, and S in the shell; (B) a second quantum dot having a core-shell structure, comprising at least three components among Ag, In, Ga, and S in the core, and at least two components among Ag, Ga, S, and Zn in the shell; and (C) polymeric compound; Including, A curable composition comprising the first quantum dot and the second quantum dot in a weight ratio of 50:50 to 5:

95.

2. In paragraph 1, A curable composition comprising the first quantum dot and the second quantum dot in a weight ratio of 50:50 to 20:

80.

3. In paragraph 1, A curable composition in which both the shell within the first quantum dot and the shell within the second quantum dot comprise ZnS.

4. In paragraph 3, A curable composition in which the first quantum dot and the second quantum dot are not combined with each other and exist separately.

5. In paragraph 1, A curable composition wherein the second quantum dot has a peak emission wavelength (PWL) in the range of 480-680 nm, more than 80% of the emission is band-edge emission, and exhibits a quantum yield (QY) of 80% to 99.9%.

6. In paragraph 1, A curable composition wherein the second quantum dot has a half-width of less than 40 nm.

7. In paragraph 1, A curable composition wherein the second quantum dot has an average diameter of 5 nm to 10 nm.

8. In paragraph 1, The second quantum dot has a size of 4.00 x 10 at 450 nm. 5 M -1 cm -1 A curable composition having a maximum absorption coefficient of:

9. In paragraph 1, The above polymerizable compound is a curable composition comprising a compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L 6 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or an ether group (*-O-*), L 7 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

10. In paragraph 1, The above curable composition is a curable composition that is a solvent-free curable composition.

11. In paragraph 10, 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:

12. In paragraph 1, The above curable composition further comprises a polymerization initiator, a light diffusing agent, a polymerization inhibitor or a combination thereof.

13. In paragraph 12, The above light diffusing agent is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.

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

15. In paragraph 14, The curable composition comprises, 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.

16. 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.

17. A cured film manufactured using a curable composition according to any one of claims 1 to 16.

18. A display device including a cured film according to Article 17.

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