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

Abstract

Provided are: a curable composition comprising (A) quantum dots and (B) a polymerizable compound, wherein the polymerizable compound includes a compound containing a specific structural unit; a cured film manufactured 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 characteristics, 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] Therefore, the solvent-free type of quantum dot ink that does not contain a solvent is the most desirable form for application to actual processes, and the current technology for applying quantum dots themselves to solvent-based compositions is now considered to have reached its limits.

[0007]

[0008] One embodiment is to provide a curable composition having excellent light stability.

[0009] Another embodiment is to provide a cured film manufactured using the curable composition.

[0010] Another embodiment is to provide a display device including the cured film.

[0011]

[0012] One embodiment provides a curable composition comprising (A) a quantum dot; and (B) a polymerizable compound, wherein the polymerizable compound comprises a structural unit-containing compound represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] X is a sulfur atom or a single bond,

[0017] R 1 is a monovalent functional group containing a carbon-carbon double bond,

[0018] R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

[0019] L 1 is a substituted or unsubstituted C1 to C20 alkylene group,

[0020] L 2 and L 3are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0021] n and m are each independently 1 to 100,

[0022] p is an integer from 0 to 20.

[0023] The above n:m can have an equivalent ratio of 1:1 to 1:9.

[0024] The above R 1 It can be represented by the following chemical formula R-1 or a monovalent cyclic functional group in which a carbon-carbon double bond is included in the ring structure.

[0025] [Chemical formula R-1]

[0026]

[0027] In the above chemical formula R-1,

[0028] R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0029] L a is a single bond, an ester group (-C(=O)O- or -OC(=O)-), a substituted or unsubstituted C3 to C20 cycloalkylene group, or a fused ring of C3 to C20 cycloalkane rings.

[0030] The monovalent cyclic functional group in which the carbon-carbon double bond is included in the ring structure may be a monovalent fused cyclic functional group in which the carbon-carbon double bond is included in the fused ring structure.

[0031] The above polymerizable compound may further include a compound represented by the following chemical formula 2.

[0032] [Chemical Formula 2]

[0033]

[0034] In the above chemical formula 2,

[0035] R 6 and R 7are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0036] L 6 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0037] L 7 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (-O-).

[0038] The compound represented by the above chemical formula 2 can be represented by the following chemical formula 2-1 or 2-2.

[0039] [Chemical Formula 2-1]

[0040]

[0041] [Chemical Formula 2-2]

[0042]

[0043] The compound represented by the above chemical formula 2 may be included in a smaller amount than the compound containing the structural unit represented by the above chemical formula 1.

[0044] The above curable composition may be a solvent-free curable composition.

[0045] 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.

[0046] The above curable composition may further include a polymerization initiator, a light diffusing agent, a polymerization inhibitor, or a combination thereof.

[0047] The light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

[0048] The above curable composition may further comprise a solvent.

[0049] 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.

[0050] 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.

[0051] The above quantum dot may include a non-cadmium-based luminescent material, and may have, for example, a core / shell structure of InP / ZnS or a core / first shell / second shell structure of InP / ZnSe / ZnS.

[0052] The quantum dot may include a core comprising Ag, In, Ga, and S; and a shell comprising at least two selected from the group consisting of Ag, Ga, Zn, and S.

[0053] Another embodiment provides a cured film manufactured using the curable composition.

[0054] Another embodiment provides a display device including the cured film.

[0055] Specific details of other aspects of the present invention are included in the detailed description below.

[0056]

[0057] By modifying the structure of a surface modifying material that modifies the quantum dot surface in a quantum dot-containing curable composition, the light resistance reliability of the quantum dot-containing curable composition can be significantly improved.

[0058]

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] Additionally, unless otherwise specified herein, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid”.

[0064] Unless otherwise specified herein, “combination” means mixing or copolymerization.

[0065] 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.

[0066] Also, unless otherwise specifically stated in this specification, " " or "*" means a part that is connected to the same or different atoms or chemical formulas.

[0067]

[0068] While viscosity and other key properties are crucial for quantum dots in quantum dot display applications, the most crucial from a product perspective are high brightness and the reliability needed to maintain that brightness. While the inherent characteristics of the quantum dot particles are likely to be fully realized in terms of brightness, reliability remains a significant hurdle to overcome.

[0069] This is because quantum dots are inherently vulnerable to oxygen, heat, and light. To overcome this vulnerability, many researchers have explored various methods. Until now, known techniques have focused on covering the quantum dot surface with polymeric materials containing heat-resistant functional groups, or passivating the quantum dot surface with aluminum, titanium, or their oxides. Recently, efforts are underway to simultaneously enhance both brightness and durability by doping small amounts of transition metals (Cu, Mg, etc.) during the quantum dot synthesis stage.

[0070] As described above, the most important property of quantum dots is the reliability in maintaining brightness. The inventors of the present invention reviewed the results of previous research and, based on this, confirmed the possibility of improving the light resistance reliability of quantum dots by passivating the surface of quantum dots with a small amount of light-stable silica. After much trial and error and failure, they completed the present invention. In the case of silicone, it is chemically stable to light. The inventors of the present invention spent a lot of time and effort to identify the most suitable silicon structure, and designed a polymer structure with a silane or siloxane structure that enables surface modification of quantum dots. In addition, by introducing a carbon-carbon double bond at the end of the polymer structure so that the polymer can be used as a polymerizable monomer, they invented the composition of a quantum dot-containing curable composition that can maximize the improvement in light resistance reliability.

[0071] The polymer structure invented by the present inventors exhibited excellent compatibility with the ligand currently in use, and also exhibited good dispersibility of quantum dots and compatibility with other components in a quantum dot-containing curable composition. In addition, the durability of the quantum dots themselves can be significantly increased. Specifically, the light resistance reliability can be improved by a silane or siloxane-based monomer having a thiol group at the terminal, but when such a monomer is used alone as a polymerizable monomer, the dispersibility of the quantum dots is significantly reduced, and in particular, it was problematic in that it could not be used in a solvent-free curable composition. However, according to one embodiment, by polymerizing a silane or siloxane-based monomer having a thiol group at the terminal and a silane or siloxane-based monomer having a monovalent functional group containing a carbon-carbon double bond at the terminal to form a polymer, the aforementioned dispersibility can be significantly improved, and ultimately, the light resistance reliability of the solvent-free curable composition can be significantly improved. Furthermore, the polymer can be used as a polymerizable monomer in a solvent-based curable composition to significantly improve light resistance reliability.

[0072] Below, each component constituting the curable composition according to one embodiment is specifically described.

[0073]

[0074] quantum dots

[0075] The quantum dots included in the curable composition according to one embodiment can 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 dots can have a maximum fluorescence emission wavelength (fluorescence λ) at 500 nm to 680 nm. em ) can have.

[0076] 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.

[0077] The above quantum dots may each independently be organic, inorganic, or a hybrid (hybrid) of organic and inorganic materials.

[0078] 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.

[0079] 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.

[0080] In one implementation example, since environmental concerns have been increasing significantly worldwide and regulations on toxic substances have been strengthened, environmentally friendly non-cadmium-based luminescent materials (such as InP / ZnS, InP / ZnSe / ZnS) with somewhat lower quantum yields were used instead of luminescent materials having cadmium-based cores, but the present invention is not limited thereto.

[0081] In one embodiment, the quantum dot may be a quantum dot including a core comprising Ag, In, Ga, and S; and a shell comprising at least two or more selected from the group consisting of Ag, Ga, Zn, and S. The quantum dot may have one or more ligands, for example, the quantum dot may have a ligand including a halide, a ligand including an alkyl group, a ligand including an alkoxy amine, or a ligand of a combination thereof, but is not necessarily limited thereto.

[0082] 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.

[0083] 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.

[0084] Meanwhile, in order to ensure dispersion stability of the quantum dots, the solvent-free curable composition according to one embodiment may further include a dispersant to include quantum dots in the form of a quantum dot dispersion. The dispersant helps the photoconversion material, such as quantum dots, to be uniformly dispersed within the solvent-free 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, and the like 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.

[0085] The above quantum dots may be surface-modified with a conventional quantum dot surface-modifying material (e.g., a thiol-based compound, etc.) or may not be surface-modified.

[0086] The quantum dots may be included in an amount of 5 wt% to 60 wt%, for example, 10 wt% to 60 wt%, for example, 20 wt% to 50 wt%, for example, 30 wt% to 50 wt%, based on the total amount of the solvent-free curable composition. When the quantum dots (e.g., quantum dot dispersion) are included within the above range, high light retention and light efficiency can be achieved even after curing.

[0087] 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.

[0088] Meanwhile, the quantum dot can react with a thiol group in the structural unit represented by the chemical formula 1 described below, and in this case, the quantum dot can be surface-modified with a monomer containing the structural unit represented by the chemical formula 1 described below.

[0089] Typically, the method for encapsulating quantum dots with silane or siloxane monomers involves adding TEOS (Tetraethyl orthosilicate) and H2O to MPTMS (3-Mercaptopropy trimethoxysilane) or MPMDMS (3-Mercaptopropyl methyl dimethoxysilane) to initiate a sol-gel reaction. This reaction requires two or more steps, which is time-consuming and reduces the quantum efficiency of the quantum dots with each step. Furthermore, it is difficult to analyze and confirm the degree of reaction for each step.

[0090] As described above, the most important property of quantum dots is the reliability of maintaining brightness even under strong BLU light, and the main purpose of the present invention is to improve the light resistance reliability of quantum dots by passivating the surface of the quantum dots with a silane binder that is stable to BLU light, replacing the existing ligand.

[0091] In the case of silica or silane, since they are chemically stable to light, the inventors of the present invention introduced a silane or siloxane monomer having a thiol group introduced at the terminal based on this, so that this monomer acts as a site for ligand substitution and a silica matrix. In addition, in order to increase the dispersibility of the siloxane monomer having a thiol group introduced in a polymerizable monomer (specifically, the dispersibility of surface-modified quantum dots in a polymerizable monomer), a silane or siloxane monomer having a carbon-carbon double bond introduced at the terminal was polymerized to synthesize a polymer, so that it also functions as a polymerizable monomer. More specifically, the above two substances (a silane or siloxane monomer having a thiol group introduced at the terminal and a silane or siloxane monomer having a carbon-carbon double bond introduced at the terminal) were split (divided) according to the content, and a sol-gel reaction was performed to finally obtain a compound containing a silane or siloxane structural unit, specifically, a compound containing a structural unit represented by the chemical formula 1 described below.

[0092] The compound manufactured as described above is applied to a quantum dot to modify the surface of the quantum dot into a quantum dot including a structural unit represented by the chemical formula 1. In the case of the silane or siloxane compound, since the ligand exchange reaction easily proceeds, the quantum dot has excellent dispersibility and also has good compatibility with other components in the curable composition. Furthermore, the silane or siloxane compound is a polymer rather than a monomer and is relatively large in size, so it is advantageous over a monomer ligand with a small size in terms of protecting the quantum dot, and thus, the durability of the entire curable composition can also be improved.

[0093] For example, a compound (polymer) including a structural unit represented by the above chemical formula 1 may have a weight average molecular weight of 1,000 g / mol to 10,000 g / mol. When the weight average molecular weight is within the above range, the ligand substitution reaction proceeds well, and the compound (polymer) including a structural unit represented by the above chemical formula 1 can well encapsulate quantum dots.

[0094]

[0095] polymeric compounds

[0096] 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. Specifically, the polymerizable compound comprises a compound containing a structural unit represented by the following chemical formula 1.

[0097] [Chemical Formula 1]

[0098]

[0099] In the above chemical formula 1,

[0100] X is a sulfur atom or a single bond,

[0101] R 1 is a monovalent functional group containing a carbon-carbon double bond,

[0102] R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

[0103] L 1 is a substituted or unsubstituted C1 to C20 alkylene group,

[0104] L 2 and L 3 are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

[0105] n and m are each independently 1 to 100,

[0106] p is an integer from 0 to 20.

[0107] For example, the n:m may have an equivalent ratio of 1:1 to 1:9, for example, 1:1.5 to 1:5. Depending on the equivalent ratio, the ratio between the thiol group and the carbon-carbon double bond-containing functional group in the polymer is determined. According to one embodiment, when n and m have an equivalent ratio in the above range, the ligand substitution reaction can easily occur. When the n:m is 1:10, the equivalent weight of the silane or siloxane-based ligand containing a thiol group at the terminal is relatively low, making it difficult for the ligand substitution reaction to easily occur. When the n:m is 1:0.5, the optical properties deteriorate rapidly, and the light resistance reliability also becomes inferior.

[0108] For example, in the above chemical formula 1, R 1 It can be represented by the following chemical formula R-1 or a monovalent cyclic functional group in which a carbon-carbon double bond is included in the ring structure.

[0109] [Chemical formula R-1]

[0110]

[0111] In the above chemical formula R-1,

[0112] R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0113] L a is a single bond, an ester group (-C(=O)O- or -OC(=O)-), a substituted or unsubstituted C3 to C20 cycloalkylene group, or a fused ring of C3 to C20 cycloalkane rings.

[0114] The fused ring of the above C3 to C20 cycloalkane rings can be represented by the following chemical formula S-1, etc., but is not necessarily limited thereto.

[0115] [Chemical Formula S-1]

[0116]

[0117] In the above chemical formula 1, R 1 When this carbon-carbon double bond is a monovalent cyclic functional group included in a ring structure or is represented by the chemical formula R-1 above, light resistance reliability can be maximized. In particular, compatibility between a compound containing a structural unit represented by the chemical formula 1 above and a polymerizable monomer represented by the chemical formula 2 below can be maximized.

[0118] For example, a monovalent cyclic functional group in which a carbon-carbon double bond is included in a ring structure may be a monovalent fused cyclic functional group in which a carbon-carbon double bond is included in a fused ring structure. Inclusion of a carbon-carbon double bond in a ring structure may mean that the carbon-carbon double bond constitutes the skeleton of a ring compound. For example, the monovalent cyclic functional group in which the carbon-carbon double bond is included in a ring structure may be represented by the following chemical formula S-2, etc., but is not necessarily limited thereto.

[0119] [Chemical Formula S-2]

[0120]

[0121] A curable composition according to one embodiment may further include a compound represented by the following chemical formula 2 as a polymerizable compound in addition to a compound containing a structural unit represented by the above chemical formula 1.

[0122] [Chemical Formula 2]

[0123]

[0124] In the above chemical formula 2,

[0125] R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

[0126] L 6 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

[0127] L 7 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (-O-).

[0128] For example, the compound represented by the above chemical formula 2 may have a molecular weight of 170 g / mol to 1,000 g / mol. When the molecular weight of the compound represented by the above chemical formula 2 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.

[0129] For example, the compound represented by the above chemical formula 2 may be represented by the following chemical formula 2-1 or 2-2, but is not necessarily limited thereto.

[0130] [Chemical Formula 2-1]

[0131]

[0132] [Chemical Formula 2-2]

[0133]

[0134] For example, the polymerizable compound having a carbon-carbon double bond at the terminal may, in addition to the compound represented by the above chemical formula 2-1 or 2-2, be ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate 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.

[0135] In addition, the curable composition according to one embodiment may further include a monomer generally used in conventional thermosetting or photocurable compositions in addition to the polymerizable compound, and for example, the monomer may further include an oxetane-based compound such as bis[1-ethyl(3-oxetanyl)]methyl ether.

[0136] For example, when the curable composition according to one embodiment is a solvent-free curable composition, the polymerizable compound 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. In this case, 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.

[0137] 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.

[0138]

[0139] light diffuser

[0140] The curable composition according to one embodiment may further comprise a light diffusing agent.

[0141] For example, the light diffusing agent may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0142] 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.

[0143] 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.

[0144] The light diffusing agent may be included in an amount of 1 wt% to 20 wt%, for example, 2 wt% to 15 wt%, for example, 3 wt% to 10 wt%, based on the total amount of the curable composition. If the light diffusing agent is included in an amount of less than 1 wt% based on the total amount of the curable composition, it is difficult to expect an effect of improving the light conversion efficiency due to the use of the light diffusing agent, and if it is included in an amount exceeding 20 wt%, there is a concern that a quantum dot sedimentation problem may occur.

[0145]

[0146] polymerization initiator

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0152] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0153] 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.

[0154] 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.

[0155] Examples of the above aminoketone compounds include 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] The 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.

[0161]

[0162] binder resin

[0163] The curable composition according to one embodiment may further comprise a binder resin.

[0164] The above binder resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination thereof.

[0165] 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.

[0166] Specific examples of the above acrylic 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] 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 a solvent-based curable composition, and a good pattern can be obtained.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] For example, when the curable composition according to one embodiment 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.

[0178]

[0179] Other additives

[0180] To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194]

[0195] menstruum

[0196] Meanwhile, the curable composition according to one embodiment may further include a solvent.

[0197] 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.;

[0198] 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.

[0199] For example, the solvent may be a polar solvent including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

[0200] 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.

[0201]

[0202] Another embodiment provides a curable composition, for example, a cured film manufactured using the curable composition, and a display device including the cured film.

[0203] 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.

[0204] (S1) Pattern forming step

[0205] 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.

[0206] (S2) Hardening stage

[0207] 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.

[0208] 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.

[0209] (1) Application and film formation stage

[0210] 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.

[0211] (2) Exposure stage

[0212] 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, 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, or electron beam may be used depending on the case.

[0213] 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).

[0214] (3) Phenomenon stage

[0215] Following the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form an image pattern. That is, when developing with an alkaline developer, the unexposed portions are dissolved, and an image color filter pattern is formed.

[0216] (4) Post-processing stage

[0217] 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.

[0218]

[0219] 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.

[0220]

[0221] (Synthesis of polymers containing Si-containing structural units)

[0222] Synthesis Example 1

[0223] A compound represented by the following chemical formula E-1 (Sigma-Aldrich) and a compound represented by the following chemical formula E-2 were reacted at an equivalent ratio of 1:5 at 70°C for 10 hours to synthesize a polymer (weight average molecular weight: 4,000 g / mol) including a structural unit represented by the following chemical formula E-3.

[0224] [Reaction Formula 1]

[0225]

[0226] [Chemical Formula E-1]

[0227]

[0228] [Chemical Formula E-2]

[0229]

[0230] [Chemical Formula E-3]

[0231]

[0232]

[0233] Synthesis Example 2

[0234] The same procedure as in Synthesis Example 1 was followed, except that a compound represented by the following chemical formula E-4 was used instead of the compound represented by the above chemical formula E-2, and the compounds represented by the above chemical formula E-1 and the above chemical formula E-4 were reacted in an equivalent ratio of 1:1.

[0235] [Chemical Formula E-4]

[0236]

[0237]

[0238] Synthesis Example 3

[0239] The same procedure as in Synthesis Example 1 was followed, except that the compound represented by the following chemical formula E-5 was used instead of the compound represented by the above chemical formula E-2.

[0240] [Chemical Formula E-5]

[0241]

[0242]

[0243] Synthesis Example 4

[0244] The same procedure as in Synthesis Example 1 was followed, except that the compound represented by the following chemical formula E-6 was used instead of the compound represented by the above chemical formula E-2.

[0245] [Chemical Formula E-6]

[0246]

[0247]

[0248] Synthesis Example 5

[0249] The same procedure as in Synthesis Example 1 was followed, except that the compound represented by the following chemical formula E-7 was used instead of the compound represented by the above chemical formula E-2.

[0250] [Chemical Formula E-7]

[0251]

[0252]

[0253] Synthesis Example 6

[0254] The same procedure as in Synthesis Example 1 was followed, except that a compound represented by the following chemical formula E-8 was used instead of the compound represented by the above chemical formula E-2, and the compounds represented by the above chemical formula E-1 and the above chemical formula E-8 were reacted in an equivalent ratio of 1:1.

[0255] [Chemical Formula E-8]

[0256]

[0257]

[0258] Comparative synthesis example 1

[0259] The same procedure as in Synthesis Example 1 was followed, except that a compound represented by the following chemical formula E-9 was used instead of the compound represented by the above chemical formula E-2, and the compounds represented by the above chemical formula E-1 and the above chemical formula E-9 were reacted in an equivalent ratio of 1:1.

[0260] [Chemical Formula E-9]

[0261]

[0262]

[0263] Comparative synthesis example 2

[0264] The same procedure as in Synthesis Example 1 was followed, except that the compound represented by the following chemical formula E-10 was used instead of the compound represented by the above chemical formula E-2.

[0265] [Chemical Formula E-10]

[0266]

[0267]

[0268] Comparative synthesis example 3

[0269] Instead of the polymer of Synthesis Example 1, a monomer represented by C-1 below was used. Me represents a methyl group and Ph represents a phenyl group.

[0270] [Chemical Formula C-1]

[0271]

[0272]

[0273] (Preparation of solvent-free curable composition)

[0274] Based on the respective components below, curable compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were prepared according to the compositions in Table 1 below. Specifically, the surface-modified green quantum dots and the polymerizable compound were mixed and stirred for 12 hours. A polymerization inhibitor was added and stirred for 5 minutes. Next, a photoinitiator was added if necessary, followed by a light diffusing agent.

[0275] (For example, in the case of Example 1, 41 g of surface-modified green quantum dots, 14 g of polymerizable compound 2, and 27 g of polymerizable compound 1 are mixed and stirred to prepare a green quantum dot dispersion, and then 11 g of the polymerizable compound 1 is additionally added thereto and stirred for 5 minutes, and then 3 g of a photoinitiator and 4 g of a light diffusing agent are added and stirred to prepare a curable composition.)

[0276]

[0277] (Unit: wt%)Example 1Example 2Example 3Example 4Example 5Example 6Comparative Example 1Comparative Example 2Comparative Example 3Quantum dot414141414141414141Polymerizable compound 1B-138--------B-2-38-------B-3--38------B-4---38-----B-5----38----B-6-----38---B-7------38--B-8-------38-B-9--------38Polymerizable compound 21414141414141414141414Photopolymerization initiator33333333Light diffusing agent444444444

[0278] (A) Quantum dots

[0279] Green quantum dots (InP / ZnSe / ZnS, Hansol Chemical)

[0280] (B) Polymerizable compound 1

[0281] (B-1) Compound of Synthesis Example 1

[0282] (B-2) Compound of Synthesis Example 2

[0283] (B-3) Compound of Synthesis Example 3

[0284] (B-4) Compound of Synthesis Example 4

[0285] (B-5) Compound of Synthesis Example 5

[0286] (B-6) Compound of Synthesis Example 6

[0287] (B-7) Compound of comparative synthesis example 1

[0288] (B-8) Compound of comparative synthesis example 2

[0289] (B-9) Compound of comparative synthesis example 3

[0290] (B) Polymerizable compound 2

[0291] A compound represented by the following chemical formula 2-2 (1,6-Hexanediol diacrylate, Miwon Specialty Chemical)

[0292] [Chemical Formula 2-2]

[0293]

[0294] (C) Photopolymerization initiator

[0295] TPO-L (Polynetron)

[0296] (D) Light diffuser

[0297] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0298]

[0299] Evaluation 1: Evaluation of heat / light resistance properties of curable compositions

[0300] The heat / light resistance properties of each of the curable compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were evaluated, and the results are shown in Table 2 below.

[0301] Specifically, 2 mL of each of the above-mentioned prepared curable compositions was spin-coated at 1,500 rpm on a glass substrate, and then exposed to 5 J for 9 seconds in a nitrogen UV exposure device to form a QD film (9 μm). The initial blue light conversion rate and post-exposure quantum efficiency (EQE) were measured using a light efficiency meter (QE-2100, Otsuka Co.).

[0302] After this, the substrate on which the QD film was formed was baked on a hot plate at 180°C in a nitrogen atmosphere for 30 minutes, and then cooled to room temperature (23°C) for 1 hour. After this, the blue light conversion rate was measured again using a light efficiency meter, and then the thermal process maintenance rate (lightfastness maintenance rate) (%) was calculated using the following formula, and the lightfastness reliability was measured by measuring the time required for the thermal process maintenance rate to drop to 90%.

[0303] ㆍThermal process maintenance rate (%) = [Light conversion rate (after baking) / Initial light conversion rate] * 100

[0304]

[0305] Quantum efficiency after exposure (%) Light resistance reliability (hr) Example 133.8590 Example 233.5460 Example 332.9260 Example 432.6293 Example 532.5760 Example 635.5702 Comparative Example 132.9186 Comparative Example 232.1105 Comparative Example 3 Curable composition cannot be manufactured due to poor dispersibility

[0306] From the above Table 2, it can be confirmed that the curable compositions according to Examples 1 to 6 are superior in quantum efficiency (optical properties) and light resistance reliability (optical properties, processability) compared to the curable compositions according to Comparative Examples 1 to 3.

[0307] (Preparation of solvent-based curable composition)

[0308] Using the components mentioned below, curable compositions according to Examples 7 to 12 and Comparative Examples 4 to 6 were prepared with the compositions shown in Table 3 below.

[0309]

[0310] (A) Quantum dots

[0311] Green quantum dots (InP / ZnSe / ZnS, Hansol Chemical)

[0312] (B) Polymerizable compound 1

[0313] (B-1) Compound of Synthesis Example 1

[0314] (B-2) Compound of Synthesis Example 2

[0315] (B-3) Compound of Synthesis Example 3

[0316] (B-4) Compound of Synthesis Example 4

[0317] (B-5) Compound of Synthesis Example 5

[0318] (B-6) Compound of Synthesis Example 6

[0319] (B-7) Compound of comparative synthesis example 1

[0320] (B-8) Compound of comparative synthesis example 2

[0321] (B-9) Compound of comparative synthesis example 3

[0322] (C) Photopolymerization initiator

[0323] TPO-L (Polynetron)

[0324] (D) Light diffuser

[0325] Titanium dioxide dispersion (rutile type TiO2; D50 (180 nm), solid content 50 wt%, Iridos Co., Ltd.)

[0326] (E) Binder resin

[0327] Cardo resin (TA01, Tacoma)

[0328] (F) solvent

[0329] Propylene glycol monomethyl ether acetate (PGMEA, Sigma-Aldrich)

[0330] (G) Other additives

[0331] Leveling agent (F-554, DIC)

[0332]

[0333] (Unit: wt%)Example 7Example 8Example 9Example 10Example 11Example 12Comparative Example 4Comparative Example 5Comparative Example 6Quantum dot12.512.512.512.512.512.512.512.512.5Polymerizable compound 1B-17.4--------B-2-7.4-------B-3--7.4------B-4---7.4-----B-5----7.4----B-6-----7.4---B-7------7.4--B-8-------7.4-B-9--------7.4Binder resin7.47.47.47.47.47.47.47.47.4Photopolymerization Initiator 0.90.90.90.90.90.90.90.90.9 Light diffuser 1.21.21.21.21.21.21.21.21.2 Solvent 707070707070707070 Other additives 0.60.60.60.60.60.60.60.60.6

[0334] Evaluation 2: Evaluation of heat / light resistance characteristics of curable compositions For each of the curable compositions according to Examples 7 to 12 and Comparative Examples 4 to 6, the heat / light resistance characteristics were evaluated as in Evaluation 1, and the results are shown in Table 4 below.

[0335]

[0336] Quantum efficiency after exposure (%) Lightfastness reliability (hr) Example 7 33.5 360 Example 8 32.7 257 Example 9 32.5 154 Example 10 31.9 140 Example 11 32.0 476 Example 12 33.8 412 Comparative Example 4 33.195 Comparative Example 5 31.577 Comparative Example 6 Curable composition cannot be manufactured due to poor dispersibility

[0337] From the above Table 4, it can be confirmed that the curable compositions according to Examples 7 to 12 are superior in quantum efficiency (optical properties) and light resistance reliability (optical properties, processability) compared to the curable compositions according to Comparative Examples 4 to 6.

[0338] 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; and (B) polymeric compound Including, The above polymerizable compound is a curable composition comprising a compound containing a structural unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X is a sulfur atom or a single bond, R 1 is a monovalent functional group containing a carbon-carbon double bond, R 2 and R 3 are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group, L 1 is a substituted or unsubstituted C1 to C20 alkylene group, L 2 and L 3 are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group, n and m are each independently 1 to 100, p is an integer from 0 to 20.

2. In paragraph 1, The above n:m is a curable composition having an equivalent ratio of 1:1 to 1:

9.

3. In paragraph 1, The above R 1 A curable composition represented by the following chemical formula R-1 or a monovalent cyclic functional group in which a carbon-carbon double bond is included in the ring structure: [Chemical formula R-1] In the above chemical formula R-1, R a is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L a is a single bond, an ester group (-C(=O)O- or -OC(=O)-), a substituted or unsubstituted C3 to C20 cycloalkylene group, or a fused ring of C3 to C20 cycloalkane rings.

4. In paragraph 3, A curable composition in which the monovalent cyclic functional group in which the carbon-carbon double bond is included in the ring structure is a monovalent fused cyclic functional group in which the carbon-carbon double bond is included in the fused ring structure.

5. In paragraph 1, A curable composition further comprising a compound represented by the following chemical formula 2. [Chemical Formula 2] In the above chemical formula 2, R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L 6 and L 8 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group, L 7 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (-O-).

6. In paragraph 5, The compound represented by the above chemical formula 2 is a curable composition represented by the following chemical formula 2-1 or 2-2: [Chemical Formula 2-1] [Chemical Formula 2-2] 7. In paragraph 5, A curable composition in which the compound represented by the above chemical formula 2 is included in a smaller amount than the compound containing the structural unit represented by the above chemical formula 1.

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 above curable composition further comprises a solvent.

13. In paragraph 12, 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.

14. 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.

15. In paragraph 1, The above quantum dot is a curable composition containing a non-cadmium-based luminescent material.

16. In paragraph 15, The above quantum dot is a curable composition having a core / shell structure of InP / ZnS or a core / first shell / second shell structure of InP / ZnSe / ZnS.

17. In paragraph 1, A curable composition, wherein the quantum dot comprises a core comprising Ag, In, Ga, and S; and a shell comprising at least two or more selected from the group consisting of Ag, Ga, Zn, and S.

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

19. A display device including the cured film of Article 18.

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