Curable composition, cured film comprising curable composition, and image display device comprising cured film

Abstract

The present invention relates to a curable composition, a cured film comprising the curable composition, and an image display device comprising the cured film. Since the curable composition of the present invention comprises a monomer containing a Si element, the use of the curable composition can enhance plasma resistance and thermal stability and improve storage properties of the composition.

Description

A curable composition, a curable film comprising the curable composition, and an image display device comprising the curable film.

[0001] The present invention relates to a curable composition, a curable film comprising the curable composition, and an image display device comprising the curable film.

[0002] Quantum dots are nanometer-sized semiconductor nanocrystals, and depending on their size and shape, the energy band gap (Bandgap, E g These quantum dots have the characteristic of changing. Due to the quantum confinement effect, the emission wavelength can be controlled solely by adjusting the size of the quantum dots, and they can exhibit excellent color purity and high photoluminescence (PL) efficiency. As such, they are receiving a lot of attention not only in displays but also in fields such as lighting sources, solar cells, semiconductor lasers / optical amplifiers, and bioimaging.

[0003] Meanwhile, color filters are used in liquid crystal displays, optical filters for cameras, etc., and are manufactured by coating fine areas colored with three or more colors onto a solid-state imaging element or a transparent substrate. Such colored thin films can typically be formed by dyeing, printing, pigment dispersion, inkjet methods, etc.

[0004] Among these, the pigment dispersion method is a method for forming a colored thin film by repeating a series of processes involving coating, exposing, developing, and heat-curing a photopolymerizable composition containing a coloring agent onto a transparent substrate provided with a black matrix. For example, Korean Patent Publication No. 1992-7002502 proposes a method for manufacturing a colored photosensitive resin composition using the pigment dispersion method. However, the above method requires coating, exposure, development, and curing processes for red, green, and blue, respectively, to form pixels; consequently, the manufacturing process becomes very lengthy, and yield management is difficult due to the large number of control factors between processes.

[0005] To overcome these difficulties, continuous attempts have been made to replace pigments with quantum dots, and consequently, quantum dots are being applied to various display devices, electronic devices, and the like. However, further research into compositions capable of stabilizing quantum dots is currently necessary to improve processability and performance.

[0006] Quantum dots consist of organic ligands weakly bonded to a surface composed of inorganic materials, and their surface is not protected by strong bonds such as covalent bonds. Consequently, efficiency is reduced when applied to thin film formation and photoconversion devices. In particular, high heat treatment processes of 100°C to 200°C are essential in the manufacturing process of thin films, and the heat generated during this process causes a decrease in the color conversion efficiency (PCE) of quantum dots and the detachment of ligands. Furthermore, due to the degradation of quantum dots by oxygen, moisture, and free radicals, there are problems such as reduced stability of compositions containing quantum dots and reduced thermal / light exposure stability of thin films, thus requiring the development of new photoconversion curable compositions.

[0007] The present invention aims to solve the aforementioned problem and other related problems.

[0008] One exemplary objective of the present invention is to provide a curable composition comprising a Si monomer that prevents the formation of particles and wrinkles during thin film formation and improves the photostability of the thin film.

[0009] Another exemplary objective of the present invention is to provide a curable film and an image display device comprising the above-mentioned curable composition.

[0010] The technical problems to be solved according to the technical concept of the invention disclosed in this specification are not limited to those for solving the problems mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below.

[0011] One example of the present invention is a curable composition comprising quantum dots, a first monomer, and a second monomer, wherein

[0012] The first monomer comprises a compound represented by the following chemical formula 1, and

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] R1 and R2 are identical or different from each other, and each independently consists of hydrogen, a hydroxyl group, an acryl group, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei,

[0017] The above X is C1~C 40 alkylene group of, C1~C 40 cycloalkylene group of, C1~C 40 alkyloxylene group of, C6~C 40 It is an arylene group or a heteroarylene group having 5 to 40 nuclei, and

[0018] n1 is an integer from 0 to 30;

[0019] The above second monomer provides a curable composition comprising at least one of the compounds represented by the following chemical formulas 2 to 4.

[0020] [Chemical Formula 2]

[0021]

[0022] [Chemical Formula 3]

[0023]

[0024] [Chemical Formula 4]

[0025]

[0026] In the above chemical formulas 2 to 4,

[0027] R3 to R 15 They are identical or different from each other, and each independently consists of hydrogen, hydroxyl groups, acryl groups, cyano groups, nitro groups, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei,

[0028] The above A1 to A6 are identical or different from each other, and each is independently C, O, S, or N, and

[0029] The above Y1 to Y3 are identical or different from one another, and each independently consists of hydrogen, deuterium, halogen, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 It is an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclei, and

[0030] n2 to n7 are identical or different from each other, and each is independently an integer from 0 to 20, and

[0031] The above R1 to R 15 of Hydrogen, hydroxyl group, acrylic group, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 aryl group and heteroaryl group having 5 to 40 nuclei, hydrogen, deuterium, halogen, cyano group, nitro group of X1 to X3, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 The aryl heteroarylamine group and the heteroarylamine group having 5 to 60 nuclei are each independently a halogen, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group of, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C6~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, and in this case, if there are multiple substituents, they may be identical or different from each other.

[0032] In the above chemical formula 1, X can be selected from the group consisting of the following X-1 to X-4.

[0033]

[0034] m1 to m4 are identical or different from each other and are each independently integers from 0 to 20.

[0035] In the above chemical formula 2, Y can be selected from the group consisting of the following Y-1 to Y-13.

[0036]

[0037] In this case, * represents the site bonded with Si in Chemical Formula 2.

[0038] The compound represented by the above chemical formula 1 may be selected from the group consisting of A-1 to A-5 below.

[0039]

[0040] The compounds represented by the above chemical formulas 2 to 4 may be selected from the group consisting of B-1 to B-12 below.

[0041]

[0042] The compounds represented by the above chemical formulas 2 to 4 may be selected from the group consisting of B-1 to B-12 below.

[0043] The curable composition of the present invention includes a monomer containing a Si element, thereby improving the plasma resistance and thermal stability of a thin film formed using the curable composition, and improving high photoconversion efficiency and the safety of the composition.

[0044] Meanwhile, the scope of the present invention is not limited by the effects described above.

[0045] Figure 1 is a graph showing the relative PCE change range at each process step in the manufacture of thin films using the compositions of Comparative Example 2, Examples 1 and 2.

[0046] Figure 2 is a graph showing the relative PCE in terms of storage stability using the compositions of Comparative Example 2 and Example 1.

[0047] The present invention will be described in detail below.

[0048] In the present invention, “alkyl” refers to a monovalent substituent derived from a straight-chain or side-chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0049] In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples of such alkenyls include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0050] In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples of such alkynyls include, but are not limited to, ethynyl and 2-propynyl.

[0051] In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, consisting of a single ring or a combination of two or more rings. Additionally, forms in which two or more rings are simply penantated or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

[0052] In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0053] In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclei. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Additionally, forms in which two or more rings are simply pendent or condensed with each other may be included, and furthermore, forms condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0054] In the present invention, “alkyloxy” refers to a monovalent substituent represented by R’O-, where R’ means an alkyl group having 1 to 40 carbon atoms. Such alkyloxy may include a linear, branched, or cyclic structure. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, etc.

[0055] In the present invention, “aryloxy” refers to a monovalent substituent represented by RO-, where R means an aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0056]

[0057] Meanwhile, each description and embodiment disclosed in this application may also be applied to other descriptions and embodiments. That is, all combinations of the various elements disclosed in this application fall within the scope of this application. Furthermore, the scope of this application should not be considered limited by the specific descriptions provided below.

[0058]

[0059] [Quantum Dot]

[0060] In the present invention, the term “quantum dot” refers to a nanocrystal exhibiting quantum confinement or exciton confinement and is a type of luminescent nanostructure (e.g., capable of emitting light upon energy excitation). The shape of the term quantum dot is not limited unless specifically defined otherwise.

[0061] The above nanostructure refers to a structure having a single region or characteristic dimensions having nanoscale dimensions. The above nanostructure may have any shape, such as a nanowire, nanorod, nanotube, multi-pod type shape having two or more pods, nanodot (or quantum dot), etc., and is not particularly limited.

[0062] The electrical and / or optical properties of the quantum dots of the present invention may vary depending on their properties (e.g., composition, size, and / or shape). For example, quantum dots may have a large surface area per unit volume, exhibit quantum confinement effects, and exhibit properties different from those of bulk materials of the same composition.

[0063] In the present invention, the type of quantum dot is not particularly limited and includes all known or commercially available quantum dots.

[0064] In one embodiment of the present invention, the quantum dots are InP, CdSe, AgInGaS, ZnSeTe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, ZnSeSTe, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, It can be selected from the group consisting of HgZnSTe and mixtures thereof.

[0065]

[0066] [First Monomer]

[0067] In the present invention, the curable composition may include a first monomer comprising a compound represented by the following chemical formula 1.

[0068] [Chemical Formula 1]

[0069]

[0070] In the above chemical formula 1,

[0071] R1 and R2 are identical or different from each other, and each independently consists of hydrogen, a hydroxyl group, an acryl group, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei,

[0072] The above X is C1~C 40 alkylene group of, C1~C 40 cycloalkylene group of, C1~C 40 alkyloxylene group of, C6~C 40 It is an arylene group or a heteroarylene group having 5 to 40 nuclei, and

[0073] n1 can be an integer from 0 to 30, 0 to 20, 0 to 15, or 0 to 12.

[0074] In the above chemical formula 1, X can be selected from the group consisting of the following X-1 to X-4.

[0075]

[0076] m1 to m4 may be identical or different from each other and may each be an integer of 0 to 30, 0 to 20, or 0 to 15, but are not limited thereto.

[0077] The compound represented by the above chemical formula 1 may be selected from the group consisting of A-1 to A-5 below.

[0078]

[0079] The above monomer has a fast curing speed during photocuring, and the strength of the cured film and the surface resistance of the composition can be easily controlled. In particular, when applying the structures of A-1 to A-5, it is easy to manufacture a photocurable composition with low viscosity.

[0080]

[0081] [Second Monomer]

[0082] In the present invention, the curable composition may include a second monomer comprising at least one of the compounds represented by the following chemical formulas 2 to 4.

[0083] [Chemical Formula 2]

[0084]

[0085] [Chemical Formula 3]

[0086]

[0087] [Chemical Formula 4]

[0088]

[0089] In the above chemical formulas 2 to 4,

[0090] R3 to R 15 They are identical or different from each other, and each independently consists of hydrogen, hydroxyl groups, acryl groups, cyano groups, nitro groups, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei,

[0091] The above A1 to A6 are identical or different from each other, and each is independently C, O, S, or N, and

[0092] The above Y1 to Y3 are identical or different from one another, and each independently consists of hydrogen, deuterium, halogen, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 It is an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclei, and

[0093] n2 to n7 are identical or different from each other, and each is independently an integer of 0 to 20, 0 to 15, or 0 to 12, and

[0094] The above R1 to R 15 of Hydrogen, hydroxyl group, acrylic group, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 aryl group and heteroaryl group having 5 to 40 nuclei, hydrogen, deuterium, halogen, cyano group, nitro group of X1 to X3, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 The aryl heteroarylamine group and the heteroarylamine group having 5 to 60 nuclei are each independently a halogen, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group of, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C6~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, and in this case, if there are multiple substituents, they may be identical or different from each other.

[0095] In the above chemical formula 2, Y can be selected from the group consisting of the following Y-1 to Y-13.

[0096]

[0097] In the above chemical formulas 2 to 4,

[0098] R3 to R 15 They are identical or different from each other, and each independently consists of hydrogen, hydroxyl groups, acryl groups, cyano groups, nitro groups, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei,

[0099] The above A1 to A6 are identical or different from each other, and each is independently C, O, S, or N, and

[0100] The above Y1 to Y3 are identical or different from one another, and each independently consists of hydrogen, deuterium, halogen, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 It is an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclei, and

[0101] n2 to n7 are identical or different from each other, and each is independently an integer of 0 to 20, 0 to 15, or 0 to 12, and

[0102] The above R1 to R 15 of Hydrogen, hydroxyl group, acrylic group, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 aryl group and heteroaryl group having 5 to 40 nuclei, hydrogen, deuterium, halogen, cyano group, nitro group of X1 to X3, C1~C 40 alkyl group of, C2~C40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 The aryl heteroarylamine group and the heteroarylamine group having 5 to 60 nuclei are each independently a halogen, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group of, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C6~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, and in this case, if there are multiple substituents, they may be identical or different from each other.

[0103] In the above chemical formula 2, Y can be selected from the group consisting of the following Y-1 to Y-13.

[0104]

[0105] The above-mentioned second monomer can impart refractive index and stereostructural characteristics to the composition, thereby controlling the stability, refractive index, surface resistance, and degree of crosslinking of the composition, and when applied to a quantum dot photocuring composition, it can provide high photoconversion efficiency and an enhanced degree of crosslinking.

[0106]

[0107] [Curable composition]

[0108] One example of the present invention provides a curable composition comprising one or more compounds comprising a first monomer and one or more compounds comprising a second monomer.

[0109] The above curable composition may be a photopolymerizable curable composition.

[0110] In particular, the Si element and heteroatom stabilize the gauge of the quantum dot while simultaneously strengthening the interaction between the monomer molecules, so that the heat resistance and plasma resistance of the thin film can be improved.

[0111] Furthermore, when multiple combinations of the first and second monomers are applied to quantum dots, low-viscosity ink can be easily produced, and the photoconversion efficiency of the quantum dots can be increased while maintaining the high rigidity of the single film. In addition, plasma resistance, thermal stability of the composition, and high photoconversion efficiency can be achieved through the effect of the functional structure of the second monomer.

[0112]

[0113] [etc]

[0114] In the present invention, the curable composition may further include a photopolymerization initiator, a light scattering agent, or a combination thereof.

[0115] The type of photopolymerization initiator is not particularly limited and may include, for example, triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, oxime ester compounds, aminoketone compounds, phosphine or phosphine oxide compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, nonimidazole compounds, or combinations thereof.

[0116] 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, and bis(trichloromethyl)-6-styryl-s-triazine. Examples 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, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0117] Examples of the above acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0118] Examples of the above benzophenone compounds include benzophenone, benzoyl benzoic acid, 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.

[0119] Examples of the above thioxanthonic compounds include thioxanthon, 2-methylthioxanthon, isopropylthioxanthon, 2,4-diethylthioxanthon, 2,4-diisopropylthioxanthon, 2-chlorothioxanthon, etc.

[0120] Examples of the above-mentioned benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0121] In the above composition, the content of the photopolymerization initiator can be appropriately adjusted by taking into account the type and content of the photopolymerizable monomer used.

[0122] In one embodiment, the content of the photopolymerization initiator may be 0.01 wt% or more, 0.1 wt% or more, 0.5 wt% or more, or 1 wt% or more based on 100 wt% of the total composition. The content of the photopolymerization initiator may be 10 wt% or less, or 5 wt% or less based on the total weight of the composition, but is not limited thereto.

[0123] It is desirable that the photopolymerization initiator be included within the above range, as this improves pattern formation and increases the sensitivity of the photo-converting curable composition, thereby tending to improve the strength of the pixel portion formed using the composition or the smoothness of the surface of the pixel portion.

[0124] The types of light scattering agents mentioned above are not particularly limited and may include, for example, barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0125] The light scattering agent reflects light that is not absorbed by the quantum dots and enables the quantum dots to reabsorb the reflected light. In other words, the light scattering agent increases the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

[0126] The form of use of the above light scattering agent is not particularly limited, and as an example, a dispersion in a solvent can be used for dispersion stability in a curable composition.

[0127] In the above composition, the light scattering agent content can be appropriately adjusted as needed.

[0128] In one embodiment, the content of the light scattering agent may be 0.1 weight% or more, 0.5 weight% or more, 1 weight% or more, or 5 weight% or more based on 100 weight% of the total composition. The content of the light scattering agent may be 10 weight% or less, or 5 weight% or less based on the total weight of the composition, but is not limited thereto.

[0129] When the above light scattering agent is included within the above content range, an improvement in light conversion efficiency due to the use of the light scattering agent can be expected, and pattern characteristics can also be improved.

[0130] In the present invention, the curable composition may further include one or more selected from the group consisting of a binder resin and a solvent.

[0131] The above binder resin may include an acrylic binder resin, a cardo-based binder resin, or a combination thereof.

[0132] Specific examples of the above-mentioned acrylic binder resins include (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, but are not limited thereto, and these may be used alone or in combination of two or more types.

[0133] In the present invention, the solvent may include propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone, or a combination thereof.

[0134] In another embodiment for achieving the above objective, the present invention provides a curable film comprising the above-mentioned curable composition and an image display device comprising the above-mentioned curable film.

[0135]

[0136] The present invention will be explained in more detail below through the following examples. However, these examples are intended to illustrate the invention and the scope of the invention is not limited to these examples.

[0137]

[0138] [Quantum Dot]

[0139] Ag / In / Ga / S (Nanosis, hereinafter 'QD-1') was prepared as a quantum dot. QD-1 is a Green QD with an Ag / In / Ga / S core, has an emission wavelength of 530 nm, and a full width at half maximum of 30 nm. The above QD-1 was prepared by dispersing it in toluene at a concentration of 30 wt%.

[0140]

[0141] [Example 1]

[0142] The prepared QD-1 was mixed with monomer A-2 at 33.0 wt%, phenylbenzyl acrylate (PB) at 28.5 wt%, and B-1 at 20 wt%, along with photopolymerization initiator TPO at 1 wt% (TCI) and light-scattering particle TiO2 (in A-2, 7 wt%). Subsequently, a curable composition was prepared by adding a dispersant BYK-111 at 0.5 wt% (BYK).

[0143] At this time, the structures of A-2, PB, TPO, and B-1 used are as follows.

[0144]

[0145] [Example 2]

[0146] The prepared QD-1 was mixed with monomers A-2 at 33.0 wt%, Phenoxy benzyl acrylate (PB) at 33.5 wt%, and B-11 at 15 wt%, photopolymerization initiator TPO at 1 wt% (TCI) and light-scattering particle TiO2 (in A-2, 7 wt%). Then, a curable composition was prepared by adding a dispersant BYK-111 at 0.5 wt% (BYK).

[0147] At this time, the structures of A-2, PB, TPO, and B-11 used are as follows.

[0148]

[0149] [Comparative Example 1]

[0150] 81.5 wt% of monomer A-2 was added to the prepared QD-1, and 1.0 wt% of TPO (TCI), a photopolymerization initiator, and 7 wt% of TiO2 (in A-2), a light-scattering particle, were mixed. Then, 0.5 wt% of BYK-111 (BYK), a dispersant, was added to prepare a curable composition.

[0151] At this time, the structure of A-2 and TPO is as follows.

[0152]

[0153] [Comparative Example 2]

[0154] The prepared QD-1 was mixed with monomer A-2 at 43.0 wt% and phenyl benzyl acrylate (PB) at 38.5 wt% (Sigma-Aldrich), photopolymerization initiator TPO at 1 wt% (TCI), and light-scattering particle TiO2 (in A-2, 7 wt%). Then, a curable composition was prepared by adding a dispersant BYK-111 at 0.5 wt% (BYK).

[0155] At this time, the structures of A-2, PB, and TPO used are as follows.

[0156]

[0157] [Experimental Example 1]

[0158] A photoconversion coating layer was prepared using the photoconversion curable composition prepared according to Examples 1 and 2 and Comparative Examples 1 and 2 by undergoing a curing process, a first thermal stabilization (POB) process, a CVD process, and a second thermal stabilization process.

[0159] At this time, film thickness, transmittance, color conversion efficiency (PCE), maximum emission wavelength, full width at half maximum (FWHM), and viscosity were measured using the following methods.

[0160] - measurement method

[0161] Film thickness was measured using a step height measuring instrument (BRUKER DektakXT), and transmittance, color conversion efficiency (PCE), maximum emission wavelength, and full width at half maximum (FWHM) were measured using a quantum efficiency measuring instrument (Otsuka Electronics QE-2100). Viscosity was measured using a Brookfield ametek DV2T viscometer, and the state of the thin film (aggregation, roughness) was observed using an electron microscope. TiO2 particle size was measured using an Otsuka Electronics ELSZ-2000.

[0162] - Curing process

[0163] After forming a curable composition using SPIN3000D of MIDAS SYSTEM, the thin film was cured using an exposure machine (SLC-1000AF-D, Jueun UV Tech).

[0164] - Chemical Vapor Deposition (CVD) process

[0165] The plasma thickness was 1-2 μm, and SiOxNy was deposited under heating conditions of 200 ℃. Subsequently, a thermal stabilization process was performed using a Corning heat stirrer (Sigma-Aldrich). The degree of curing (crosslinkage) of the completed thin film was measured using an ALPHA ±.

[0166] The results are shown in Table 1 and Figure 1 below.

[0167] Classification Process Step Absorption Rate (%) PCE (%) Degradation Rate (%) Viscosity (cps) Example 1 Max Emission Wavelength (534 nm) Half Width (30.7 nm) Curing 79.59 15.92-18 1st Thermal Stability 79.79 14.73-7.47 CVD 80.30 14.26-10.43 2nd Thermal Stability 80.04 14.60-8.29 Example 2 Max Emission Wavelength (534 nm) Half Width (30.8 nm) Curing 79.16 15.80-19 1st Thermal Stability 79.23 14.46-8.48 CVD 79.32 14.08-10.86 2nd Thermal Stability 79.36 14.45 -8.86 Comparative Example 1 Maximum Emission Wavelength (535 nm) Half-width (31 nm) Curing 77.06 13.39 -17 1st Thermal Stability 77.03 11.88 -11.3 CVD 77.25 11.29 -15.7 2nd Thermal Stability 77.04 11.53 -13.90 Comparative Example 2 Maximum Emission Wavelength (534 nm) Half-width (31 nm) Curing 78.16 14.20 -19 1st Thermal Stability 78.23 12.58 -9.81 CVD 78.05 12.16 -13.6 5 2nd Thermal Stability 78.11 12.23 -12.09

[0168] When comparing the PCE of Examples 1 and 2 and Comparative Examples 1 and 2 at the same thickness of 7 μm using the compositions of Examples 1 and 2 and Comparative Examples 1 and 2, Comparative Example 2, which used a mixture of the second monomer, showed a lower degradation rate compared to Comparative Example 1; however, Examples 1 and 2, which contain Si elements, showed a significantly reduced degradation rate compared to Comparative Example 2, exhibiting excellent plasma resistance and thermal stability. This confirmed that not only do Si elements and heteroatoms stabilize the quantum dot gauge, but the combination of the first and second monomers also strengthens intermolecular interactions, thereby improving heat resistance and plasma resistance.

[0169] In addition, it was confirmed that a thin film with improved efficiency and stability can be formed while maintaining a viscosity of 20 cps or less suitable for solvent-free inkjet.

[0170]

[0171] [Experimental Example 2]

[0172] In order to confirm whether the storage stability of the above-mentioned curable composition was improved, the prepared curable compositions Example 1 and Comparative Example 2 were each placed in brown vials, sealed, and stored for a certain period under conditions of 25°C and 60% humidity. Subsequently, the thin film was spin-coated to a thickness of 10 μm, and after curing by irradiating with an exposure device, the range of PCE change of the thin film was measured using a quantum efficiency meter (Otsuka Electronics QE-2100).

[0173] As shown in FIG. 2, in Example 1 and Comparative Example 2 using the same A-2 monomer, the composition of Example 1, in which B-1 monomer was applied simultaneously with A-2 monomer, showed results in maintaining most of the PCE change range even when stored for more than 60 days by suppressing the re-aggregation of quantum dots and self-curing of monomers due to the structural steric hindrance effect of the methoxysilane group. Thus, it was confirmed that the storage stability of the composition using the monomer according to one example of the present invention is significantly improved.

Claims

A curable composition comprising quantum dots, a first monomer, and a second monomer, The first monomer comprises a compound represented by the following chemical formula 1, and [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are identical or different from each other, and each independently consists of hydrogen, a hydroxyl group, an acryl group, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 The alkynyl group of, C -6 ~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, X are identical or different from each other, and each independently C1~C 40 alkylene group of, C1~C 40 cycloalkylene group of, C1~C 40 alkyloxylene group of, C6~C 40 It is an arylene group or a heteroarylene group having 5 to 40 nuclei, and n1 is an integer from 0 to 30; A curable composition comprising at least one of the compounds represented by the following chemical formulas 2 to 4, wherein the second monomer comprises: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 2 to 4, R3 to R 15 They are identical or different from each other, and each independently consists of hydrogen, hydroxyl groups, acryl groups, cyano groups, nitro groups, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, The above A1 to A6 are identical or different from each other, and each is independently C, O, S, or N, and The above Y1 to Y3 are identical or different from one another, and each independently consists of hydrogen, deuterium, halogen, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 It is an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclei, and n2 to n7 are identical or different from each other, and each is independently an integer from 0 to 20, and The above R1 to R 15 of Hydrogen, hydroxyl group, acrylic group, cyano group, nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C6~C 40 aryl group and heteroaryl group having 5 to 40 nuclei, hydrogen, deuterium, halogen, cyano group, nitro group of X1 to X3, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclei, C6~C 60 aryl group, heteroaryl group with 5 to 60 nuclei, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C3~C 40 alkylsilyl group of, C6~C 60 arylsilyl group of, C1~C 40 alkylboron group of, C6~C 60 arylboron group of, C6~C 60 arylphosphine group of, C6~C 60 arylphosphine oxide group, C6~C 60 The arylamine group of, C5~C 60 The aryl heteroarylamine group and the heteroarylamine group having 5 to 60 nuclei are each independently a halogen, a cyano group, a nitro group, C1~C 40 alkyl group of, C2~C 40 alkenyl group, C2~C 40 alkynyl group, C3~C 40 cycloalkyl group of, C1~C 40 alkyloxy group of, C6~C 60 The aryloxy group of, C6~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclei, and in this case, if there are multiple substituents, they may be identical or different from each other. In paragraph 1, The above chemical formula 1 is a curable composition selected from the group consisting of X-1 to X-4 below: m1 to m4 are identical or different from each other and are each independently integers from 0 to 20. In paragraph 1, A curable composition in which Y in the above chemical formula 2 is selected from the group consisting of the following Y-1 to Y-13: In this case, * represents the site bonded with Si in Chemical Formula 2. In paragraph 1, A curable composition comprising a compound represented by the above chemical formula 1, selected from the group consisting of A-1 to A-5 below: . In paragraph 1, A curable composition comprising a compound represented by the above chemical formulas 2 to 4, selected from the group consisting of B-1 to B-12 below: . In paragraph 1, The above-mentioned curable composition further comprises a photopolymerization initiator, a light scattering agent, or a combination thereof. In paragraph 1, The above curable composition further comprises one or more of a binder resin and a solvent. In paragraph 1, The above quantum dots comprise InP, CdSe, AgInGaS, ZnSeTe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, ZnSeSTe, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. A curable composition. In Paragraph 7, The above binder resin is a curable composition comprising an acrylic binder resin, a cardo-based binder resin, or a combination thereof. In Paragraph 7, The above solvent comprises propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone, or a combination thereof, a curable composition. In paragraph 1, The above-mentioned curable composition is a curable composition having a refractive index of 1.50 or higher. A curable film comprising the curable composition of claim 1. An image display device comprising the curing film of Clause 12.

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