Photo-conversion curable composition, cured film comprising same photo-conversion curable composition, and image display device comprising same cured film

Abstract

The present invention relates to a photo-conversion curable composition, a cured film comprising the photo-conversion curable composition, and an image display device comprising the cured film. The curable composition of the present invention comprises a crosslinkable-type antioxidant having an acrylic group, thereby preventing the oxidation of a thin film, preventing wrinkles and particles, and improving light stability by using the curable composition.

Description

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

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

[0002] Quantum dots are nanometer-sized semiconductor nanocrystals that have different energy band gaps (Bandgap, E) depending on their size and shape. g ) has the characteristic of changing. These quantum dots can control the emission wavelength simply by adjusting the size of the quantum dots due to the quantum confinement effect, and can exhibit excellent color purity and high PL (photoluminescence) efficiency, so they are receiving much attention not only in displays but also in fields such as lighting sources, solar cells, semiconductor lasers / optical amplifiers, and bio-imaging.

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

[0004] Among them, the pigment dispersion method is a method of forming a colored thin film by repeating a series of processes of coating, exposing, developing, and thermally curing a photopolymerizable composition containing a coloring agent on a transparent substrate provided with a black matrix. For example, Korean Patent Publication No. 1992-7002502 proposes a method for producing a colored photosensitive resin composition using the pigment dispersion method. However, the method requires coating, exposing, developing, and curing processes for red, green, and blue, respectively, to form pixels, which makes the manufacturing process very long and increases the number of control factors between processes, making it difficult to manage yield.

[0005] To address these challenges, ongoing efforts have been made to replace pigments with quantum dots, leading to their application in various display devices, electronic devices, and more. However, further research is needed on compositions that can stabilize quantum dots to improve processability and performance.

[0006] Quantum dots are formed by weakly bonding organic ligands to an inorganic surface, and the surface is not protected by strong bonds such as covalent bonds. This reduces efficiency when applied to thin film formation and light conversion devices. In particular, the thin film manufacturing process necessarily includes a high heat treatment process of 60℃ to 300℃, and the heat generated during this process causes a decrease in the color conversion efficiency (PCE) of the quantum dots and the detachment of the ligands. In addition, there is a problem that the stability of the composition containing the quantum dots and the heat / light exposure stability of the thin film are reduced due to the phenomenon of quantum dots being degraded by oxygen, moisture, and free radicals.

[0007] Against this backdrop, the inventors of the present invention have conducted research efforts to develop a curing composition having excellent stability and improved performance, and have developed a curing composition containing an antioxidant that participates in crosslinking, including an acrylic group.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 001) Korean Patent Publication No. 1992-7002502

[0011] The present invention aims to solve the above-mentioned problems and other problems related thereto.

[0012] An exemplary object of the present invention is to provide a curable composition that includes a cross-linking-participating antioxidant, which prevents the formation of particles and wrinkles during thin film formation and improves the photostability of the thin film.

[0013] Another exemplary object of the present invention is to provide a cured film and an image display device comprising the curable composition.

[0014] The technical problem to be achieved according to the technical idea of ​​the invention disclosed in this specification is not limited to the problem to solve the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0015] As one aspect for achieving the above purpose, one example of the present invention is

[0016] A curable composition comprising a quantum dot, a photopolymerizable monomer and an antioxidant,

[0017] The above photopolymerizable monomer comprises at least one of the compounds represented by the following chemical formulas 1 and 2,

[0018] The above antioxidant provides a curable composition comprising at least one compound represented by the following chemical formulae 3 and 4.

[0019] [Chemical Formula 1]

[0020]

[0021] [Chemical Formula 2]

[0022]

[0023] [Chemical Formula 3]

[0024]

[0025] [Chemical Formula 4]

[0026]

[0027] In the above chemical formulas 1 to 4,

[0028] R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411are the same or different from each other, and each independently represents 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 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0029] The above R 302 Inland R 310 and R 402 Inland R 409 At least one of them is a hydroxyl group,

[0030] The above A1 and A2 are the same or different from each other, and are each independently C, O, S or N,

[0031] The above X is C1~C 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 Alkyloxylene group, C6~C 40 An arylene group or a heteroarylene group having 5 to 40 nuclear atoms,

[0032] The above Y is C1~C 40 Alkyl group or C6~C 40 is an aryl group,

[0033] In the above chemical formula 2, m1 and m2 are the same or different from each other, and are each independently an integer from 0 to 2,

[0034] In the above chemical formulas 1 and 2, n is the same or different from each other and is independently an integer from 0 to 12,

[0035] The above R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 of Acrylic, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C6~C 40 An aryl group of , a heteroaryl group having 5 to 40 nuclear atoms, C1~C of the above X 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 Alkyloxylene group, C6~C 40 A heteroarylene group having 5 to 40 arylene atoms, C1 to C of Y 40 Alkyl group and C6~C 40 The aryl group of each independently represents a halogen, a cyano group, a nitro group, a 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, C6~C 60 Aryloxy group, 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 nuclear atoms. In this case, when there are multiple substituents, they may be the same or different, and may be combined with each other or condensed with each other to form a ring.

[0036] Another example of the present invention provides a cured film comprising the curable composition.

[0037] Another example of the present invention provides an image display device including the cured film.

[0038] Since the curable composition of the present invention includes a crosslinking-participating antioxidant having an acrylic group, the curable composition can be used to prevent oxidation of a thin film, as well as to prevent wrinkles and particle formation, and to improve photostability.

[0039] Meanwhile, the scope of the present invention is not limited by the effects described above.

[0040] Figure 1 shows the results of confirming the degree of crosslinking of a thin film manufactured using a curable composition according to an example of the present invention by measuring it using an infrared spectroscopy (FT-IR).

[0041] Figure 2 shows the results of confirming the structural stability of a thin film manufactured after storing a curable composition according to an example of the present invention for one week.

[0042] The present invention is specifically described as follows.

[0043] Meanwhile, each description and embodiment disclosed in this application can also be applied to each other description and embodiment. In other words, all combinations of the various elements disclosed in this application fall within the scope of this application. Furthermore, the scope of this application is not limited by the specific descriptions described below.

[0044] As one aspect for achieving the above purpose, the present invention

[0045] A curable composition comprising a quantum dot, a photopolymerizable monomer and an antioxidant,

[0046] The above photopolymerizable monomer is at least one of the compounds represented by the following chemical formulas 1 and 2,

[0047] The curable composition provides a curable composition in which the antioxidant is at least one of the compounds represented by the following chemical formulae 3 and 4.

[0048] [Chemical Formula 1]

[0049]

[0050] [Chemical Formula 2]

[0051]

[0052] [Chemical Formula 3]

[0053]

[0054] [Chemical Formula 4]

[0055]

[0056] In the above chemical formulas 1 to 4,

[0057] R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 are the same or different from each other, and each independently represents 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 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0058] The above R 302 Inland R 310 and R 402 Inland R 409 At least one of them is a hydroxyl group,

[0059] The above A1 and A2 are the same or different from each other, and are each independently C, O, S or N,

[0060] The above X is C1~C 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 Alkyloxylene group, C6~C 40 An arylene group or a heteroarylene group having 5 to 40 nuclear atoms,

[0061] The above Y is C1~C 40 Alkyl group or C6~C 40 is an aryl group,

[0062] In the above chemical formula 2, m1 and m2 are the same or different from each other, and are each independently an integer from 0 to 2,

[0063] In the above chemical formulas 1 and 2, they are the same or different from each other, and each independently n is an integer from 0 to 12,

[0064] The above R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 of Acrylic, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C6~C 40 An aryl group of , a heteroaryl group having 5 to 40 nuclear atoms, C1~C of the above X 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 Alkyloxylene group, C6~C 40 An arylene group and a heteroarylene group having 5 to 40 nuclear atoms, C1 to C of Y 40 Alkyl group and C6~C 40 The aryl group of each independently represents a halogen, a cyano group, a nitro group, a 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, C6~C 60 Aryloxy group, C6~C 60 It may be substituted with one or more substituents selected from the group consisting of aryl groups and heteroaryl groups having 5 to 40 nuclear atoms, and in this case, when there are multiple substituents, they may be the same or different from each other, and may be combined with each other or condensed with each other to form a ring.

[0065] In one embodiment of the present invention, R in the chemical formula 3 302 Inland R 306At least one of them may be a (meth)acrylic group, and R in the above chemical formula 4 406 Inland R 409 At least one of which may be a (meth)acrylic group.

[0066] In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0067] In the present invention, "alkenyl" means a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon double bond. Examples of such alkenyl include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0068] In the present invention, "alkynyl" refers to a monovalent substituent derived from an unsaturated hydrocarbon having 2 to 40 carbon atoms and a straight or branched chain having at least one carbon-carbon triple bond. Examples of such alkynyl include, but are not limited to, ethynyl and 2-propynyl.

[0069] In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a single ring or a combination of two or more rings. Furthermore, forms in which two or more rings are simply attached to each other (pendant) or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

[0070] 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 cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0071] In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, at least one carbon atom in the ring, preferably 1 to 3 carbon atom, is substituted with a heteroatom such as N, O, S, or Se. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included, and a form 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.

[0072] In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl 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, and pentoxy.

[0073] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R represents aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0074] In the present invention, "cycloalkylidene" means a divalent group formed from a cycloalkane having two substituents on one carbon atom of the cycloalkane. Specifically, it can be represented by the following structural formula:

[0075]

[0076] In this formula, q determines the size of the ring and is an integer greater than or equal to 1. For example, if q is 2, cyclobutylidene can be formed. In various embodiments, cycloalkylidene is a divalent C3-C 40 It may be a cyclic moiety, examples of which include, but are not limited to, cyclopropylidene, cyclobutylidene, cyclopentylidene, and cyclohexylidene.

[0077]

[0078] [quantum dot]

[0079] In the present invention, the term "quantum dot" refers to a nanocrystal exhibiting quantum confinement or exciton confinement, and is a type of nanostructure that is luminescent (e.g., capable of emitting light upon energy excitation). The term "quantum dot" herein is not limited in shape unless specifically defined.

[0080] The above nanostructure refers to a structure having a single region or characteristic dimension with nanoscale dimensions. The nanostructure may have any shape, such as a nanowire, nanorod, nanotube, multi-pod type shape with two or more pods, nanodot (or quantum dot), etc., and is not particularly limited thereto.

[0081] The electrical and / or optical properties of the quantum dots of the present invention are their physical properties (e.g.,

[0082] (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.

[0083] In the present invention, the type of the quantum dot is not particularly limited and includes all known or commercially available quantum dots.

[0084] In one embodiment of the present invention, the quantum dot comprises 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.

[0085]

[0086] [Photopolymerizable monomer]

[0087] In the present invention, the curable composition comprises at least one photopolymerizable monomer among the compounds represented by chemical formulae 1 and 2.

[0088] [Chemical Formula 1]

[0089]

[0090] [Chemical Formula 2]

[0091]

[0092] In the above chemical formulas 1 and 2,

[0093] R 101 , R 102 and R 201 Inland R 203 are identical or different from each other, and each is independent 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 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0094] The above A1 and A2 are the same or different from each other, and are each independently C, O, S or N,

[0095] The above X is C1~C 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 Alkyloxylene group, C6~C 40 An arylene group or a heteroarylene group having 5 to 40 nuclear atoms,

[0096] The above Y is C1~C 40 Alkyl group or C6~C 40 is an aryl group,

[0097] In the above chemical formula 2, m1 and m2 are the same or different from each other, and are each independently an integer from 0 to 2,

[0098] In the above chemical formulas 1 and 2, n is the same or different from each other and is independently an integer from 0 to 12,

[0099] The above R 101 , R 102 and R 201 Inland R 203 of Acrylic, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C6~C 40 An aryl group of , a heteroaryl group having 5 to 40 nuclear atoms, C1~C of the above X 40 alkylene group, C1~C 40 Cycloalkylene group, C1~C 40 Alkyloxylene group, C6~C 40 Arylene group of, heteroarylene group having 5 to 40 nuclear atoms, C1~C of Y 40 Alkyl group and C6~C 40 The aryl group of each independently represents a halogen, a cyano group, a nitro group, a 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, C6~C 60 Aryloxy group, 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 nuclear atoms, and in this case, when there are multiple substituents, they may be the same or different from each other.

[0100] In one embodiment of the present invention, Y may be substituted with one of the following structural formulas.

[0101]

[0102] At this time, * indicates the site that combines with Y.

[0103] Preferably, the photopolymerizable monomer includes both a compound represented by the chemical formula 1 and a compound represented by the chemical formula 2.

[0104] The curable composition according to the present invention is characterized by being a solvent-free type that does not contain a solvent. To implement such a solvent-free type composition, by using a monomer such as the compound represented by the above chemical formulas 1 and / or 2, not only can quantum dots be excellently dispersed, but also problems such as reduced jetting properties and poor film properties caused by the inclusion of a solvent can be improved.

[0105] As an example of the present invention, the compound represented by the above chemical formula 1 may include two or more (meth)acrylate groups, and the compound represented by the above chemical formula 2 may include one or more (meth)acrylate groups.

[0106] As an example of the present invention, the compound represented by the compound 1 may include a trifunctional (meth)acrylic group or a tetrafunctional (meth)acrylic group.

[0107] In one embodiment of the present invention, the compound represented by the above chemical formula 1 may be selected from the group consisting of X-1 to X-26 below.

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] * indicates a part connected to O in the above chemical formula 1.

[0114] In one embodiment of the present invention, the compound represented by the above chemical formula 1 may be selected from the group consisting of A-1 to A-9 below.

[0115]

[0116] In one embodiment of the present invention, the compound represented by the above chemical formula 2 may be selected from the group consisting of B-1 to B-8 below.

[0117]

[0118] In the present invention, the compound represented by any one of the chemical formulas 1 and 2 may be included in an amount of 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, based on 100 parts by weight of the total curable composition.

[0119] In the present invention, the compound represented by either of the chemical formulas 1 and 2 may be included in an amount of 50 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, based on 100 parts by weight of the total curable composition.

[0120]

[0121] [Antioxidant]

[0122] The antioxidant comprises at least one of the compounds represented by the following chemical formulas 3 and 4.

[0123] [Chemical Formula 3]

[0124]

[0125] [Chemical Formula 4]

[0126]

[0127] In the above chemical formulas 3 and 4,

[0128] R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411are the same or different from each other, and each independently represents 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 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0129] The above R 302 Inland R 310 and R 402 Inland R 409 At least one of them is a hydroxyl group,

[0130] The above R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 of Acrylic, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group and C6~C 40 The aryl group and the heteroaryl group having 5 to 40 nuclear atoms are each independently selected from the group consisting of 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 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 nuclear atoms, and in this case, when there are multiple substituents, they may be the same or different from each other.

[0131] In one embodiment of the present invention, the compound represented by the chemical formula 3 may be represented by the following structure.

[0132] or

[0133] Quantum dots are formed by weakly bonding organic ligands to an inorganic surface. The surface is not protected by strong bonds such as covalent bonds, which reduces efficiency when applied to thin film formation and photoconversion devices. In particular, the heat generated during the heat treatment process in the thin film manufacturing process can cause a decrease in the color conversion efficiency (PCE) of quantum dots and ligand detachment. Furthermore, the stability of quantum dots can be significantly reduced due to the deterioration of quantum dots by oxygen, moisture, and free radicals. Therefore, there is a need to improve stability under heat and light exposure. Accordingly, an antioxidant may be added to the curable composition.

[0134] Conventional antioxidants are simple molecules that do not participate in cross-linking as simple additives, so the degree of cross-linking decreases depending on the amount added after exposure, and they have the disadvantage of precipitating or forming particles depending on temperature changes.

[0135] In the present invention, the compound represented by either of the above chemical formulae 3 and 4 is a cross-linking-participating antioxidant, which has an acrylic group and participates in polymer cross-linking upon exposure, thereby preventing wrinkles and particle formation in the thin film and improving photostability. In addition, after forming ink or a thin film using a curable composition, the photopolymerizable monomer or quantum dot may be oxidized by oxygen, moisture, or free radicals penetrating into the interior, thereby reducing efficiency, but the cross-linking-participating antioxidant suppresses this phenomenon.

[0136] In the present invention, the antioxidant may be included in an amount of 0.1 part by weight or more, 0.5 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, or 7 parts by weight or more, based on 100 parts by weight of the curable composition.

[0137] In the present invention, the antioxidant may be included in an amount of 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less, based on 100 parts by weight of the total curable composition.

[0138] When the antioxidant is included within the above range, it is advantageous in solving the problem of reduced luminescence efficiency. When the antioxidant is included below the above range, the effect of suppressing the reduction in luminescence efficiency of the quantum dots after the process cannot be secured. When the antioxidant is included above the above range, thermal curing may not be completely achieved or wrinkles may occur in the thin film.

[0139]

[0140] [etc]

[0141] In the present invention, the curable composition may further include a photopolymerization initiator, a light scattering agent, or a combination thereof.

[0142] The type of the photopolymerization initiator is not particularly limited, and may include, for example, a triazine compound, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, an oxime ester compound, an aminoketone compound, a phosphine or phosphine oxide compound, a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, a biimidazole compound, or a combination thereof.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] Examples of the above thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, etc.

[0147] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

[0148] In the above composition, the content of the photopolymerization initiator can be appropriately adjusted in consideration of the type and content of the photopolymerizable monomer used.

[0149] 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.

[0150] When a photopolymerization initiator is included within the above range, pattern formation is improved and the photoconversion curable composition has high sensitivity, so the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion tend to be improved, which is preferable.

[0151] The type of the above light scattering agent is not particularly limited, and may include, for example, barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconia (ZrO2), or a combination thereof.

[0152] The light-scattering agent reflects light that is not absorbed by the quantum dots and allows the reflected light to be reabsorbed by the quantum dots. In other words, the light-scattering agent can increase the amount of light absorbed by the quantum dots, thereby increasing the photoconversion efficiency of the curable composition.

[0153] The form of use of the above light scattering agent is not particularly limited, and for example, a form of dispersion dispersed in a solvent can be used to ensure dispersion stability in a curable composition.

[0154] In the above composition, the content of the light-scattering agent can be appropriately adjusted as needed.

[0155] In one embodiment, the content of the light-scattering agent may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, or 5 wt% or more, based on 100 wt% of the total weight of the composition. The content of the light-scattering agent may be 10 wt% or less, or 5 wt% or less, based on the total weight of the composition, but is not limited thereto.

[0156] When the above light scattering agent is included in the above content range, an effect of improving the light conversion efficiency by using the light scattering agent can be expected, and the pattern characteristics can also be improved.

[0157] In the present invention, the curable composition may further include at least one selected from the group consisting of a binder resin and a solvent.

[0158] The above binder resin may include an acrylic binder resin, a cardo binder resin, or a combination thereof.

[0159] Specific examples of the above acrylic binder resin include, but are not limited to, (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, etc., and these may be used alone or in combination of two or more.

[0160] 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, cyclohexylacrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone, or a combination thereof.

[0161] As another aspect for achieving the above object, the present invention provides a cured film comprising the curable composition and an image display device comprising the cured film.

[0162]

[0163] Hereinafter, the present invention will be described in more detail through the following examples. However, these examples are intended to exemplify the present invention and the scope of the present invention is not limited to these examples.

[0164]

[0165] [quantum dot]

[0166] InP / ZnSe / ZnS (Nanosys, hereinafter referred to as 'QD-1') and Ag / In / Ga / S (Nanosys, hereinafter referred to as 'QD-2') were prepared as quantum dots. QD-1 is an InP core-based green QD, has a size of 535 nm and a half width of 34 nm to 40 nm. QD-2 is an Ag / In / Ga / S core-based green QD, has a size of 530 nm and a half width of 30 nm to 35 nm. The above QD-1 and QD-2 were prepared by dispersing them in toluene at a concentration of 30 wt%, respectively.

[0167]

[0168] [Examples 1 and 2]

[0169] To the prepared QD-1 quantum dots, monomers 1,6-hexanediol diacrylate (HDDA, denoted as MN-1, Sigma-Aldrich) and benzyl acrylate (BZA, denoted as MN-2, Sigma-Aldrich) were applied, and 2 wt% (Example 1) or 4 wt% (Example 2) of CROX-1 (product number ZIKANOX-395, SONGWON) was added as an antioxidant, and TPO (TCI) as a photopolymerization initiator (denoted as PI-1), TiO2 (in HDDA) as a light-scattering particle (denoted as SP-1) and BYK-111 dispersant, and BYK-2013 as an ink composition dispersion stabilizer were mixed in the wt%s shown in Table 1 to prepare a curable composition. The structures of CROX-1, TPO, HDDA, and BZA used are as follows.

[0170]

[0171]

[0172] [Examples 3 and 4]

[0173] A curable composition was prepared using the same process as in Examples 1 and 2, except that 2 wt% (Example 3) or 4 wt% (Example 4) of CROX-2 (product number ZIKANOX-549DF, SONGWON) was used as an antioxidant.

[0174] The structure of CROX-2 used is as follows.

[0175]

[0176] [Examples 5 and 6]

[0177] A curable composition was prepared by the same process as in Examples 1 and 2, except that QD-2 quantum dots were applied and 2 wt% (Example 5) or 4 wt% (Example 6) of CROX-1 (product number ZIKANOX-395, SONGWON) was used as an antioxidant.

[0178]

[0179] [Examples 7 and 8]

[0180] A curable composition was prepared using the same process as in Examples 5 and 6, except that 2 wt% (Example 7) or 4 wt% (Example 8) of CROX-2 (product number ZIKANOX-549DF, SONGWON) was used as an antioxidant.

[0181]

[0182] [Comparative Example 1]

[0183] A curable composition was prepared using the same process as Example 1, except that only HDDA was used as a monomer and no antioxidant was used.

[0184]

[0185] [Comparative Example 2]

[0186] A curable composition was prepared using the same process as Example 5, except that only HDDA was used as a monomer and no antioxidant was used.

[0187]

[0188] [Comparative Example 3]

[0189] A curable composition was prepared using the same process as Example 1, except that only HDDA was used as a monomer and OX-1 (product number P0932, TCI) was used as an antioxidant at 4 wt%.

[0190] The structure of OX-1 used is as follows.

[0191]

[0192]

[0193] [Comparative Example 4]

[0194] A curable composition was prepared using the same process as Example 5, except that only HDDA was used as a monomer and OX-1 (product number P0932, TCI) was used as an antioxidant at 4 wt%.

[0195]

[0196] [Experimental Example]

[0197] A photoconversion coating layer was prepared using the photoconversion curable compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4, and the film thickness, transmittance, color conversion efficiency (PCE), maximum emission wavelength, full width at half maximum (FWHM), and viscosity at this time were measured using the following methods, and the results are shown in Tables 2 and 3 below.

[0198] The film thickness was measured using a step measurement device (BRUKER DektakXT), and the transmittance, color conversion efficiency (PCE), maximum emission wavelength, and full width at half maximum (FWHM) were measured using a quantum efficiency meter (Otsuka Electronics QE-2100). The viscosity was measured using a Brookfield ametek DV2T viscometer, and the state of the thin film (aggregation, roughness) was observed using an electron microscope. The TiO2 particle size was measured using Otsuka Electronics ELSZ-2000.

[0199] A thin film was produced by spin-coating a curable composition using SPIN3000D from MIDAS SYSTEM Co., Ltd., and the thin film was cured using an exposure device (JooEun Yu V-Tech Co., Ltd., SLC-1000AF-D). The degree of curing (crosslinking) of the thin film was then measured using ALPHA ± (BRUKER Co., Ltd.).

[0200] In addition, the photoconversion coating layer manufactured using the photoconversion curable composition manufactured by Examples 1 to 8 and Comparative Examples 1 to 4 was left under a 100 lx yellow light for 48 hours, and the light quantity and wavelength were measured using IS-ST100 (Ocean Insight) to confirm the reduction rate of the photoconversion efficiency.

[0201]

[0202]

[0203] As shown in Tables 2 and 3 above, the photoconversion curable compositions of Examples 1 to 8 of the present invention were compositions to which a crosslinking-participating antioxidant additive was applied, and it was confirmed that the PCE efficiency decrease phenomenon was improved after 48 hours compared to Comparative Examples 1 to 2.

[0204] In addition, when a thin film was manufactured with the composition of Example 6, the crosslinking degree of the thin film was improved and a stronger film was formed compared to Comparative Example 4 in which a simple additive (OX-1) that does not participate in crosslinking was applied, which was confirmed by FT-IR measurement (Fig. 1). In the case of Comparative Example 4, an antioxidant was introduced, and the photostability was improved compared to Comparative Example 2, but it was confirmed that the crosslinking degree actually decreased because a bulky antioxidant that lowers the crosslinking degree was introduced.

[0205] Conventional antioxidants have large molecular weights and bulky structures. Therefore, increasing their content to prevent oxidation reduces the degree of cross-linking of the monomer, making it difficult to form a strong film. However, when applying an antioxidant with an acrylic group, as in the examples of the present invention, it was confirmed that the amount of uncured monomer was small, as shown in Figure 1.

[0206] This is because by including an antioxidant having an acrylic group in the curable composition, the composition has an antioxidant effect not only in the solvent-free ink composition but also after thin film formation, and at the same time, it forms a polymer by crosslinking with a monomer upon exposure, thereby stabilizing the quantum dot surface and improving film planarization and crosslinking.

[0207] Based on these results, when the compositions of Example 8 and Comparative Example 4 were stored for a week at low temperature (10°C) and a thin film was formed again, it was confirmed that in the case of Comparative Example 4, particles were visible when forming the thin film, whereas the composition of Example 8 formed an excellent thin film without particles (Fig. 2).

[0208] In particular, it was confirmed that the photoconversion curable compositions of Examples 5 to 8 using QD-2 had an excellent color conversion efficiency (PCE) value of 35% or more and a viscosity of less than 20cp, making them suitable as photoconversion curable compositions included in ink-discharging type color filters and image display devices. In addition, it was confirmed that the emission wavelength was 530 nm to 540 nm and the half-width was 30 nm to 32 nm, showing excellent color purity.

[0209] Ultimately, the present invention reliably achieves low-viscosity, solvent-free, and high-efficiency thin films, significantly improving thermal process stability and surface uniformity of the coating. When forming thin films using quantum dots, there should be no difference in efficiency after initial exposure and after heat treatment, and minimal change in efficiency after exposure to air for a certain period of time is considered desirable.

[0210] From the above description, those skilled in the art will understand that the present invention can be implemented in other specific forms without altering its technical spirit or essential characteristics. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention should be interpreted as encompassing all changes or modifications derived from the meaning and scope of the following claims and their equivalent concepts, rather than the detailed description above.

Claims

1. A curable composition comprising a quantum dot, a photopolymerizable monomer and an antioxidant, The above photopolymerizable monomer comprises at least one of the compounds represented by the following chemical formulas 1 and 2, A curable composition, wherein the antioxidant comprises at least one of the compounds represented by the following chemical formulas 3 and 4. [Chemical Formula 1] [Chemical formula 2] [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 1 to 4, R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 are the same or different from each other, and each independently represents hydrogen, hydroxyl group, acrylic group, cyano group, nitro group, C1~C 40 Alkyl group of C2~C 40 Alkenyl group of C2~C 40 Alkynyl group, C6~C 40 is selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms, Above R 302 Inland R 310 and R 402 Inland R 409 At least one of them is a hydroxyl group, The above A's are the same or different from each other, and each is independently C, O, S or N, The above X is C1~C 40 Alkylene group, C1~C 40 Cycloalkylene group of C1~C 40 Cycloalkylidene group of C1~C 40 Alkyloxylene group, C6~C 40 is an arylene group or a heteroarylene group having 5 to 40 nuclear atoms, The above Y is C1~C 40 Alkyl group or C6~C 40 is an aryl group, In the above chemical formula 2, m1 and m2 are the same or different from each other, and are each independently an integer from 0 to 2. In the above chemical formulas 1 and 2, n is the same as or different from each other and is independently an integer from 0 to 12, Above R 101 , R 102 , R 201 Inland R 203 , R 301 Inland R 311 and R 401 Inland R 411 of Acrylic, C1~C 40 Alkyl group of C2~C 40 Alkenyl group of C2~C 40 Alkynyl group, C6~C 40 An aryl group of , a heteroaryl group having 5 to 40 nuclear atoms, C1 to C of the above X 40 Alkylene group, C1~C 40 Cycloalkylene group of C1~C 40 Cycloalkylidene group of C1~C 40 Alkyloxylene group, C6~C 40 Arylene group of Y, heteroarylene group having 5 to 40 nuclear atoms, C1 to C of Y 40 Alkyl group and C6~C 40 The aryl group of each is independently a halogen, a cyano group, a nitro group, a C1~C 40 Alkyl group of C2~C 40 Alkenyl group of C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group of C1~C 40 Alkyloxy group, C6~C 60 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 nuclear atoms, and when there are multiple substituents, they may be the same or different from each other, and may be combined with each other or condensed with each other to form a ring.

2. In paragraph 1, Above R 302 Inland R 306 and R 406 Inland R 409 A curable composition, wherein at least one of the above is a (meth)acrylic group.

3. In paragraph 1, A curable composition, wherein X in the chemical formula 1 is selected from the group consisting of X-1 to X-26 below.

4. In paragraph 1, A curable composition, wherein the compound represented by the above chemical formula 1 is selected from the group consisting of A-1 to A-9 below.

5. In paragraph 1, A curable composition, wherein the compound represented by the above chemical formula 2 is selected from the group consisting of B-1 to B-8 below.

6. In paragraph 1, A curable composition, wherein the antioxidant is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total curable composition.

7. In paragraph 1, The above curable composition further comprises a photopolymerization initiator, a light scattering agent or a combination thereof.

8. In paragraph 1, The above curable composition further comprises at least one of a binder resin and a solvent.

9. In paragraph 8, The above binder resin is a curable composition comprising an acrylic binder resin, a cardo binder resin or a combination thereof.

10. In paragraph 8, A curable composition comprising the solvent selected from the group consisting of 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, cyclohexylacrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone or a combination thereof.

11. A cured film comprising the curable composition of clause 1.

12. An image display device including a cured film according to Article 11.

Images