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

Abstract

This invention relates to a photocurable composition, a cured film comprising the photocurable composition, and an image display device comprising the cured film. The cured composition of this invention comprises a crosslinkable antioxidant having an acrylic group; therefore, using the cured composition not only achieves antioxidant properties of the film but also prevents wrinkles and particles, and improves photostability.

Description

Technical Field

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

[0002] Quantum dots are nanoscale semiconductor nanocrystals with a band gap (E0). g The properties of quantum dots vary with their size and shape. Due to the quantum confinement effect, the emission wavelength can be tuned simply by adjusting the size of the quantum dot, and they can exhibit excellent color purity and high PL (photoluminescence) efficiency. Therefore, they have attracted attention not only in the display field, but also in lighting sources, solar cells, semiconductor lasers / optical amplifiers, and bioimaging.

[0003] On the other hand, color filters are used in liquid crystal display devices, optical filters for cameras, etc., and are made by coating a fine area colored with three or more colors onto a solid imaging element or a transparent substrate. Such colored films can typically be formed by dyeing, printing, pigment dispersion, inkjet printing, etc.

[0004] One method is pigment dispersion, which involves repeatedly coating, exposing, developing, and thermally curing a photopolymerizable composition containing a colorant onto a transparent substrate with a black matrix to form a colored film. For example, Korean Patent Publication No. 1992-7002502 discloses a method for manufacturing a colored photosensitive resin composition using pigment dispersion. However, in this method, to form pixels, red, green, and blue pigments require separate coating, exposure, development, and curing processes, resulting in a very long manufacturing process and increased inter-process control factors, making yield management difficult.

[0005] To address these challenges, researchers have been continuously exploring the use of quantum dots to replace pigments, leading to their application in various display devices and electronic components. However, further research is needed to improve the processability and performance of quantum dots, particularly regarding their stabilizing composition.

[0006] Quantum dots exist as weakly bound organic ligands to surfaces composed of inorganic materials. Their surfaces are not protected by strong bonds such as covalent bonds, leading to efficiency degradation when forming thin films and applying them to optical conversion devices. In particular, the thin film manufacturing process requires high-temperature heat treatment at 60°C to 300°C, where the heat generates a decrease in the color conversion efficiency (PCE) of the quantum dots and ligand detachment. Furthermore, the quantum dots are degraded by oxygen, moisture, and free radicals, resulting in reduced stability of quantum dot-containing compositions and decreased thermal / optical exposure stability of the thin films.

[0007] Against this backdrop, the inventors have devoted themselves to developing curing compositions with excellent stability and improved performance, and have developed a curing composition containing an antioxidant that participates in crosslinking by an acrylic group.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Korean Patent Publication No. 1992-7002502 Summary of the Invention

[0011] Technical issues

[0012] The purpose of this invention is to solve the aforementioned problems and other related problems.

[0013] An exemplary object of the present invention is to provide a curable composition comprising a crosslinkable antioxidant, thereby preventing the formation of particles and wrinkles during film formation and improving the light stability of the film.

[0014] Another exemplary object of the present invention is to provide a cured film comprising the above-described curable composition, and an image display device.

[0015] The technical problems to be solved by the inventive concept disclosed in this specification are not limited to those for solving the problems mentioned above. Other problems not mentioned will be clearly understood by those skilled in the art from the following description.

[0016] Technical solution

[0017] As one way to achieve the above-mentioned objectives, one example of the present invention provides a curable composition comprising quantum dots, photopolymerizable monomers, and antioxidants.

[0018] The photopolymerizable monomer comprises one or more compounds represented by the following chemical formulas 1 and 2.

[0019] The antioxidant comprises one or more compounds represented by the following chemical formulas 3 and 4:

[0020] [Chemical Formula 1]

[0021]

[0022] [Chemical Formula 2]

[0023]

[0024] [Chemical Formula 3]

[0025]

[0026] [Chemical Formula 4]

[0027]

[0028] Of the above chemical formulas 1 to 4,

[0029] R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 They may be the same as or different from each other, and each is independently selected from hydrogen, hydroxyl, acrylate, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 It is a group composed of aryl groups and heteroaryl groups with 5 to 40 nuclei.

[0030] The R 302 To R 310 and R 402 To R 409 One or more of them are hydroxyl groups.

[0031] A1 and A2 may be the same as or different from each other, and each is independently C, O, S or N.

[0032] X is C1~C 40 Alkylene, C1~C 40 Cycloalkylene group, C1~C 40 Cycloalkylidene group, C1~C 40 alkyloxylene group, C6~C 40 arylene groups or heteroarylene groups with 5 to 40 nuclei,

[0033] The Y is C1~C40 Alkyl or C6~C 40 Aryl,

[0034] In the above chemical formula 2, m1 and m2 may be the same or different from each other, and each is an independent integer from 0 to 2.

[0035] In the above chemical formulas 1 and 2, n may be the same or different from each other, and each is an independent integer from 0 to 12.

[0036] The R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 Acrylic group, C1~C 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 aryl, heteroaryl with 5 to 40 nuclei, C1 to C1 of X 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkane alkyl groups, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene, heteroarylene with 5 to 40 nuclei, C1 to C1 of Y 40 Alkyl groups and C6~C 40 Each aryl group can be independently selected from halogen, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 cycloalkyl, C1~C 40 alkoxy groups, C6~C 60 aryloxy group, C6~C 60 The aryl group is replaced by one or more substituents from the group consisting of aryl groups and heteroaryl groups with 5 to 40 atomic nuclei. If there are multiple substituents, they may be the same or different from each other, and may be bonded to each other or condensed to form a ring.

[0037] Another example of the present invention provides a cured film comprising the above-described curable composition.

[0038] Another example of the present invention provides an image display device comprising the above-described cured film.

[0039] The effects of the invention

[0040] The curable composition of the present invention contains a crosslinkable antioxidant having an acrylic group. Therefore, by using the curable composition, not only can the film be protected against oxidation, but also wrinkles and particle formation can be prevented, and light stability can be improved.

[0041] On the other hand, the scope of the present invention is not limited by the effects described above. Attached Figure Description

[0042] Figure 1 The degree of crosslinking of the film manufactured from the curable composition of an example of the present invention was measured and confirmed using a Fourier transform infrared spectroscopy (FT-IR).

[0043] Figure 2 This is the result of confirming the structural stability of the film manufactured from the curable composition of an example of the present invention after storing it for one week. Detailed Implementation

[0044] The present invention will now be described in detail.

[0045] On the other hand, the various descriptions and embodiments disclosed in this application are also applicable to various 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 to be limited by the following specific description.

[0046] As a means of achieving the above-mentioned objectives, the present invention provides a curable composition comprising quantum dots, photopolymerizable monomers, and antioxidants.

[0047] The photopolymerizable monomer is one or more compounds represented by the following chemical formulas 1 and 2.

[0048] The antioxidant is one or more of the compounds represented by the following chemical formulas 3 and 4:

[0049] [Chemical Formula 1]

[0050]

[0051] [Chemical Formula 2]

[0052]

[0053] [Chemical Formula 3]

[0054]

[0055] [Chemical Formula 4]

[0056]

[0057] Of the above chemical formulas 1 to 4,

[0058] R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 They may be the same as or different from each other, and each is independently selected from hydrogen, hydroxyl, acrylate, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 It is a group composed of aryl groups and heteroaryl groups with 5 to 40 nuclei.

[0059] The R 302 To R 310 and R 402 To R 409 One or more of them are hydroxyl groups.

[0060] A1 and A2 may be the same as or different from each other, and each is independently C, O, S or N.

[0061] X is C1~C 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkane alkyl groups, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene groups or heteroarylene groups with 5 to 40 nuclei,

[0062] The Y is C1~C 40 Alkyl or C6~C 40 Aryl,

[0063] In the above chemical formula 2, m1 and m2 may be the same or different from each other, and each is an independent integer from 0 to 2.

[0064] In the above chemical formulas 1 and 2, n may be the same or different from each other, and each is an independent integer from 0 to 12.

[0065] The R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 Acrylic group, C1~C 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40aryl, heteroaryl with 5 to 40 nuclei, C1 to C1 of X 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkane alkyl groups, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene, heteroarylene with 5 to 40 nuclei, C1 to C1 of Y 40 Alkyl groups and C6~C 40 Each aryl group can be independently selected from halogen, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 cycloalkyl, C1~C 40 alkoxy groups, C6~C 60 aryloxy group, C6~C 60 The aryl group is replaced by one or more substituents from the group consisting of aryl groups and heteroaryl groups with 5 to 40 atomic nuclei. If there are multiple substituents, they may be the same or different from each other, and may be bonded to each other or condensed to form a ring.

[0066] As an example of the present invention, R in the above chemical formula 3... 302 To R 306 At least one of them can be (meth)acrylate group, R in the above chemical formula 4. 406 To R 409 At least one of them can be (meth)acrylate.

[0067] In this invention, "alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

[0068] In this invention, "alkenyl" refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples of such alkenyl groups include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0069] In this invention, "alkynyl" refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples of such alkynyl groups include ethynyl and 2-propynyl, but are not limited thereto.

[0070] In this invention, "aryl" refers to a monovalent substituent of an aromatic hydrocarbon having 6 to 60 carbon atoms, derived from a single ring or a combination of two or more rings. Furthermore, it may also include forms in which two or more rings are simply attached to each other or condensed together. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, anthracene, etc., but are not limited thereto.

[0071] In this 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 groups include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, etc., but are not limited thereto.

[0072] In this invention, "heteroaryl" refers to a monovalent substituent derived from a mono- or poly-heterocyclic aromatic hydrocarbon with 5 to 60 atomic nuclei. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted by heteroatoms such as N, O, S, or Se. Furthermore, it may include forms in which two or more rings are simply attached to or condensed together, and further may include forms condensed with an aryl group. Examples of such heteroaryl groups include: 6-membered monocyclic groups such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic groups such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isooxazolyl, 2-pyridinyl, and 2-pyrimidinyl, but are not limited thereto.

[0073] In this invention, "alkoxy" is a monovalent substituent represented by R'O-, where R' refers to an alkyl group having 1 to 40 carbon atoms. Such alkoxy groups can include linear, branched, or cyclic structures. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, pentoxy, etc., but are not limited thereto.

[0074] In this invention, "aryloxy group" is a monovalent substituent represented by RO-, where R refers to an aryl group having 6 to 60 carbon atoms. Examples of such aryloxy groups include phenoxy, naphthoxy, diphenoxy, etc., but are not limited thereto.

[0075] In this invention, "cycloalkane-based" refers to a divalent group formed from a cycloalkane having two substituents on one carbon atom. Specifically, it can be represented by the following structural formula.

[0076]

[0077] In this case, q determines the size of the ring and is an integer greater than or equal to 1. For example, if q is 2, a cyclobutyrate group can be formed. In various embodiments, the cycloalkane group can be a divalent C3-C... 40 Examples of such cycloalkylidene groups include cyclopropylidene, cyclobutidene, cyclopentidene, and cyclohexidene, but are not limited to these.

[0078] [Quantum dot]

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

[0080] The aforementioned nanostructure refers to a region or structure with a characteristic dimension that has a nanoscale size. The nanostructure can have any shape, such as nanowires, nanorods, nanotubes, multi-legged shapes with two or more legs, nanodots (or quantum dots), etc., without any particular limitation.

[0081] The electrical and / or optical properties of the quantum dots of the present invention can vary depending on their physical properties (e.g., composition, size, and / or shape). For example, quantum dots have a large surface area per unit volume, which can exhibit quantum confinement effects, and can exhibit different physical properties than bulky materials of the same composition.

[0082] In this invention, the type of quantum dot is not particularly limited, including all known or commercially available quantum dots.

[0083] As one embodiment of the present invention, the quantum dots can be selected from InP, CdSe, AgInGaS, ZnSeTe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZn The group consists of Te, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, ZnSeSTe, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof.

[0084] [Photopolymerizable monomers]

[0085] In this invention, the curable composition comprises one or more photopolymerizable monomers selected from the compounds represented by chemical formulas 1 and 2:

[0086] [Chemical Formula 1]

[0087]

[0088] [Chemical Formula 2]

[0089]

[0090] In the above chemical formulas 1 and 2,

[0091] R 101 R 102 and R 201 To R 203 They may be the same as or different from each other, and each is independently selected from hydrogen, hydroxyl, acrylate, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 It is a group composed of aryl groups and heteroaryl groups with 5 to 40 nuclei.

[0092] A1 and A2 may be the same as or different from each other, and each is independently C, O, S or N.

[0093] X is C1~C 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkane alkyl groups, C1~C 40 Oxidized alkenyl group, C6~C40 arylene groups or heteroarylene groups with 5 to 40 nuclei,

[0094] The Y is C1~C 40 Alkyl or C6~C 40 Aryl,

[0095] In the above chemical formula 2, m1 and m2 may be the same or different from each other, and each is an independent integer from 0 to 2.

[0096] In the above chemical formulas 1 and 2, n may be the same or different from each other, and each is an independent integer from 0 to 12.

[0097] The R 101 R 102 and R 201 To R 203 Acrylic group, C1~C 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 aryl, heteroaryl with 5 to 40 nuclei, C1 to C1 of X 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene, heteroarylene with 5 to 40 nuclei, C1 to C1 of Y 40 Alkyl groups and C6~C 40 Each aryl group can be independently selected from halogen, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 cycloalkyl, C1~C 40 alkoxy groups, C6~C 60 aryloxy group, C6~C 60 The aryl group is substituted with one or more substituents from the group consisting of aryl groups and heteroaryl groups with 5 to 40 nuclei. If there are multiple substituents, they may be the same or different from each other.

[0098] As an implementation example of the present invention, Y can be replaced by one of the following structural formulas.

[0099]

[0100] At this point, * indicates the location where it bonds with the Y bond.

[0101] Preferably, the photopolymerizable monomer comprises both the compound represented by chemical formula 1 and the compound represented by chemical formula 2.

[0102] The curable composition of the present invention is characterized by being solvent-free. To achieve this solvent-free composition, by using monomers such as compounds represented by the above-described chemical formulas 1 and / or 2, not only can quantum dots be dispersed excellently, but the problems of reduced sprayability and poor coating properties caused by the presence of solvents can also be improved.

[0103] As an example of the present invention, the compound represented by the above chemical formula 1 may contain two or more (meth)acrylate groups, and the compound represented by the above chemical formula 2 may contain one or more (meth)acrylate groups.

[0104] As an example of the present invention, the compound represented by compound 1 may contain a trifunctional (meth)acrylate group or a tetrafunctional (meth)acrylate group.

[0105] As an example of the present invention, the compound represented by the above chemical formula 1 can be selected from the group consisting of X-1 to X-26:

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] * indicates the part that is connected to the O in the above chemical formula 1.

[0112] As an example of the present invention, the compound represented by the above chemical formula 1 can be selected from the group consisting of A-1 to A-9 below:

[0113]

[0114] As an example of the present invention, the compound represented by the above chemical formula 2 is selected from the group consisting of B-1 to B-8:

[0115]

[0116] In this invention, relative to 100 parts by weight of the curable composition, the content of the compound represented by either Chemical Formula 1 or Chemical Formula 2 may be 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.

[0117] In this invention, the content of the compound represented by any of the above chemical formulas 1 and 2 may be less than 50 parts by weight, less than 40 parts by weight, less than 35 parts by weight, or less than 30 parts by weight, relative to 100 parts by weight of the total curable composition.

[0118] [Antioxidants]

[0119] Antioxidants contain one or more compounds represented by the following chemical formulas 3 and 4:

[0120] [Chemical Formula 3]

[0121]

[0122] [Chemical Formula 4]

[0123]

[0124] In the above chemical formulas 3 and 4,

[0125] R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 They may be the same as or different from each other, and each is independently selected from hydrogen, hydroxyl, acrylate, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 It is a group composed of aryl groups and heteroaryl groups with 5 to 40 nuclei.

[0126] The R 302 To R 310 and R 402 To R 409 One or more of them are hydroxyl groups.

[0127] The R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 Acrylic group, C1~C 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group and C6~C 40 The aryl group and heteroaryl groups with 5 to 40 nuclei can each be independently selected from halogens, cyano groups, nitro groups, C1 to C2 groups.40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 cycloalkyl, C6~C 60 The aryl group is substituted with one or more substituents from the group consisting of aryl groups and heteroaryl groups with 5 to 40 nuclei. If there are multiple substituents, they may be the same or different from each other.

[0128] As an example of the present invention, the compound represented by the above chemical formula 3 can be represented by the following structure.

[0129] or

[0130] Quantum dots exist as weakly bound organic ligands to surfaces composed of inorganic materials. Their surfaces are not protected by strong bonds such as covalent bonds, leading to decreased efficiency when forming thin films and applying them to light conversion devices. In particular, the heat generated during the heat treatment process in thin film manufacturing 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 degradation caused by oxygen, moisture, and free radicals. Therefore, it is necessary to improve their stability under heat and light exposure. Antioxidants can be added to the curing composition to address this.

[0131] Traditional antioxidants are simple additives, which are simple molecules that do not participate in cross-linking. Therefore, the degree of cross-linking will decrease depending on the amount added after exposure, and they also have the disadvantage of precipitation or particle formation with temperature changes.

[0132] In this invention, the compound represented by any of the above chemical formulas 3 and 4 serves as a crosslinkable antioxidant, possessing an acrylic group and participating in polymer crosslinking during exposure, thus preventing wrinkles and particle formation in the film and improving photostability. Furthermore, after forming an ink or film using a curable composition, the efficiency may decrease due to the oxidation of photopolymerizable monomers or quantum dots caused by oxygen, moisture, and free radicals penetrating into the interior; the crosslinkable antioxidant suppresses this phenomenon.

[0133] In this invention, the content of the antioxidant may be 0.1 parts by weight or more, 0.5 parts 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, relative to 100 parts by weight of the curable composition.

[0134] In this invention, the content of the antioxidant may be less than 20 parts by weight, less than 15 parts by weight, less than 10 parts by weight, less than 7 parts by weight, less than 5 parts by weight, or less than 3 parts by weight, relative to 100 parts by weight of the total curable composition.

[0135] When the antioxidant content is within the above range, it is advantageous in solving the problem of decreased luminescence efficiency. When the antioxidant content is below the above range, it is not possible to ensure the effect of suppressing the decrease in luminescence efficiency of quantum dots after the process; when the content is above the above range, thermosetting may be incomplete or the film may wrinkle.

[0136] [other]

[0137] In this invention, the curable composition may further comprise a photopolymerization initiator, a light scattering agent, or a combination thereof.

[0138] There are no particular limitations on the types of photopolymerization initiators mentioned above. For example, they may include triazine compounds, acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, oxime ester compounds, amino ketone compounds, phosphine or phosphine oxide compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, or combinations thereof.

[0139] Examples of the aforementioned triazine compounds include 2,4,6-trichloro-triazine, 2-phenyl-4,6-bis(trichloromethyl)-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine. 2-Biphenyl-4,6-bis(trichloromethyl)-triazine, bis(trichloromethyl)-6-styryl-triazine, 2-(naphthyl-1-yl)-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxynaphthyl-1-yl)-4,6-bis(trichloromethyl)-triazine, 2,4-bis(trichloromethyl)-6-piperyl-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-triazine, etc.

[0140] Examples of the aforementioned acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one.

[0141] Examples of the aforementioned benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0142] Examples of the aforementioned thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0143] Examples of the aforementioned benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin dimethyl ketal.

[0144] In the above composition, the content of the photopolymerization initiator can be appropriately adjusted considering the type and content of the photopolymerizable monomers used.

[0145] In one embodiment, based on 100% by weight of the total composition, the content of the photopolymerization initiator may be 0.01% by weight or more, 0.1% by weight or more, 0.5% by weight or more, or 1% by weight or more. Based on the total weight of the composition, the content of the photopolymerization initiator may be 10% by weight or less or 5% by weight or less, but is not limited thereto.

[0146] When the content of the photopolymerization initiator is within the above range, pattern formation is improved and the photoconversion curable composition is made more sensitive, thereby tending to improve the strength of the pixel portion formed by the composition or the smoothness of the pixel portion surface, which is therefore preferred.

[0147] There are no particular restrictions on the types of light scattering agents mentioned above; for example, they may include barium sulfate (BaSO4), calcium carbonate (CaCO3), titanium dioxide (TiO2), zirconium oxide (ZrO2), or combinations thereof.

[0148] The light scattering agent reflects light that is not absorbed by the quantum dots, allowing 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 improving the light conversion efficiency of the curable composition.

[0149] There are no particular limitations on the form in which the light scattering agent is used. For example, to improve the dispersion stability in a curable composition, a light scattering agent in the form of a dispersion in a solvent can be used.

[0150] The content of light scattering agent in the above composition can be adjusted as needed.

[0151] In one embodiment, based on 100% by weight of the total composition, the content of the light scattering agent may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, or 5% by weight or more. Based on the total weight of the composition, the content of the light scattering agent may be 10% by weight or less, or 5% by weight or less, but is not limited thereto.

[0152] When the content of the light scattering agent is within the above-mentioned range, it is expected that the light conversion efficiency will be improved by using the light scattering agent, and the pattern characteristics will also become excellent.

[0153] In this invention, the curable composition may further comprise one or more selected from the group consisting of adhesive resins and solvents.

[0154] The adhesive resin may comprise acrylic adhesive resin, Cardo adhesive resin, or a combination thereof.

[0155] Specific examples of the acrylic adhesive resins mentioned above 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, etc., but are not limited thereto, and they can be used alone or in combination of two or more.

[0156] In this invention, the solvent may comprise propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, propylene carbonate, γ-butyrolactone, acetone, or combinations thereof.

[0157] As another way to achieve the above objectives, the present invention provides a cured film comprising the above-described curable composition and an image display device comprising the cured film.

[0158] The present invention will now be described in more detail through the following embodiments. However, these embodiments are merely illustrative examples, and the scope of the present invention is not limited to these embodiments.

[0159] [Quantum dot]

[0160] 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 a green QD based on the InP core, with a size of 535 nm and a full width at half maximum (FWHM) of 34 nm to 40 nm. QD-2 is a green QD based on the Ag / In / Ga / S core, with a size of 530 nm and a FWHM of 30 nm to 35 nm. QD-1 and QD-2 were dispersed in toluene at a concentration of 30% by weight, respectively, for preparation.

[0161] [Examples 1 and 2]

[0162] The prepared QD-1 quantum dots were treated with monomers 1,6-hexanediol diacrylate (HDDA, denoted as MN-1, Sigma-Aldrich) and benzyl acrylate (BZA, denoted as MN-2, Sigma-Aldrich), and CROX-1 (product number ZIKANOX-395, SONGWON) was added at 2% by weight (Example 1) or 4% by weight (Example 2) as an antioxidant. A photopolymerization initiator (denoted as PI-1) TPO (TCI), light scattering particles (denoted as SP-1) TiO2 (dispersed in HDDA), BYK-111 dispersant, and ink composition dispersion stabilizer BYK-2013 as an additive were mixed according to the weight percentages in Table 1 to prepare a curable composition. The structures of CROX-1, TPO, HDDA, and BZA used are as follows.

[0163]

[0164] [Table 1]

[0165]

[0166] [Examples 3 and 4]

[0167] The curable composition was prepared by using 2% by weight (Example 3) or 4% by weight (Example 4) of CROX-2 (product number ZIKANOX-549DF, Matsubara Corporation) as an antioxidant, otherwise by the same process as in Examples 1 and 2.

[0168] The structure of the CROX-2 used is as follows.

[0169]

[0170] [Examples 5 and 6]

[0171] The curable composition was manufactured by applying QD-2 quantum dots and using CROX-1 (product number ZIKANOX-395, Matsubara Corporation) at 2% by weight (Example 5) or 4% by weight (Example 6) as an antioxidant, except that the curable composition was manufactured by the same process as in Examples 1 and 2.

[0172] [Examples 7 and 8]

[0173] The curable composition was prepared by using 2% by weight (Example 7) or 4% by weight (Example 8) of CROX-2 (product number ZIKANOX-549DF, Matsubara Corporation) as an antioxidant, otherwise by the same process as in Examples 5 and 6.

[0174] [Comparative Example 1]

[0175] The curable composition was manufactured using only HDDA as the monomer and without any antioxidants, except that the process was the same as in Example 1.

[0176] [Comparative Example 2]

[0177] The curable composition was manufactured using only HDDA as the monomer and without any antioxidants, except through the same process as in Example 5.

[0178] [Comparative Example 3]

[0179] The curable composition was manufactured using only HDDA as the monomer and 4% by weight of OX-1 (product number P0932, TCI) as an antioxidant, except that the curable composition was manufactured using the same process as in Example 1.

[0180] The structure of the OX-1 used is as follows.

[0181]

[0182] [Comparative Example 4]

[0183] The curable composition was manufactured using only HDDA as the monomer and 4% by weight of OX-1 (product number P0932, TCI) as an antioxidant, except that the curable composition was manufactured using the same process as in Example 5.

[0184] [Experimental Example]

[0185] A light conversion coating was manufactured using the light conversion curable compositions prepared according to Examples 1 to 8 and Comparative Examples 1 to 4. The film thickness, transmittance, color conversion efficiency (PCE), maximum emission wavelength, full width at half maximum (FWHM), and viscosity were measured by the method described below, and the results are shown in Tables 2 and 3 below.

[0186] Film thickness was measured using a step measurement instrument (BRUKER, Dektak XT). 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). Viscosity was measured using a Brookfield Ametek DV2T viscometer. The film's state (agglomeration, roughness) was observed using an electron microscope. TiO2 particle size was measured using an Otsuka Electronics ELSZ-2000.

[0187] Thin films were prepared using the SPIN3000D spin-coated curable composition from MIDAS SYSTEM and cured using an exposure machine (Jueun UV Tech, SLC-1000AF-D). The degree of curing (crosslinking) of the films was then measured using an ALPHA ± (Bruker) instrument.

[0188] In addition, after placing the light conversion coating made from the light conversion curable composition according to Examples 1 to 8 and Comparative Examples 1 to 4 under a 100 lx yellow lamp for 48 hours, the light intensity and wavelength were measured using an IS-ST100 (Ocean Insight Corporation) to confirm the rate of reduction in light conversion efficiency.

[0189] [Table 2]

[0190]

[0191] [Table 3]

[0192]

[0193] As shown in Tables 2 and 3 above, the light conversion curable compositions of Examples 1 to 8 of the present invention with the application of crosslinkable antioxidant additives showed that the PCE efficiency reduction phenomenon was improved after 48 hours compared with Comparative Examples 1 to 2.

[0194] Furthermore, FT-IR measurements confirmed that when the film was manufactured with the composition of Example 6, compared to Comparative Example 4, which used a simple additive (OX-1) that did not participate in crosslinking, the degree of crosslinking of the film was improved, resulting in a more robust film. Figure 1 It was confirmed that although the photostability of Comparative Example 4 was improved compared to Comparative Example 2 due to the introduction of an antioxidant, the degree of crosslinking was actually reduced due to the introduction of a bulky antioxidant that reduces the degree of crosslinking.

[0195] Conventional antioxidants have large molecular weights and large volumes. Therefore, increasing their content for antioxidant purposes reduces the degree of monomer crosslinking, making it difficult to form a robust film. However, when using an antioxidant with acrylic groups as shown in the embodiments of the present invention, such as... Figure 1 As shown, it can be confirmed that there are relatively few uncured monomers.

[0196] This is achieved by including an acrylic-based antioxidant in the curable composition, which not only provides antioxidant effects after the formation of the solvent-free ink composition but also after the formation of the film. At the same time, it crosslinks with the monomer during exposure to form a polymer, thereby achieving quantum dot surface stability and film planarization, and improving the degree of crosslinking.

[0197] Based on these results, when the compositions of Example 8 and Comparative Example 4 were stored at a low temperature (10°C) for one week before being formed into films, it was confirmed that particles were visible during the formation of the film in Comparative Example 4, while the composition of Example 8 could be formed into an excellent particle-free film. Figure 2 ).

[0198] In particular, the color conversion efficiency (PCE) of the photoconversion curable compositions of Examples 5 to 8 using QD-2 was confirmed to be above 35%, which is excellent, and the viscosity was below 20 cP, making them suitable as photoconversion curable compositions for use in color filters and image display devices with ink ejection methods. Furthermore, the emission wavelength was confirmed to be 530 nm to 540 nm, and the full width at half maximum (FWHM) was 30 nm to 32 nm, exhibiting excellent color purity.

[0199] Ultimately, this invention stably achieves low-viscosity, solvent-free, and high-efficiency thin films. While improving thermal process stability, it also simultaneously improves the surface uniformity of the coating, thereby significantly enhancing stability. When forming thin films using quantum dots, the efficiency after initial exposure should be identical to that after heat treatment, and the efficiency change after being exposed to air for a certain period should also be minimal to be considered a preferred result.

[0200] Those skilled in the art will understand from the foregoing description that the invention can be implemented in other specific ways without altering its technical concept or essential features. Accordingly, the embodiments described above should be understood to be exemplary in all respects and not limiting. The scope of the invention should be defined by the following claims, not by the foregoing detailed description, and all modifications or variations derived from the meaning, scope, and equivalents of the claims should be interpreted as falling within the scope of the invention.

Claims

1. A curable composition comprising quantum dots, a photopolymerizable monomer, and an antioxidant. The photopolymerizable monomer comprises one or more compounds represented by the following chemical formulas 1 and 2. The antioxidant comprises one or more compounds represented by the following chemical formulas 3 and 4: Chemical Formula 1 Chemical formula 2 Chemical formula 3 Chemical Formula 4 Of the above chemical formulas 1 to 4, R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 They may be the same as or different from each other, and each is independently selected from hydrogen, hydroxyl, acrylate, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 It is a group composed of aryl groups and heteroaryl groups with 5 to 40 nuclei. The R 302 To R 310 and R 402 To R 409 One or more of them are hydroxyl groups. The A's may be the same as or different from each other, and each is independently C, O, S, or N. X is C1~C 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkyl ide groups, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene or heteroarylene with 5 to 40 nuclei The Y is C1~C 40 Alkyl or C6~C 40 Aryl, In the above chemical formula 2, m1 and m2 may be the same or different from each other, and each is an independent integer from 0 to 2. In the above chemical formulas 1 and 2, n may be the same or different from each other, and each is an independent integer from 0 to 12. The R 101 R 102 R 201 To R 203 R 301 To R 311 and R 401 To R 411 Acrylic group, C1~C 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C6~C 40 aryl, heteroaryl with 5 to 40 nuclei, C1 to C1 of X 40 Alkylene, C1~C 40 Cycloalkylene, C1~C 40 cycloalkyl ide groups, C1~C 40 Oxidized alkenyl group, C6~C 40 arylene, heteroarylene with 5 to 40 nuclei, C1 to C1 of Y 40 Alkyl groups and C6~C 40 Each aryl group can be independently selected from halogen, cyano, nitro, C1~C. 40 Alkyl groups, C2~C 40 alkenyl, C2~C 40 alkynyl group, C3~C 40 cycloalkyl, C1~C 40 alkoxy groups, C6~C 60 aryloxy group, C6~C 60 The aryl group is substituted with one or more substituents from the group consisting of aryl groups and heteroaryl groups with 5 to 40 nuclei. If there are multiple substituents, they may be the same or different from each other, and may be bonded to or condensed with each other to form a ring.

2. The curable composition according to claim 1, wherein, The R 302 To R 306 and R 406 To R 409 One or more of them are (meth)acrylate groups.

3. The curable composition according to claim 1, wherein, X in the above chemical formula 1 is selected from the group consisting of X-1 to X-26 below: 。 4. The curable composition according to claim 1, wherein, The compound represented by the above chemical formula 1 is selected from the group consisting of A-1 to A-9 below: 。 5. The curable composition according to claim 1, wherein, The compound represented by the above chemical formula 2 is selected from the group consisting of B-1 to B-8 below: 。 6. The curable composition according to claim 1, wherein, The antioxidant content is 0.1 to 5 parts by weight relative to 100 parts by weight of the total curable composition.

7. The curable composition according to claim 1, wherein, The curable composition further comprises a photopolymerization initiator, a light scattering agent, or a combination thereof.

8. The curable composition according to claim 1, wherein, The curable composition further comprises one or more of an adhesive resin and a solvent.

9. The curable composition according to claim 8, wherein, The adhesive resin comprises acrylic adhesive resin, calorie adhesive resin, or a combination thereof.

10. The curable composition according to claim 8, wherein, The solvent comprises propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, propylene carbonate, γ-butyrolactone, acetone, or combinations thereof.

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

12. An image display device comprising the cured film of claim 11.

Images