Hardening components

Abstract

The objective is to provide a curable composition comprising semiconductor particles and a polyfunctional polymerizable compound, which exhibits good optical properties. [Solution] The present invention relates to a curable composition comprising semiconductor particles (A) and a polymerizable compound (B), wherein the polymerizable compound (B) comprises a polymerizable compound (B-1) having at least one functional group that exhibits coordination ability to the semiconductor particles (A), and a polymerizable compound (B-2) which is a polyfunctional (meth)acrylate that does not contain a functional group that exhibits coordination ability to the semiconductor particles (A), and the content of the semiconductor particles (A) in 100% by mass of the curable composition is 32% by mass or more.

Description

Technical Field

[0001] The present invention relates to a curable composition containing semiconductor particles and a polymerizable compound.

Background Art

[0002] Patent Document 1 discloses a curable composition containing semiconductor particles and a polyfunctional polymerizable compound.

Prior Art Document

Patent Document

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the curable composition containing semiconductor particles and a polyfunctional polymerizable compound disclosed in Patent Document 1, the optical properties may not be sufficient.

[0005] Therefore, an object of the present invention is to provide a curable composition containing semiconductor particles and a polyfunctional polymerizable compound, which has good optical properties.

Means for Solving the Problems

[0006] The present invention that has achieved the above problems is as follows. [1] A curable composition containing semiconductor particles (A) and a polymerizable compound (B), where the polymerizable compound (B) includes a polymerizable compound (B-1) containing at least one functional group capable of coordinating to the semiconductor particles (A), and a polymerizable compound (B-2) which is a polyfunctional (meth)acrylate that does not contain a functional group capable of coordinating to the semiconductor particles (A), and the content of the semiconductor particles (A) in 100% by mass of the curable composition is 32% by mass or more. [2] The curable composition according to [1], wherein the weight average molecular weight of the polymerizable compound (B-2) is 180 or more. [3] The curable composition according to [1] or [2], wherein the polymerizable compound (B-1) is a (meth)acrylate compound. [4] The polymerizable compound (B-1) is represented by the following formula (d): (X-R 1 -) n -R 2 …(d) In formula (d), X is a (meth)acryloyl group, R 1 is a divalent group, R 2 is an n-valent group, n is an integer of 1 or more, and when n is 2 or more, a plurality of X-R 1 - may be the same or different from each other. The curable composition according to [3], wherein the dipole moment of (HR 1 -) n -R 2 obtained by substituting X with a hydrogen atom (H) is 0.5 D to 2.0 D. [5] The curable composition according to any one of [1] to [4], wherein the semiconductor particles (A) are InP-based materials. [6] The curable composition according to any one of [1] to [5], wherein the functional group showing the coordination ability of the polymerizable compound (B-1) is at least one selected from a carboxy group, an amino group which may have a substituent, and a thiol group. [7] Further, the curable composition according to any one of [1] to [6], which contains a solvent (F), and the content of the solvent (F) in 100% by mass of the curable composition is 0.5 to 10% by mass. [8] The curable composition according to any one of [1] to [7], which is an ink for an inkjet printer. [Advantages of the Invention]

[0007] According to the present invention, the optical properties of the curable composition can be improved. [Embodiments for Carrying out the Invention]

[0008] The curable composition of the present invention comprises semiconductor particles (A) and predetermined polymerizable compounds (B-1) and (B-2) as polymerizable compounds (B), and may further optionally contain at least one selected from the group consisting of polymerization initiators (C), polymerization initiator aids (C1), antioxidants (D), light scattering agents (E), solvents (F), and leveling agents (H).

[0009] In this specification, unless otherwise specified, the compounds exemplified as components may be used individually or in combination of two or more. Furthermore, when using multiple types of components, unless otherwise specified, the content should be adjusted by the total amount of all components used.

[0010] <Semiconductor particles (A)> The semiconductor particle (A) is preferably a light-emitting inorganic semiconductor particle that absorbs primary light and emits light of a different wavelength than the primary light, and it is preferable that the light-emitting inorganic semiconductor particle converts the wavelength of blue light, which is the primary light, to the wavelength of light of a different color. The semiconductor particle (A) preferably emits green or red light, and it is more preferable that it absorbs blue light and emits green or red light.

[0011] In this specification, "blue" refers to all light that is perceived as blue (all light with intensity in the blue wavelength range, e.g., 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light that is perceived as green (all light with intensity in the green wavelength range, e.g., 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to all light that is perceived as red (all light with intensity in the red wavelength range, e.g., 585 nm to 780 nm), and is not limited to light of a single wavelength.

[0012] The emission spectrum of the green-emitting semiconductor particle (A) preferably includes a peak with a maximum value in the wavelength range of 500 nm to 560 nm, more preferably a peak with a maximum value in the wavelength range of 510 nm to 550 nm, and even more preferably a peak with a maximum value in the wavelength range of 520 nm to 540 nm. This expands the displayable color gamut of the green light of the display device. The peak preferably has a full width at half maximum of 15 nm to 80 nm, more preferably 15 nm to 60 nm, even more preferably 15 nm to 50 nm, and even more preferably 15 nm to 45 nm. This expands the displayable color gamut of the green light of the display device.

[0013] The emission spectrum of the red-emitting semiconductor particle (A) preferably includes a peak with a maximum value in the wavelength range of 590 nm to 750 nm, more preferably a peak with a maximum value in the wavelength range of 610 nm to 700 nm, and even more preferably a peak with a maximum value in the wavelength range of 615 nm to 650 nm. This expands the displayable color gamut of the red light of the display device. The peak preferably has a full width at half maximum of 15 nm to 80 nm, more preferably 15 nm to 60 nm, even more preferably 15 nm to 50 nm, and even more preferably 15 nm to 45 nm. This expands the displayable color gamut of the red light of the display device.

[0014] Examples of semiconductor particles (A) include quantum dots and particles composed of compounds having a perovskite crystal structure (hereinafter also referred to as "perovskite compounds"), with quantum dots being preferred from the viewpoint of durability. Quantum dots are luminescent semiconductor nanoparticles with a particle diameter of 1 nm to 100 nm (preferably 1 nm to 50 nm, more preferably 1 nm to 30 nm), which utilize the band gap of the semiconductor to absorb ultraviolet light or visible light (e.g., blue light) and emit light. The particle diameter that best exhibits the effects of the present invention is 1 nm to 20 nm, preferably 3 nm to 17 nm, and more preferably 7 nm to 15 nm. If the particle diameter becomes too large, the luminescence efficiency when the semiconductor particles are concentrated tends to decrease, so particle diameters within the above range are preferable as they more clearly exhibit the effects of the present invention.

[0015] Examples of quantum dots include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZn Examples include compounds of group 12 elements and group 16 elements such as SeTe and HgZnSTe; compounds of group 13 elements and group 15 elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs; and compounds of group 14 elements and group 16 elements such as PdS and PbSe.

[0016] If the quantum dots contain sulfur (S) or senium (Se), quantum dots that have been surface-modified with metal oxides or organic materials may be used. Using surface-modified quantum dots prevents the extraction of S or Se by reactive components contained in or potentially contained in the curable composition. Furthermore, the quantum dots may form a core-shell structure by combining the above-mentioned compounds. Examples of such combinations include nanoparticles in which the core is CdSe and the shell is ZnS, and nanoparticles in which the core is InP and the shell is ZnSeS. The semiconductor particle (A) is preferably a quantum dot, preferably an InP-based material, and preferably has an InP core and a ZnSeS shell.

[0017] Since the energy state of a quantum dot depends on its size, the emission wavelength can be freely selected by changing the particle size. Furthermore, because the light emitted from quantum dots has a narrow spectral width, it is advantageous for widening the color gamut of display devices. In addition, quantum dots have high responsiveness, which is advantageous in terms of primary light utilization efficiency.

[0018] The curable composition may contain two or more types of semiconductor particles (A). For example, the curable composition may contain only one type of semiconductor particle (A) that absorbs primary light and emits green light, or it may contain two or more types in combination. Similarly, the curable composition may contain only one type of semiconductor particle (A) that absorbs primary light and emits red light, or it may contain two or more types in combination.

[0019] The semiconductor particle (A) may be a ligand-containing semiconductor particle that includes an organic ligand (G) that coordinates to the semiconductor particle. In this case, the content of the semiconductor particle (A) containing the organic ligand (G) should be within the range of the present invention, including a preferred range. The organic ligand (G) is, for example, an organic compound having a polar group that exhibits coordinating ability to semiconductor particles. The organic ligand (G) can coordinate to the surface of the semiconductor particle. The organic ligand (G) usually coordinates to the semiconductor particle via its polar group. Preferably, at least some of the molecules of the organic ligand (G) are coordinated to the semiconductor particle, and all or almost all of the molecules may be coordinated to the semiconductor particle. The semiconductor particle (A) may contain one or more organic ligands (G). When the semiconductor particle (A) contains an organic ligand (G), the stability and dispersibility of the semiconductor particle (A), as well as the luminescence intensity of the curable composition and cured film, can be improved. The coordination of the organic ligand (G) to the semiconductor particles can be confirmed by the uniform dispersion of the semiconductor particles (A) in a dispersion medium suitable for the organic ligand.

[0020] The polar group of the organic ligand (G) is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2), and more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group. Having these polar groups improves the coordination to semiconductor particles, improving the stability and dispersibility of semiconductor particles (A) in the curable composition, and improving the luminescence intensity of the curable composition and cured film. The organic ligand (G) may have one or more polar groups.

[0021] The organic ligand (G) is given by the following formula (x): X A -R X (x) Examples of organic compounds are given by the formula, where X A The above polar group is R XThis is a monovalent hydrocarbon group which may contain heteroatoms (such as N, O, S, halogen atoms, etc.). This hydrocarbon group may have one or more unsaturated bonds, such as carbon-carbon double bonds. This hydrocarbon group may have a linear, branched, or cyclic structure. The number of carbon atoms in this hydrocarbon group is, for example, 1 to 40, or 1 to 30. The methylene group contained in this hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0022] R X This may include polar groups as exemplified above.

[0023] X A Specific examples of organic ligands having a carboxyl group include formic acid, acetic acid, propionic acid, as well as saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, alpha-linolenic acid, gamma-linolenic acid, stearic acid, dihomo-gamma-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenaline (docosatetraenoic acid).

[0024] X A Specific examples of organic ligands having a thiol group or an amino group include the example X shown above. A Examples include organic ligands in which the carboxyl group of an organic ligand having a carboxyl group is replaced with a thiol group or an amino group.

[0025] In addition to the above, examples of organic ligands represented by formula (x) include compound (G-1) and compound (G-2).

[0026] [Compound (G-1)] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). The semiconductor particle (A) may contain only one type of compound (G-1) or two or more types.

[0027] Examples of compound (G-1) include the compound represented by the following formula (G-1a). Compound (G-1) may also be the acid anhydride of the compound represented by formula (G-1a).

[0028] [ka] [In formula (G-1a), R B R represents a divalent hydrocarbon group. B If present, they may be the same or different. The hydrocarbon group may have one or more substituents. If there are multiple substituents, they may be the same or different, and they may be bonded to each other to form a ring with the atom to which each substituent is bonded. The alkylene group contained in the hydrocarbon group may be interrupted by at least one of -O-, -S-, -SO2-, -CO-, and -NH-. p represents an integer between 1 and 10.

[0029] R B Examples of divalent hydrocarbon groups represented by this symbol include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups that combine these.

[0030] Examples of linear hydrocarbon groups include linear or branched alkanediyl groups, which typically have 1 to 50 carbon atoms, preferably 1 to 20, and more preferably 1 to 10. Examples of alicyclic hydrocarbon groups include monocyclic or polycyclic cycloalkanediyl groups, which typically have 3 to 50 carbon atoms, preferably 3 to 20, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include monocyclic or polycyclic arenediyl groups, which typically have 6 to 20 carbon atoms.

[0031] Examples of substituents that the hydrocarbon group may have include C1-C50 alkyl groups, C3-C50 cycloalkyl groups, C6-C20 aryl groups, carboxyl groups, amino groups, halogen atoms, etc., with carboxyl groups, amino groups, or halogen atoms being preferred.

[0032] The divalent group to which the alkylene group contained in the hydrocarbon group is substituted is preferably at least one of -O-, -CO-, and -NH-, more preferably at least one of -CO- and -NH-, and even more preferably -NH-. p is preferably 1 or 2.

[0033] Examples of compounds represented by formula (G-1a) include those represented by the following formulas (1-1) to (1-9).

[0034] [ka]

[0035] Examples of compounds represented by formula (G-1a) include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionic acid, and 3-mercapto-2-methylpropionic acid. Among these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0036] Another example of compound (G-1) is a polycarboxylic acid compound, preferably compound (G-1b) in which -SH in formula (G-1a) is substituted with a carboxyl group (-COOH).

[0037] Examples of compounds (G-1b) include succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanediic acid, tetradecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, dodecafluorosveric acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenodioic acid, sebacic acid, hexadecafluorosebacic acid, acetylenedicarboxylic acid, trans-aconitic acid, 1,3-adamantanedicarboxylic acid, bicyclo[2.2.2]octane-1,4- Dicarboxylic acids, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, cis- or trans-1,3-cyclohexanedicarboxylic acid, cis- or trans-1,4-cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, 3-fluorophthalic acid, isophthalic acid, Tetrafluoroisophthalic acid, terephthalic acid, tetrafluoroterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,1'-ferrocenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-franzicarboxylic acid, benzophenone-2,4'-dicarboxylic acid monohydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid Rubonic acid, 3,5-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbendicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorendic acid, 1H-imidazole-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,Examples include 10-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiglycolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutanoic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidenediphenoxyacetic acid, 1,3-acetonedicarboxylic acid, methylenedisalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl)isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid, 1,3,5-benzenetricarboxylic acid, etc.

[0038] The molecular weight of compound (G-1) is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, even more preferably 1000 or less, even more preferably 800 or less, and even more preferably 500 or less. The molecular weight of compound (G-1) is usually 100 or more.

[0039] The above molecular weight may be either a number-average molecular weight or a weight-average molecular weight. The number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight, respectively, measured on a standard polystyrene basis by gel permeation chromatography (GPC).

[0040] The content ratio of compound (G-1) to semiconductor particle (A) is preferably 0.001 or more and 1 or less by mass ratio, more preferably 0.01 or more and 0.5 or less, and even more preferably 0.02 or more and 0.45 or less.

[0041] When the semiconductor particles (A) contain compound (G-1), the content of compound (G-1) in the curable composition is preferably 0.1% to 20% by mass, more preferably 0.2% to 20% by mass, even more preferably 0.2% to 10% by mass, even more preferably 0.5% to 10% by mass, and even more preferably 0.5% to 8% by mass, relative to the total amount of solids in the curable composition.

[0042] In this specification, the total amount of solids in a curable composition means the sum of the components contained in the curable composition, excluding the solvent (F). The content of each component in the solids of a curable composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content of each component in the solids of a curable composition may be calculated from the formulation at the time of preparation of the curable composition.

[0043] [Compound (G-2)] Compound (G-2) is a compound different from compound (G-1), containing a polyalkylene glycol structure and having polar groups at its molecular ends. Preferably, the molecular ends are those of the longest carbon chain in compound (G-2) (the carbon atoms in the carbon chain may be replaced by other atoms such as oxygen atoms). The semiconductor particle (A) may contain only one compound (G-2) or two or more compounds. The semiconductor particle (A) may contain compound (G-1) or compound (G-2), or may contain compound (G-1) and compound (G-2). Compounds containing a polyalkylene glycol structure and having the above-mentioned first and second functional groups shall be classified as compound (G-1).

[0044] The structure of polyalkylene glycol is as follows:

[0045] [ka] This refers to a structure represented by the formula. In the formula, n is an integer greater than or equal to 2, and RC This refers to an alkylene group, such as an ethylene group or a propylene group.

[0046] Examples of compound (G-2) include polyalkylene glycol compounds represented by the following formula (G-2a).

[0047] [ka]

[0048] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z C is a divalent or trivalent base, n is an integer greater than or equal to 2, m is 1 or 2, and R C This is an alkylene group.

[0049] X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2), and more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group.

[0050] Y is a monovalent group. Examples of group Y include monovalent hydrocarbon groups that may have substituents (N, O, S, halogen atoms, etc.). The alkylene group contained in the hydrocarbon group may be interrupted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the hydrocarbon group is between 1 and 12. The hydrocarbon group may have unsaturated bonds.

[0051] Examples of Y include alkyl groups having 1 to 12 carbon atoms and having a linear, branched, or cyclic structure; alkoxy groups having 1 to 12 carbon atoms and having a linear, branched, or cyclic structure. The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The alkylene groups contained in the alkyl and alkoxy groups may be interrupted by -O- and -S-. Y is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and more preferably a linear alkoxy group having 1 to 4 carbon atoms.

[0052] Y may contain a polar group. The polar group may be at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2). The polar group is preferably located at the terminal end of group Y.

[0053] Z C It is a divalent or trivalent group. Group Z C Examples include divalent or trivalent hydrocarbon groups that may contain heteroatoms (such as N, O, S, or halogen atoms). The hydrocarbon group preferably has 1 to 24 carbon atoms. The hydrocarbon group may have unsaturated bonds.

[0054] divalent Z C Examples include alkylene groups having 1 to 24 carbon atoms and having a linear, branched, or cyclic structure; and alkenylene groups having 1 to 24 carbon atoms and having a linear, branched, or cyclic structure. The number of carbon atoms in the alkylene group and alkenylene group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The alkylene groups contained in the alkylene group and alkenylene group may be interrupted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Trivalent group Z C As for the divalent group Z mentioned above, C We can give an example of a group obtained by removing one hydrogen atom from the same group.

[0055] Z C The group Z may have a branched structure. C In a branch chain separate from the branch chain containing the polyalkylene glycol structure shown in formula (G-2a) above, the branch chain may have a polyalkylene glycol structure separate from the polyalkylene glycol structure shown in formula (G-2a) above.

[0056] Z C Preferably, it is a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

[0057] R C The molecule is an alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

[0058] In formula (G-2a), n is an integer greater than or equal to 2, preferably between 2 and 540, more preferably between 2 and 120, and even more preferably between 2 and 60.

[0059] The molecular weight of compound (G-2) is preferably 150 to 10,000, more preferably 150 to 5,000, and even more preferably 150 to 4,000. Within this range, the stability and dispersibility of the semiconductor particles (A), as well as the luminescence intensity of the curable composition and cured film, can be improved. The molecular weight may be either a number-average molecular weight or a weight-average molecular weight. The number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight on a standard polystyrene basis, measured by GPC, respectively.

[0060] When the semiconductor particles (A) contain compound (G-2), the content ratio of compound (G-2) to semiconductor particles in the curable composition is preferably 0.001 to 2 by mass, more preferably 0.01 to 1.5, and even more preferably 0.1 to 1. When the content ratio is within this range, the stability and dispersibility of the semiconductor particles (A), as well as the luminescence intensity of the curable composition and cured film, can be improved.

[0061] When the semiconductor particles (A) contain compound (G-2), the content of compound (G-2) in the curable composition is preferably 0.1% to 40% by mass, more preferably 0.1% to 20% by mass, even more preferably 1% to 15% by mass, and even more preferably 2% to 12% by mass, relative to the total amount of solids in the curable composition. Within this range, the stability and dispersibility of the semiconductor particles (A), as well as the luminescence intensity of the curable composition and cured film, can be improved.

[0062] When semiconductor particles (A) contain organic ligands (G), the ratio of the content of organic ligands (G) to semiconductor particles in the curable composition is preferably 0.001 to 1 by mass, more preferably 0.01 to 0.8, and even more preferably 0.02 to 0.5. When this content ratio is within this range, the stability and dispersibility of the semiconductor particles (A), as well as the luminescence intensity of the curable composition and cured film, can be improved. The content of organic ligands (G) refers to the total content of all organic ligands contained in the curable composition.

[0063] The semiconductor particles (A) make up 32% by mass or more of 100% by mass of the curable composition, preferably 33-60% by mass, more preferably 35-55% by mass, and even more preferably 38-50% by mass. In this invention, the polymerizable compound (B-2), which is a polyfunctional acrylate that does not contain functional groups that exhibit coordination ability to the semiconductor particles (A), is also included, along with a polymerizable compound (B-1) that contains at least one functional group that exhibits coordination ability to the semiconductor particles (A), even when the semiconductor particles (A) are present at such a high concentration. Therefore, the optical properties of the curable composition can be improved. Furthermore, the effect of good film-forming properties when the curable composition is applied can also be obtained.

[0064] <Polymerizable compound (B)> Polymerizable compound (B) is a compound that can be polymerized by active radicals, acids, etc., generated from a polymerization initiator (C) described later. Polymerizable compound (B) includes polymerizable compound (B-1) which contains at least one functional group that exhibits coordination ability to the semiconductor particles (A), and polymerizable compound (B-2) which is a polyfunctional (meth)acrylate that does not contain a functional group that exhibits coordination ability to the semiconductor particles (A).

[0065] The functional group exhibiting the above-mentioned coordinating ability is preferably at least one selected from a carboxyl group, an optionally substituted amino group, and a thiol group. The substituents that the amino group may have include alkyl groups, cycloalkyl groups, and aryl groups, with alkyl groups being preferred, and methyl or ethyl groups being more preferred. When the amino group has substituents, the number of substituents is 1 or 2, preferably 2, and more preferably a dialkylamino group. In other words, the polymerizable compound (B-1) is preferably a polymerizable compound containing at least one selected from a carboxyl group, an optionally substituted amino group, and a thiol group; more preferably a polymerizable compound containing at least one carboxyl group and an optionally substituted amino group (a dialkylamino group is preferred, and a dimethylamino group or diethylamino group is more preferred); and even more preferably a polymerizable compound containing at least one carboxyl group from the viewpoint of film formation.

[0066] Furthermore, it is preferable that the polymerizable compound (B-2) is a polyfunctional (meth)acrylate that does not contain carboxyl groups, amino groups, substituted amino groups, or thiol groups.

[0067] Examples of polymerizable compounds (B) include photopolymerizable compounds that harden upon irradiation with light, and thermopolymerizable compounds that harden upon heat, with photopolymerizable compounds being preferred. The weight-average molecular weight of the photopolymerizable compound is, for example, 100 to 3000, preferably 150 to 2000, and more preferably 180 to 1500. In particular, it is preferable that the weight-average molecular weight of the polymerizable compound (B-2) satisfies the above range. When the weight-average molecular weight of the polymerizable compound (B-2) falls within this range, the fluidity of the coating solution improves, and the film-forming properties become good.

[0068] Examples of photopolymerizable compounds include photoradical polymerizable compounds that harden by radical polymerization reactions upon irradiation with light, and photocationic polymerizable compounds that harden by cationic polymerization reactions upon irradiation with light. Specifically, as photocationic polymerizable compounds, oxetane compounds, epoxy compounds, and vinyl ether compounds described in Japanese Patent Application Publication No. 2024-61630 can be used. The photopolymerizable compound is preferably a photoradical polymerizable compound.

[0069] Examples of photoradical polymerizable compounds include compounds having polymerizable ethylenically unsaturated bonds, and are preferably (meth)acrylate compounds. Examples of (meth)acrylate compounds include monofunctional (meth)acrylate compounds having one (meth)acryloyloxy group in the molecule, difunctional (meth)acrylate compounds having two (meth)acryloyloxy groups in the molecule, and trifunctional or higher (meth)acrylate compounds having three or more (meth)acryloyloxy groups in the molecule. Note that "(meth)acrylate" means acrylate and / or methacrylate. The same applies to "(meth)acryloyl," "(meth)acrylic acid," etc.

[0070] Examples of monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), hexadecyl (meth)acrylate, octa Decyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl Examples include hydroxyhydroxyphthalic acid, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, ethyl carbitol (meth)acrylate (ethoxyethoxyethyl (meth)acrylate), 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.

[0071] Examples of difunctional (meth)acrylate compounds include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, and eth Di(meth)acrylates of aliphatic hydrocarbon compounds with 2 to 20 carbon atoms having two or more hydroxyl groups, such as ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol (4 mg per mole) Di(meth)acrylates obtained by adding 1 mole or more of ethylene oxide or propylene oxide to a diol, in which two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups; di(meth)acrylates obtained by adding 2 to 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, in which two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups; triols obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane. Examples include di(meth)acrylates of polyols having intramolecular ether bonds, such as di(meth)acrylates in which two hydroxyl groups are substituted by (meth)acryloyloxy groups; di(meth)acrylates of polyols having intramolecular ester bonds, such as neopentyl glycol hydroxypivalate di(meth)acrylate; and di(meth)acrylates of heterocyclic polyols, such as di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl) isocyanurate are substituted by (meth)acryloyloxy groups.

[0072] Examples of trifunctional or more (meth)acrylate compounds include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propylene glycol-modified tri(meth)acrylate. Examples include limethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, propoxylated glycerin tri(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, and dipentaerythritol pentaacrylate maleate monoester.

[0073] The polymerizable compound (B-1) preferably has a dipole moment (D: Debye) calculated by the following procedure between 0.5D and 2.0D, more preferably between 0.7D and 1.8D, even more preferably between 0.7D and 1.5D, and even more preferably between 0.8D and 1.5D. By using a polymerizable compound (B-1) within this range, semiconductor particles can be dispersed well even when packed at high concentrations, improving the optical properties after film formation, as well as improving film formation performance. The inventors speculate that this is because the dipole moment of the polymerizable compound (B-1) depends on the electronegativity and molecular structure of the atoms constituting the polymerizable compound (B-1). When the dipole moment is within an appropriate range, intermolecular interactions such as electrostatic repulsion occur between the polymerizable compound (B-1) and the semiconductor particles (A), thereby suppressing aggregation of the densely packed semiconductor particles (A) and improving dispersibility. However, if the dipole moment of the polymerizable compound (B-1) is too small, the interaction between the polymerizable compound (B-1) and the semiconductor particle (A) will not work sufficiently. Conversely, if the dipole moment of the polymerizable compound (B-1) is too large, the polymerizable compounds (B-1) will tend to aggregate with each other. Therefore, it is preferable that the dipole moment of the polymerizable compound (B-1) be within an appropriate range. The dipole moment was calculated using the molecular structure visualization program Avogadro (Ver. 1.2.0). Specifically, the polymerizable compound (B-1) is a (meth)acrylate compound and the following formula (d) (XR 1 -) n -R 2 …(d) [In formula (d), X is a (meth)acryloyl group, R 1 It is a divalent group, R 2 is an n-valence base, where n is an integer greater than or equal to 1, and if n is 2 or greater, multiple XR 1 -These may be the same or different from each other. When expressed as such, X is replaced with a hydrogen atom (H) (HR 1 -) n -R 2 The dipole moment in the lowest energy state configuration of the compound represented by was calculated. In equation (d), n is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3.

[0074] The polymerizable compound (B-1) is preferably one or more compounds having a carboxyl group or an amino group which may have a substituent, from among the monofunctional (meth)acrylate compounds, difunctional (meth)acrylate compounds, and trifunctional or more functional (meth)acrylate compounds, and a compound having a carboxyl group is more preferred. That is, the polymerizable compound (B-1) is mono(2-acryloyloxyethyl) succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, and dipentaerythritol pentaacrylate maleate monoester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl It is preferably at least one (meth)acrylate, and more preferably at least one of mono(2-acryloyloxyethyl) succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, and dipentaerythritol pentaacrylate maleate monoester.

[0075] The content of polymerizable compound (B-1) in 100% by mass of the curable composition is preferably 1% by mass or more, more preferably 3 to 20% by mass, even more preferably 3 to 15% by mass, and still more preferably 3 to 13% by mass.

[0076] The polymerizable compound (B-2) is, from the viewpoint of improving the physical properties of the film after curing, a (meth)acrylate compound that does not contain a functional group that shows coordination ability to semiconductor particles (A) among the above-mentioned bifunctional (meth)acrylate compounds and trifunctional or more (meth)acrylate compounds (i.e., polyfunctional (meth)acrylate compounds), preferably a (meth)acrylate compound that does not contain a functional group that shows coordination ability to semiconductor particles (A) among the above-mentioned bifunctional (meth)acrylate compounds, more preferably a di(meth)acrylate of a polyol having an intramolecular ether bond that does not contain a functional group that shows coordination ability to semiconductor particles (A), more preferably one or more of dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate, and even more preferably one or more of dipropylene glycol diacrylate and tripropylene glycol diacrylate.

[0077] The content of polymerizable compound (B-2) in 100% by mass of the curable composition is preferably 30 to 60% by mass, more preferably 40 to 57% by mass, and even more preferably 45 to 55% by mass.

[0078] The content of polymerizable compound (B-1) per 100 parts by mass of polymerizable compound (B-2) is preferably 5 to 30 parts by mass, preferably 10 to 25 parts by mass, and more preferably 15 to 23 parts by mass.

[0079] The total content of polymerizable compound (B-1) and polymerizable compound (B-2) in 100% by mass of polymerizable compound (B) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 100% by mass.

[0080] The total content of semiconductor particles (A), polymerizable compound (B-1), and polymerizable compound (B-2) in 100% by mass of the curable composition of the present invention is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass.

[0081] <Polymerization initiator (C)> The curable composition may further contain a polymerization initiator (C). The polymerization initiator (C) is a compound that generates active radicals, acids, etc., upon the action of light or heat, and can initiate the polymerization of the polymerizable compound (B). The curable composition may contain one or more polymerization initiators (C). Examples of polymerization initiators (C) include photopolymerization initiators such as oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine compounds, benzoin compounds, benzophenone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds; and thermal polymerization initiators such as azo compounds and organic peroxides. Specifically, as the oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, and quinone compounds, compounds exemplified in Japanese Patent Application Publication No. 2024-61630 can be used.

[0082] Acylphosphine compounds are compounds having a substructure represented by the following formula (1) (where * indicates a bond).

[0083] [ka]

[0084] The acylphosphine compound may be an acylphosphine oxide compound such as a monoacylphosphine oxide compound, a bisacylphosphine oxide compound, or a triacylphosphine oxide compound, with monoacylphosphine oxide compounds or bisacylphosphine oxide compounds being preferred, and bisacylphosphine oxide compounds being more preferred.

[0085] Examples of acylphosphine compounds include the compound represented by the following formula (1A).

[0086] [ka] [In formula (1A), 'a' represents an integer between 1 and 3. R 1 and R 2 Each of these independently represents a hydrocarbon group having 1 to 25 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, or -OCO-. If there are multiple R1s, they may be the same or different, and multiple R 2 If they exist, they may be identical or different.

[0087] R 1 and R 2 Examples of hydrocarbon groups having 1 to 25 carbon atoms represented by this formula include saturated hydrocarbon groups having 1 to 25 carbon atoms, unsaturated hydrocarbon groups having 2 to 25 carbon atoms, and aromatic hydrocarbon groups having 6 to 25 carbon atoms.

[0088] Examples of the saturated hydrocarbon groups having 1 to 25 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.

[0089] Examples of the C2-C25 unsaturated hydrocarbon group include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and eicosenyl groups; alkynyl groups such as ethynyl, propynyl, hexynyl, desinyl, and eicosinyl groups; and cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl groups. The number of carbon atoms in the unsaturated hydrocarbon group is preferably 2-20, more preferably 2-15, and even more preferably 2-10.

[0090] Examples of the aromatic hydrocarbon group having 6 to 25 carbon atoms include phenyl group, xylyl group, dimethylphenyl group, trimethylphenyl group, dipropylphenyl group, di(2,2-dimethylpropyl)phenyl group, naphthyl group, benzyl group, phenylethyl group, and phenylbutyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, even more preferably 6 to 15, and even more preferably 6 to 12.

[0091] R 1 and R 2 The hydrocarbon group represented by may have substituents such as halogen atoms, cyano groups, and nitro groups. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom.

[0092] The -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, or -OCO-, and adjacent -CH2- will not be substituted with the same type of group at the same time, nor will terminal -CH2- be substituted.

[0093] a represents an integer from 1 to 3, preferably 1 or 2, more preferably 2.

[0094] R 1 and R 2The hydrocarbon group having 1 to 25 carbon atoms represented is preferably an aromatic hydrocarbon group having 6 to 25 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, even more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, even more preferably a phenyl group, a xylyl group, a dimethylphenyl group, or a trimethylphenyl group, even more preferably a phenyl group, a dimethylphenyl group, or a trimethylphenyl group, and even more preferably a phenyl group or a trimethylphenyl group.

[0095] Examples of acylphosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-dipentyloxyphenyl), and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, with bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide being preferred. Commercially available acylphosphine compounds such as OMNIRAD® 819 (manufactured by IGM Resins) may also be used.

[0096] From the viewpoint of increasing the luminescence intensity of the curable composition and cured film, it is preferable that the photopolymerization initiator contains at least an acylphosphine oxide compound.

[0097] If the curable composition contains a polymerization initiator (C), the content of the polymerization initiator (C) is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 15% by mass or less, even more preferably 0.5% by mass or more and 10% by mass or less, even more preferably 1% by mass or more and less than 10% by mass, even more preferably 1% by mass or more and 9% by mass or less, and even more preferably 1% by mass or more and 8% by mass or less, and may also be 6% by mass or less or 5% by mass or less.

[0098] <Polymerization initiator (C1)> The curable composition may further contain polymerization initiators (C1) along with a polymerization initiator (C), and may contain two or more polymerization initiators (C1). The polymerization initiator (C1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound (B) initiated by the polymerization initiator (C). Examples of polymerization initiators (C1) include photopolymerization initiators such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, as well as thermal polymerization initiators. Specifically, polymerization initiators described in Japanese Patent Application Publication No. 2024-61630 can be used.

[0099] When the curable composition contains a polymerization initiator (C1), the content of the polymerization initiator (C1) in the curable composition is preferably 0.1 parts by mass or more and 300 parts by mass or less, more preferably 0.1 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of the polymerizable compound (B). When the content of the polymerization initiator (C1) is within the above range, the sensitivity of the curable composition can be further improved.

[0100] <Antioxidant (D)> The curable composition may contain an antioxidant (D), and may contain two or more types of antioxidants (D). The antioxidant (D) is not particularly limited as long as it is an antioxidant commonly used in industry, and can be a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, etc. For example, the antioxidant described in Japanese Patent Application Publication No. 2024-61630 can be used.

[0101] As phenolic antioxidants, those having a hindered phenol structure in which a bulky organic group is bonded to at least one ortho position of a phenolic hydroxyl group are preferred. The bulky organic group is preferably a secondary or tertiary alkyl group, specifically including isopropyl, s-butyl, t-butyl, s-amyl, and t-amyl groups. Among these, tertiary alkyl groups are preferred, and t-butyl or t-amyl groups are particularly preferred.

[0102] As a phosphorus-based antioxidant, an antioxidant having a group represented by the following formula (e1) is preferred.

[0103] [ka] [In formula (e1), R e1 ~R e5 Each of these independently represents either a hydrogen atom or an alkyl group, and * represents a bond.

[0104] R e1 It is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, or a t-butyl group. R e2 and R e4 Each of these is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom. R e3 and R e5 Each of these is preferably an alkyl group, more preferably a secondary or tertiary alkyl group, and even more preferably a t-butyl group or a t-amyl group. The two units enclosed in parentheses are R e1 They may also bond together to form a ring. e1 To combine them means R e1 This refers to a configuration in which groups with hydrogen atoms removed from them are bonded together, and two R e1 If both are hydrogen atoms, then R in one of the benzene rings e1 The carbon atom to which it is bonded, and the R in the other benzene ring. e1 This refers to a form of bonding where carbon atoms are directly bonded to each other.

[0105] As the antioxidant (D), a phenolic antioxidant or a phosphorus-based antioxidant is preferred, more preferably an antioxidant having at least one of the above-mentioned hindered phenol structure and the group represented by formula (e1), even more preferably an antioxidant having both the above-mentioned hindered phenol structure and the group represented by formula (e1), and Smirizer® GP is particularly preferred.

[0106] When the curable composition contains an antioxidant (D), the content of the antioxidant (D) is preferably 0.01% to 30% by mass relative to the total amount of solids in the curable composition, from the viewpoint of improving the luminescence intensity and heat resistance of the curable composition and the cured film, but may be 0.1% to 20% by mass, 0.2% to 10% by mass, 0.5% to 5% by mass, or 0.5% to 2% by mass.

[0107] <Light scattering agent (E)> The curable composition may further contain a light scattering agent (E). The inclusion of a light scattering agent (E) improves the scattering of light from a light source irradiated onto the cured film formed from the curable composition. The curable composition may contain two or more types of light scattering agents (E).

[0108] Examples of light scattering agents (E) include metal or metal oxide particles, and inorganic particles such as glass particles. Examples of metal oxides include TiO2, SiO2, BaTiO3, and ZnO, and TiO2 particles are preferred because they efficiently scatter light.

[0109] When the curable composition contains a light scattering agent (E), the content of the light scattering agent (E) in the curable composition is, for example, 0.001% by mass or more and 30% by mass or less, preferably 0.01% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less, relative to the total amount of solids in the curable composition.

[0110] <Solvent (F)> The curable composition may contain a solvent (F), but if it contains a solvent (F), it is preferable that the content be low, and even more preferable that it does not contain a solvent (F). The content of solvent (F) in the curable composition is preferably 10% by mass or less, preferably 10 to 0% by mass, more preferably 5 to 0.5% by mass, even more preferably 3 to 0.5% by mass, even more preferably 2 to 0.5% by mass, even more preferably 1 to 0.5% by mass, and may also be 0% by mass, based on the total amount of the curable composition. By reducing the content of solvent (F), it becomes easier to control the film thickness when forming the cured film, and it is possible to reduce manufacturing costs and the burden on the global environment and the working environment due to the solvent. The curable composition may contain two or more types of solvent (F).

[0111] As the solvent (F), solvents described in Japanese Patent Publication No. 2024-61630 can be used.

[0112] <Leveling agent (H)> The curable composition may contain a leveling agent (H), and may contain two or more types of leveling agents (H). Examples of leveling agents (H) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom, which may have polymerizable groups in their side chains. Specifically, as leveling agents (H), those described in Japanese Patent Application Publication No. 2024-61630 can be used.

[0113] When the curable composition contains a leveling agent (H), the content of the leveling agent (H) in the curable composition is, for example, 0.001% by mass or more and 1.0% by mass or less, preferably 0.005% by mass or more and 0.75% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.05% by mass or more and 0.5% by mass or less, relative to the total amount of solids in the curable composition. When the content of the leveling agent (H) is within the above range, the flatness of the cured film can be improved.

[0114] <Resin (I)> The curable composition may contain resin(I), but a low content is preferable. The resin(I) content is preferably 10% by mass or less, more preferably 10-0% by mass, even more preferably 5-0.5% by mass, even more preferably 3-0.5% by mass, even more preferably 2-0.5% by mass, particularly preferably 1-0.5% by mass, and may also be 0% by mass. By reducing the resin(I) content, the viscosity of the curable composition can be reduced, which in turn can improve the ejectability, especially when ejected from the ejection head of an inkjet printer. The curable composition may contain two or more types of resin(I).

[0115] As resin (I), resins such as those described in Japanese Patent Publication No. 2024-61630 can be used.

[0116] <Other ingredients> The curable composition may optionally contain other additives such as dispersants, plasticizers, and fillers.

[0117] Examples of dispersants include, but are not limited to, cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. Dispersants are preferably used in combination when the curable composition contains a light scattering agent (E). The inclusion of a dispersant in the curable composition improves the dispersibility of the light scattering agent (E) in the curable composition.

[0118] The dispersant content in the curable composition is preferably 10% by mass or less, more preferably 10 to 0% by mass, even more preferably 5 to 0.1% by mass, even more preferably 3 to 0.2% by mass, preferably 1 to 0.2% by mass, and may also be 0% by mass, based on the total amount of solids in the curable composition. Furthermore, from the viewpoint of viscosity reduction, it is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0119] The additive content in the curable composition is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and may also be 0% by mass, based on the total amount of solids in the curable composition.

[0120] <Method for producing a curable composition> The curable composition of the present invention can be manufactured by a method comprising the step of mixing a predetermined component and other components used as needed.

[0121] The mixing order of each component is not particularly limited, but after mixing semiconductor particles (A) and polymerizable compound (B) to obtain a dispersion, the curable composition of the present invention can be prepared by mixing the dispersion with other components as needed.

[0122] The ligand-containing semiconductor particle (A) may be prepared by preparing or creating semiconductor particles to which organic ligands are coordinated, and then subjecting them to a ligand reduction treatment to reduce the amount of organic ligands coordinating to the semiconductor particles. The ligand reduction treatment can be a process of extracting the organic ligands coordinated to the semiconductor particles into a suitable solvent.

[0123] When the curable composition of the present invention is used as an ink for an inkjet printer, the curable composition can be ejected from the ejection head of the inkjet printer at a temperature of 40°C or higher. The temperature of the curable composition when ejected from the ejection head of the inkjet printer may be 45°C or higher, 50°C or higher, or 80°C or lower.

[0124] <Cured film> The curable composition of the present invention can form a cured film by irradiation with ultraviolet or visible light. The cured film containing semiconductor particles (A) can emit light of a different wavelength than the irradiated light. Therefore, the cured film containing semiconductor particles (A) can be used as a wavelength conversion film.

[0125] The thickness of the cured film is, for example, 0.5 μm or more and 40 μm or less, preferably 1 μm or more and 35 μm or less, and more preferably 5 μm or more and 30 μm or less.

[0126] <Method for manufacturing hardened film> A cured film can be obtained by curing a film (layer) made of a curable composition. Specifically, a cured film can be obtained by applying a curable composition to a substrate to form a coating film, and then exposing the obtained coating film to light. Alternatively, a cured film may be obtained by further thermal curing (post-bake) after the exposure. Thermal curing can further advance the polymerization of the polymerizable compound (B). Alternatively, curing may be performed by thermal curing before exposure, or the film may be embedded in a bank and sealed around it before curing.

[0127] As substrates, glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicone, and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed, or substrates on which a color filter is formed, can be used. Preferred substrates are glass plates and silicone substrates.

[0128] For applying the curable composition, various printing methods such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, electrostatic printing, and plateless printing, as well as coating methods such as gravure coating, roll coating, knife coating, air knife coating, bar coating, dip coating, kiss coating, spray coating, die coating, comma coating, inkjet, spin coating, and slit coating, or combinations thereof, can be used as appropriate.

[0129] For exposure, a light source that generates light with a wavelength between 250 nm and 450 nm is preferred. Light below 350 nm may be filtered out using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. Exposure may be performed in an atmospheric environment or in an inert gas (nitrogen, argon, etc.) atmosphere, but an inert gas atmosphere is preferred. The exposure amount in the exposure process is preferably 50 to 1000 mJ / cm². 2 That is the case.

[0130] The preferred temperature for thermosetting is 100 to 220°C. The curing time in the curing process is preferably 30 seconds to 2 hours. The curing process may be carried out in either an atmospheric or an inert gas atmosphere.

[0131] Furthermore, a patterned cured film can be formed from a curable composition by patterning using methods such as photolithography, inkjet printing, or other printing methods. However, since photolithography results in the loss of expensive curable composition material, it is preferable to use the inkjet method from the viewpoint of reducing material loss.

[0132] One method for manufacturing a patterned cured film by inkjet is to form banks on a substrate, selectively deposit a curable composition into the areas partitioned by the banks on the substrate using an inkjet method, and then cure the composition by exposure (and, if necessary, thermal curing). As the substrate, the substrates exemplified in the description of the manufacturing method of the cured film can be used.

[0133] Methods for forming a bank include photolithography and inkjet, with inkjet being preferred. Examples of inkjet methods include the bubble jet (registered trademark) method, which uses an electrothermal converter as an energy generating element, or the piezo jet method, which uses a piezoelectric element.

[0134] As the light source used for exposure, the light source exemplified in the description of the manufacturing method for the cured film described above can be used. Furthermore, the thermal curing conditions after exposure can be found in the description of the manufacturing method for the cured film described above.

[0135] <Wavelength conversion film and display device> Unpatterned or patterned cured films can be suitably used as wavelength conversion films (wavelength conversion filters) that emit light of a different wavelength than the light incident from light-emitting parts such as LEDs. In particular, it is preferable that the patterned cured film be positioned above light-emitting elements such as LEDs corresponding to each pattern. By individually converting the wavelength of each light-emitting element, the shape of the emission spectrum of red, green, blue, etc. can be appropriately controlled, and high color reproducibility can be achieved. Display members having wavelength conversion films can be suitably used in display devices such as liquid crystal displays and organic EL displays.

[0136] The cured film has the function of converting the wavelength of irradiated light, and therefore can be used as a color conversion layer (wavelength conversion film) for display devices. Examples of such display devices include those described in Japanese Patent Publication No. 2006-309219, Japanese Patent Publication No. 2006-310303, Japanese Patent Publication No. 2013-15812, Japanese Patent Publication No. 2009-251129, Japanese Patent Publication No. 2014-2363, etc. The cured film according to the present invention is useful as a color conversion layer (wavelength conversion film) for display devices, particularly for liquid crystal display devices, organic EL display devices, or inorganic EL display devices. [Examples]

[0137] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit described above and below, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0138] <Measurement, Evaluation> The measurements or evaluations in the following examples and comparative examples were performed by the methods described below.

[0139] [Optical properties] A curable composition was applied to a 5cm square glass substrate (Corning Eagle XG) using a spin-coating method to a coating thickness of 10μm. A backlight section was created by placing a light diffuser plate on a backlight that used a blue LED lamp with a peak emission wavelength of 450 nm as a point light source. The film formed on the glass substrate was used as a measurement sample, and this measurement sample was placed on the surface of the light diffuser plate with the coated surface facing upwards. With the backlight turned on in this state, the light emitted from the film was observed visually, and the optical properties were evaluated according to the following criteria. A: No color unevenness is observed within the film surface, and the color conversion rate is high. B: No color unevenness is observed within the film surface, but the color conversion rate is slightly low. C: Color unevenness is observed within the film surface.

[0140] [Film forming property] A curable composition was applied to a 5cm square glass substrate (Corning Eagle XG) by spin coating to a thickness of 10μm. The resulting film was visually observed, and its film-forming properties were evaluated according to the following criteria. A: No granular defects are observed within the film surface. B: Granular defects are observed within the film surface.

[0141] [Membrane thickness] The film thickness (μm) was measured using a laser microscope after scraping a portion of the curable composition deposited on glass from the central area.

[0142] Examples 1-4, Comparative Examples 1-2 A predetermined amount of semiconductor particles (A) and polymerizable compound (B-2) were mixed. The mixture was stirred using an ultrasonic cleaner and a touch mixer until no large lumps remained. A predetermined amount of polymerizable compound (B-1) was then added to the mixture. The mixture was stirred on an 80°C hot stirrer to obtain a dispersion.

[0143] Semiconductor particles (A-1): Ligand-containing dots containing oleic acid as an organic ligand and having an InP / ZnSeS structure. These dots were obtained by removing toluene under reduced pressure from a toluene dispersion of ligand-containing dots (maximum peak wavelength of emission spectrum 530 nm). Semiconductor particles (A-2): Ligand-containing dots containing the organic ligand oleic acid and having an InP / ZnSeS structure. These dots were obtained by removing toluene under reduced pressure from a toluene dispersion of ligand-containing dots (maximum peak wavelength of the emission spectrum: 620 nm). Polymerizable compound (B-1-1): Pentaerythritol triacrylate succinate monoester (dipole moment: 0.92D) Polymerizable compound (B-1-2): Mono-2-(acryloyloxy)ethyl succinic acid (MAES) (dipole moment: 0.90D) Polymerizable compound (B-1-3): 2-diethylaminoethyl acrylate (dipole moment: 0.75D) Polymerizable compound (B-2-1): Tripropylene glycol diacrylate (TPGDA) (Dipole moment: 0.24D)

[0144] The emission spectra and peak wavelengths of semiconductor particles (A-1) and (A-2) were measured using an absolute PL quantum yield analyzer (Hamamatsu Photonics K.K. "C9920-02", excitation light 450 nm, room temperature, under atmospheric conditions) with a dispersion of semiconductor particles (A-1) diluted to an absorbance of 0.4 at a wavelength of 450 nm as the measurement sample.

[0145] Furthermore, the dipole moment values ​​shown in parentheses for the polymerizable compounds (B-1-1), (B-1-2), (B-1-3), and (B-2-1) are as described above, with respect to the polymerizable compounds (B-1-1), (B-1-2), (B-1-3), and (B-2-1) respectively given by formula (d):(XR 1 -) n -R 2 Represented as follows, the compound obtained by substituting X with a hydrogen atom (H): (HR 1 -) n -R 2 This value represents the dipole moment in the estimated lowest energy state configuration, calculated using the molecular structure visualization program Avogadro (Ver. 1.2.0).

[0146] Table 1 shows the results of film-forming properties and optical characteristics measured in the above procedure for the examples and comparative examples. In Table 1, the parts of each component are calculated on a solid content basis.

[0147] [Table 1]

[0148] The curable compositions obtained in Examples 1-4 exhibited excellent optical properties. Furthermore, the curable compositions obtained in Examples 1-3 possessed both excellent optical properties and good film-forming properties. On the other hand, Comparative Example 1, which contained the same amount of semiconductor particles (A) as Examples 1-4 and did not contain polymerizable compound (B-1), exhibited inferior optical properties and film-forming properties. Comparative Example 2, which contained 30% by mass of semiconductor particles (A) and did not have a high concentration, did not contain polymerizable compound (B-1), but its optical properties were rated as B, and it did not suffer from the optical property degradation problems seen in Comparative Example 1.

Claims

1. A curable composition comprising semiconductor particles (A) and a polymerizable compound (B), The polymerizable compound (B) comprises a polymerizable compound (B-1) having at least one functional group that exhibits coordination ability to the semiconductor particles (A), and a polymerizable compound (B-2) which is a polyfunctional (meth)acrylate that does not contain any functional groups that exhibit coordination ability to the semiconductor particles (A). A curable composition in which the content of semiconductor particles (A) in 100% by mass of the curable composition is 32% by mass or more.

2. The curable composition according to claim 1, wherein the weight-average molecular weight of the polymerizable compound (B-2) is 180 or more.

3. The curable composition according to claim 1, wherein the polymerizable compound (B-1) is a (meth)acrylate compound.

4. The polymerizable compound (B-1) is represented by the following formula (d), (X-R １ -) ｎ -R ２ …(d) In formula (d), X is a (meth)acryloyl group, and R １ It is a divalent group, R ２ is an n-valence base, where n is an integer greater than or equal to 1, and if n is 2 or greater, there are multiple X-R １ - may be the same or different from each other. The (HR １ −) ｎ −R ２ The curable composition according to claim 3, wherein the dipole moment is 0.5 D to 2.0 D.

5. The curable composition according to claim 1, wherein the semiconductor particle (A) is an InP-based material.

6. The curable composition according to claim 1, wherein the functional group exhibiting coordination ability of the polymerizable compound (B-1) is at least one selected from a carboxyl group, an optionally substituted amino group, and a thiol group.

7. Furthermore, the curable composition according to claim 1, wherein the composition further contains a solvent (F), and the content of the solvent (F) in 100% by mass of the curable composition is 0.5 to 10% by mass.

8. The curable composition according to claim 1, which is an ink for inkjet printers.

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