Resin composition, resin film and display device

Abstract

This invention provides a resin composition, a resin film formed from the resin composition, and a display device comprising the resin film. The resin composition is a resin composition containing semiconductor particles and can form a resin film exhibiting good luminous intensity. Specifically, the resin composition is a resin composition containing semiconductor particles (A) and resin (B), wherein the content of polymerizable compound (C) and polymerization initiator (D) is 0.01% by mass or less relative to the total solid content of the resin composition, and the ratio of the content of semiconductor particles (A) to the content of resin (B) is 0.60 or more by mass.

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a resin film formed therefrom, and a display device comprising the resin film. [Previous Technology]

[0002] Patent Document 1 describes a curable resin composition comprising semiconductor particles, a polymer having specific structural units, a polymerizable unsaturated compound, and a polymerization initiator, and a curable film formed using the curable resin composition. This curable film is used as a wavelength conversion film or a light-emitting layer in a light-emitting display element. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2016-065178 [Summary of the Invention]

[0004] [The problem that the invention aims to solve]

[0005] One object of the present invention is to provide a resin composition comprising semiconductor particles, which can be formed into a resin film exhibiting good luminous intensity. Another object of the present invention is to provide a resin film formed from said resin composition, and a display device comprising said resin film. [Means for Solving the Problem]

[0006] The present invention provides a resin composition, a resin film, and a display device as shown below. [1] A resin composition comprising semiconductor particles (A) and resin (B), wherein the content of polymerizable compound (C) and polymerization initiator (D) is 0.01% by mass or less relative to the total solid content of the resin composition, and the ratio of the content of semiconductor particles (A) to the content of resin (B) is 0.60 or more by mass. [2] The resin composition as described in [1] further comprises or does not contain an organic ligand (F), wherein the ratio of the total content of semiconductor particles (A) and the organic ligand (F) to the content of resin (B) is greater than 1.00 by mass. [3] The resin composition as described in [1] or [2], wherein the content of polymerizable compound (C) and the polymerization initiator (D) is 0% by mass relative to the total solid content of the resin composition. [4] A resin composition as described in any one of [1] to [3], wherein the weight average molecular weight of the resin (B) is 150 or less relative to the acid value of the resin (B). [5] A resin composition as described in any one of [1] to [4], further comprising a light scattering agent (E). [6] A resin composition as described in any one of [1] to [5], wherein the viscosity at 25°C is 100 mPa·s or more and 30,000 mPa·s or less. [7] A resin film formed from a resin composition as described in any one of [1] to [6]. [8] A display device comprising a resin film as described in [7]. [Effects of the Invention]

[0007] A resin composition, a resin film formed from the resin composition, and a display device comprising the resin film may be provided, wherein the resin composition is a resin composition comprising semiconductor particles and can be formed into a resin film exhibiting good luminous intensity.

Implementation Method

[0009] <Resin Composition> The resin composition of the present invention (hereinafter also simply referred to as "resin composition") comprises semiconductor particles (A) and resin (B).

[0010] [1] Semiconductor particle (A) The semiconductor particle (A) emits light with a wavelength different from that of the primary light, preferably by converting the wavelength of the blue light, which is the primary light, into a wavelength of light with a different color. The semiconductor particle (A) preferably emits green or red light, and more preferably by absorbing blue light and emitting green or red light.

[0011] The semiconductor particle (A) may be, for example, a red luminescent semiconductor particle emitting light with a peak emission wavelength in the wavelength region of 605 nm or higher and 665 nm or lower, a green luminescent semiconductor particle emitting light with a peak emission wavelength in the wavelength region of 500 nm or higher and 560 nm or lower, or a blue luminescent semiconductor particle emitting light with a peak emission wavelength in the wavelength region of 420 nm or higher and 480 nm or lower. The semiconductor particle (A) is preferably a red luminescent semiconductor particle and / or a green luminescent semiconductor particle. The peak emission wavelength of the semiconductor particle (A) can be confirmed, for example, by measuring the emission spectrum using a UV-Vis spectrophotometer.

[0012] The full width at half maximum (FWHM) of the emission spectrum of the semiconductor particle (A) is preferably below 60 nm, more preferably below 55 nm, further preferably below 50 nm, and most preferably below 45 nm. This allows for the emission of light with higher color purity. The lower limit of the FWHM of the emission spectrum of the semiconductor particle (A) is not particularly limited and can be above 5 nm or above 15 nm.

[0013] The semiconductor particle (A) is a particle containing semiconductor crystals, preferably a nanoparticle containing semiconductor crystals. As a preferred example of the semiconductor particle (A), examples include semiconductor quantum dots (hereinafter also referred to as "quantum dots") and particles of compounds having a perovskite-type crystal structure (hereinafter also referred to as "perovskite compounds"), more preferably quantum dots.

[0014] The average particle size of the quantum dots is, for example, 0.5 nm or more and 20 nm or less, preferably 1 nm or more and 15 nm or less (e.g., 2 nm or more and 15 nm or less). The energy state of the quantum dots depends on their size, so the emission wavelength can be freely selected by changing the particle size. For example, in the case of quantum dots composed only of CdSe, the peak wavelengths of the emission spectra when the particle sizes are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. The average particle size of the semiconductor particles (A) can be determined using a scanning transmission electron microscope.

[0015] Quantum dots may be made of semiconductor materials, for example, semiconductor materials containing one or more elements selected from the group consisting of elements selected from Group 2, Group 11, Group 12, Group 13, Group 14, Group 15 and Group 16 of the periodic table.

[0016] Specific examples of semiconductor materials that can constitute quantum dots include: compounds of Group 14 and Group 16 elements such as SnS2, SnS, SnSe, SnTe, PbS, PbSe, and PbTe; compounds of Group 13 and Group 15 elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, and InGaP; and compounds of Group 13 and Group 16 elements such as Ga2O3, Ga2S3, Ga2Se3, Ga2Te3, In2O3, In2S3, In2Se3, and In2Te3. Compounds of Group 12 and Group 16 elements, including ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, ZnSTe, ZnSeS, ZnSeTe, CdSTe, CdSeTe, HgSTe, HgSeS, HgSeTe; Compounds of Group 15 and Group 16 elements, including As2O3, As2S3, As2Se3, As2Te3, Sb2O3, Sb2S3, Sb2Se3, Sb2Te3, Bi2O3, Bi2S3, Bi2Se3, Bi2Te3; Compounds of Group 2 and Group 16 elements, including MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe. Si, Ge, and other elemental forms of Group 14, Group 15, or Group 16 elements.

[0017] A quantum dot can be a single-layer structure containing a single semiconductor material, or a core-shell structure in which the surface of a nucleus (core) containing a single semiconductor material is covered by a coating layer (shell) containing one or more semiconductor materials different from the core. In the latter case, the semiconductor material constituting the shell is usually a material with a higher band gap energy than the semiconductor material constituting the core. A quantum dot can have two or more shells. The shape of a quantum dot is not particularly limited; for example, it can be spherical or approximately spherical, rod-shaped, disk-shaped, etc.

[0018] The perovskite compound is a compound having a perovskite-type crystalline structure with components A, B, and X. A is the component located at each vertex of the hexahedron centered on B in the perovskite-type crystalline structure, and is a monovalent cation. X represents the component located at each vertex of the octahedron centered on B in the perovskite-type crystalline structure, and is at least one ion selected from the group consisting of halide ions and thiocyanate ions. B is the component located at the center of the hexahedron where A is located at the vertex and the octahedron where X is located at the vertex in the perovskite-type crystalline structure, and is a metal ion.

[0019] From the viewpoint of maintaining a good crystal structure, the average particle size of the semiconductor particles containing the perovskite compound is preferably 3 nm or more, more preferably 4 nm or more, and even more preferably 5 nm or more, and usually 50 nm or less.

[0020] The perovskite compound consisting of A, B, and X is not particularly limited and can be any compound having a three-dimensional structure, a two-dimensional structure, or a quasi-two-dimensional structure. In the case of a three-dimensional structure, the perovskite compound is represented by ABX(3+δ). In the case of a two-dimensional structure, the perovskite compound is represented by A2BX(4+δ). Here, δ is a number that can be appropriately varied according to the charge balance of B, and is greater than or equal to -0.7 and less than or equal to 0.7.

[0021] Preferred specific examples of perovskite compounds having a three-dimensional perovskite-type crystalline structure represented by ABX(3+δ) include: CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbI3, CH3NH3PbBr(3-y)Iy (0 < y < 3), CH3NH3PbBr(3-y)Cly (0 < y < 3), (H2N=CH-NH2)PbBr3, (H2N=CH-NH2)PbCl3, (H2N=CH-NH2)PbI3. CH3NH3Pb(1-a)CaaBr3(0<a≦0.7), CH3NH3Pb(1-a)SraBr3(0<a≦0.7), CH3NH3Pb(1-a)LaaBr(3+δ)(0< a≦0.7, 0<δ≦0.7), CH3NH3Pb(1-a)BaaBr3 (0<a≦0.7), CH3NH3Pb(1-a)DyaBr(3+δ) (0<a≦0.7, 0<δ≦0.7), CH3NH3Pb(1-a)NaaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), CH3NH3Pb(1-a)LiaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb(1-a)NaaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb(1-a)LiaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), CH3NH3Pb(1-a)NaaBr(3+δ-y)Iy (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH3NH3Pb(1-a)LiaBr(3+δ-y)Iy (0<a≦0.7, -0.7≦δ<0, 0<y<3), C H3NH3Pb(1-a)NaaBr(3+δ-y)Cly (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH3NH3Pb(1-a)LiaBr(3+δ-y)Cly (0<a≦0.7, -0.7≦δ<0, 0<y<3), (H2N=CH-NH2)Pb(1-a)NaaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), (H2N=CH-NH2)Pb(1-a)LiaBr(3+δ) (0<a≦0.7, -0.7≦δ<0), (H2N =CH-NH2)Pb(1-a)NaaBr(3+δ-y)Iy (0<a≦0.7, -0.7≦δ<0, 0<y<3), (H2N=CH-NH2)Pb(1-a)NaaBr(3+δ-y)Cly (0<a≦0.7, -0.7 ≤ δ < 0, 0 < y < 3), CsPbBr3, CsPbCl3, CsPbI3, CsPbBr(3 - y)Iy (0 < y < 3), CsPbBr(3 - y)Cly (0 < y < 3), CH3NH3PbBr(3 - y)Cly (0 < y < 3), CH3NH3Pb(1 - a)ZnaBr3 (0 < a ≤ 0.7), CH3NH3Pb(1 - a)AlaBr(3 + δ) (0 < a ≤ 0.7, 0 ≤ δ ≤ 0.7), CH3NH3Pb(1 - a)CoaBr3 (0 < a ≤ 0.7), CH3NH3Pb(1 - a)MnaBr3 (0 < a ≤ 0.7), CH3NH3Pb(1 - a)MgaBr3 (0 < a ≤ 0.7), CsPb(1 - a)ZnaBr3 (0 < a ≤ 0.7), CsPb(1 - a)AlaBr(3 + δ) (0 < a ≤ 0.7, 0 < δ ≤ 0.7), CsPb(1 - a)CoaBr3 (0 < a ≤ 0.7), CsPb(1 - a)MnaBr3 (0 < a ≤ 0.7), CsPb(1 - a)MgaBr3 (0 < a ≤ 0.7), CH3NH3Pb(1 - a)ZnaBr(3 - y)Iy (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)AlaBr(3 + δ - y)Iy (0 < a ≤ 0.7, 0 < δ ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)CoaBr(3 - y)Iy (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)MnaBr(3 - y)Iy (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)MgaBr(3 - y)Iy (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)ZnaBr(3 - y)Cly (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)AlaBr(3 + δ - y)Cly (0 < a ≤ 0.7, 0 < δ ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)CoaBr(3 + δ - y)Cly (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)MnaBr(3 - y)Cly (0 < a ≤ 0.7, 0 < y < 3), CH3NH3Pb(1 - a)MgaBr(3 - y)Cly (0 < a ≤ 0.7, 0 < y < 3), (H2N=CH-NH2)ZnaBr3 (0 < a ≤ 0.7), (H2N=CH-NH2)MgaBr3 (0 < a ≤ 0.7), (H2N=CH-NH2)Pb(1 - a)ZnaBr(3 - y)Iy (0 < a ≤ 0.7, 0 < y < 3), (H2N=CH-NH2)Pb(1 - a)ZnaBr(3 - y)Cly (0 < a ≤ 0.7, 0 < y < 3), etc.

[0022] Preferred specific examples of perovskite compounds having a two-dimensional perovskite-type crystalline structure represented by A2BX(4+δ) can be listed as follows: (C4H9NH3)2PbBr4, (C4H9NH3)2PbCl4, (C4H9NH3)2PbI4, (C7H15NH3)2PbBr4, (C7H15NH3)2PbCl4, (C7H15NH3)2PbI4, (C4H9NH3)2Pb(1-a)Lia Br(4+δ) (0<a≦0.7, -0.7≦δ<0), (C4H9NH3)2Pb(1-a)NaaBr(4+δ) (0<a≦0 .7, -0.7≦δ<0), (C4H9NH3)2Pb(1-a)RbaBr(4+δ) (0<a≦0.7, -0.7≦δ<0), (C7H15NH3)2Pb(1-a)NaaBr(4+δ) (0<a≦0.7, -0.7≦δ<0), (C7H15NH3)2Pb(1-a)LiaBr (4+δ) (0<a≦0.7, -0.7≦δ<0), (C7H15NH3)2Pb(1-a)RbaBr(4+δ) (0<a≦0.7, -0.7≦δ<0), (C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Iy (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2Pb(1-a)LiaBr(4+δ-y )Iy (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Iy (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Cly (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2Pb(1-a)LiaBr(4+δ-y )Cly (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Cly (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C4H9NH3)2PbBr4, (C7H15NH3)2PbBr4, (C4H9NH3)2PbBr(4-y)Cly (0<y<4), (C4H9NH3)2PbBr(4-y)Iy (0<y<4), (C4H9NH3)2Pb(1-a)ZnaBr4 (0<a≦0.7), (C4H9NH3)2Pb(1-a)MgaBr4 (0<a≦0.7 ), (C4H9NH3)2Pb(1-a)CoaBr4 (0<a≦0.7), (C4H9NH3)2Pb(1-a)MnaBr4 (0<a≦0.7), (C7H15NH3)2Pb(1-a)ZnaBr4 (0<a≦0.7), (C7H15NH3)2Pb(1-a)MgaBr4 (0<a≦0.7), (C7H15NH3)2Pb(1-a)CoaBr4 (0<a≦0.7), (C7H15NH3)2Pb(1-a)MnaBr4 (0<a≦0.7), (C4H9NH3)2Pb(1-a)ZnaBr(4-y)Iy (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)MgaBr(4-y)Iy (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)CoaBr(4-y)Iy (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)MnaBr(4-y)Iy (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)ZnaBr(4-y)Cly (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)MgaBr(4-y)Cly (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)CoaBr(4-y)Cly (0<a≦0.7, 0<y<4), (C4H9NH3)2Pb(1-a)MnaBr(4-y)Cly (0<a≦0.7, 0<y<4), etc. .

[0023] The resin composition may contain only one type of semiconductor particle (A) that emits light of a specific wavelength when emitted from a light source, or it may contain two or more types of semiconductor particles (A) that emit light of different wavelengths. For example, the resin composition may contain only one type of quantum dot that emits light of a specific wavelength when emitted from a light source, or it may contain two or more types of quantum dots that emit light of different wavelengths. Examples of the specific wavelength of light include, for example, red light, green light, and blue light.

[0024] Relative to the total amount of solid components in the resin composition, the content of semiconductor particles (A) in the resin composition is, for example, 1% by mass or more and 60% by mass or less, preferably 10% by mass or more and 55% by mass or less, more preferably 10% by mass or more and 50% by mass or less, even more preferably 10% by mass or more and 45% by mass or less, and may also be 10% by mass or more and 40% by mass or less. In this specification, the total amount of solid components refers to the sum of the components contained in the resin composition after removing the solvent (G). The content of solid components in the resin composition can be determined by known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid component of the resin composition can also be calculated based on the formulation during the preparation of the resin composition.

[0025] [2] Organic ligand (F) Semiconductor particles (A) may also exist in the resin composition in a state where organic ligands are coordinated. Hereinafter, semiconductor particles coordinated with organic ligands are also referred to as semiconductor particles containing ligands. The organic ligands coordinated to the semiconductor particles are, for example, organic compounds having polar groups that exhibit coordination ability to semiconductor particles. The organic ligands may be organic ligands added considering the constraints on the synthesis of semiconductor particles containing ligands or for the purpose of stabilization. For example, in Japanese Patent Publication No. 2015-529698, from the viewpoint of controlling particle size, semiconductor particles containing ligands contain hexanoic acid as an organic ligand, and for the purpose of stabilization after synthesis, the organic ligand is replaced with DDSA (dodecenyl succinic acid). The organic ligands may, for example, be coordinated to the surface of the semiconductor particles (A). The resin composition may contain one or more organic ligands (F).

[0026] The polar group of the organic ligand is preferably at least one group selected from the group consisting of thiol (-SH), carboxyl (-COOH), and amine (-NH2). Polarity selected from this group may be advantageous in terms of improving coordination with the semiconductor particle (A). High coordination can help improve the stability and dispersibility of the semiconductor particle (A) in the resin composition, as well as improve the luminescence intensity of the resin film. The polar group is more preferably at least one group selected from the group consisting of thiol and carboxyl groups. The organic ligand (F) may have one or more polar groups.

[0027] The organic ligand may be, for example, an organic compound represented by the following formula (X). XA-RX (X) Wherein, XA is the polar group, and RX is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds. The hydrocarbon group may have a straight-chain, branched-chain, or cyclic structure. The number of carbon atoms in the hydrocarbon group may be, for example, 1 or more and 40 or less, or 1 or more and 30 or less. The methylene group contained in the hydrocarbon group may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0028] The base RX may also contain a polar base. For a specific example of such a polar base, please refer to the description of the polar base XA.

[0029] Specific examples of organic ligands having a carboxyl group as a polar group XA include: formic acid, acetic acid, propionic acid, and other saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include: saturated fatty acids such as butyric acid, valeric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, docosahexaenoic acid, and lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenoic acid, erucic acid, and nervonic acid; and linolenic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, dihomeno-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenaline. Polyunsaturated fatty acids such as docosatraenoic acid (docosatetraenoic acid).

[0030] Specific examples of organic ligands having a thiol group or an amino group as a polar group XA include organic ligands formed by replacing the carboxyl group of the organic ligands having a carboxyl group as a polar group XA as illustrated above with a thiol group or an amino group.

[0031] In addition to the above, compounds (F-1) and (F-2) can be listed as organic ligands represented by the formula (X).

[0032] 〔Compound (F-1)〕Compound (F-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). Because compound (F-1) has a carboxyl group and / or a thiol group, it can serve as a ligand for the semiconductor particle (A). Containing compound (F-1) in the resin composition is beneficial in improving the stability and dispersibility of the semiconductor particle (A) and the luminescence intensity of the resin film. The resin composition may contain only one compound (F-1) or may contain two or more compounds (F-1).

[0033] An example of compound (F-1) is the compound represented by the following formula (F-1a). Compound (F-1) may also be the acid anhydride of the compound represented by formula (F-1a).

[0034] [Chemical 1] [In the formula, RB represents a divalent hydrocarbon group; when multiple RBs are present, they may be the same or different; the hydrocarbon group may have more than one substituent; when multiple substituents are present, they may be the same or different, and they may bond to each other and form a ring together with the atoms they are bonded to; the -CH2- contained in the hydrocarbon group may be substituted to at least one of -O-, -S-, -SO2-, -CO- and -NH-; p represents an integer from 1 to 10]

[0035] The divalent hydrocarbon group represented by RB can be, for example, a chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc.

[0036] As a chain hydrocarbon group, examples include straight-chain or branched alkyl diesters, which typically have 1 to 50 carbon atoms, preferably 1 to 20, and more preferably 1 to 10. As an alicyclic hydrocarbon group, examples include monocyclic or polycyclic cycloalkyl diesters, which typically have 3 to 50 carbon atoms, preferably 3 to 20, and more preferably 3 to 10. As an aromatic hydrocarbon group, examples include monocyclic or polycyclic aromatic diesters, which typically have 6 to 20 carbon atoms.

[0037] Examples of substituents that may be present in the hydrocarbon group include: alkyl groups with 1 to 50 carbon atoms, cycloalkyl groups with 3 to 50 carbon atoms, aryl groups with 6 to 20 carbon atoms, carboxyl groups, amino groups, halogen atoms, etc. Preferably, the substituents that may be present in the hydrocarbon group are carboxyl groups, amino groups, or halogen atoms.

[0038] Where the -CH2- contained in the hydrocarbon group is substituted with at least one of -O-, -CO- and -NH-, the substitution of -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0039] As a compound represented by formula (F-1a), for example, compounds represented by formulas (1-1) to (1-9) can be listed below.

[0040] [Chemical 2]

[0041] Specific examples of compounds represented by formula (F-1a) can be shown by chemical names, such as: mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetylglycine, 3-methoxybutyl 3-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, etc. Among these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0042] Another example of compound (F-1) is a polycarboxylic acid compound, preferably a compound (F-1b) formed by substituting -SH in formula (F-1a) with a carboxyl group (-COOH).

[0043] As compounds (F-1b), the following compounds can be listed for example: succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanedioic acid, octadecanoic acid, nonadecanedioic acid, dodecanoic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenic acid, sebacic acid, hexafluorosecanedioic acid, acetylenic acid, trans-torsinolic acid, 1,3-adamantanedicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, cis-1,3-cyclohexanedicarboxylic acid or trans-1,3-cyclohexanedicarboxylic acid, cis-1 4-Cyclohexanedicarboxylic acid 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-furandicarboxylic acid, diphenylcarboxylic acid Ketone-2,4'-dicarboxylic acid monohydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 2,3-pyridine dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbene dicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorobridged acid, 1H-imidazolium-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane 1,10-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiethanolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethyldioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidene diphenoxyacetic acid, 1,3-propanone dicarboxylic acid, methylene disalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl)isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-phenylenediamine, 1,3,5-benzenetricarboxylic acid, etc.

[0044] From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the resin film, the molecular weight of compound (F-1) is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, even more preferably 1000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of compound (F-1) is typically 100 or more.

[0045] The molecular weight may be either the number average molecular weight or the weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and weight average molecular weight converted from standard polystyrene, respectively, determined by gel permeation chromatography (GPC).

[0046] In the resin composition, compound (F-1) preferably has at least a portion of its molecules coordinated to semiconductor particles (A), or all or almost all of its molecules coordinated to semiconductor particles (A). That is, the resin composition preferably contains compound (F-1) coordinated to semiconductor particles (A), and may also contain both compound (F-1) coordinated to semiconductor particles (A) and compound (F-1) not coordinated to semiconductor particles (A).

[0047] The compound (F-1) contained in the semiconductor particle (A) may be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particle (A) and the luminescence intensity of the resin film. The compound (F-1) can typically be located in the semiconductor particle (A) via a first functional group and / or a second functional group. The compound (F-1) can, for example, be located on the surface of the semiconductor particle (A).

[0048] When the resin composition contains compound (F-1), the content ratio of compound (F-1) to semiconductor particles (A) in the resin composition, by mass ratio, is preferably 0.001 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, and even more preferably 0.02 or more and 0.45 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film.

[0049] When the resin composition contains compound (F-1), the content of compound (F-1) in the resin composition, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film, is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 20% by mass or less, further preferably 0.2% by mass or more and 10% by mass or less, further preferably 0.5% by mass or more and 10% by mass or less, and particularly preferably 0.5% by mass or more and 8% by mass or less.

[0050] 〔Compound (F-2)〕Compound (F-2) is a compound different from compound (F-1), and is a compound containing a polyalkylene glycol structure and having a polar group at the molecule's end. The molecule's end is preferably the end of the longest carbon chain in compound (F-2) (the carbon atom in the carbon chain may be replaced by other atoms such as oxygen atoms). The resin composition may contain only one compound (F-2), or it may contain two or more. The resin composition may contain compound (F-1) or compound (F-2), or it may contain both compound (F-1) and compound (F-2). Furthermore, a compound containing a polyalkylene glycol structure and having both the first and second functional groups belongs to compound (F-1).

[0051] The polyalkylene glycol structure refers to the structure represented by the following formula (n is an integer greater than or equal to 2).

[0052] [Chemical 3] In the formula, RC is an alkyl group, such as alkyl ethyl, alkyl propyl, etc.

[0053] As a specific example of compound (F-2), polyalkylene glycol compounds represented by the following formula (F-2a) can be listed.

[0054] [Chemical 4]

[0055] In formula (F-2a), X is a polar group, Y is a monovalent group, and ZC is a divalent or trivalent group. n is an integer greater than or equal to 2. m is 1 or 2. RC is an alkyl group.

[0056] In the resin composition, compound (F-2) preferably has at least a portion of its molecules coordinated to semiconductor particle (A), or all or almost all of its molecules coordinated to semiconductor particle (A). That is, the resin composition preferably contains compound (F-2) coordinated to semiconductor particle (A), and may also contain compound (F-2) coordinated to semiconductor particle (A) and compound (F-2) not coordinated to semiconductor particle (A).

[0057] The compound (F-2) contained in the semiconductor particle (A) may be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particle (A) and the luminescence intensity of the resin film. The compound (F-2a) can typically be contained in the semiconductor particle (A) via a polar group X. In the case where the base Y contains a polar group, the compound (F-2a) can also be contained in the semiconductor particle (A) via the polar group of base Y, or via both polar groups X and Y. The compound (F-2) can, for example, be contained on the surface of the semiconductor particle (A).

[0058] The polar group X is preferably at least one group selected from the group consisting of thiol groups (-SH), carboxyl groups (-COOH), and amino groups (-NH2). Polarity selected from this group may be advantageous in terms of improving coordination with the semiconductor particles (A). In particular, from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the resin film, the polar group X is more preferably at least one group selected from the group consisting of thiol groups and carboxyl groups.

[0059] Base Y is a monovalent base. There are no particular restrictions on base Y; examples of monovalent hydrocarbon groups that can have substituents (N, O, S, halogen atoms, etc.) can be listed. The -CH2- contained in this hydrocarbon group can be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0060] The hydrocarbon group has, for example, 1 or more and 12 or less carbon atoms. The hydrocarbon group may also have unsaturated bonds. Examples of the group Y include: alkyl groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 12 or less carbon atoms; alkoxy groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 12 or less carbon atoms. The alkyl group and alkoxy group preferably have 1 or more and 8 or less carbon atoms, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less carbon atoms. The -CH2- group contained in the alkyl group and alkoxy group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Preferably, the group Y is a straight-chain or branched-chain alkoxy group with 1 or more and 4 or less carbon atoms, more preferably a straight-chain alkoxy group with 1 or more and 4 or less carbon atoms.

[0061] The base Y may contain a polar group. Examples of such a polar group include at least one group selected from the group consisting of thiols (-SH), carboxyl groups (-COOH), and amine groups (-NH2). As described above, compounds containing a polyalkylene glycol structure and having both the first and second functional groups belong to compound (F-1). Preferably, the polar group is disposed at the end of the base Y.

[0062] The ZC group is a divalent or trivalent group. There are no particular restrictions on the ZC group, and examples include divalent or trivalent hydrocarbon groups that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 24 or less. The hydrocarbon group may also have unsaturated bonds.

[0063] Examples of divalent ZC groups include: alkyl groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 24 or less carbon atoms; and alkenyl groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 24 or less carbon atoms. Preferably, the alkyl and alkenyl groups have 1 or more and 12 or less carbon atoms, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less carbon atoms. The -CH2- group contained in the alkyl and alkenyl groups may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Examples of trivalent ZC groups include groups formed by removing one hydrogen atom from the divalent ZC groups described above.

[0064] The ZC base may have a branched structure. The ZC base having a branched structure may also have a polyalkylene glycol structure different from the polyalkylene glycol structure represented by the formula (F-2a) in a branched chain that is different from the branched chain containing the polyalkylene glycol structure represented by the formula (F-2a).

[0065] Wherein, the ZC is preferably a straight-chain or branched alkyl group having 1 or more and 6 or less carbon atoms, and more preferably a straight-chain alkyl group having 1 or more and 4 or less carbon atoms.

[0066] RC is an alkyl group, preferably a straight-chain or branched alkyl group having 1 or more and 6 or fewer carbon atoms, and more preferably a straight-chain alkyl group having 1 or more and 4 or fewer carbon atoms.

[0067] In formula (F-2a), n is an integer greater than or equal to 2, preferably greater than or equal to 2 and less than 540, more preferably greater than or equal to 2 and less than 120, and even more preferably greater than or equal to 2 and less than 60.

[0068] The molecular weight of the compound (F-2) may be, for example, 150 or more and 10,000 or less. From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the resin film, it is preferable to be 150 or more and 5,000 or less, and more preferably 150 or more and 4,000 or less.

[0069] The molecular weight may be either the number average molecular weight or the weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and weight average molecular weight converted from standard polystyrene as determined by GPC, respectively.

[0070] When the resin composition contains compound (F-2), the content ratio of compound (F-2) to semiconductor particles (A) in the resin composition, by mass ratio, is preferably 0.001 or more and 2 or less, more preferably 0.01 or more and 1.5 or less, and even more preferably 0.1 or more and 1 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film.

[0071] When the resin composition contains compound (F-2), the content of compound (F-2) in the resin composition, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film, is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 2% by mass or more and 10% by mass or less, relative to the total amount of solid components in the resin composition.

[0072] When the resin composition includes compound (F-1) and compound (F-2), the content ratio of compound (F-2) to compound (F-1) in the resin composition, by mass ratio, is preferably 1 or more and 50 or less, more preferably 5 or more and 40 or less, and even more preferably 10 or more and 25 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the resin film.

[0073] The resin composition may further include compound (F-3), which is a compound other than compound (F-1) and compound (F-2) and has the ability to coordinate with semiconductor particles (A). Examples of compound (F-3) include organic acids, organic amine compounds, and thiols. Compound (F-3) may be silicone oil modified with carboxyl and amine or thiols. By including this compound (F-3) in the resin composition, the properties of the resin film (contact angle, surface tension, and other surface properties) can be adjusted. Furthermore, compound (F-3) does not contain resin (B), polymerizable compound (C), polymerization initiator (D), polymerization initiation aid (D1), light scattering agent (E), solvent (G), antioxidant (H), or leveling agent (I).

[0074] When the resin composition contains compound (F-3), the content ratio of compound (F-3) to semiconductor particles (A) in the resin composition, by mass ratio, is preferably 0.001 or more and 2 or less, more preferably 0.01 or more and 1.5 or less, and even more preferably 0.1 or more and 1 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film.

[0075] When the resin composition contains compound (F-3), the content of compound (F-3) in the resin composition, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film, is preferably 0.1% by mass or more and 40% by mass or less, more 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, and more preferably 0.2% by mass or more and 10% by mass or less, in relation to the total amount of solid components in the resin composition.

[0076] When the resin composition contains an organic ligand (F), the content ratio of the organic ligand (F) to the semiconductor particles (A) in the resin composition, by mass ratio, is preferably 0.001 or more and 1 or less, more preferably 0.01 or more and 0.8 or less, and even more preferably 0.02 or more and 0.5 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the resin film. The content of the organic ligand (F) mentioned herein refers to the total content of all organic ligands contained in the resin composition.

[0077] Regarding the total content of semiconductor particles (A) and organic ligands (F) in the resin composition, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the resin film, it is preferably 10% by mass or more and 75% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and even more preferably 30% by mass or more and 65% by mass or less, relative to the total amount of solid components in the resin composition.

[0078] [3] Resin (B) Resin (B) may contain one or more resins. The following resins [K1] to [K4] are listed as resins (B). Resin [K1]: a copolymer of at least one (a) (hereinafter also referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a monomer (c) (which is different from (a)) (hereinafter also referred to as "(c)") capable of copolymerizing with (a); Resin [K2]: a resin obtained by reacting a monomer (b) (hereinafter also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms with an ethylene unsaturated bond, and a copolymer of (a) and (c); Resin [K3]: a resin obtained by reacting a copolymer of (a) and (b) with (c); Resin [K4]: a resin obtained by reacting a copolymer of (a) and (b) with (c), and then reacting it with a carboxylic anhydride.

[0079] As for (a), examples include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, succinic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid. Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene anhydride, and other unsaturated dicarboxylic acid anhydrides; unsaturated mono[(meth)acrylic acid alkyl] esters of di- or higher polycarboxylic acids, such as succinate mono[2-(meth)acrylic acid oxyethyl] ester and phthalate mono[2-(meth)acrylic acid oxyethyl] ester; unsaturated (meth)acrylates containing both hydroxyl and carboxyl groups in the same molecule, such as (meth)acrylate α-(hydroxymethyl) ester. Among these, (meth)acrylate and maleic anhydride are preferred from the viewpoint of copolymerization reactivity. In this specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid. The same applies to "(meth)acrylyl", "(meth)acrylate", etc.

[0080] (b) For example, a monolith having a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of the group consisting of an oxecyclopropane ring, an oxecyclobutane ring, and a tetrahydrofuran ring) and an ethylene unsaturated bond. (b) Preferably, a monolith having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

[0081] As in (b), examples include: (meth)acrylate glycidyl ester, (meth)acrylate β-methylglycidyl ester, (meth)acrylate β-ethylglycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4- Monomers of bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc., containing oxocyclic propane rings and vinyl unsaturated bonds; Monomers of 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, etc., having an oxetane ring and an ethylene-like unsaturated bond; Monomers of tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc., having a tetrahydrofuran ring and an ethylene-like unsaturated bond, etc. Regarding the aspect that the reactivity of resins [K2] to [K4] is high and unreacted residues are not easily left during the manufacture of (b), as (b), it is preferable to be a monolithic form having an oxopropane ring and an ethylene unsaturated bond.

[0082] As (c), examples include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,6]decane-8-yl methacrylate (in this art, it is commonly referred to as "( Dicyclopentyl methacrylate; also sometimes called tricyclodecyl methacrylate, tricyclo[5.2.1.02,6]decen-8-yl methacrylate (commonly known as dicyclopentenyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, allyl methacrylate, propargyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, etc.; hydroxyl-containing methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid. Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1].[1] Bicyclic unsaturated compounds such as hepta-2-ene; dicarbonyl amide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimido-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide hexanoate, N-succinimido-3-maleimide propionate, and N-(9-acridyl)maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, from the viewpoint of copolymerization reactivity and the heat resistance of resin (B), styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc., are preferred.

[0083] Among all the structural units constituting resin [K1], the ratio of structural units derived from each of the structural units in resin [K1] is preferably: structural units derived from (a): 2 mol% or more and 60 mol% or less; structural units derived from (c): 40 mol% or more and 98 mol% or less; more preferably: structural units derived from (a): 10 mol% or more and 50 mol% or less; structural units derived from (c): 50 mol% or more and 90 mol% or less. If the ratio of structural units in resin [K1] is within the aforementioned range, there is a tendency for the resin composition to have excellent storage stability and the obtained resin film to have excellent solvent resistance. Furthermore, when resin (B) contains structural units derived from (a), it may contain two or more structural units derived from (a). In this case, the ratio of structural units derived from (a) (content rate on a mol basis) is the sum of the ratios of each structural unit. The same applies to structural units derived from other monomers such as (b) and (c).

[0084] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Chemical Publishers Co., Ltd., 1st Edition, 1st Printing, March 1, 1972) and the references described in that literature.

[0085] Specifically, the following method can be used: A specified amount of (a) and (c), the polymerization initiator, and the solvent are placed into a reaction vessel. For example, nitrogen is used to replace the oxygen, thereby creating a deoxygenated environment. The mixture is then stirred while being heated and kept at a constant temperature. There are no particular limitations on the polymerization initiator and solvent used; those commonly used in the field can be used. For example, as a polymerization initiator, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) or organic peroxides (benzoyl peroxide, etc.). As a solvent, any solvent that dissolves the monomers can be used; examples include solvents that can be included in the resin composition (G) and solvents described later.

[0086] The obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or from a solid (powder) obtained by methods such as reprecipitation. If the solvent (G) described later is used as the solvent during polymerization, the reaction solution can be used directly in the preparation of the resin composition, thus simplifying the manufacturing steps of the resin composition.

[0087] The resin [K2] can be manufactured by adding a cyclic ether of (b) having 2 to 4 carbon atoms to a carboxylic acid and / or carboxylic anhydride in (a) to the copolymer of (a) and (c) in the same manner as described in the method for manufacturing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same as the ratio described for resin [K1].

[0088] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer. After producing the copolymer of (a) and (c), the environment inside the flask is replaced with air instead of nitrogen, and the reaction is carried out in the presence of (b), a reaction catalyst for the carboxylic acid or carboxylic anhydride and the cyclic ether (e.g., an organophosphorus compound, a metal complex, an amine compound, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.), for example, at a temperature above 60°C and below 130°C for 1 to 10 hours, thereby producing resin [K2].

[0089] Compared to (a) 100 mol, the amount used in (b) is preferably 5 mol or more and 80 mol or less, and more preferably 10 mol or more and 75 mol or less. By setting it within this range, there is a tendency for the storage stability of the resin composition and the balance between the solvent resistance, heat resistance and mechanical strength of the obtained resin film to become better.

[0090] Examples of organophosphorus compounds used as reaction catalysts include triphenylphosphine. Examples of amine compounds used as reaction catalysts include aliphatic tertiary amine compounds or aliphatic quaternary ammonium salt compounds; specific examples include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride. From the viewpoint of the luminescence intensity of the resin film, organophosphorus compounds are preferred as reaction catalysts.

[0091] The amount of the reaction catalyst used is preferably 0.001 parts by mass or more and 5 parts by mass or less, relative to the total amount of 100 parts by mass of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more and 5 parts by mass or less, relative to the total amount of 100 parts by mass of (a), (b) and (c).

[0092] The charging method, reaction temperature, and time, among other reaction conditions, can be appropriately adjusted taking into account the heat generated by the manufacturing equipment or polymerization. Furthermore, similarly to polymerization conditions, the charging method or reaction temperature can be appropriately adjusted taking into account the heat generated by the manufacturing equipment or polymerization.

[0093] Regarding resin [K3], as a first stage, the copolymer of (b) and (c) is obtained in the same manner as the manufacturing method of the resin [K1]. Similarly, the obtained copolymer can be used directly from the solution after the reaction, or from a concentrated or diluted solution, or can be extracted in solid (powder) form by methods such as reprecipitation.

[0094] Relative to the total number of moles of all structural units constituting the copolymer, the ratios of structural units derived from (b) and (c) are preferably: structural units derived from (b): 5 mol% or more and 95 mol% or less, structural units derived from (c): 5 mol% or more and 95 mol% or less, more preferably: structural units derived from (b): 10 mol% or more and 90 mol% or less, structural units derived from (c): 10 mol% or more and 90 mol% or less.

[0095] Resin [K3] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as those for manufacturing resin [K2]. The amount of (a) used in reaction with the copolymer is preferably 5 mol or more and 80 mol or less relative to 100 mol of (b).

[0096] Resin [K4] is a resin obtained by further reacting a carboxylic anhydride with resin [K3]. The carboxylic anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride. Examples of carboxylic anhydrides include: maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of carboxylic anhydride used is preferably 0.5 mol to 1 mol relative to the amount used in (a).

[0097] As resins [K1], [K2], [K3], and [K4], examples include: (meth)acrylate benzyl ester / (meth)acrylate copolymer, styrene / (meth)acrylate copolymer, etc. [K1]; resins obtained by adding glycidyl methacrylate to (meth)acrylate benzyl ester / (meth)acrylate copolymer, resins obtained by adding glycidyl methacrylate to (meth)acrylate tricyclodecyl ester / styrene / (meth)acrylate copolymer, resins obtained by adding glycidyl methacrylate to (meth)acrylate tricyclodecyl ester / (meth)acrylate benzyl ester / (meth)acrylate copolymer, etc. [K2]; resins obtained by reacting (meth)acrylate with a copolymer of (meth)acrylate tricyclodecyl ester / (meth)acrylate glycidyl ester, resins obtained by reacting (meth)acrylate with a copolymer of (meth)acrylate tricyclodecyl ester / (meth)acrylate glycidyl ester, etc. [K3]; A resin is obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate to obtain a resin, and the obtained resin is further reacted with tetrahydrophthalic anhydride to obtain a resin such as resin [K4]. Resin (B) is preferably at least one selected from the group consisting of resin [K2], resin [K3] and resin [K4].

[0098] As a further example of resin (B), the resin described in Japanese Patent Application Publication No. 2018-123274 can be cited. Such resin can be exemplified as a polymer (hereinafter also referred to as "resin (Ba)") having double bonds in its side chains and containing, in its main chain, a constitutive unit (α) represented by formula (I) and a constitutive unit (β) represented by formula (II), and further containing an acid group. The acid group can be introduced into the resin (Ba) for example by including a constitutive unit (γ) derived from an monomer containing an acid group (e.g., (meth)acrylic acid). Preferably, the resin (Ba) contains constitutive units (α), (β), and (γ) in its main chain backbone.

[0099] [Chemical 5] [In the formula, RA and RB may be the same or different, representing hydrogen atoms or hydrocarbon groups with 1 to 25 carbon atoms; n represents the average number of repeating units of the constituent unit represented by formula (I), and is a number greater than 1]

[0100] [Chemical 6] [In the formula, RC, whether the same or different, represents a hydrogen atom or a methyl group; RD, whether the same or different, represents a straight-chain or branched-chain hydrocarbon group with 4 to 20 carbon atoms; m represents the average number of repeating units of the constituent unit represented by formula (II), and is a number greater than 1]

[0101] In the resin (Ba), from the viewpoint of the heat resistance or storage stability of the resin (Ba), the content of the constituent unit (α) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less, relative to the total amount of all monolithic units providing the main chain backbone of the resin (Ba). In Formula (I), n represents the average number of repeating units of the constituent unit (α) in the resin (Ba), and n can be set in such a way that the content of the constituent unit (α) is within the range described above.

[0102] From the viewpoint of solvent resistance of the resin film, the content ratio of the constituent unit (β) relative to 100% by mass of all monolithic units providing the main chain backbone of the resin (Ba) is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 75% by mass or less. In Formula (II), m represents the average number of repeating units of the constituent unit (β) in the resin (Ba), and m can be set such that the content ratio of the constituent unit (β) is within the aforementioned range.

[0103] From the viewpoint of the solubility of the resin (Ba) relative to the solvent (G), the content of the constituent unit (γ) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 45% by mass or less, relative to the total amount of all monolithic units providing the main chain skeleton of the resin (Ba).

[0104] The resin (B) may include one or more of the group consisting of the resins [K1], [K2], [K3], [K4] and (Ba).

[0105] Regarding resin (B), the ratio of weight-average molecular weight Mw to acid value (unit: mgKOH / g) (Mw / acid value) is preferably 150 or less, more preferably 120 or less, even more preferably 100 or less, even more preferably 90 or less, particularly preferably 85 or less, and most preferably 70 or less. A Mw / acid value within this range is advantageous for improving the luminescence intensity of the resin film. This is believed to be because the dispersion of semiconductor particles (A) in the resin composition is improved. It is believed that the higher the dispersion, the higher the luminescence intensity of the resin film. Mw / acid value is typically 20 or more, but can also be 30 or more, or 40 or more.

[0106] Regarding the Mw of resin (B), it can be adjusted by appropriately combining the selection of raw materials used, the loading method, the reaction temperature and time, and other reaction conditions. The acid value of resin (B) can be adjusted by the content of monomer components with acid groups (such as (a) described above).

[0107] The Mw of resin (B) is the weight-average molecular weight converted from standard polystyrene by GPC. Specifically, it can be determined according to the determination method described in the Examples section below. Alternatively, the Mw of resin (B) contained in the resin composition can also be determined by GPC. The acid value of resin (B) is a value determined as the amount of potassium hydroxide (mg) required to neutralize 1 g of resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution. Specifically, it can be determined according to the determination method described in the Examples section below. Alternatively, the acid value of resin (B) contained in the resin composition can also be determined, for example, by structural analysis.

[0108] The Mw of resin (B) is typically greater than 2900. From the viewpoint of setting the Mw / acid value within the aforementioned range, and even from the viewpoint of increasing the luminescence intensity of the resin film, it is preferably 3000 or more and 12000 or less, more preferably 3000 or more and 10000 or less, further preferably 3000 or more and 9000 or less, and further preferably 3500 or more and 8500 or less.

[0109] The molecular weight distribution of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] determined by GPC is, for example, 1.0 or more and 6.0 or less, and from the viewpoint of improving the luminescence intensity of the resin film, it is preferably 1.2 or more and 4.0 or less.

[0110] From the viewpoint of setting the Mw / acid value within the aforementioned range, and even from the viewpoint of improving the luminescence intensity of the resin film, the acid value of resin (B) is preferably 90 mgKOH / g or higher and 150 mgKOH / g or lower, more preferably 90 mgKOH / g or higher and 140 mgKOH / g or lower, further preferably 90 mgKOH / g or higher and 130 mgKOH / g or lower, further preferably 90 mgKOH / g or higher and 120 mgKOH / g or lower, and particularly preferably 95 mgKOH / g or higher and 110 mgKOH / g or lower. The acid value of resin (B) within the aforementioned range is also advantageous in improving the solvent resistance of the resin film.

[0111] From the viewpoint of improving the luminescence intensity of the resin film, resin (B) is preferably a resin containing a double bond equivalent of 300 g / eq or more and 2000 g / eq or less, and more preferably a resin containing a double bond equivalent of 500 g / eq or more and 1500 g / eq or less. Examples of resins having a double bond equivalent of 300 g / eq or more and 2000 g / eq or less include (meth)acrylic resins. Resin (B) is preferably a (meth)acrylic resin.

[0112] Relative to the total amount of solid components in the resin composition, the content of resin (B) in the resin composition is, for example, 5% by mass or more and 85% by mass or less, preferably 10% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 85% by mass or less, and may also be 30% by mass or more and 80% by mass or less. If the content of resin (B) is within the aforementioned range, there is a tendency for the semiconductor particles (A) to be easily dispersed and for the luminescence intensity of the resin film to easily increase.

[0113] The ratio of the content of semiconductor particles (A) to the content of resin (B) is 0.60 or more by mass. If this ratio is within this range, a resin film with good luminescence intensity can be formed. If this ratio is small, the luminescence intensity of the resin film formed from the resin composition is easily reduced. From the viewpoint of improving the luminescence intensity of the resin film, this ratio is preferably 0.65 or more, more preferably 0.70 or more, even more preferably 0.75 or more, and also preferably 0.80 or more, 0.90 or more, 1.00 or more, 1.10 or more, 1.20 or more, or 1.30 or more.

[0114] If the ratio of the content of semiconductor particles (A) to the content of resin (B) is too large, it may be difficult to form a resin film. Therefore, the ratio is preferably 2.50 or less, more preferably 2.00 or less, more preferably 1.70 or less, and even more preferably 1.50 or less.

[0115] The ratio of the total content of semiconductor particles (A) and organic ligands (F) to the content of resin (B) is preferably greater than 1.00 by mass. If this ratio is within this range, it is easier to form a resin film with good luminescence intensity. If this ratio is small, the luminescence intensity of the resin film formed from the resin composition is easily reduced. From the viewpoint of improving the luminescence intensity of the resin film, this ratio is preferably 1.02 or more, more preferably 1.05 or more, and also preferably 1.10 or more, 1.20 or more, 1.50 or more, or 1.80 or more.

[0116] If the ratio of the total content of semiconductor particles (A) and organic ligands (F) to the content of resin (B) is too large, it may be difficult to form a resin film. Therefore, the ratio is preferably 3.00 or less, more preferably 2.50 or less, and even more preferably 2.20 or less.

[0117] As will be described in detail later, in order to further improve the luminescence intensity of the resin film, it is preferable to uniformly add resin (B) to the dispersion of semiconductor particles (A) when preparing the resin composition.

[0118] [4] Polymerizing compound (C) and polymerization initiator (D) The resin composition of the present invention is substantially free of polymerizing compound (C) and polymerization initiator (D). In this specification, "substantially free" means that the content is 0.01% by mass or less relative to the total amount of solid components in the resin composition. The content of polymerizing compound (C) and polymerization initiator (D) is preferably 0.005% by mass or less, and more preferably 0% by mass.

[0119] The resin composition of the present invention, which substantially does not contain the polymerizable compound (C) and the polymerization initiator (D), is advantageous in forming a resin film with good luminescence intensity. Resin films containing quantum dot-like semiconductor particles were previously prepared by coating a curable composition containing semiconductor particles, resin, polymerizable compound, and polymerization initiator, curing it by light or heat, and then developing it as needed. However, the inventors have discovered that semiconductor particles can sometimes deteriorate due to active free radicals or acids generated from the polymerization initiator by light or heat, thereby sometimes reducing the luminescence intensity of the resin film. The resin composition of the present invention substantially does not contain the polymerization initiator, and therefore does not cause the main cause of such deterioration. Therefore, the deterioration of semiconductor particles can be prevented or suppressed, resulting in the easy formation of a resin film with good luminescence intensity.

[0120] The resin composition of the present invention is substantially free of both the polymerization initiator (D) and the polymerizable compound (C). This is because, from the viewpoint of luminescence intensity, when the polymerization initiator (D) is substantially absent, the presence of the polymerizable compound (C) in the resin composition results in unreacted polymerizable compound (C) in the resin film formed by the resin composition, which may become a major cause of reduced luminescence intensity of the resin film. Furthermore, in display devices containing resin films, the polymerizable compound (C) may migrate to layers adjacent to the resin film, which is an undesirable situation.

[0121] Polymerizable compound (C) is a compound that can be polymerized by active free radicals, acids, etc. generated by a self-polymerization initiator (D), and refers to a compound with a weight average molecular weight of 2900 or less. Examples of polymerizable compounds (C) with a weight average molecular weight of 2900 or less include photopolymerizable compounds such as compounds with ethylene unsaturated bonds, for example (meth)acrylate compounds. The weight average molecular weight of polymerizable compound (C) is the weight average molecular weight converted from standard polystyrene as determined by GPC. The weight average molecular weight of polymerizable compound (C) is usually 150 or more.

[0122] A compound having ethylene unsaturated bonds is, for example, a polymeric compound having three or more ethylene unsaturated bonds. Examples of such polymerizable compounds include: 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, tri(2-(meth)acryloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified 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, etc.

[0123] Other examples of polymerizable compounds (C) are thermally polymerizable compounds. The resin composition of the present invention preferably also substantially does not contain thermally polymerizable compounds. "Substantially does not contain" means, as described above, that the content of thermally polymerizable compounds relative to the total amount of solid components in the resin composition is preferably 0.005% by mass or less, and more preferably 0% by mass. Known thermally polymerizable compounds can be cited as examples. The thermally polymerizable compounds described in this specification refer to compounds with a weight average molecular weight of 2900 or less.

[0124] A polymerization initiator (D) is a compound that initiates the polymerization of a polymerizable compound (C). A polymerization initiator (D) is, for example, a compound that generates active free radicals, acids, etc., through the action of light or heat. Examples of polymerization initiators (D) include photopolymerization initiators such as oxime compounds, biimidazole compounds, triazine compounds, and acetyphosphine compounds, and thermal polymerization initiators such as azo compounds or organic peroxides.

[0125] Examples of oxime compounds include those having a partial structure represented by the following formula (d1). * indicates a bond.

[0126] [Chemistry 7]

[0127] Examples of oxime compounds having a partial structure represented by formula (d1) include: N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di-di-2-yl ... Compounds including: (oxacyclopentylmethyloxy)benzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetyoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in Japanese Patent Application Publication No. 2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, and International Publication No. 2012 / 132558.

[0128] As a biimidazole compound, for example, compounds represented by formula (d5) can be listed.

[0129] [Chemical 8] [In formula (d5), RE~RJ represent aryl groups with 6 to 10 carbon atoms that may have substituents]

[0130] Aryl groups having 6 to 10 carbon atoms include, for example, phenyl, toluene, xylene, ethylphenyl, and naphthyl. Substituents include, for example, halogen atoms and alkoxy groups having 1 to 4 carbon atoms. Alkoxy groups having 1 to 4 carbon atoms include, for example, methoxy, ethoxy, propoxy, and butoxy.

[0131] Examples of biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Application Publication No. 06-75372, Japanese Patent Application Publication No. 06-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)biimidazole, etc. Imidazole compounds containing phenyl group (phenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (e.g., see Japanese Patent Publication No. 7-10913, etc.). More specifically, compounds represented by the following formulas or mixtures thereof can be listed.

[0132] [Chemical 9]

[0133] Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0134] Examples of phosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0135] Other photopolymerization initiators besides those mentioned above include, for example: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin compounds; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(diethylamino)benzophenone, and other benzophenone compounds; quinone compounds such as 9,10-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, and titanium decene compounds, etc.

[0136] Other examples of polymerization initiators (D) are thermal polymerization initiators. The resin composition of the present invention is preferably substantially free of thermal polymerization initiators. "Substantially free" means, as described above, that the content of thermal polymerization initiators relative to the total amount of solid components in the resin composition is preferably 0.005% by mass or less, and more preferably 0% by mass. Known thermal polymerization initiators can be cited as examples.

[0137] From the viewpoint of improving the luminescence intensity of the resin film, the resin composition is preferably substantially free of polymerization initiators (D1). A polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound (C) initiated by a polymerization initiator (D). Examples of polymerization initiators (D1) include photopolymerization initiators such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, as well as thermal polymerization initiators.

[0138] As amine compounds, examples include: triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc.

[0139] Examples of alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0140] Examples of thioxanthone compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0141] As a carboxylic acid compound, examples include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methyl ethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0142] [5] Light scattering agent (E) The resin composition may contain a light scattering agent (E). The resin film formed from the resin composition may exhibit light scattering properties. The resin composition may contain two or more light scattering agents (E).

[0143] Examples of light scattering agents (E) include inorganic particles such as metal or metal oxide particles and glass particles. Examples of metal oxides include TiO2, SiO2, BaTiO3, and ZnO, with TiO2 particles being preferred for efficient light scattering. The particle size of the light scattering agent (E) is, for example, about 0.03 μm or more and about 20 μm or less, preferably 0.05 μm or more and about 1 μm or less, and more preferably 0.05 μm or more and about 0.5 μm or less.

[0144] As a light scattering agent (E), it may also be a product in which the light scattering agent is pre-dispersed in part or all of the solvent (G) using a dispersant. Commercially available dispersants may be used. Examples of commercially available dispersants include: DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, and 2001 manufactured by BYK-Chemie Japan. 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc. The SOLSPERSE series manufactured by Lubrizol Corporation of Japan includes models such as 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, and 76500. BASF manufactures EFKA series products including 46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, and 1503; Ajinomoto Precision Technology... Fine-Techno manufactures Ajisper PA111, PB711, PB821, PB822, PB824, etc.

[0145] The content of light scattering agent (E) in the resin composition is, for example, 0.001% by mass or more and 50% by mass or less, relative to the total amount of solid components in the resin composition. From the viewpoint of improving the light scattering ability and luminescence intensity of the resin film, it is preferably 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 20% by mass or less.

[0146] [6] Solvent (G) The resin composition may contain solvent (G). There are no particular limitations on the solvent (G) as long as it is a solvent for dissolving the resin (B), and solvents commonly used in this field may be used. Examples include: ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more solvents (G) may be used together.

[0147] As ester solvents, examples include: methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone, etc.

[0148] As an ether solvent, examples include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole, etc.

[0149] As an ether ester solvent, examples include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, etc.

[0150] As ketone solvents, examples include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone, etc.

[0151] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of acetamide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0152] The solvent (G) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone or toluene, or a mixture of two or more of these.

[0153] Solvent (G) is a component other than the solid component, such as the solvent contained in the semiconductor particles (A) or resin (B). The content of solvent (G) in the resin composition is the ratio of the total mass of all solvents contained in the composition to the total mass of the composition, and is, for example, 40% by mass or more and 95% by mass or less, preferably 55% by mass or more and 90% by mass or less, relative to the total mass of the resin composition. In other words, the solid content of the resin composition is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 45% by mass or less. If the content of solvent (G) is within the above range, the flatness of the composition layer during coating becomes better, and there is also a tendency to easily form a resin film with an appropriate film thickness.

[0154] [7] Antioxidant (H) The resin composition may contain an antioxidant (H). As an antioxidant (H), there are no particular limitations on the antioxidant commonly used in industry, such as phenolic antioxidants, phosphorus antioxidants, phosphorus / phenolic compound antioxidants and sulfur antioxidants. Two or more antioxidants (H) may be used together.

[0155] The phosphorus / phenol composite antioxidant can be a compound having one or more phosphorus atoms and phenol structures in its molecule. From the viewpoint of the luminescence intensity of the resin film, the antioxidant (H) is preferably a phosphorus / phenol composite antioxidant.

[0156] As phenolic antioxidants, examples include: Irganox 1010 (registered trademark: pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (3,3',3'',5,5',5''-hexa-tert-butyl-α,α',α''-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, manufactured by BASF), and Irganox 3114 (Irganox... 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF (s.). Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-dimethyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF (s.). Irganox 1035: thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF (s.). Irganox 1135: Irganox 1035. 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 alkyl ester of phenylpropionic acid, manufactured by BASF (s.). Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF (s.). Irganox 3125 (Irganox 3125, manufactured by BASF (s.). Irganox 565 (2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tertiary butylaniline)-1,3,5-triazine, manufactured by BASF (s.). Adekastab (registered trademark) AO-80. AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)-1,1-dimethylethyl)-2,4,8,10-tetraoxazolo(5,5) Undecane, manufactured by ADEKA (stock), Sumilizer (registered trademark) BHT, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical (stock), Cyanox 1790 (registered trademark, manufactured by Cytec (stock), Vitamin E (manufactured by Eisai (stock), etc.)

[0157] As phosphorus-based antioxidants, examples include: Irgafos 168 (a registered trademark: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF), Irgafos 12 (a mixture of tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-6-yl]oxy]ethyl]amine, manufactured by BASF), and Irgafos 38 (a mixture of tris[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-6-yl]oxy]ethyl]amine, manufactured by BASF). 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite (manufactured by BASF), Adekastab (registered trademark) 329K, Adekastab PEP36, Adekastab PEP-8 (and above, manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (and above, manufactured by GE), Ultranox 626 (manufactured by GE), etc.

[0158] As a phosphorus / phenol complex antioxidant, examples include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphazenecycloheptane) (manufactured by Sumitomo Chemical Co., Ltd.).

[0159] As sulfur-based antioxidants, examples include: dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearate thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetra[methylene(3-dodecylthio)propionate]methane.

[0160] When the resin composition contains an antioxidant (H), the content of antioxidant (H) in the resin composition relative to 100 parts by weight of resin (B) is, for example, 0.01 parts by weight or more and 10.0 parts by weight or less. From the viewpoint of the luminescence amount and heat resistance of the resin film, it is more preferably 0.1 parts by weight or more and 8.0 parts by weight or less, more preferably 1.0 parts by weight or more and 7.0 parts by weight or less, and even more preferably 2.0 parts by weight or more and 6.0 parts by weight or less.

[0161] When the resin composition contains an antioxidant (H), and the total value of the semiconductor particles (A) and organic ligands (F) in the resin composition is set to 100 parts by mass, the content of the antioxidant (H) in the resin composition is, for example, 0.01 parts by mass or more and 0.5 parts by mass or less. From the viewpoint of the luminescence amount and heat resistance of the resin film, it is more preferably 0.02 parts by mass or more and 0.4 parts by mass or less, more preferably 0.03 parts by mass or more and 0.3 parts by mass or less, and even more preferably 0.03 parts by mass or more and 0.2 parts by mass or less.

[0162] [8] Other components and viscosity of resin composition The resin composition may also include polymerization inhibitors, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, leveling agents and other additives known in the art as needed.

[0163] The viscosity of the resin composition at 25°C is, for example, 50 mPa·s or more and 30,000 mPa·s or less. From the viewpoint of ensuring good coatability of the resin composition and the appearance of the resin film formed by coating, it is more preferably 80 mPa·s or more and 30,000 mPa·s or less, more preferably 100 mPa·s or more and 25,000 mPa·s or less, and even more preferably 200 mPa·s or more and 20,000 mPa·s or less. The viscosity of the resin composition can be measured using a Brookfield rotational viscometer.

[0164] <Method for manufacturing resin composition> The resin composition can be manufactured by a method including the step of mixing a specified component and other components used as needed. The method for manufacturing resin composition may further include the step of preparing resin (B).

[0165] The method for manufacturing the resin composition preferably includes: a step of preparing or preparing a dispersion of semiconductor particles (A) (dispersion preparation step), and a step of adding resin (B) to the dispersion (resin addition step).

[0166] The dispersion preparation step may be a step of preparing a dispersion of semiconductor particles (A), or a step of preparing a commercially available dispersion of semiconductor particles (A). The dispersion preparation step may also include a step of adding an organic ligand to the dispersion of semiconductor particles (A) (which may also contain an organic ligand). Additionally, the dispersion preparation step may include a step of replacing all or part of the organic ligand contained in the dispersion of semiconductor particles (A) with another organic ligand, or a step of replacing all or part of the solvent contained in the dispersion with another solvent. When the resin composition contains an organic ligand (F), the organic ligand (F) is preferably contained in the dispersion of semiconductor particles (A) prepared or processed in the dispersion preparation step. The solvent contained in the dispersion obtained in the dispersion preparation step is preferably at least one of the solvents (G) contained in the resin composition.

[0167] The resin addition step is, for example, adding a solution containing resin (B) to a dispersion of semiconductor particles (A). The solvent contained in the dispersion may be the same as or different from the solvent contained in the solution containing resin (B). Preferably, the solvent contained in the solution containing resin (B) is at least one of the solvents (G) contained in the resin composition.

[0168] From the viewpoint of improving the luminescence intensity of the resin film, it is preferable to add the solution containing resin (B) to the dispersion of semiconductor particles (A) by uniform addition. In particular, by specifying the mixing amount in such a way that the ratio of the total content of semiconductor particles (A) and organic ligands (F) to the content of resin (B) is greater than 1.00 by mass, and then uniformly adding the solution containing resin (B), the luminescence intensity of the resin film formed from the obtained resin composition can be improved more effectively. It is believed that when the concentration of semiconductor particles (A) coordinated by semiconductor particles (A) or organic ligands (F) to resin (B) is high to the extent that the ratio is greater than 1.00, the effect of improving luminescence intensity by uniform addition is particularly effective. In addition, if the ratio is greater than 1.00, even with uniform addition, a resin composition with good dispersion of semiconductor particles (A) and a relatively high concentration of semiconductor particles (A) can be prepared.

[0169] Uniform addition of the solution containing resin (B) refers to the continuous addition of the solution from the start of its addition until the total amount has been added. The time from the start of addition to the total amount being added is, for example, 30 seconds or more and 60 minutes or less, preferably 30 seconds or more and 30 minutes or less. The temperature of the dispersion and the solution when adding the solution containing resin (B) to the dispersion of semiconductor particles (A) is, for example, 10°C or more and 100°C or less, preferably 25°C or more and 80°C or less. The addition rate in uniform addition is, for example, 1.0 g / h or more and 500 g / h or less, preferably 5 g / h or more and 500 g / h or less, more preferably 10 g / h or more and 450 g / h or less.

[0170] The addition of the resin (B) solution to the dispersion of semiconductor particles (A) is preferably carried out while stirring the dispersion. The stirring speed is, for example, 50 rpm or more and 500 rpm or less, preferably 100 rpm or more and 300 rpm or less.

[0171] Other components to be included in the resin composition besides semiconductor particles (A), organic ligands (F), and resin (B) may be added to the dispersion of semiconductor particles (A) before the resin addition step, may be included in the solution containing resin (B) during the resin addition step, or may be added after the resin addition step. As described above, the solvent contained in the dispersion of semiconductor particles (A) and the solvent contained in the solution containing resin (B) may be at least a portion of the solvent (G) contained in the resin composition. After the resin addition step, the solvent may also be added as part of the solvent (G) contained in the resin composition.

[0172] <Resin Film and Manufacturing Method Thereof> The resin film of the present invention is a film formed from the resin composition of the present invention. The resin film can be obtained, for example, by a method including the step of coating the resin composition onto a substrate and then drying it. The resin film can be formed on the entire surface of the substrate, or it can be formed on a portion of the substrate in a patterned manner. Examples of methods for forming the resin film in a patterned manner include inkjet printing and printing. Examples of printing methods include stencil printing, screen printing, and printing application using a coating apparatus.

[0173] As a substrate, examples include: quartz glass, borosilicate glass, alumina silicate glass, soda-lime glass with silicon dioxide coating on the surface, etc.; or resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc.; silicon; and aluminum, silver, silver / copper / palladium alloy thin films formed on the substrate, etc.

[0174] The patterned resin film can be fabricated, for example, by coating a resin composition onto a substrate using a spacer mask to form a patterned composition layer. Examples of resin composition coating methods include spin coating, slot coating, and a combination of slot and spin coating.

[0175] Next, a resin film is obtained by drying the composition layer (removing volatile components such as solvents). Examples of drying methods include heat drying, reduced pressure drying, or combinations thereof. The temperature for heat drying is preferably 30°C or higher and 250°C or lower, more preferably 50°C or higher and 235°C or lower. The heating time is preferably 10 seconds or higher and 180 minutes or lower, more preferably 30 seconds or higher and 90 minutes or lower. In the case of reduced pressure drying, it is preferably carried out at a pressure of 50 Pa or higher and 150 Pa or lower. Regarding the drying of the composition layer, multiple drying steps with different drying temperatures can be performed in multiple stages.

[0176] The thickness of the resin film is not particularly limited, and can be selected appropriately according to the purpose. For example, it can be 1 μm or more and 30 μm or less, preferably 3 μm or more and 25 μm or less, more preferably 5 μm or more and 25 μm or less, and even more preferably 5 μm or more and 20 μm or less. The shape and size of the patterned resin film are not particularly limited. For example, the top view of the patterned resin film is square.

[0177] The resin film can emit light with a wavelength different from the irradiated light by irradiating it with ultraviolet or visible light. By selecting the composition or particle size of the semiconductor particles (A), the wavelength of the emitted light can be selected. The resin film has the function of converting the wavelength of the irradiated light, and therefore can be used as a color conversion layer in display devices, etc.

[0178] The resin film exhibits good luminescence intensity. Regarding the resin film, the luminescence intensity measured according to the measurement method in the Example 1 section described later is preferably 120 μW or more, more preferably 150 μW or more, even more preferably 160 μW or more, and even more preferably 165 μW or more.

[0179] <Display Device> The resin film of the present invention exhibits good luminous intensity, and is therefore effectively used as a color conversion layer (wavelength conversion layer) in display devices, particularly liquid crystal display devices, organic electroluminescence (EL) display devices, or inorganic EL display devices. Examples of such display devices include those described in Japanese Patent Application Publication No. 2006-309219, Japanese Patent Application Publication No. 2006-310303, Japanese Patent Application Publication No. 2013-15812, Japanese Patent Application Publication No. 2009-251129, and Japanese Patent Application Publication No. 2014-2363.

[0180] The display device of the present invention includes the resin film, and typically further includes a light source. The display device is not particularly limited, and may further include, for example, a light absorption layer, a light reflection member (reflective film, etc.), a diffusion film, a brightness enhancement part, a prism, a light guide plate, a dielectric material layer between components, etc.

[0181] The light-absorbing layer is a layer that has wavelength selectivity, transmitting light within a specific wavelength range and absorbing light within other wavelength ranges. The light-absorbing layer is typically a layer containing colorants such as dyes or pigments, and can be disposed on the resin film. As a light-absorbing layer, those previously known as color filters can be used.

[0182] The light-reflecting component is a component used to reflect light from a light source toward the resin film, and may be a mirror, a film of reflective particles, a reflective metal film, or a reflector, etc. The diffusion film is a film used to diffuse light from a light source or light emitted from the resin film, and may be an amplifying diffusion film, etc. The brightness enhancement section is a component used to reflect and return a portion of the light in the direction of light transmission.

[0183] A typical prism has a substrate portion and a prism portion. The substrate portion may be omitted depending on the adjacent component. The prism can be attached to the adjacent component via any suitable adhesive layer (e.g., an adhesive layer, a bonding agent layer). The prism is constructed by arranging multiple unit prisms protruding towards the opposite side (back side) of the viewing side. By arranging the convex portions of the prisms towards the back side, the light passing through the prisms is easily focused. In addition, if the convex portions of the prisms are arranged towards the back side, compared with the case where the convex portions are arranged towards the viewing side, less light is reflected that does not incident on the prisms, resulting in a display device with high brightness.

[0184] Any suitable light guide plate can be used as the light guide plate. For example, in order to deflect light from the lateral direction in the thickness direction, a light guide plate with a lens pattern formed on the back side or a light guide plate with a prism shape formed on the back side and / or the viewing side is used.

[0185] The display device may include a layer containing one or more dielectric materials in the optical path between adjacent components (layers). One or more dielectric materials may include, for example, vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, gels, hardening materials, optical bonding materials, refractive index matching or mismatched materials, refractive index gradient materials, cladding or anti-cladding materials, spacers, silicone, brightness enhancing materials, scattering or diffusing materials, reflective or antireflective materials, wavelength selective materials, wavelength selective antireflective materials, or other suitable media known in the art, but are not limited to these, and may also include any suitable material.

[0186] Specific examples of display devices include devices using wavelength conversion materials for EL displays or liquid crystal displays. Specifically, examples include: a display device in which a resin film serving as a wavelength conversion layer is disposed between a blue light source and a light guide plate along the end face (side face) of a light guide plate, serving as a backlight emitting white light (on-edge type backlight), and a light absorption layer is disposed on the side of the light guide plate; a display device in which a resin film serving as a wavelength conversion layer is disposed on a light guide plate, serving as a backlight emitting white light from a blue light source placed on the end face (side face) of the light guide plate via the light guide plate, and a light absorption layer is disposed on the wavelength conversion layer; and a display device in which a resin film is disposed near the light-emitting portion of a blue light source and serves as a wavelength conversion layer, serving as a backlight emitting white light from the irradiated light (on-chip type backlight), and a light absorption layer is disposed on the wavelength conversion layer, etc. [Examples]

[0187] Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts.

[0188] <Measurement and Evaluation> (1) Luminescence intensity of resin film On a 5 cm square glass substrate (eagle 2000; manufactured by Corning Corporation), a resin composition was coated using a film applicator (AP75 manufactured by Taiyu Machinery Co., Ltd.), dried at 100°C for 3 minutes on a heating plate, and then dried at 180°C for 10 minutes to form a resin film with a thickness of 10 μm, thereby obtaining a substrate with a resin film.

[0189] A narrow-pointing sensing backlight (OPF series; manufactured by OPTEX Fa) consisting of a light-emitting diode (LED) lamp with an emission wavelength of 444 nm and a scratch-resistant cover is prepared as the backlight. The backlight is placed with the scratch-resistant cover facing upwards, and an optical fiber for detecting the emission, connected to the spectrometer described below, is positioned at a height of 4 cm above the surface of the scratch-resistant cover. A reference glass substrate (eagle 2000; manufactured by Corning) is placed on the surface of the scratch-resistant cover of the backlight. In this state, the backlight is turned on, and the light intensity of the backlight is adjusted so that the total radiant flux (μW) of the backlight passing through the reference glass substrate (eagle 2000; manufactured by Corning) becomes 1500 μW.

[0190] Next, the substrate with the resin film that was fabricated is placed on the surface of the glass substrate. In this state, a backlight is turned on, and the luminous intensity (unit: μW) of the light emitted from the resin film is measured as the cumulative radiant flux in the range of wavelengths from 485 nm to 780 nm. The luminous intensity is measured using a spectrometer (manufactured by Ocean Optics).

[0191] (2)Weight-average molecular weight Mw of resin The weight-average molecular weight Mw of resin was determined by GPC method under the following conditions. Apparatus: K2479 (manufactured by Shimadzu Corporation) Column: Shimadzu Shim-pack GPC-80M Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI (Refractive Index) Calibration standard materials: TSK Standard Polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0192] (3) The acid value of the resin is accurately weighed. 3 g of resin solution is dissolved in a mixed solvent of 90 g of acetone and 10 g of water. 0.1% KOH aqueous solution is used as the titrant. The acid value of the resin solution is determined by an automatic titration device (com-555 manufactured by Hiranuma Sangyo Co., Ltd.). The acid value of each 1 g of solid component (mgKOH / g) is calculated based on the acid value of the solution and the solid component of the solution.

[0193] (4)The solid component of the resin solution is determined by measuring about 1 g of resin solution in an aluminum cup, drying it at 180°C for 1 hour, and then measuring its mass. The solid component (mass %) of the resin solution is calculated based on the amount of mass reduction.

[0194] (5) Viscosity of resin composition (25°C) The viscosity was measured using a Brookfield rotational viscometer at a constant temperature of 25°C and a rotation speed of 3 rpm.

[0195] <Manufacturing Example 1: Preparation of a dispersion of semiconductor particles (A-1)> A toluene dispersion of InP / ZnSeS quantum dots coordinated with oleic acid as an organic ligand (F) was prepared. The dispersion was subjected to vacuum distillation to remove toluene. 70 parts of cyclohexyl acetate were added relative to 30 parts of solids to obtain a dispersion of semiconductor particles (A-1) (30% solids).

[0196] <Manufacturing Example 2: Preparation of a dispersion of light scattering agent (E-1)> To 70 parts of titanium dioxide nanoparticles, 3 parts of DISPERBYK 21116 (manufactured by BYK-Chemie Japan) were added, and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added in a total amount of 100 parts. Then, the mixture was stirred using a coating shaker until it was fully dispersed, thereby obtaining a dispersion of light scattering agent (E-1) (73% solid content).

[0197] <Manufacturing Example 3: Preparation of Resin (B-1) Solution> In a flask including a stirrer, a reflux cooling tube with a thermometer, a dropping funnel, and a nitrogen inlet tube, 110 parts of PGMEA were added, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 80°C. 25 parts of dicyclopentyl methacrylate, 26 parts of methyl methacrylate, 16 parts of methacrylic acid, and 14 parts of 2,2'-azobis(2,4-dimethylpentanilide) were dissolved in 110 parts of PGMEA to obtain a solution. The solution was added dropwise into the flask using the dropping funnel, and the mixture was stirred at 80°C for 3 hours. Next, 16 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts of triphenylphosphine were added to a flask, heated to 110°C, and stirred for 8 hours to allow the carboxylic acid and epoxy groups in the polymer to react, thereby introducing polymerizable unsaturated bonds. Then, 17 parts of 1,2,3,6-tetrahydrophthalic anhydride were added, and the reaction continued for 3 hours to introduce carboxylic acid groups into the side chains. The reaction solution was cooled to room temperature to obtain resin (B-1) solution. Regarding resin (B-1), the weight-average molecular weight (Mw) converted from standard polystyrene is 5200, the molecular weight distribution is 2.3, the acid value is 100 mgKOH / g, and the solid content in the resin (B-1) solution is 40% by mass.

[0198] <Manufacturing Example 4: Preparation of Resin (B-2) Solution> Except that methyl methacrylate was set to 23 parts by mass, methacrylic acid to 19 parts by mass, and 2,2'-azobis(2,4-dimethylpentanonitrile) to 10 parts by mass, the resin (B-2) solution was obtained in the same manner as in Manufacturing Example 3. Regarding resin (B-2), the weight-average molecular weight (Mw) converted from standard polystyrene was 8400, the molecular weight distribution was 2.2, the acid value was 100 mgKOH / g, and the solid content in the resin (B-2) solution was 40% by mass.

[0199] <Examples 1-3, Comparative Example 1, Comparative Example 2> The resin composition was prepared in the following order. First, the dispersion (80°C) of semiconductor particles (A-1) containing organic ligand (F) obtained in Manufacturing Example 1 was uniformly added to the resin (B-1) solution (25°C) obtained in Manufacturing Example 3 for 30 seconds. Next, the dispersion of light scattering agent (E-1) obtained in Manufacturing Example 2, antioxidant (H-1), and solvent (G-1) as part of solvent (G) were added and mixed to obtain the resin composition.

[0200] The contents of each component in the resin composition, determined based on the amount added, are shown in Table 1. In Table 1, the contents of components other than solvent (G) are converted from solid components (unit: parts by mass). The unit of solvent (G) content is parts by mass. For example, semiconductor particles (A-1) are formulated as a dispersion of semiconductor particles (A-1) in the preparation of the resin composition, but the contents shown in Table 1 are the amount of semiconductor particles (A-1) contained in the dispersion itself. The solvent (G) in Table 1 includes the solvent contained in the dispersion or solution used in the preparation of the resin composition.

[0201] Regarding the content of organic ligand (F) in the resin composition shown in Table 1, the concentration of organic ligand (F) in the dispersion of semiconductor particles (A-1) obtained in Manufacturing Example 1 was determined according to the following method, and the concentration was calculated accordingly. That is, after the dispersion of semiconductor particles (A-1) was vacuum dried at 150°C to remove the solvent, the weight change of the remaining solid components was measured from 50°C to 550°C using a thermogravimetric analyzer "TGDTA6200" at a heating rate of 5°C / min. The weight change from 50°C to 500°C was taken as the weight of organic ligand (F), and the concentration of organic ligand (F) in the dispersion of semiconductor particles (A-1) was calculated.

[0202] <Example 3> Except that the resin composition was obtained in Example 1, the resin composition was obtained in the same manner as in Example 1, except that the resin (B-2) solution obtained in Manufacturing Example 4 was used instead of the resin (B-1) solution obtained in Manufacturing Example 3.

[0203] <Comparative Example 2> Except that the content of each component in the resin composition is set as shown in Table 1, the resin composition is obtained in the same manner as in Example 1.

[0204] The luminescence intensity of the resin film formed from the obtained resin composition was measured and evaluated according to the above description. The results are shown in Table 1. The mass ratio of the content of semiconductor particles (A) in the resin composition to the content of resin (B) ((A) / (B) in Table 1), the mass ratio of the total content of semiconductor particles (A) and organic ligands (F) in the resin composition to the content of resin (B) ([(A)+(F)] / (B) in Table 1), and the viscosity of the resin composition at 25°C are also shown in Table 1.

[0205] [Table 1] Example Comparative example 1 2 3 1 2 Semiconductor particles (A) A-1 34.0 43.4 34.0 10.9 28.2 Organic ligands (F) 13.1 16.7 13.1 4.2 10.8 Resin (B) B-1 45.3 33.2 77.3 53.4 B-2 45.3 Light scattering agent (E) E-1 5.0 5.0 5.0 5.0 5.0 Antioxidants (H) H-1 2.6 1.7 2.6 2.6 2.6 total 100 100 100 100 100 Solvent (G) G-1 66 66 66 66 66 G-2 56 56 56 56 56 Resin (B) Mw 5200 5200 8400 5200 5200 acid value 100 100 100 100 100 Mw / acid value 52 52 84 52 52 (A) / (B) 0.75 1.31 0.75 0.14 0.53 [(A) + (F)] / (B) 1.04 1.81 1.04 0.20 0.73 viscosity of resin composition (mPa･s) 105 102 110 125 109 Luminous intensity (μW) 169 173 146 69 114

[0206] The abbreviations of the components shown in Table 1 are detailed below. 〔1〕Organic ligand (F): Oleic acid 〔2〕Solvent (G-1): PGMEA (Propylene glycol monomethyl ether acetate) 〔3〕Solvent (G-2): Cyclohexyl acetate 〔4〕Antioxidant (H-1): Sumilizer-GP (Phosphorus / phenol complex antioxidant, manufactured by Sumitomo Chemical Co., Ltd., 100% solid content) [Simplified Explanation of the Diagram]

[0008] None

Claims

1. A resin composition comprising semiconductor particles (A), resin (B) and organic ligand (F), wherein the content of polymerizable compound (C) and polymerization initiator (D) is 0.01% by mass or less relative to the total amount of solid components of the resin composition, the ratio of the content of semiconductor particles (A) to the content of resin (B) is 0.60 or more by mass, and the ratio of the content of organic ligand (F) to the content of semiconductor particles (A) in the resin composition is 0.01 or more and 0.8 or less by mass.

2. The resin composition as claimed in claim 1, wherein, The total content of the semiconductor particles (A) and the organic ligands (F) relative to the content of the resin (B) is greater than 1.00 by mass.

3. The resin composition as claimed in claim 1, wherein the content of the polymerizable compound (C) and the polymerization initiator (D) is 0 by mass relative to the total amount of solid components of the resin composition.

4. The resin composition as claimed in claim 1, wherein the weight average molecular weight of the resin (B) is 150 or less relative to the acid value of the resin (B).

5. The resin composition as claimed in claim 1, further comprising a light scattering agent (E).

6. The resin composition as claimed in claim 1, wherein the viscosity at 25°C is 100 mPa·s or more and 30,000 mPa·s or less.

7. A resin film formed from a resin composition as described in any one of claims 1 to 6.

8. A display device comprising a resin film as described in claim 7.