Curable composition

Abstract

The present invention provides a curable composition containing semiconductor particles, which can suppress reduction in the residual film rate of a cured product when cured at a low temperature. The present invention is a curable composition containing semiconductor particles (A) and a resin (C), wherein the value X calculated from the acid value and the weight average molecular weight Mw of the resin (C) according to the following formula (1) is 10 to 59.75, and the double bond equivalent of the resin (C) is 100 g / eq or more and less than 600 g / eq. X = {acid value (mg-KOH / g) x weight average molecular weight Mw} / 10000 … (1)

Description

Technical Field

[0001] This invention relates to a curable composition comprising semiconductor particles. Background Technology

[0002] Patent document 1 describes the following: After a curable composition containing quantum dots (A) and a photopolymerizable compound (B) is dried at 100°C for 3 minutes (pre-baking) to form a film, it is exposed to light to perform an exposure process. After development, it is heat-cured at 180°C for 1 hour (post-baking) to perform a heat-curing process to obtain a cured film.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2022-170673 Summary of the Invention

[0006] Curable compositions containing semiconductor particles such as quantum dots are preferred because they can be cured at lower temperatures, which can reduce energy costs. The inventors conducted research and discovered that when the aforementioned curable compositions are cured at low temperatures, there is a problem with poor residual film yield in the cured film.

[0007] Therefore, the object of the present invention is to provide a curable composition containing semiconductor particles that can suppress the decrease in the development residue rate of the cured product during low-temperature curing.

[0008] The present invention that accomplishes the above-mentioned tasks is described below.

[0009] [1] A curable composition comprising semiconductor particles (A) and resin (C).

[0010] The value X, calculated from the acid value and weight-average molecular weight Mw of the above resin (C) using the following formula (1), is 10–59.75.

[0011] The double bond equivalent of the above resin (C) is 100 g / eq or more and less than 600 g / eq.

[0012] X = {acid value (mg - KOH / g) × weight-average molecular weight Mw} / 10000 … (1)

[0013] [2] According to the curable composition of [1], wherein the acid value of the resin (C) is less than 85 mg-KOH / g.

[0014] [3] The curable composition according to [1] or [2], wherein the weight-average molecular weight Mw of the resin (C) is 5000 or more.

[0015] [4] The curable composition according to any one of [1] to [3], wherein the mass ratio (A / C) of the semiconductor particles (A) to the resin (C) is 0.65 or more.

[0016] [5] The curable composition according to any one of [1] to [4], wherein it further comprises a polymeric compound (D) and the mass ratio (C / D) of the resin (C) to the polymeric compound (D) is 2 or more.

[0017] [6] The curable composition according to any one of [1] to [5], wherein it further comprises a polymeric compound (D), wherein the polymeric compound (D) comprises a polymeric compound having one or more cyclic hydrocarbon groups and two olefinic unsaturated bonds within one molecule.

[0018] [7] The curable composition according to [6], wherein the polymeric compound (D) further comprises a polymeric compound having an acidic functional group and three or more olefinic unsaturated bonds within one molecule.

[0019] [8] The curable composition according to any one of [1] to [7], wherein it further comprises a light scattering agent (B).

[0020] According to the present invention, it is possible to suppress the decrease in the residual film rate of the cured product formed by curing a curable composition containing semiconductor particles at low temperature. Detailed Implementation

[0021] <<Curing Compositions>>

[0022] The curable composition preferably includes, in addition to semiconductor particles (A) and resin (C), at least one of organic ligands (G), light scattering agents (B), polymerizable compounds (D), polymerization initiators (E), light stabilizers (F), leveling agents (H) and solvents (J), as needed.

[0023] It should be noted that the compounds exemplified as ingredients in this specification are not particularly limited, and one or more in combination may be used. Furthermore, there are no particular limitations on the content of multiple ingredients; adjustments can be made based on the total amount of each ingredient.

[0024] <Semiconductor Particles (A)>

[0025] Semiconductor particles (A) are preferably luminescent inorganic semiconductor particles that absorb primary light and emit light of a different wavelength than the primary light. More preferably, the luminescent inorganic semiconductor particles absorb primary light and emit green or red light. Even more preferably, the wavelength of blue light, which is the primary light, is converted into the wavelength of red light or the wavelength of green light.

[0026] In this specification, "blue" refers to all light that is visually perceived as blue (all light with intensity in the blue wavelength region, such as 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light that is visually perceived as green (all light with intensity in the green wavelength region, such as 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to all light that is visually perceived as red (all light with intensity in the red wavelength region, such as 585 nm to 780 nm), and is not limited to light of a single wavelength.

[0027] Examples of semiconductor particles (A) include quantum dots and particles composed of compounds having a perovskite-type crystal structure (hereinafter also referred to as "perovskite compounds"), with quantum dots being preferred. Quantum dots are luminescent inorganic semiconductor particles with a particle size of 1 nm to 100 nm, which emit light by utilizing the band gap of semiconductors and absorbing ultraviolet or visible light (e.g., blue light).

[0028] Examples of quantum dots include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, Cd ZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnS Compounds of Group IIB elements and Group VIA elements such as eTe, HgZnSTe; compounds of Group IIIA elements and Group VA elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs; compounds of Group IVA elements and Group VIA elements such as PdS, PbSe, etc.

[0029] When quantum dots contain sulfur (S) or selenium (Se), surface-modified quantum dots made of metal oxides or organic compounds can also be used. By using surface-modified quantum dots, it is possible to prevent the removal of S and Se by reactive components contained in or potentially contained in the curable composition.

[0030] Furthermore, quantum dots can also be combined with the aforementioned compounds to form core-shell structures. Examples of such combinations include particles with a CdSe core and a ZnS shell, and particles with an InP core and a ZnSeS shell.

[0031] The energy state of quantum dots depends on their size, thus allowing for free selection of the emission wavelength by changing the particle size. Furthermore, the narrow spectral width of light emitted from quantum dots is beneficial for achieving a wide color gamut in display devices. Moreover, the high responsivity of quantum dots also offers advantages in primary light utilization efficiency.

[0032] Perovskite compounds are compounds with a perovskite-type crystal structure whose components are A, B, and X.

[0033] A is the composition at each vertex of the hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.

[0034] X represents the composition of each vertex of the octahedron centered at B in the perovskite crystal structure, and is selected from at least one ion among halide ions and thiocyanate ions.

[0035] B is the component located at the center of the hexahedron with vertex A and the octahedron with vertex X in the perovskite crystal structure, and it is a metal ion.

[0036] As a perovskite compound with components A, B, and X, there are no particular limitations; it can be a compound with any of the following structures: three-dimensional, two-dimensional, or quasi-two-dimensional.

[0037] In the case of a three-dimensional structure, the perovskite compound is composed of ABX. （3＋δ） express.

[0038] In the case of a two-dimensional structure, perovskite compounds are composed of A2BX. （4＋δ） express.

[0039] Here, δ is a number that can be appropriately changed according to the charge balance of B, ranging from -0.7 to 0.7.

[0040] As a perovskite compound and derived from ABX （3+δ） Preferred specific examples of compounds having a three-dimensional perovskite-type crystal structure can be given as follows:

[0041] CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbI3, CH3NH3PbBr （3-y） I y (0 < y < 3), CH3NH3PbBr （3-y） Cl y(0<y<3)、(H2N=CH-NH2)PbBr3、(H2N=CH-NH2)PbCl3、(H2N=CH-NH2)PbI3、

[0042] CH3NH3Pb （1-a） Ca a Br3(0<a≤0.7)、CH3NH3Pb （1-a） Sr a Br3(0<a≤0.7)、CH3NH3Pb （1-a） La a Br （3＋δ） (0 < a ≤ 0.7, 0 < δ ≤ 0.7) CH3NH3Pb （1-a） Ba a Br3(0<a≤0.7)、CH3NH3Pb （1-a） Dy a Br （3＋δ） (0 < a ≤ 0.7, 0 < δ ≤ 0.7)

[0043] CH3NH3Pb （1-a） Na a Br （3＋δ） (0 < a ≤ 0.7, -0.7 ≤ δ < 0) CH3NH3Pb （1-a） LI a Br （3＋δ） (0 < a ≤ 0.7, -0.7 ≤ δ < 0)

[0044] CsPb （1-a） Na a Br （3＋δ） (0<a≤0.7,-0.7≤δ<0)、CsPb （1-a） LI a Br （3＋δ） (0 < a ≤ 0.7, -0.7 ≤ δ < 0)

[0045] CH3NH3Pb （1-a） Na a Br （3＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb （1-a） LI a Br （3＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb （1-a） Na a Br （3＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb（1-a） LI a Br （3＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<3)、

[0046] (H2N=CH-NH2)Pb （1-a） Na a Br （3＋δ） (0<a≤0.7,-0.7≤δ<0)、(H2N=CH-NH2)Pb （1-a） LI a Br （3＋δ） (0<a≤0.7,-0.7≤δ<0)、(H2N=CH-NH2)Pb （1-a） Na a Br （3＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<3)、(H2N=CH-NH2)Pb （1-a） Na a Br （3＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<3)、

[0047] CsPbBr3、CsPbCl3、CsPbI3、CsPbBr （3-y） I y (0<y<3)、CsPbBr （3-y） Cl y (0<y<3)、CH3NH3PbBr （3-y） Cl y (0<y<3)、

[0048] CH3NH3Pb （1-a） Zn a Br3(0<a≤0.7)、CH3NH3Pb （1-a） Al a Br （3＋δ） (0<a≤0.7,0≤δ≤0.7)、CH3NH3Pb （1-a） Co a Br3(0<a≤0.7)、CH3NH3Pb （1-a） Mn a Br3(0<a≤0.7)、CH3NH3Pb （1-a） Mg a Br3(0<a≤0.7)、

[0049] CsPb （1-a） Zn a Br3(0<a≤0.7)、CsPb（1-a） Al a Br （3＋δ） (0<a≤0.7,0<δ≤0.7)、CsPb （1-a） Co a Br3(0<a≤0.7)、CsPb （1-a） Mn a Br3(0<a≤0.7)、CsPb （1-a） Mg a Br3(0<a≤0.7)、

[0050] CH3NH3Pb （1-a） Zn a Br （3-y） I y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Al a Br （3＋δ-y） I y (0<a≤0.7,0<δ≤0.7,0<y<3)、CH3NH3Pb （1-a） Co a Br （3-y） I y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Mn a Br （3-y） I y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Mg a Br （3-y） I y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Zn a Br （3-y） Cl y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Al a Br （3＋δ-y） Cl y (0<a≤0.7,0<δ≤0.7,0<y<3)、CH3NH3Pb （1-a） Co a Br （3＋δ-y） Cl y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Mn a Br （3-y） Cl y (0<a≤0.7,0<y<3)、CH3NH3Pb （1-a） Mga Br （3-y） Cl y (0<a≤0.7, 0<y<3),

[0051] (H2N=CH-NH2)Zn a Br3 (0<a≤0.7), (H2N=CH-NH2)Mg a Br3 (0<a≤0.7), (H2N=CH-NH2)Pb （1-a） Zn a Br （3-y） I y (0<a≤0.7, 0<y<3), (H2N=CH-NH2)Pb （1-a） Zn a Br （3-y） Cl y (0 < a ≤ 0.7, 0 < y < 3), etc.

[0052] As a perovskite compound composed of A2BX （4+δ） Preferred specific examples of compounds having a two-dimensional perovskite-type crystal structure can be given as follows:

[0053] (C4H9NH3)2PbBr4, (C4H9NH3)2PbCl4, (C4H9NH3)2PbI4, (C7H 15 NH3)2PbBr4, (C7H 15 NH3)2PbCl4, (C7H 15 NH3) 2PbI4, (C4H9NH3) 2Pb （1-a） LI a Br （4＋δ） (0<a≤0.7, -0.7≤δ<0), (C4H9NH3)2Pb （1-a） Na a Br （4＋δ） (0<a≤0.7, -0.7≤δ<0), (C4H9NH3)2Pb （1-a） Rb a Br （4＋δ） (0 < a ≤ 0.7, -0.7 ≤ δ < 0)

[0054] (C7H) 15 NH3)2Pb （1-a） Na a Br （4＋δ） (0<a≤0.7, -0.7≤δ<0), (C7H 15 NH3)2Pb （1-a） LI a Br （4＋δ）(0.a≤0.7,−0.7≤δ<0)、(C7H 15 NH3)2Pb （1-a） RbaBr （4＋δ） (0:a≤0.7,-0.7≤δ<0)、

[0055] (C4H9NH3)2Pb （1-a） Ankle a Br （4＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb （1-a） LI a Br （4＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb （1-a） Rb a Br （4＋δ-y） I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、

[0056] (C4H9NH3)2Pb （1-a） Ankle a Br （4＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb （1-a） LI a Br （4＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb （1-a） Rb a Br （4＋δ-y） Cl y (0<a≤0.7,-0.7≤δ<0,0<y<4)、

[0057] (C4H9NH3)2PbBr4、(C7H 15 NH3)2PbBr4、

[0058] (C4H9NH3)2PbBr （4-y） Cl y (0<y<4)、(C4H9NH3)2PbBr （4-y） I y (0<y<4)、

[0059] (C4H9NH3)2Pb （1-a） Zn a Br4(0<a≤0.7)、(C4H9NH3)2Pb（1-a） Mg a Br4(0<a≤0.7)、(C4H9NH3)2Pb （1-a） Co a Br4(0<a≤0.7)、(C4H9NH3)2Pb （1-a） Mn a Br4(0<a≤0.7)、

[0060] (C7H 15 NH3)2Pb （1-a） Zn a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb （1-a） Mg a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb （1-a） Co a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb （1-a） Mn a Br4(0<a≤0.7)、

[0061] (C4H9NH3)2Pb （1-a） Zn a Br （4-y） I y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb （1-a） Mg a Br （4-y） I y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb （1-a） Co a Br （4-y） I y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb （1-a） Mn a Br （4-y） I y (0<a≤0.7,0<y<4)、

[0062] (C4H9NH3)2Pb （1-a） Zn a Br （4-y） Cl y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb （1-a） Mg a Br （4-y） Cl y(0<a≤0.7, 0<y<4), (C4H9NH3)2Pb （1-a） Co a Br （4-y） Cl y (0<a≤0.7, 0<y<4), (C4H9NH3)2Pb （1-a） Mn a Br （4-y） Cl y (0 < a ≤ 0.7, 0 < y < 4), etc.

[0063] The content of semiconductor particles (A) in the curable composition is preferably 3% to 60% by mass relative to 100% by mass of the solid components of the curable composition, more preferably 10% to 55% by mass, further preferably 20% to 50% by mass, and particularly preferably 30% to 50% by mass.

[0064] In this specification, the total amount of solid components in the curable composition refers to the sum of components obtained by removing the solvent (J) from the components contained in the curable composition. The content of solid components in the curable composition can be determined using known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid components of the curable composition can also be calculated based on the formulation during the preparation of the curable composition.

[0065] <Organic Ligands (G)>

[0066] Semiconductor particles (A) can exist in the curable composition in a coordinated state with organic ligands (G). The organic ligand (G) is, for example, an organic compound having a polar group that exhibits coordination ability with the semiconductor particles (A). The organic ligand (G) can, for example, be coordinated to the surface of the semiconductor particles (A). The curable composition may contain one or more organic ligands (G).

[0067] The organic ligand (G) preferably has at least a portion of its molecules coordinated to the semiconductor particle (A), or all or almost all of its molecules coordinated to the semiconductor particle (A). From the viewpoint of improving the stability and dispersibility of the semiconductor particle (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, it is advantageous to include the organic ligand (G) coordinated to the semiconductor particle (A).

[0068] The polar group of the organic ligand (G) is, for example, at least one group selected from the group consisting of thiol (-SH), carboxyl (-COOH), and amino (-NH2). Polar groups selected from this group are advantageous in terms of improving coordination with the semiconductor particle (A). High coordination contributes to improved stability and dispersibility of the semiconductor particle (A) in the curable composition, and to increased luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer. More preferably, the polar group is at least one group selected from thiol and carboxyl groups. The organic ligand (G) may have one or more polar groups.

[0069] The organic ligand (G) can be, for example, an organic compound represented by the following formula (x).

[0070] X A -R X (x)

[0071] In the formula, X A R is the polar group mentioned above. X It is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). This 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 is, for example, 1–40, or 1–30. The methylene group contained in this hydrocarbon group may be substituted by -O–, -S–, -C(=O)–, -C(=O)–O–, -O–C(=O)–, -C(=O)–NH–, -NH–, etc.

[0072] Group R X It may contain polar groups. A specific example of such a polar group can be found by referring to polar group X. A The above record.

[0073] As X has a carboxyl group as a polar group A Specific examples of organic ligands, besides formic acid, acetic acid, and propionic acid, include 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, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, and ceramide; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosapentaenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, octadecanoic acid, dihedral-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and adrenaline (docosahexaenoic acid).

[0074] X has a thiol group or an amino group as a polar group ASpecific examples of organic ligands include those exemplified above that have a carboxyl group as a polar group X. A The carboxyl group of the organic ligand is replaced by a thiol or amino organic ligand.

[0075] In addition to the above, compounds (G-1) and (G-2) can be cited as organic ligands represented by the above formula (x).

[0076] [Compound (G-1)]

[0077] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). Because compound (G-1) has a carboxyl group and / or a thiol group, it can serve as a ligand coordinated to the semiconductor particle (A). The curable composition may contain only one compound (G-1) or may contain two or more compounds.

[0078] An example of compound (G-1) is a compound represented by the following formula (G-1a). Compound (G-1) can also be an anhydride of a compound represented by formula (G-1a).

[0079]

[0080] [In the formula, R] B This indicates a divalent hydrocarbon group. When multiple R groups are present... B At this time, they can be the same or different. The above-mentioned hydrocarbon group can have more than one substituent. When multiple substituents are present, they can be the same or different, and they can bond to each other and form a ring together with the separately bonded atoms. The -CH2- contained in the above-mentioned hydrocarbon group can be replaced by at least one of -O-, -S-, -SO2-, -CO-, and -NH-. p represents an integer from 1 to 10.

[0081] As R B The divalent hydrocarbon group can be represented by, for example, chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining them.

[0082] As a chain hydrocarbon group, examples include straight-chain or branched alkane dimethyl groups, 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 cycloalkane dimethyl groups, 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 dimethyl groups, which typically have 6 to 20 carbon atoms.

[0083] Examples of substituents that can be present in the aforementioned 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, and halogen atoms. The preferred substituents for the aforementioned hydrocarbon group are carboxyl groups, amino groups, or halogen atoms.

[0084] When the -CH2- group in the above-mentioned hydrocarbon group is substituted with at least one of -O-, -CO-, and -NH-, the group substituting for -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0085] As a compound represented by formula (G-1a), for example, compounds represented by the following formulas (1-1) to (1-9) can be cited.

[0086]

[0087] If specific examples of compounds represented by formula (G-1a) are given by chemical names, examples include 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-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionic acid, and 3-mercapto-2-methylpropionic acid. Among these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0088] Another example of compound (G-1) is a polycarboxylic acid compound, preferably a compound (G-1b) in which the -SH group in formula (G-1a) is replaced by a carboxyl group (-COOH).

[0089] Examples of compounds (G-1b) include the following compounds.

[0090] Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, dodecyl octanoic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenic acid, sebacic acid, hexafluorosecanic acid, acetylenic acid, trans-aconitic 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- or trans-1,3-cyclohexanedicarboxylic acid, cis- or trans-1 4-Cyclohexanedicarboxylic acid, 1,1-Cyclopentanediacetic acid, 1,2,3,4-Cyclopentanetetracarboxylic acid, Decahydro-1,4-Naphthalenedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, Phthalic acid, 3-Fluorophthalic acid, Isophthalic acid, Tetrafluoroisophthalic acid, Terephthalic acid, Tetrafluoroterephthalic acid, 2,5-Dimethylterephthalic acid, 2,6-Naphthalenedicarboxylic acid, 2,3-Naphthalenedicarboxylic acid, 1,4-Naphthalenedicarboxylic acid, 1,1'-Ferrocenedicarboxylic acid, 2,2'-Biphenyldicarboxylic acid, 4,4'-Biphenyldicarboxylic acid, 2,5-Furfurandicarboxylic acid, Benzophenone-2,4'-Dimethyl 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, chloramphenicol, 1H-imidazolium-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,1 O-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiethanolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylenediphenoxyacetic acid, 1,3-acetonedicarboxylic 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-phenyltricarboxylic acid, etc.

[0091] From the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, the molecular weight of compound (G-1) is preferably 3000 or less, more preferably 2500 or less, further 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 (G-1) is typically 100 or more.

[0092] The molecular weight mentioned above can be either number-average or weight-average. In this case, the number-average molecular weight and weight-average molecular weight are the converted numbers of standard polystyrene determined by gel permeation chromatography (GPC), respectively.

[0093] When the curable composition contains compound (G-1), the content ratio of compound (G-1) to semiconductor particles (A) in the curable composition is preferably 0.001 to 1 by mass, more preferably 0.01 to 0.5, and even more preferably 0.02 to 0.45. This content ratio is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film is used as a wavelength conversion layer.

[0094] From the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity when the cured film is used as a wavelength conversion layer, when the curable composition contains compound (G-1), the content of compound (G-1) in the curable composition relative to the total amount of solid components in the curable composition is preferably 0.1% to 20% by mass, more preferably 0.2% to 20% by mass, even more preferably 0.2% to 10% by mass, even more preferably 0.5% to 10% by mass, and particularly preferably 0.5% to 8% by mass.

[0095] [Compound (G-2)]

[0096] Compound (G-2) is a different compound from compound (G-1), and is a compound containing a polyalkylene glycol structure with polar groups at the molecular ends. The molecular ends are preferably the ends of the longest carbon chain in compound (G-2) (the carbon atoms in the carbon chain can be replaced by other atoms such as oxygen atoms).

[0097] The curable composition may contain only one compound (G-2) or more than one compound. The curable composition may contain compound (G-1) or compound (G-2), or it may contain both compound (G-1) and compound (G-2).

[0098] It should be noted that compounds containing a polyalkylene glycol structure and having the aforementioned first and second functional groups belong to compound (G-1).

[0099] The polyalkylene glycol structure refers to the structure represented by the following formula (n is an integer greater than or equal to 2).

[0100]

[0101] In the formula, R C It is an alkylene group, for example, ethylene, propylene, etc.

[0102] As a specific example of compound (G-2), polyalkylene glycol compounds represented by the following formula (G-2a) can be cited.

[0103]

[0104] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z is a polar group. C It is a divalent or trivalent group. n is an integer greater than or equal to 2. m is 1 or 2. R C It is an alkylene group.

[0105] The polar group X is preferably at least one group selected from the group consisting of thiol (-SH), carboxyl (-COOH), and amino (-NH2). Polar groups selected from this group are advantageous in improving coordination with the semiconductor particles (A). From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, the polar group X is more preferably at least one group selected from thiol and carboxyl groups.

[0106] Group Y is a monovalent group. There are no particular restrictions on group Y; examples include monovalent hydrocarbon groups that can have substituents (N, O, S, halogen atoms, etc.). The -CH₂- group in this hydrocarbon group can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the above hydrocarbon groups is, for example, 1 to 12. This hydrocarbon group can have unsaturated bonds.

[0107] Examples of group Y include alkyl groups having a straight-chain, branched, or cyclic structure with 1 to 12 carbon atoms; and alkoxy groups having a straight-chain, branched, or cyclic structure with 1 to 12 carbon atoms. The alkyl and alkoxy groups preferably have 1 to 8 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4. The -CH2- group contained in the alkyl and alkoxy groups can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. Group Y is preferably a straight-chain or branched alkoxy group with 1 to 4 carbon atoms, more preferably a straight-chain alkoxy group with 1 to 4 carbon atoms.

[0108] Group Y may contain a polar group. Examples of such a polar group include at least one group selected from thiol (-SH), carboxyl (-COOH), and amino (-NH2). However, as described above, compounds containing a polyalkylene glycol structure and having the aforementioned first and second functional groups belong to compound (G-1). This polar group is preferably disposed at the end of group Y.

[0109] Group Z C It is a divalent or trivalent group. As a group Z... C There are no particular restrictions; examples can be divalent or trivalent hydrocarbon groups that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in this hydrocarbon group can be, for example, 1 to 24. This hydrocarbon group may have unsaturated bonds.

[0110] For group Z, which is a divalent group C Examples include alkylene groups having a linear, branched, or cyclic structure with 1 to 24 carbon atoms; and alkenyl groups having a linear, branched, or cyclic structure with 1 to 24 carbon atoms. The number of carbon atoms in the alkyl and alkenyl groups is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The -CH2- group contained in the alkyl and alkenyl groups can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. For the trivalent group Z... C Examples can be cited from the group Z, which is a divalent group as described above. C A group obtained by removing one hydrogen atom from a group.

[0111] Group Z C It can have branches. A branched group Z C It is also possible to have a polyalkylene glycol structure different from the polyalkylene glycol structure shown in the above formula (G-2a) in a branch that is different from the branch containing the polyalkylene glycol structure shown in the above formula (G-2a).

[0112] Among them, group Z C Preferably, it is a straight-chain or branched alkylene group having 1 to 6 carbon atoms, and more preferably a straight-chain alkylene group having 1 to 4 carbon atoms.

[0113] R C It is an alkylene group, preferably a straight-chain or branched alkylene group having 1 to 6 carbon atoms, and more preferably a straight-chain alkylene group having 1 to 4 carbon atoms.

[0114] In formula (G-2a), n is an integer of 2 or more, preferably 2 to 540, more preferably 2 to 120, and even more preferably 2 to 60.

[0115] The molecular weight of compound (G-2) can be, for example, around 150 to 10,000. From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, a molecular weight of 150 to 5,000 is preferred, and more preferably 150 to 4,000. This molecular weight can be either number-average or weight-average. In this case, the number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight converted from standard polystyrene as determined by GPC, respectively.

[0116] When the curable composition contains compound (G-2), the content ratio of compound (G-2) to semiconductor particles (A) in the curable composition is preferably 0.001 to 2 by mass, more preferably 0.01 to 1.5, and even more preferably 0.1 to 1. This content ratio is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer.

[0117] When the curable composition contains compound (G-2), from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, the content of compound (G-2) in the curable composition relative to the total amount of solid components of the curable composition is preferably 0.1% to 40% by mass, more preferably 0.1% to 20% by mass, even more preferably 1% to 15% by mass, and even more preferably 2% to 12% by mass.

[0118] When the curable composition contains an organic ligand (G), the ratio of the content of the organic ligand (G) to the semiconductor particles (A) in the curable composition is preferably 0.001 to 1 by mass, more preferably 0.01 to 0.8, and even more preferably 0.02 to 0.5. This content ratio is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer. The content of the organic ligand (G) referred to here means the total content of all organic ligands contained in the curable composition.

[0119] From the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, the total content of semiconductor particles (A) and organic ligands (G) in the curable composition is preferably 10% to 75% by mass, more preferably 12% to 70% by mass, relative to the total amount of solid components in the curable composition.

[0120] <Resin (C)>

[0121] Examples of resins (C) include resins [K1] to [K6].

[0122] Resin [K1]: A copolymer having structural units from at least one (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(a)"), and structural units from a monomer (c) that can copolymerize with (a) (but is different from (a)) (hereinafter also referred to as "(c)");

[0123] Resin [K2]: A copolymer having structural units from (a) above, structural units from (c) above, and structural units from monomers (b) (hereinafter also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond;

[0124] Resin [K3]: a copolymer having structural units formed by adding the above-described (b) to structural units derived from (a) above, and structural units derived from (c) above;

[0125] Resin [K4]: a copolymer having structural units formed by adding the above (b) to the structural unit from (a) above, further by ester bonding of carboxylic anhydrides, and structural units from (c) above;

[0126] Resin [K5]: a copolymer having structural units formed by adding the above-mentioned (a) to the structural units from the above-mentioned (b) and structural units from the above-mentioned (c);

[0127] Resin [K6]: a copolymer having structural units formed by adding the above (a) to the structural unit from (b) above, further by ester bonding of carboxylic anhydride, and structural units from (c) above.

[0128] Examples of unsaturated monocarboxylic acids, such as (meth)acrylic acid, crotonic acid, and ortho-, meta-, and para-vinylbenzoic acid, can be cited as (a).

[0129] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, zeaxanthin, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid.

[0130] 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.

[0131] Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic acid bicyclic [2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides;

[0132] Unsaturated mono[(meth)acryloyloxyethyl] esters of di- or higher polycarboxylic acids, such as mono[2-(meth)acryloyloxyethyl] ester of succinate and mono[2-(meth)acryloyloxyethyl] ester of phthalate;

[0133] Unsaturated (meth)acrylates such as α-(hydroxymethyl)(meth)acrylic acid, which contain both hydroxyl and carboxyl groups in the same molecule.

[0134] Among these, from the perspective of copolymerization reactivity, (meth)acrylic acid, mono[2-(meth)acryloyloxyethyl] succinate, and maleic anhydride are preferred.

[0135] In this specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid. The same applies to "(meth)acryloyl", "(meth)acrylate", etc.

[0136] (b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of an oxecyclopropane ring, an oxecyclobutane ring, and a tetrahydrofuran ring) and an olefinic unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0137] Examples of (b) include monomers having oxetyl and olefinic unsaturated bonds (b1) (hereinafter sometimes referred to as "(b1)"), monomers having oxetyl and olefinic unsaturated bonds (b2) (hereinafter sometimes referred to as "(b2)"), monomers having tetrahydrofuranyl and olefinic unsaturated bonds (b3) (hereinafter sometimes referred to as "(b3)"), etc.

[0138] Examples of (b1) include monomers (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which aliphatic unsaturated hydrocarbons are epoxidized, and monomers (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which alicyclic unsaturated hydrocarbons are epoxidized.

[0139] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, 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(glycidyl)acrylate, glycidyl ether, β-methyl-m-vinylbenzyl glycidyl ether, β-methyl-p-vinylbenzyl ... Glyceryl oxymethyl styrene, 2,4-bis(glyceryl oxymethyl)styrene, 2,5-bis(glyceryl oxymethyl)styrene, 2,6-bis(glyceryl oxymethyl)styrene, 2,3,4-tris(glyceryl oxymethyl)styrene, 2,3,5-tris(glyceryl oxymethyl)styrene, 2,3,6-tris(glyceryl oxymethyl)styrene, 3,4,5-tris(glyceryl oxymethyl)styrene, 2,4,6-tris(glyceryl oxymethyl)styrene, etc.

[0140] Examples of compounds represented by formula (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (BI), and compounds represented by formula (BII).

[0141]

[0142] In equations (BI) and (BII), R e and R f It refers to an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, wherein the hydrogen atoms in the alkyl group may be replaced by hydroxyl groups.

[0143] X e and X f Indicates a single key, -R g -、 -R g -O-、 -R g -S- or -R g -NH-.

[0144] R g Denotes alkyldiyl groups with 1 to 6 carbon atoms.

[0145] This indicates the bonding site with O.

[0146] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0147] Examples of alkyl groups in which hydrogen atoms are replaced by hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0148] As R e and R f Preferably, hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups, and 2-hydroxyethyl groups can be used; more preferably, hydrogen atoms and methyl groups can be used.

[0149] Examples of alkyldiyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0150] As X e and X f Preferably, single bonds, methylene, ethylene, etc. can be included. -CH2-O- and -CH2CH2-O-, more preferably, single bonds, -CH2CH2-O-( (Indicates the binding site with O).

[0151] Examples of compounds represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among these, compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15) are more preferred.

[0152]

[0153] Examples of compounds represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among these, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15) are more preferred.

[0154]

[0155] The compounds represented by formula (BI) and formula (BII) can be used individually or in combination of two or more. When the compounds represented by formula (BI) and formula (BII) are used together, their content ratio [compound represented by formula (BI):compound represented by formula (BII)] on a molar basis is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

[0156] As (b2), monomers having oxetyl and (meth)acryloyloxy groups are more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc.

[0157] As (b3), monomers having tetrahydrofuranyl and (meth)acryloyloxy groups are more preferred. Specifically, examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0158] As for (b), (b1) is preferred in terms of further improving reliability such as reagent resistance.

[0159] Considering the high reactivity of resins [K3] to [K6] during manufacturing and the difficulty in retaining unreacted (b), monomers having oxocyclic propane rings and olefinic unsaturated bonds are preferred as (b).

[0160] As (c), examples include, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0] 2,6 [Decane-8-yl ester (in this technical field, it is commonly referred to as "(meth)acrylate dicyclopentyl ester". Additionally, it is sometimes called "(meth)acrylate tricyclodecyl ester"), (meth)acrylate tricyclo[5.2.1.0] 2,6 Decen-8-yl ester (in this technical field, it is commonly referred to as "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentoxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate adamantyl ester, (meth)acrylate allyl ester, (meth)acrylate propargyl ester, (meth)acrylate phenyl ester, (meth)acrylate naphthyl ester, (meth)acrylate benzyl ester, and other (meth)acrylate esters;

[0161] 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate, and other methacrylates containing hydroxyl groups;

[0162] Diethyl maleate, diethyl fumarate, diethyl itaconic acid, and other dicarboxylic acid diesters;

[0163] Bicyclic [2.2.1]hept-2-ene, 5-methylbicyclic [2.2.1]hept-2-ene, 5-ethylbicyclic [2.2.1]hept-2-ene, 5-hydroxybicyclic [2.2.1]hept-2-ene, 5-hydroxymethylbicyclic [2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclic [2.2.1]hept-2-ene, 5-methoxybicyclic [2.2.1]hept-2-ene, 5-ethoxybicyclic [2.2.1]hept-2-ene, 5,6-dihydroxybicyclic [2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclic [2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclic [2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclic [2.2.1]hept-2-ene, 5,6-diethoxybicyclic [2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclic [2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclic [2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclic [2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclic [2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclic [2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclic [2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclic [2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclic [2.2.1]hept-2-ene, and other bicyclic unsaturated compounds;

[0164] N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, N-(9-acridyl)maleimide and other dicarbonylimide derivatives;

[0165] 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.

[0166] From the perspective of copolymerization reactivity, the preferred materials are methyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentyl methacrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene.

[0167] In resin [K1], the ratio of structural units from each unit is preferably 2 mol% to 60 mol% from (a) and 40 mol% to 98 mol% or less from (c) among all structural units constituting resin [K1]. More preferably, the ratio is 10 mol% to 50 mol% from (a) and 50 mol% to 90 mol% from (c).

[0168] When the ratio of structural units of resin [K1] is within the above range, there is a tendency for excellent storage stability and solvent resistance.

[0169] 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, published by Kagaku Doujin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the references cited in that literature.

[0170] Specifically, the following method can be used: a specified amount of (a) and (c), polymerization initiator and solvent, etc. are loaded into a reaction vessel, for example, by replacing oxygen with nitrogen to create a deoxygenated atmosphere, while stirring, heating and keeping warm.

[0171] There are no particular limitations on the polymerization initiators and solvents used; substances commonly used in the art can be used. For example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) and organic peroxides (benzoyl peroxide, tert-butyl peroxide-2-ethylhexanoate, etc.) can be used as polymerization initiators. As for solvents, any solvent capable of dissolving the monomers is acceptable, and solvents described later as solvents (J) can be used.

[0172] The resulting copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or from a substance extracted in solid (powder) form by methods such as reprecipitation. If the solvent (J) described later is used as the solvent during polymerization, the reaction solution can be used directly in the preparation of the composition, thus simplifying the manufacturing process.

[0173] In resin [K2], the ratio of structural units from each unit is preferably 2 to 45 mol% from (a), 2 to 95 mol% from (b), and 1 to 65 mol% from (c) among all structural units constituting resin [K2]. More preferably, the ratio is 5 to 40 mol% from (a), 5 to 80 mol% from (b), and 5 to 60 mol% from (c).

[0174] When the ratio of the structural units of resin [K2] is within the above range, there is a tendency for the composition to have excellent storage stability and developability when forming colored patterns.

[0175] Resin [K2] can be manufactured, for example, in the same manner as the method described in the manufacturing method of resin [K1].

[0176] The resin [K3] can be manufactured by adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic anhydride in (a) to a copolymer of (a) and (c).

[0177] First, the copolymers of (a) and (c) are manufactured in the same manner as described in the method for manufacturing resin [K1]. In this case, the ratio of structural units from each unit is preferably the same as the ratio described with respect to resin [K1].

[0178] 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 from (a) in the copolymer described above.

[0179] After the copolymer of (a) and (c) is produced, the atmosphere inside the flask is replaced with air instead of nitrogen, and in the presence of (b), a reaction catalyst for carboxylic acid or carboxylic anhydride with cyclic ether (e.g., organophosphorus compounds, metal complexes, amine compounds, etc.) and a polymerization inhibitor (e.g., hydroquinone, p-methoxyphenol, etc.), resin [K3] can be produced, for example, by reacting at 60°C to 130°C for 1 to 10 hours.

[0180] The amount of (b) used relative to 100 moles of (a) is preferably 5 to 80 moles, more preferably 10 to 75 moles. Within this range, it is possible to suppress the decrease in the development residue rate of the cured film when the curable composition is cured at low temperature.

[0181] Examples of organophosphorus compounds that can be used as reaction catalysts include triphenylphosphine. Examples of amine compounds that can be used as reaction catalysts include aliphatic tertiary amine compounds or aliphatic quaternary ammonium salts; specific examples include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride. Organophosphorus compounds are preferred as reaction catalysts.

[0182] The amount of reaction catalyst used is preferably 0.001 to 5 parts by mass relative to the total amount of (a), (b) and (c) 100 parts by mass.

[0183] The amount of polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to the total amount of (a), (b) and (c) 100 parts by mass.

[0184] The reaction conditions, such as the feeding method, reaction temperature, and time, can be appropriately adjusted taking into account the manufacturing equipment and the calorific value of polymerization. It should be noted that the feeding method and reaction temperature can be appropriately adjusted, similarly to the polymerization conditions, taking into account the manufacturing equipment and the calorific value of polymerization.

[0185] Resin [K4] is obtained by further reacting resin [K3] with carboxylic anhydride. The carboxylic anhydride is reacted with a hydroxyl group generated from the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether.

[0186] Examples of carboxylic anhydrides include succinic anhydride, 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, and 5,6-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride.

[0187] The amount of carboxylic anhydride used is 1 mole relative to the amount of (b), preferably 0.5 moles to 1 mole.

[0188] For resin [K5], as the first stage, the same method as for manufacturing resin [K1] is followed to obtain copolymers of (b) and (c). Similarly, for the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance obtained as a solid (powder) through methods such as reprecipitation can be used.

[0189] The ratio of structural units from (b) and (c) relative to the total molar number of all structural units constituting the copolymer is preferably 5 mol% to 95 mol% from (b) and 5 mol% to 95 mol% from (c), more preferably 10 mol% to 90 mol% from (b) and 10 mol% to 90 mol% from (c).

[0190] Resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether from (b) in the copolymer of (b) and (c) under the same conditions as the manufacturing method of resin [K3].

[0191] The amount of (a) used in the reaction with the above copolymer is preferably 5 to 120 moles relative to 100 moles of (b), and more preferably 20 to 110 moles.

[0192] Resin [K6] is obtained by further reacting resin [K5] with carboxylic anhydride. The carboxylic anhydride is reacted with a hydroxyl group generated from the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride.

[0193] Examples of carboxylic anhydrides include succinic anhydride, 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, and 5,6-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride.

[0194] The amount of carboxylic anhydride used is 1 mole relative to the amount of (a), preferably 0.1 to 1 mole, more preferably 0.2 to 1 mole, and even more preferably 0.3 to 1 mole.

[0195] As resins [K1], [K2], [K3], [K4], [K5], and [K6], for example:

[0196] Resins such as benzyl methacrylate / (meth)acrylate copolymer, styrene / (meth)acrylate copolymer, (meth)acrylate / succinic acid mono[2-(meth)acryloyloxyethyl] ester / (meth)acrylate dicyclopentyl ester / (meth)acrylate methyl acrylate copolymer [K1];

[0197] Glycidyl methacrylate / benzyl methacrylate / methacrylic acid copolymer, glycidyl methacrylate / styrene / methacrylic acid copolymer, 3,4-epoxytricyclic acrylic acid [5.2.1.0] 2,6 [Decyl ester / (meth)acrylate / (meth)acrylate methyl acrylate copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0] 2,6 Decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0] 2,6 [K2] decyl ester / (meth)acrylic acid / (meth)acrylic acid benzyl ester copolymer and other resins;

[0198] Resins obtained by adding glycidyl methacrylate to a copolymer of benzyl methacrylate and methacrylic acid, resins obtained by adding glycidyl methacrylate to a copolymer of tricyclodecyl methacrylate and styrene and methacrylic acid, and resins obtained by adding glycidyl methacrylate to a copolymer of tricyclodecyl methacrylate and benzyl methacrylate and methacrylic acid, etc. [K3];

[0199] A resin obtained by adding glycidyl methacrylate to a copolymer of dicyclopentyl methacrylate / methyl methacrylate / methacrylic acid and further esterifying it with tetrahydrophthalic anhydride or succinic anhydride; a resin obtained by adding glycidyl methacrylate to a copolymer of dicyclopentyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid and further esterifying it with tetrahydrophthalic anhydride or succinic anhydride, etc. [K4]

[0200] Resins such as (K5) obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate, and resins obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate, styrene and glycidyl (meth)acrylate.

[0201] Resins such as [K6] are obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate and further esterifying it with tetrahydrophthalic anhydride or succinic anhydride; resins such as adding (meth)acrylic acid to a copolymer of dicyclopentyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / glycidyl (meth)acrylate and further esterifying it with tetrahydrophthalic anhydride or succinic anhydride.

[0202] The resin (C) contained in the curable composition preferably includes at least one selected from resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6], more preferably includes at least one selected from resin [K3], resin [K4], resin [K5] and resin [K6], even more preferably includes at least one selected from resin [K4] and resin [K6], and particularly preferably includes resin [K6].

[0203] As a further example of resin (C), the resin described in Japanese Patent Application Publication No. 2018-123274 can be cited. As such resin, a polymer (hereinafter also referred to as "resin (Ca)") having double bonds in the side chain, and having a main chain containing a constitutive unit (α) represented by formula (I) and a constitutive unit (β) represented by formula (II) below, and further containing an acid group can be cited.

[0204] Acid groups can be introduced into the resin (Ca) by including a constituent unit (γ) from an acid-containing monomer (e.g., (meth)acrylic acid). The resin (Ca) preferably includes constituent units (α), (β), and (γ) on its main chain backbone.

[0205]

[0206] [In the formula, R] Aand R B "Same or different" indicates a hydrocarbon group with 1 to 25 hydrogen or carbon atoms. "n" represents the average number of repeating units in formula (I), and is a number greater than 1.

[0207]

[0208] [In the formula, R] C Same or different, indicating a hydrogen atom or a methyl group. R D "Same or different" indicates a straight-chain or branched hydrocarbon group with 4 to 20 carbon atoms. "m" represents the average number of repeating units in formula (II), which is 1 or more.

[0209] In the resin (Ca), from the viewpoint of the storage stability of the resin (Ca), the content ratio of the constituent unit (α) is, for example, 0.5% to 50% by mass, preferably 1% to 40% by mass, and more preferably 5% to 30% by mass, relative to 100% by mass of the total amount of all monomer units that impart the backbone of the resin (Ca). In formula (I), n represents the average number of repeating units of the constituent unit (α) in the resin (Ca), and n can be set such that the content ratio of the constituent unit (α) falls within the above range.

[0210] From the viewpoint of solvent resistance, the content of the constituent unit (β) is 10% to 90% by mass relative to the total amount of all monomer units imparting the backbone of the resin (Ca) main chain, preferably 20% to 80% by mass, and more preferably 30% to 75% by mass. In Formula (II), m represents the average number of repeating units of the constituent unit (β) in the resin (Ca), and m can be set such that the content of the constituent unit (β) falls within the above range.

[0211] From the viewpoint of the solubility of resin (Ca) relative to solvent (J), the content ratio of the constituent unit (γ) is 100% by mass relative to the total amount of all monomer units that impart the backbone of the resin (Ca) main chain, for example, 0.5% to 50% by mass, preferably 2% to 50% by mass, and more preferably 5% to 45% by mass.

[0212] In this invention, it is important that the value X, calculated from the acid value and weight-average molecular weight Mw of the resin (C) using the following formula (1), is 10 to 59.75. By setting the value X to this range, it is possible to suppress the decrease in the residual film rate (hereinafter, sometimes simply referred to as residual film rate) of the cured film when the curable composition is cured at low temperatures. The value X is preferably 12.50 or more, more preferably 16.50 or more, and even more preferably 58 or less, more preferably 56.25 or less. The value X is preferably 12.50 to 56.25, more preferably 16.50 to 56.25.

[0213] X = {acid value (mg - KOH / g) × weight-average molecular weight Mw} / 10000 … (1)

[0214] The acid value of resin (C) is determined as the amount (mg) of potassium hydroxide required to neutralize 1g of resin (C), and can be determined, for example, by titration using an aqueous solution of potassium hydroxide. Specifically, it can be determined according to the determination method described in the section on examples described later. Alternatively, for resin (C) contained in the composition, the acid value can be determined, for example, by performing structural analysis.

[0215] The weight-average molecular weight (Mw) of resin (C) is the weight-average molecular weight converted from standard polystyrene by GPC, and can be determined according to the determination method described in the examples section below. Alternatively, Mw can also be determined by GPC for resin (C) contained in the curable composition.

[0216] The weight-average molecular weight (Mw) of resin (C) is not particularly limited as long as it meets the above-mentioned value X. For example, it is 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 5,500 or more. Alternatively, it is 100,000 or less, preferably 50,000 or less, more preferably 20,000 or less, even more preferably 8,000 or less, and even more preferably 7,500 or less. The weight-average molecular weight (Mw) of resin (C) is preferably 5,000 to 8,000, more preferably 5,500 to 7,500. Especially from the viewpoint of achieving good patterning properties after exposure and development, a Mw of 5,000 or more is preferred. The Mw of resin (C) can be adjusted by appropriately combining the selection of raw materials used, the feeding method, the reaction temperature, and the reaction time.

[0217] The acid value of resin (C) is not particularly limited as long as it meets the above-mentioned value X. Preferably, it is 150 mg-KOH / g or less, more preferably 110 mg-KOH / g or less, further preferably 85 mg-KOH / g or less, particularly preferably 80 mg-KOH / g or less, most preferably 75 mg-KOH / g or less, and preferably 20 mg-KOH / g or more, more preferably 25 mg-KOH / g or more, and further preferably 30 mg-KOH / g or more. The acid value of resin (C) is preferably 25 mg-KOH / g to 80 mg-KOH / g, more preferably 30 mg-KOH / g to 75 mg-KOH / g. The acid value of resin (C) can be adjusted according to the content of monomer components with acid groups (e.g., (a) above) and the content of carboxylic anhydrides.

[0218] Furthermore, it is important that the double bond equivalent of resin (C) is 100 g / eq or more and less than 600 g / eq. By setting the double bond equivalent to the above range, the reduction in the residual film rate of the cured film when the curable composition is cured at low temperature can be suppressed. The double bond equivalent of resin (C) is preferably 200 g / eq or more, more preferably 250 g / eq or more, further preferably 300 g / eq or more, and preferably 500 g / eq or less, more preferably 450 g / eq or less, and even more preferably 400 g / eq or less. The double bond equivalent of resin (C) is preferably 250 g / eq to 450 g / eq, more preferably 300 g / eq to 400 g / eq. As a resin having the above double bond equivalent, (meth)acrylic resins can be cited. Resin (C) is preferably composed of (meth)acrylic resin.

[0219] The content of resin (C) in the curable composition relative to the total amount of solid components in the curable composition is, for example, 5% to 80% by mass, preferably 10% to 70% by mass, more preferably 13% to 60% by mass, and even more preferably 17% to 55% by mass. When the content of resin (C) is within the above range, it is possible to suppress the decrease in the residual film rate of the cured film obtained by curing the coating film of the curable composition at low temperature.

[0220] The mass ratio (A / C) of the semiconductor particles (A) to the resin (C) is preferably 0.65 or more, more preferably 1 or more, even more preferably 1.5 or more, and preferably less than 10, more preferably 8 or less, and even more preferably 5 or less.

[0221] <Light Scattering Agent (B)>

[0222] Examples of light scattering agents (B) include inorganic particles such as metal or metal oxide particles and glass particles. Examples of metal oxides include TiO2, SiO2, BaTiO3, and ZnO; from the viewpoint of efficient light scattering, TiO2 particles are preferred. The particle size of the light scattering agent (B) is, for example, about 0.03 μm to 20 μm, preferably 0.05 μm to 1 μm, and more preferably 0.05 μm to 0.5 μm.

[0223] As a light scattering agent (B), a substance obtained by pre-dispersing the light scattering agent in part or all of the solvent (J) using a dispersant (I) can be used. Commercially available products can be used as the dispersant (I). Examples of commercially available products include:

[0224] BYK-Chemie Japan manufactures DISPERBYK series including 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, and 2000. 2001, 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.;

[0225] The following models are manufactured by Lubrizol Corporation of Japan: SOLSPERSE-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, 76500, etc.

[0226] BASF manufactured EFKA-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, 1503, etc.

[0227] Ajisper PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Precision Technology Co., Ltd.

[0228] The content of light scattering agent (B) in the curable composition is, for example, 0.001% to 50% by mass relative to the total amount of solid components in the curable composition. From the viewpoint of improving the light scattering ability and luminescence intensity when the cured film of the curable composition is used as a wavelength conversion layer, it is preferably 1% to 40% by mass, more preferably 2% to 30% by mass, further preferably 5% to 30% by mass, and even more preferably 8% to 30% by mass.

[0229] <Polymerizing Compounds (D)>

[0230] Polymerizable compound (D) is a compound that can be polymerized by active free radicals, acids, etc., generated by the polymerization initiator (E) described later. Examples of polymerizable compounds (D) include photopolymerizable compounds such as compounds with olefinic unsaturated bonds, and (meth)acrylate compounds. Other examples of polymerizable compounds (D) are thermopolymerizable compounds. Curable compositions may contain two or more polymerizable compounds (D).

[0231] Examples of polymerizable compounds (D) include photopolymerizable compounds (Dα) having two intramolecular olefinic unsaturated bonds and photopolymerizable compounds (Dβ) having three or more intramolecular olefinic unsaturated bonds. In the photopolymerizable compound (Dβ), the number of intramolecular olefinic unsaturated bonds is preferably six or less. The olefinic unsaturated bonds are preferably (meth)acryloyloxy groups. The weight-average molecular weight of the polymerizable compound (D) is preferably 150 to 2900, more preferably 250 to 1500. The polymerizable compound (D) preferably contains one or more photopolymerizable compounds (Dα) and (Dβ), more preferably one or more photopolymerizable compounds (Dβ). The photopolymerizable compound (D) may also contain one or more photopolymerizable compounds (Dα) and one or more photopolymerizable compounds (Dβ).

[0232] As photopolymerizable compounds (Dα) with two intramolecular olefinic unsaturated bonds, examples include difunctional (meth)acrylate compounds, such as alkylene glycol di(meth)acrylates, polyoxyalkylene glycol di(meth)acrylates, halogen-substituted alkylene glycol di(meth)acrylates, aliphatic polyol di(meth)acrylates, hydrogenated dicyclopentadiene or tricyclodecanediol di(meth)acrylates, and di... Alkanediol or dialkyldiol Di(meth)acrylates of alkyldialkyl alcohols, di(meth)acrylates of alkylene oxide adducts of bisphenol A or bisphenol F, and epoxy di(meth)acrylates of bisphenol A or bisphenol F, etc.

[0233] More specific examples of the aforementioned difunctional (meth)acrylate compounds include ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, bis(trimethylolpropane)dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Acrylic esters, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, di(meth)acrylate of neopentyl hydroxypentanoate, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, 1,3-di... Alkyl-2,5-diyldi(meth)acrylate (Alternative name: di-) Alkanediol di(meth)acrylate, acetal compounds of hydroxyneopental and trimethylolpropane [chemical name: 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dimethylolpropane] Di(meth)acrylate of alkylene, di(meth)acrylate of tri(hydroxyethyl)isocyanurate, di(meth)acrylate of ethoxylated bisphenol A, di(meth)acrylate of propoxylated bisphenol A, di(meth)acrylate of ethoxylated bisphenol F, di(meth)acrylate of propoxylated bisphenol F, etc.

[0234] The photopolymerizable compound (Dα) having two olefinic unsaturated bonds within its molecule is preferably a photopolymerizable compound (Dα1) having one or more cyclic hydrocarbon groups and two olefinic unsaturated bonds within one molecule, and the polymerizable compound (D) preferably contains one or more photopolymerizable compounds (Dα1). In the photopolymerizable compound (Dα1), the cyclic hydrocarbon group is preferably an aromatic hydrocarbon group, and the aromatic hydrocarbon group is more preferably phenylene. In addition, in the photopolymerizable compound (Dα1), the number of cyclic hydrocarbon groups within one molecule is preferably two. Specific examples of the photopolymerizable compound (Dα1) include di(meth)acrylate of ethoxylated bisphenol A, di(meth)acrylate of propoxylated bisphenol A, di(meth)acrylate of ethoxylated bisphenol F, and di(meth)acrylate of propoxylated bisphenol F.

[0235] Examples of polymerizable compounds (Dβ) having three or more olefinic unsaturated bonds within their molecules include compounds (Dβ1) having three or more olefinic unsaturated bonds (especially (meth)acryloyloxy) and an acidic functional group, and compounds (Dβ2) having three or more olefinic unsaturated bonds (especially (meth)acryloyloxy) and no acidic functional group. The polymerizable compound (D) preferably includes at least one of compounds (Dβ1) and (Dβ2), and more preferably includes at least one of compound (Dβ1). Examples of the aforementioned acidic functional group include, for example, a carboxyl group, a sulfonic acid group, and a phosphate group. The acidic functional group is preferably a carboxyl group.

[0236] The number of olefinic unsaturated bonds (especially (meth)acryloyloxy) in molecule (Dβ1) is, for example, 3 to 6, preferably 3 to 5, and more preferably 3. The number of acidic functional groups in molecule (Dβ1) is 1 or more, preferably 1. When it has 2 or more acidic functional groups, the individual acidic functional groups may be different or the same, and it is preferable to have at least one carboxyl group.

[0237] As compound (Dβ1), examples include compounds obtained by esterifying a compound having three or more (meth)acryloyloxy and hydroxyl groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid or a dicarboxylic anhydride. Examples of such compounds include those obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, those obtained by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, those obtained by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and those obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Among these, the compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

[0238] Commercially available examples of compounds (Dβ1) include "ARONIX M-510" manufactured by Toa Synthetic Co., Ltd., whose main component is a dicarboxylic acid anhydride adduct of pentaerythritol tri(meth)acrylate, and "ARONIX M-520D" manufactured by Toa Synthetic Co., Ltd., whose main component is a dicarboxylic acid anhydride adduct of dipentaerythritol penta(meth)acrylate. These commercially available products have a carboxyl group as an acidic functional group.

[0239] The number of olefinic unsaturated bonds (especially (meth)acryloyloxy) in the compound (Dβ2) is preferably 3 to 6, more preferably 4 to 6.

[0240] Examples of compounds (Dβ2) 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)acryloyloxyethyl) 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

[0241] The polymerizable compound (D) in the curable composition, by including compound (Dα) (especially compound (Dα1)), can suppress the decrease in the residual film rate of the cured film obtained by curing the coating film of the curable composition at low temperature. In addition, it can also reduce the residue of the curable composition after development. Therefore, it is preferable that by including compound (Dβ), the decrease in the residual film rate of the cured film obtained by curing the coating film of the curable composition at low temperature can be suppressed. In addition, it can also make the curing during exposure and the patterning during development good, thereby improving the dispersion of semiconductor particles (A) and increasing the luminescence intensity when the cured film is used as a wavelength conversion layer. Therefore, it is preferable.

[0242] Of the 100% by mass of polymeric compound (D) contained in the curable composition, compound (Dα) (compound (Dα1)) is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and may also be 70% by mass or less.

[0243] Of the 100% by mass of polymeric compound (D) contained in the curable composition, compound (Dβ) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and may be 100% by mass or less, or 60% by mass or less.

[0244] When the polymerizable compound (D) in the curable composition comprises both compound (Dα) and compound (Dβ), it is preferable to include compounds (Dα1) and (Dβ1). The total content of compound (Dα1) and compound (Dβ1) relative to 100% by mass of polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may also be 100% by mass. The content of compound (Dα1) relative to 100% by mass of compound (Dα1) and compound (Dβ1) is preferably greater than 50% by mass, more preferably 53% by mass or more, further preferably 55% by mass or more, and may also be 70% by mass or less.

[0245] When the polymerizable compound (D) in the curable composition comprises both compound (Dβ1) and compound (Dβ2), the total content of compound (Dβ1) and compound (Dβ2) relative to 100% by mass of polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may also be 100% by mass. The content of compound (Dβ2) relative to 100% by mass of compound (Dβ1) and compound (Dβ2) is preferably greater than 50% by mass, more preferably 53% by mass or more, further preferably 55% by mass or more, and may also be 70% by mass or less.

[0246] The content of the polymeric compound (D) in the curable composition (the total amount when multiple compounds are included) relative to 100% by mass of the total solid components of the curable composition is preferably 3% to 30% by mass, more preferably 4% to 20% by mass, and even more preferably 5% to 15% by mass. When the content of the polymeric compound (D) is within the above range, it is possible to suppress the decrease in the residual film rate of the cured film obtained by curing the coating film of the curable composition at low temperature.

[0247] From the viewpoint of suppressing the reduction of the residual film rate of the cured film, the mass ratio (C / D) of the above-mentioned resin (C) to polymerizable compound (D) in the curable composition is preferably 2 or more, more preferably 2.3 or more, even more preferably 2.5 or more, and preferably 8 or less, more preferably 7 or less, even more preferably 6 or less. When the mass ratio (C / D) of the above-mentioned resin (C) to polymerizable compound (D) satisfies the above range, it is preferable that the photopolymerizable compound (D) includes one or more photopolymerizable compounds (Dα1), more preferably that the photopolymerizable compound (D) includes one or more photopolymerizable compounds (Dα1) and one or more photopolymerizable compounds (Dβ1).

[0248] <Polymerization Initiator (E)>

[0249] A polymerization initiator (E) is a compound that can generate active free radicals, acids, etc., under the action of light or heat, thereby initiating the polymerization of a polymerizable compound (D). A curable composition may contain one or more polymerization initiators (E).

[0250] Examples of polymerization initiators (E) include oxime compounds, such as those represented by formula (EA). The polymerization initiator (E) comprising compounds represented by formula (EA) can suppress the decrease in the residual film rate of the cured film when the curable composition is cured at low temperatures, and is also advantageous from the viewpoint of achieving good patterning after exposure and development. Furthermore, the compound comprising formula (EA) can also enhance the luminescence intensity (fluorescence intensity) evaluated in the examples described later.

[0251]

[0252] [In the formula,]

[0253] R ea1 It indicates a branched hydrocarbon group with 3 to 20 carbon atoms that can have substituents.

[0254] R ea2 ~R ea5 Each can independently represent a hydrocarbon group with 1 to 20 carbon atoms that can have substituents.

[0255] n represents any integer from 0 to 4.

[0256] The -CH2- group in the above hydrocarbon group can be replaced by -O-, -S-, -CO-, or -OCO-.

[0257] As R ea1 The branched hydrocarbon group with 3 to 20 carbon atoms can be represented by saturated hydrocarbon groups with 3 to 20 carbon atoms and unsaturated hydrocarbon groups with 3 to 20 carbon atoms.

[0258] As R ea1The term refers to a branched saturated hydrocarbon group with 3 to 20 carbon atoms. Examples include 1-methylethyl (isopropyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl), 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, and 1,3-dimethylbutyl 2,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylpentyl, 2,2-Dimethylpentyl, 3,3-Dimethylpentyl, 1,2-Dimethylpentyl, 1,3-Dimethylpentyl, 2,3-Dimethylpentyl, 1-Ethylpentyl, 2-Ethylpentyl, 3-Ethylpentyl, 1-Methylhexyl, 2-Methylhexyl, 3-Methylhexyl, 4-Methylhexyl, 1,1-Dimethylhexyl, 2,2-Dimethylhexyl, 3 3-Dimethylhexyl, 1,2-Dimethylhexyl, 1,3-Dimethylhexyl, 2,3-Dimethylhexyl, 1-Ethylhexyl, 2-Ethylhexyl, 3-Ethylhexyl, 1-Methylheptyl, 2-Methylheptyl, 3-Methylheptyl, 4-Methylheptyl, 1,1-Dimethylheptyl, 2,2-Dimethylheptyl, 3,3-Dimethylheptyl, 1,2-Dimethylheptyl, 1,3-Dimethylheptyl, 2,3-Dimethylheptyl, 1-Ethylheptyl, 2-Ethylheptyl, 3-Ethylheptyl, 1-Methyloctyl, 2-Methyloctyl, 3 -Methyl octyl, 4-methyl octyl, 1,1-dimethyl octyl, 2,2-dimethyl octyl, 3,3-dimethyl octyl, 1,2-dimethyl octyl, 1,3-dimethyl octyl, 2,3-dimethyl octyl, 1-ethyl octyl, 2-ethyl octyl, 3-ethyl octyl, 1-methyl nonyl, 2-methyl nonyl, 3-methyl nonyl, 4-methyl nonyl, dimethyl nonyl, ethyl nonyl, methyl decyl, dimethyl decyl, ethyl decyl, methyl undecyl, dimethyl undecyl, ethyl undecyl, methyl dodecyl, and other branched alkyl groups.

[0259] R ea1 The branched alkyl group can be any one of branched primary alkyl group, branched secondary alkyl group, or branched tertiary alkyl group.

[0260] R ea1 The branched saturated hydrocarbon group represented preferably has 4 or more carbon atoms, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0261] As R ea1 The branched unsaturated hydrocarbon group represented can be exemplified by the above R ea1The group represented by the branched saturated hydrocarbon group containing at least one carbon-carbon single bond replaced by a carbon-carbon double bond or a carbon-carbon triple bond, etc.

[0262] As R ea1 The branched unsaturated hydrocarbon groups represented include, for example, alkenyl groups such as isopropenyl, isobutylenyl, isopentenyl, isohexenyl, isoheptenyl, isooctenyl, isononenyl, and isodetenyl; and alkynyl groups such as isopropynyl, isobutynyl, isopentenyl, isohexynyl, isoheptynyl, isooctynyl, isononynyl, and isodeynyl.

[0263] R ea1 The branched unsaturated hydrocarbon group represented preferably has 4 or more carbon atoms, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0264] As R ea2 R ea3 R ea4 and R ea5 The hydrocarbon groups representing 1 to 20 carbon atoms can include saturated hydrocarbon groups with 1 to 20 carbon atoms, unsaturated hydrocarbon groups with 2 to 20 carbon atoms, and aromatic hydrocarbon groups with 6 to 20 carbon atoms. R ea2 R ea3 R ea4 and R ea5 The hydrocarbon groups represented can be the same or different.

[0265] Examples of saturated hydrocarbon groups with 1 to 20 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, further preferably 1 to 10, and even more preferably 1 to 8.

[0266] Examples of unsaturated hydrocarbon groups with 2 to 20 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and eicoseneyl alkenyl groups; acetylenyl, propynyl, hexynyl, dedecynyl, and eicoseneyl alkenyl alkenyl groups; and cyclopentenyl, cyclohexenyl, and cycloheptenyl alkenyl groups. The number of carbon atoms in the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

[0267] Examples of aromatic hydrocarbon groups with 6 to 20 carbon atoms include phenyl, xylyl, trimethylphenyl, dipropylphenyl, di(2,2-dimethylpropyl)phenyl, naphthyl, benzyl, phenylethyl, and phenylbutyl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and even more preferably 6 to 12.

[0268] As R ea1 R ea2 R ea3 R ea4 and R ea5 The hydrocarbon group can have substituents, such as halogen atoms, cyano groups, and nitro groups. The preferred halogen atoms are fluorine, bromine, chlorine, and iodine atoms.

[0269] The -CH2- group in the above hydrocarbon group can be replaced by -O-, -S-, -CO- or -OCO-, the adjacent -CH2- groups are not replaced by the same group at the same time, and the terminal -CH2- group is not replaced.

[0270] n represents any integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, further preferably an integer of 0 or 1, and even more preferably 0.

[0271] -OCO-R ea4 base( The bonding position (indicating the bonding site with the phenyl group) can be this -OCO-R ea4 The phenyl group is bonded to any one of the 2, 3, or 4 positions, preferably the 3 or 4 position, more preferably the 4 position.

[0272] R ea1 The branched hydrocarbon group representing 3 to 20 carbon atoms is preferably a branched saturated hydrocarbon group representing 3 to 20 carbon atoms, more preferably a branched alkyl group representing 3 to 20 carbon atoms, and even more preferably a branched alkyl group representing 3 to 10 carbon atoms. It is preferably selected from one or more of 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 1-ethylheptyl, 2-ethylheptyl, and 3-ethylheptyl.

[0273] R ea2 R ea3 R ea4 and R ea5The hydrocarbon group represented by carbon atoms of 1 to 20 is preferably a saturated hydrocarbon group of 1 to 20 carbon atoms, an unsaturated hydrocarbon group of 2 to 20 carbon atoms, more preferably a saturated hydrocarbon group of 1 to 20 carbon atoms, even more preferably a chain saturated hydrocarbon group of 1 to 10 carbon atoms, and even more preferably a chain alkyl group of 1 to 8 carbon atoms.

[0274] R ea2 Preferably, it is a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 6 carbon atoms.

[0275] R ea3 Preferably, it is a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 3 carbon atoms.

[0276] R ea4 Preferably, it is a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 3 carbon atoms.

[0277] R ea5 Preferably, it is a chain or branched alkyl group having 1 to 8 carbon atoms, more preferably a chain or branched alkyl group having 1 to 6 carbon atoms.

[0278] Furthermore, for polymerization initiators (E) that are oxime compounds, compounds represented by formula (EB) can be cited as examples. By including compounds represented by formula (EB) in the polymerization initiator (E), it is possible to suppress the decrease in the residual film rate of the cured film when the curable composition is cured at low temperature.

[0279]

[0280] [In the formula,]

[0281] R eb1 It indicates a branched hydrocarbon group with 3 to 20 carbon atoms that can have substituents.

[0282] R eb2 ~R eb4 Each can independently represent a hydrocarbon group with 1 to 20 carbon atoms that can have substituents.

[0283] m represents any integer from 0 to 4.

[0284] The -CH2- group in the above hydrocarbon group can be replaced by -O-, -S-, -CO-, or -OCO-.

[0285] As R eb1 The branched hydrocarbon group with 3 to 20 carbon atoms can be represented by saturated hydrocarbon groups with 3 to 20 carbon atoms and unsaturated hydrocarbon groups with 3 to 20 carbon atoms.

[0286] As R eb1The branched saturated hydrocarbon group representing 3 to 20 carbon atoms can be exemplified by the above-mentioned R groups. ea1 The same group as the branched saturated hydrocarbon group representing 3 to 20 carbon atoms.

[0287] R eb1 The branched alkyl group can be any of a branched primary alkyl group, a branched secondary alkyl group, or a branched tertiary alkyl group.

[0288] R eb1 The branched saturated hydrocarbon group represented preferably has 4 or more carbon atoms, more preferably 5 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0289] As R eb1 The branched unsaturated hydrocarbon group represented can be exemplified by the above R eb1 The group represented by the branched saturated hydrocarbon group containing at least one carbon-carbon single bond replaced by a carbon-carbon double bond or a carbon-carbon triple bond, etc.

[0290] As R eb1 The branched unsaturated hydrocarbon group can be represented by, for example, alkenyl groups such as isopropenyl, isobutenyl, isopentenyl, isohexenyl, isoheptenyl, isooctenyl, isononenyl, and isodetenyl; and alkynyl groups such as isopropynyl, isobutynyl, isopentenyl, isohexynyl, isoheptynyl, isooctynyl, isononynyl, and isodeynyl.

[0291] R eb1 The branched unsaturated hydrocarbon group represented preferably has 4 or more carbon atoms, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0292] As R eb2 R eb3 and R eb4 The hydrocarbon groups representing 1 to 20 carbon atoms can include saturated hydrocarbon groups with 1 to 20 carbon atoms, unsaturated hydrocarbon groups with 2 to 20 carbon atoms, and aromatic hydrocarbon groups with 6 to 20 carbon atoms. R eb2 R eb3 and R eb4 The hydrocarbon groups represented can be the same or different.

[0293] Examples of saturated hydrocarbon groups with 1 to 20 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, further preferably 1 to 10, and even more preferably 1 to 8.

[0294] Examples of unsaturated hydrocarbon groups with 2 to 20 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and eicoseneyl alkenyl groups; acetylenyl, propynyl, hexynyl, dedecynyl, and eicoseneyl alkenyl alkenyl groups; and cyclopentenyl, cyclohexenyl, and cycloheptenyl alkenyl groups. The number of carbon atoms in the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

[0295] Examples of aromatic hydrocarbon groups with 6 to 20 carbon atoms include phenyl, xylyl, trimethylphenyl, dipropylphenyl, di(2,2-dimethylpropyl)phenyl, naphthyl, benzyl, phenylethyl, and phenylbutyl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and even more preferably 6 to 12.

[0296] As R eb1 R eb2 R eb3 and R eb4 The hydrocarbon group may have substituents, including halogen atoms, cyano groups, and nitro groups. The halogen atom is preferably a fluorine atom, bromine atom, chlorine atom, or iodine atom, and more preferably a fluorine atom.

[0297] The -CH2- group in the above hydrocarbon group can be replaced by -O-, -S-, -CO- or -OCO-, especially by -O-. The adjacent -CH2- groups are not replaced by the same group at the same time, and the terminal -CH2- group is not replaced.

[0298] m represents any integer from 0 to 4, preferably an integer from 1 to 3, more preferably an integer from 2 to 3, and even more preferably 3.

[0299] When m is 1 or more, it is preferable to... -R eb4 At least one of the 2, 4, and 6 positions of the bonded phenyl group is bonded with -R eb4 ( (Indicates the bonding site with the phenyl group), more preferably in -R eb4 At least two of the 2, 4, and 6 positions of the bonded phenyl group are bonded with -R eb4 Further optimization in -R eb4 The bonded phenyl group has bonds at all positions of the 2, 4, and 6 positions. -R eb4 .

[0300] R eb1 The branched hydrocarbon group representing 3 to 20 carbon atoms is preferably a branched saturated hydrocarbon group representing 3 to 20 carbon atoms, more preferably a branched alkyl group representing 3 to 20 carbon atoms, and even more preferably a branched alkyl group representing 3 to 10 carbon atoms. It is preferably selected from one or more of 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 1-ethylheptyl, 2-ethylheptyl, and 3-ethylheptyl.

[0301] R eb2 The hydrocarbon group represented by carbon atoms is 1 to 20, preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 17 carbon atoms, even more preferably an aromatic hydrocarbon group with 7 to 15 carbon atoms, and particularly preferably an aromatic hydrocarbon group with 8 to 13 carbon atoms. In any of these preferred embodiments, it is preferable to have 1 to 8 (especially 1 to 5) fluorine atoms as substituents and to have 1 to 2 -CH2- atoms replaced with -O-.

[0302] As R eb2 The preferred embodiment has an aromatic hydrocarbon group with 8 to 13 carbon atoms, preferably any one of (eb2-1) to (eb2-6) below.

[0303]

[0304] R eb3 and R eb4 Each of the hydrocarbon groups representing 1 to 20 carbon atoms is preferably a saturated hydrocarbon group with 1 to 20 carbon atoms, an unsaturated hydrocarbon group with 2 to 20 carbon atoms, more preferably a saturated hydrocarbon group with 1 to 20 carbon atoms, even more preferably a chain-like saturated hydrocarbon group with 1 to 10 carbon atoms, even more preferably a chain-like alkyl group with 1 to 8 carbon atoms, and particularly preferably a chain-like alkyl group with 1 to 3 carbon atoms.

[0305] It should be noted that in formula (EB), when the -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -OCO-, the number of carbon atoms in the replaced part is counted according to the number of carbon atoms in the original -CH2-.

[0306] Examples of polymerization initiators (E) other than those represented by formulas (EA) and (EB) include oxime compounds (excluding those represented by formulas (EA) and (EB)), alkylphenyl ketone compounds, biimidazole compounds, triazine compounds and acylphosphine compounds, as well as thermal polymerization initiators such as azo compounds and organic peroxides.

[0307] One example of an oxime compound (excluding compounds represented by formula (EA) and formula (EB)) is an oxime compound having a first molecular structure represented by the following formula (1). Hereinafter, this oxime compound will also be referred to as "oxime compound (1)".

[0308]

[0309] Including oxime compound (1) as a polymerization initiator (E) may be advantageous from the viewpoint of increasing luminescence intensity. One reason speculated to be that, due to the unique molecular structure of oxime compound (1), the absorption wavelength of oxime compound (1) changes significantly before and after the oxime compound (1) is cleaved (decomposed) to initiate photopolymerization, thus oxime compound (1) has a high photoradical polymerization initiation ability.

[0310] In equation (1), R 1 R represents 11 OR 11 COR 11 SR 11 CONR 12 R 13 Or CN.

[0311] R 11 R 12 and R 13 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0312] R 11 R 12 or R 13 The hydrogen atom of the group represented can be ORed 21 COR 21 SR 21 NR 22 R 23CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 CN, halogen atom, or COOR 21 replace.

[0313] R 21 R 22 and R 23 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0314] R 21 R 22 or R 23 The hydrogen atom of the indicated group can be replaced by CN, halogen atom, hydroxyl or carboxyl group.

[0315] R 11 R 12 R 13 R 21 R 22 or R 23 When the indicated group has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupt 1 to 5 times.

[0316] R 24 It represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0317] R 11 R 12 R 13 R 21 R 22 or R 23 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic. Additionally, R... 12 With R 13 and R 22 With R23 They can each form a ring together.

[0318] The binding sites of the second molecular structure, which is the molecular structure other than the first molecular structure, are represented by the oxime compound (1).

[0319] As R in equation (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Alkyl groups representing 1 to 20 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

[0320] As R in equation (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Aryl groups representing 6 to 30 carbon atoms include, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracene, phenanthryl, phenyl groups substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracene, etc.

[0321] As R in equation (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Aryl groups representing 7 to 30 carbon atoms include, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, etc.

[0322] As R in equation (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Heterocyclic groups representing 2 to 20 carbon atoms include, for example, pyridyl, pyrimidinyl, furanyl, thiophene, tetrahydrofuranyl, dioxolane, and benzo[a]yl. 2-Azolyl, Tetrahydropyranyl, Pyrrolidinyl, Imidazolyl, Pyrazolyl, Thiazolyl, Isothiazolyl azolealkyl, isopropyl Zolpidemyl, piperidinyl, piperazine, morpholinyl, etc., preferably five- to seven-membered heterocyclic rings.

[0323] R in equation (1) 12 With R 13 and R 22 With R 23 The fact that they can form a ring together refers to R 12 With R 13 and R 22 With R 23 They can each form a ring together with the nitrogen, carbon, or oxygen atoms they are attached to.

[0324] As R in equation (1) 12 With R 13 and R 22 With R 23 Rings that can be formed together include, for example, cyclopentane rings, cyclohexane rings, cyclopentene rings, benzene rings, piperidine rings, morpholine rings, lactone rings, lactam rings, etc., preferably five- to seven-membered rings.

[0325] As R in equation (1) 11 R 12 R 13 R 21 R 22 and R 23 Halogen atoms that can be present in the form of substituents include fluorine, chlorine, bromine, and iodine atoms.

[0326] R in equation (1) 1 R is preferred 11 More preferably, it is an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0327] An example of a second molecular structure connected to the first molecular structure represented by formula (1) is the structure represented by formula (2) below. The second molecular structure refers to any other molecular structure part besides the first molecular structure described above that is present in the oxime compound (1).

[0328] In formula (2) " The bonding site represented by "" is the same as the "" in equation (1) The "-" indicates a direct bond. That is, when the structure of the second molecule is the structure represented by formula (2), the "-" in formula (2) indicates a direct bond. The benzene ring in formula (1) has a "- The carbonyl group is directly bonded.

[0329]

[0330] In equation (2), R 2 and R 3 Each represents R independently. 11 OR 11 SR 11 COR 11 CONR 12 R 13 NR 12 COR 11 OCOR 11 COOR 11 SCOR 11 OCSR 11 COSR 11 CSOR 11 CN or halogen atoms.

[0331] There are multiple R 2 At the same time, they can be the same or different.

[0332] There are multiple R 3 At the same time, they can be the same or different.

[0333] R 11 R 12 and R 13 It means the same as above.

[0334] s and t each independently represent integers from 0 to 4.

[0335] L represents a sulfur atom, CR 31 R 32 CO or NR 33 .

[0336] R 31 R 32 and R 33 Each can be independently represented by a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms.

[0337] R 31 R 32 or R 33 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic, R 31 R 32 and R 33 Each can independently form a ring together with an adjacent benzene ring.

[0338] R 4 It represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-1).

[0339]

[0340] (In equation (2-1), L) 1 Indicates -O-, -S-, -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0341] R 22 It means the same as above.

[0342] L 2 This refers to a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms.

[0343] L 2 When the indicated group has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 22 -, -NR 22 COO-、-OCONR 22 The alkylene moiety can be branched or cyclic, and can be interrupted 1 to 5 times.

[0344] R 4a OR 41 SR 41 CONR 42 R 43 NR 42 COR 43 OCOR 41 COOR 41 SCOR 41 OCSR 41 COSR 41 CSOR 41 CN or halogen atoms.

[0345] There are multiple R 4a At the same time, they can be the same or different.

[0346] R 41 R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms, R 41 R42 and R 43 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic, R 42 With R 43 They can form a ring together.

[0347] v represents an integer from 1 to 3.

[0348] The binding site is indicated by the first molecular structure of the oxime compound (1).

[0349] R in equation (2) 11 R 12 R 13 R 21 R 22 R 23 R 24 R 31 R 32 and R 33 and R in the above formula (2-1) 22 R 41 R 42 and R 43 Examples of alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, and aralkyl groups with 7 to 30 carbon atoms are the same as R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 The examples are the same.

[0350] R in equation (2) 11 R 12 R 13 R 21 R 22 R 23 R 24 and R in the above formula (2-1) 22 Examples of heterocyclic groups with 2 to 20 carbon atoms are similar to R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 The examples are the same.

[0351] R in equation (2) 31 R 32 and R 33The ability of each ring to independently form a ring with an adjacent benzene ring refers to R. 31 R 32 and R 33 Each can independently form a ring together with an adjacent benzene ring and the nitrogen atom to which it is attached.

[0352] R in equation (2) 31 R 32 and R 33 An example of a ring that can be formed together with an adjacent benzene ring is R in equation (1). 12 With R 13 and R 2 With R 23 The same applies to examples of rings that can be formed together.

[0353] L in the above formula (2-1) 2 It refers to a group obtained by removing v hydrogen atoms from an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0354] Examples of alkyl groups derived by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include methylene, ethylene, propylene, methyl ethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, propane-2,2-diyl, etc., when v is 1.

[0355] As a group formed by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, examples of aryl groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenyl sulfide-4,4'-diyl, and diphenyl sulfone-4,4'-diyl.

[0356] As a group formed by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, for example, when v is 1, examples include the group represented by formula (a) and the group represented by formula (b).

[0357]

[0358] In equations (a) and (b), L3 and L 5 L represents an alkylene group having 1 to 10 carbon atoms. 4 and L 6 Indicates a single bond or an alkylene group having 1 to 10 carbon atoms.

[0359] Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, methyl ethylene, butylene, 1-methyl propyleneene, 2-methyl propyleneene, 1,2-dimethyl propyleneene, 1,3-dimethyl propyleneene, 1-methyl butylene, 2-methyl butylene, 3-methyl butylene, 4-methyl butylene, 2,4-dimethyl butylene, 1,3-dimethyl butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0360] As a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms, examples include 2,5-pyridinidyl, 2,6-pyridinidyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazolyldiyl, 2,5-benzofurandiyl, 2,5-benzothiaphenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolyl, 2,5-benzothiazolyl, 2,5-benzo[…]. Dicyclic heterocyclic groups such as azole dimethyl.

[0361] As R in equation (2) 2 and R 3 and R in the above formula (2-1) 4a Examples of halogen atoms that can be represented include fluorine, chlorine, bromine, and iodine atoms.

[0362] From the viewpoint of the solubility and / or developability of the composition in solvent (J), a preferred example of the structure represented by formula (2) is the structure represented by formula (2a) below.

[0363]

[0364] In formula (2a), L' represents a sulfur atom or NR. 50 R 50 R represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. 2 R 3 R 4 , s, and t represent the same meaning as above.

[0365] From the same point of view as above, another preferred example of the structure represented by equation (2) is the structure represented by equation (2b) below.

[0366]

[0367] In equation (2b), R 44 It represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-2).

[0368]

[0369] (In equation (2-2), L) 11 express -O- or -OCO-, Indicates with L 12 The bonding site, L 12 R represents an alkylene group having 1 to 20 carbon atoms, which can be interrupted by 1 to 3 -O- groups. 44a OR 55 or COOR 55 R 55 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0370] R 44 Preferably, the group represented by formula (2-2) is preferred. In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (J) and the developability of the curable composition.

[0371] L 12 The alkylene group represented preferably has 1 to 10 carbon atoms, more preferably 1 to 4.

[0372] R 44a Preferably, it is a hydroxyl or carboxyl group, more preferably a hydroxyl group.

[0373] The method for manufacturing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited. For example, it can be manufactured by the method described in Japanese Patent Application Publication No. 2011-132215.

[0374] Another example of a second molecular structure connected to the first molecular structure represented by equation (1) is the structure represented by equation (3) below.

[0375] In formula (3) " The bonding site represented by "" is the same as the "" in equation (1) The "-" indicates a direct bond. That is, when the structure of the second molecule is the structure represented by formula (3), the "-" in formula (3) indicates a direct bond. The benzene ring in formula (1) has a "- The carbonyl group is directly bonded.

[0376]

[0377] In equation (3), R 5It represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0378] R 5 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic.

[0379] R 5 The hydrogen atoms of the group represented can be derived from R. 21 OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 NR 22 COR 21 OCOR 21 COOR 21 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 SCOR 21 OCSR 21 COSR 21 CSOR 21 hydroxyl group, nitro group, CN, halogen atom, or COOR 21 replace.

[0380] R 21 R 22 and R 23 It means the same as above.

[0381] R 21 R 22 or R 23 The hydrogen atom of the indicated group can be replaced by CN, halogen atom, hydroxyl or carboxyl group.

[0382] R 21 R 22 and R 23 When the indicated group has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24-, -SCO-, -COS-, -OCS-, or -CSO- interrupt 1 to 5 times.

[0383] R 24 It means the same as above.

[0384] R 21 R 22 and R 23 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic. Additionally, R... 22 With R 23 They can form a ring together.

[0385] R 6 R 7 R 8 and R 9 Each represents R independently. 61 OR 61 SR 61 COR 62 CONR 63 R 64 NR 65 COR 61 OCOR 61 COOR 62 SCOR 61 OCSR 61 COSR 62 CSOR 61 Hydroxyl group, nitro group, CN or halogen atom.

[0386] R 61 R 62 R 63 R 64 and R 65 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0387] R 61 R 62 R 63 R 64 or R 65 The hydrogen atoms of the group represented can be obtained by OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR)22 ) - OCOR 23 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 CN, halogen atom, or COOR 21 replace.

[0388] R 6 With R 7 R 7 With R 8 and R 8 With R 9 They can each form a ring together.

[0389] The binding site is indicated by the first molecular structure of the oxime compound (1).

[0390] R in equation (3) 5 R 21 R 22 R 23 R 24 R 61 R 62 R 63 R 64 and R 65 Examples of alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, and heterocyclic groups with 2 to 20 carbon atoms are the same as R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 The examples are the same.

[0391] R in equation (3) 22 With R 23 The ability to form a ring together refers to R 22 With R 23 They can form a ring together with the connected nitrogen, carbon, or oxygen atoms.

[0392] R in equation (3) 22 With R 23 Examples of rings that can be formed together are R in equation (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0393] As R in equation (3)6 R 7 R 8 and R 9 The halogen atom represented can replace R. 5 R 21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of halogen atoms that are hydrogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0394] From the viewpoint of solubility in solvent (J) and / or developability of the curable composition, in one preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0395]

[0396] [In formula (3-1), Z represents a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group obtained by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms.]

[0397] When the group represented by Z has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 24 -, -NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- are interrupted 1 to 5 times. The alkylene moiety can be branched or cyclic.

[0398] R 21 R 22 and R 24 This indicates the same meaning as above.

[0399] From the same point of view as above, Z in formula (3-1) is preferably methylene, ethylene, or phenylene.

[0400] Considering the same viewpoint as above, R in equation (3-1) 21 and R 22 Preferably, it is an alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 30 carbon atoms, more preferably methyl, ethyl or phenyl.

[0401] From the same perspective as above, in another preferred embodiment, R 7 It is a nitro group.

[0402] The method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited. For example, it can be manufactured by the methods described in Japanese Patent Application Publication No. 2000-80068 and Japanese Patent Application Publication No. 2011-178776.

[0403] Another example of a second molecular structure connected to the first molecular structure represented by equation (1) is the structure represented by equation (4) below.

[0404] In formula (4) " The bonding site represented by "" is the same as the "" in equation (1) The "-" indicates a direct bond. That is, when the structure of the second molecule is the structure represented by formula (4), the "-" in formula (4) indicates a direct bond. The benzene ring in formula (1) has a "- The carbonyl group is directly bonded.

[0405]

[0406] In equation (4), R 71 It represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0407] R 71 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic.

[0408] R 71 The hydrogen atoms of the group represented can be derived from R. 21 OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 NR 22 COR 21 OCOR 21 COOR 21 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 SCOR21 OCSR 21 COSR 21 CSOR 21 hydroxyl group, nitro group, CN, halogen atom, or COOR 21 replace.

[0409] R 21 R 22 and R 23 It means the same as above.

[0410] R 21 R 22 or R 23 The hydrogen atom of the indicated group can be replaced by CN, halogen atom, hydroxyl or carboxyl group.

[0411] R 21 R 22 and R 23 When the indicated group has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupt 1 to 5 times.

[0412] R 24 It means the same as above.

[0413] R 21 R 22 and R 23 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic. Additionally, R... 22 With R 23 They can form a ring together.

[0414] R 72 R 73 And 3 R 74 Each represents R independently. 61 OR 61 SR 61 COR 62 CONR 63 R 64 NR 65 COR 61 OCOR 61 COOR 62 SCOR 61 OCSR 61 COSR 62 CSOR61 Hydroxyl group, nitro group, CN or halogen atom.

[0415] R 61 R 62 R 63 R 64 and R 65 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0416] R 61 R 62 R 63 R 64 or R 65 The hydrogen atoms of the group represented can be obtained by OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 CN, halogen atom, or COOR 21 replace.

[0417] R 72 With R 73 and 2 R 74 They can each form a ring together.

[0418] The binding site is indicated by the first molecular structure of the oxime compound (1).

[0419] R in equation (4) 71 R 21 R 22 R 23 R 24 R 61 R 62 R 63 R 64 and R 65 Examples of alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, and heterocyclic groups with 2 to 20 carbon atoms are the same as R in formula (1). 11 R12 R 13 R 21 R 22 R 23 and R 24 The examples are the same.

[0420] R in equation (4) 22 With R 23 The ability to form a ring together refers to R 22 With R 23 They can form a ring together with the nitrogen, carbon, or oxygen atoms they are attached to.

[0421] R in equation (4) 22 With R 23 Examples of rings that can be formed together are R in equation (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0422] As R in equation (4) 72 R 73 and R 74 The halogen atom represented can replace R. 71 R 21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of halogen atoms that are hydrogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0423] The method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited. For example, it can be manufactured by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0424] Another example of a second molecular structure connected to the first molecular structure represented by equation (1) is the structure represented by equation (5) below.

[0425] In formula (5) " The bonding site represented by "" is the same as the "" in equation (1) The "-" indicates a direct bond. That is, when the structure of the second molecule is the structure represented by formula (5), the "-" in formula (5) indicates a direct bond. The pyrrole ring in formula (1) has a "- The carbonyl group is directly bonded.

[0426]

[0427] In equation (5), R 81 It represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0428] R 81 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic.

[0429] R 81 The hydrogen atoms of the group represented can be derived from R. 21 OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 NR 22 COR 21 OCOR 21 COOR 21 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 SCOR 21 OCSR 21 COSR 21 CSOR 21 hydroxyl group, nitro group, CN, halogen atom, or COOR 21 replace.

[0430] R 21 R 22 and R 23 It means the same as above.

[0431] R 21 R 22 or R 23 The hydrogen atom of the indicated group can be replaced by CN, halogen atom, hydroxyl or carboxyl group.

[0432] R 21 R 22 and R 23 When the indicated group has an alkylene moiety, the alkylene moiety can be -O-, -S-, -COO-, -OCO-, or -NR. 24 -, -NR24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupt 1 to 5 times.

[0433] R 24 It means the same as above.

[0434] R 21 R 22 and R 23 When the indicated group has an alkyl moiety, the alkyl moiety can be branched or cyclic. Additionally, R... 22 With R 23 They can form a ring together.

[0435] R 82 R 83 R 84 R 85 and R 86 Each represents R independently. 61 OR 61 SR 61 COR 62 CONR 63 R 64 NR 65 COR 61 OCOR 61 COOR 62 SCOR 61 OCSR 61 COSR 62 CSOR 61 Hydroxyl group, nitro group, CN or halogen atom.

[0436] R 61 R 62 R 63 R 64 and R 65 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0437] R 61 R 62 R 63 R 64 or R 65 The hydrogen atoms of the group represented can be obtained by OR 21 COR 21 SR 21 NR 22 R 23 CONR22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 CN, halogen atom, or COOR 21 replace.

[0438] R 83 With R 84 R 84 With R 85 and R 85 With R 86 They can each form a ring together.

[0439] The binding site is indicated by the first molecular structure of the oxime compound (1).

[0440] R in equation (5) 81 R 21 R 22 R 23 R 24 R 61 R 62 R 63 R 64 and R 65 Examples of alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, and heterocyclic groups with 2 to 20 carbon atoms are the same as R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 The examples are the same.

[0441] R in equation (5) 22 With R 23 The ability to form a ring together refers to R 22 With R 23 They can form a ring together with the nitrogen, carbon, or oxygen atoms they are attached to.

[0442] R in equation (5) 22 With R 23 Examples of rings that can be formed together are R in equation (1). 12 With R 13 and R 22 With R23 The same applies to examples of rings that can be formed together.

[0443] As R in equation (5) 82 R 83 R 84 R 85 and R 86 The halogen atom represented can replace R. 81 R 21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of halogen atoms that are hydrogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0444] The method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited. For example, it can be manufactured by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0445] Another example of a second molecular structure connected to the first molecular structure represented by equation (1) is the structure represented by equation (6) below.

[0446] In formula (6) " The bonding site represented by "" is the same as the "" in equation (1) The "-" indicates a direct bond. That is, when the structure of the second molecule is the structure represented by formula (6), the "-" in formula (6) indicates a direct bond. The benzene ring in formula (1) has a "- The carbonyl group is directly bonded.

[0447]

[0448] In equation (6), there are 4 R's. 91 R 92 R 93 R 94 R 95 R 96 and R 97 Each represents R independently. 61 OR 61 SR 61 COR 62 CONR 63 R 64 NR 65 COR 61 OCOR 61 COOR62 SCOR 61 OCSR 61 COSR 62 CSOR 61 Hydroxyl group, nitro group, CN or halogen atom.

[0449] R 61 R 62 R 63 R 64 and R 65 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0450] R 61 R 62 R 63 R 64 or R 65 The hydrogen atoms of the group represented can be obtained by OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 、-NR 22 -OR 23 -N (COR) 22 ) - OCOR 23 -C (=N-OR) 21 )-R 22 -C (=N-OCOR) 21 )-R 22 CN, halogen atom, or COOR 21 replace.

[0451] R 21 R 22 and R 23 It means the same as above.

[0452] R 92 With R 93 R 94 With R 95 R 95 With R 96 and R 96 With R 97 They can each form a ring together.

[0453] The binding site is indicated by the first molecular structure of the oxime compound (1).

[0454] R in equation (6)21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms, and heterocyclic groups with 2 to 20 carbon atoms are the same as R in formula (1). 11 R 12 R 13 R 21 R 22 and R 23 The examples are the same.

[0455] R in equation (6) 22 With R 23 The ability to form a ring together refers to R 22 With R 23 They can form a ring together with the nitrogen, carbon, or oxygen atoms they are attached to.

[0456] R in equation (6) 22 With R 23 Examples of rings that can be formed together are R in equation (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0457] As R in equation (6) 91 R 92 R 93 R 94 R 95 R 96 and R 97 The halogen atom represented can replace R. 21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of halogen atoms that contain hydrogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0458] The method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited. For example, it can be manufactured by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0459] As an oxime compound other than the compound represented by formula (EA), the compound represented by formula (EB), and the oxime compound (1), examples can be given of oxime compounds having a partial structure represented by the following formula (d1). Indicates the bonding site.

[0460]

[0461] Examples of oxime compounds having a partial structure represented by formula (d1) include, for example, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxane-3-dioxane-3-yl]ethane-1-imine. Compounds including: heterocyclopentylmethoxy[]benzoyl]-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-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, etc. Alternatively, commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine), OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine) (all manufactured by BASF) and N-1919 (manufactured by ADEKA) can be used.

[0462] The oxime compound having a partial structure represented by formula (d1) is preferably selected from at least one of N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine.

[0463] Alkylphenyl ketone compounds are compounds having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have substituents. Indicates the bonding site.

[0464]

[0465] Examples of compounds having the structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as OMNIRAD (registered trademark) 369, OMNIRAD907, and OMNIRAD379 (all manufactured by IGM Resins) can also be used.

[0466] Examples of compounds having the structure represented by formula (d3) include oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyladimethyl ketal.

[0467] From the viewpoint of sensitivity, alkylphenyl ketone compounds are preferably compounds having the structure represented by formula (d2).

[0468] Examples of biimidazole compounds include those represented by formula (d5).

[0469]

[0470] In equation (d5), RE ~R J This indicates an aryl group with 6 to 10 carbon atoms that can have substituents.

[0471] Examples of aryl groups with 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, and naphthyl, with phenyl being the most preferred.

[0472] Examples of substituents include halogen atoms and alkoxy groups having 1 to 4 carbon atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms being preferred. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, with methoxy being preferred.

[0473] 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 (e.g., 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'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Biimidazole (alkoxyphenyl), 2,2'-bis(2-chlorophenyl)-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 Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carbonylalkoxy group (e.g., see Japanese Patent Application Publication No. 7-10913, etc.). Among these, compounds represented by the following formulas or mixtures thereof are preferred.

[0474]

[0475] 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, and 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. Among these, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine is preferred.

[0476] Examples of acylphosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0477] Other examples of photopolymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoyl peroxide, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzoyl, methyl benzoylformate, and titanium ceramsite compounds.

[0478] The content of polymerization initiator (E) in the curable composition is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of polymeric compound (D), more preferably 0.1 to 200 parts by mass, further preferably 3 to 150 parts by mass, and even more preferably 5 to 80 parts by mass. Furthermore, the content of polymerization initiator (E) in the curable composition is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the combined amount of resin (C) and polymeric compound (D), more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 10 parts by mass. When the content of polymerization initiator (E) is within the above range, it is possible to suppress the decrease in the residual film rate of the cured film when the curable composition is cured at low temperatures, and it is also advantageous from the viewpoint of achieving good patterning after exposure and development.

[0479] The content of polymerization initiator (E) in the curable composition relative to the total amount of solid components in the curable composition is, for example, 0.01% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 0.2% to 10% by mass, further preferably 0.3% to 8% by mass, even more preferably 0.5% to 5% by mass, and particularly preferably less than 3% by mass.

[0480] The polymerization initiator (E) preferably contains at least one oxime compound, more preferably contains at least one of the compounds represented by formula (EA), the compound represented by formula (EB), and the oxime compound (1), further preferably contains at least one of the compounds represented by formula (EA) and the compound represented by formula (EB), even more preferably contains at least one of the compounds represented by formula (EA), and even more preferably contains the compound represented by formula (EA-1) described later. As described above, both the compound represented by formula (EA) and the compound represented by formula (EB) can suppress the decrease in the residual film rate of the cured film when the curable composition is cured at low temperature. In addition, the compound represented by formula (EA) can also improve the fluorescence intensity of the cured film. The content of the compound represented by formula (EA) is 100% by mass, preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass (i.e., the polymerization initiator (E) contains the compound represented by formula (EA) but does not contain the compound represented by formula (EB)).

[0481] When the polymerization initiator (E) includes at least one of the compounds represented by formula (EA) and formula (EB), the total content of the compounds represented by formula (EA) and formula (EB) in the polymerization initiator (E) relative to the total amount of the polymerization initiator (E) is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, further preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, particularly more preferably 90% to 100% by mass, especially preferably 95% to 100% by mass, and may also be 100% by mass.

[0482] <Light stabilizer (F)>

[0483] As a light stabilizer (F), in addition to known light stabilizers (Fa), any additive that has the function of stabilizing the component relative to light is acceptable. The light stabilizer (F) of the present invention also includes antioxidants (Fb) and ultraviolet absorbers (Fc) that absorb light and render it harmless. The curable composition may contain two or more light stabilizers (F).

[0484] <Light stabilizer (Fa)>

[0485] Examples of light stabilizers (Fa) include hindered amine light stabilizers, acrylate light stabilizers, nickel-based light stabilizers, and oxalamide-based light stabilizers.

[0486] <Antioxidant (Fb)>

[0487] As an antioxidant (Fb), there are no particular limitations as long as it is an industrially commonly used antioxidant; phenolic antioxidants, phosphorus-based antioxidants, phosphorus / phenolic complex antioxidants, and sulfur-based antioxidants can be used. The curable composition may contain two or more antioxidants (Fb).

[0488] Phosphorus / phenol complex antioxidants are, for example, compounds having one or more phosphorus atoms and phenolic structures in their molecules. From the viewpoint of the developability and luminescence intensity of the curable composition, antioxidants (Fb) preferably include phosphorus / phenol complex antioxidants.

[0489] Examples of phenolic antioxidants include, for instance, Irganox 1010 (Irganox 1010: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), and Irganox 3114 (Irganox 1010: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), and Irganox 3114 (Irganox 1010: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation). 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 Corporation), Irganox (registered trademark) 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox (registered trademark) 1035 (Irganox 1035: thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox (registered trademark) 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 alkyl ester of phenylpropionic acid, manufactured by BASF Corporation), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylaniline)-1,3,5-triazine, manufactured by BASF Corporation), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxazolo(5,5) Undecane (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Sitech Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0490] Examples of phosphorus-based antioxidants include, for instance, Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), and Irgafos 38 (Irgafos... 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Corporation, Adekastab 329K, Adekastab PEP36, Adekastab PEP-8 (all manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston 618, Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), etc.

[0491] As a phosphorus / phenol complex antioxidant, for example, Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d,f] [1.3.2] di Phosphoric cycloheptane (manufactured by Sumitomo Chemical Co., Ltd.), etc.

[0492] Examples of sulfur-based antioxidants include, for example, dialkyl thiodipropionate compounds such as dilaurate thiodipropionate, dimyristyl thiodipropionate, or distearate thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetra[methylene(3-dodecylthio)propionate]methane.

[0493] <UV absorber (Fc)>

[0494] Examples of ultraviolet absorbers (Fc) include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole and (2-(2,4-dihydroxyphenyl)-2H-benzotriazole); benzophenone compounds such as 2-hydroxy-4-octoxybenzophenone; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol.

[0495] The content of light stabilizer (F) in the curable composition (which is a total amount when multiple types are included) is, for example, 1 to 50 parts by mass relative to 100 parts by mass of resin (C), preferably 5 to 40 parts by mass from the viewpoint of luminescence intensity, and more preferably 7 to 30 parts by mass.

[0496] When the curable composition contains a light stabilizer (F), the light stabilizer (F) is preferably an antioxidant (Fb) and / or an ultraviolet absorber (Fc).

[0497] <Leveling agent (H)>

[0498] Examples of leveling agents (H) include silicone surfactants, fluorinated surfactants, and silicone surfactants containing fluorine atoms. These may have polymerizable groups on their side chains. Preferably, the leveling agent (H) comprises a silicone surfactant. The curable composition may contain two or more leveling agents (H).

[0499] As organosilicon surfactants, examples include surfactants with intramolecular siloxane bonds. Specifically, examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (Momentive Performance Materials Japan Co., Ltd.).

[0500] As fluorinated surfactants, examples include surfactants with intramolecular fluorocarbon chains. Specifically, examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFACF554, MEGAFAC F575, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronics Chemicals Co., Ltd.), and Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon... SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Research Institute Co., Ltd.), etc.

[0501] As organosilicon surfactants containing fluorine atoms, examples include surfactants with intramolecular siloxane bonds and fluorocarbon chains. Specifically, examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0502] When the curable composition contains a leveling agent (H), the content of the leveling agent (H) in the curable composition relative to the total amount of the curable composition is, for example, 0.001% to 1.0% by mass, preferably 0.005% to 0.75% by mass, and more preferably 0.01% to 0.5% by mass. When the content of the leveling agent (H) is within the above range, the flatness of the cured film of the curable composition can be improved when used as a wavelength conversion layer.

[0503] <Solvent (J)>

[0504] The solvent (J) is the substance that dissolves the resin (C) and, in the preferred embodiment, the polymerizable compound (D) and the polymerization initiator (E). Examples of solvents (J) include ester solvents (solvents containing -COO- and not containing -O-), ether solvents (solvents containing -O- and not containing -COO-), ether ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- and not containing -COO-), alcohol solvents (solvents containing OH and not containing -O-, -CO-, and COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0505] Examples of ester solvents 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.

[0506] Examples of ether solvents 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, and 1,4-di(ethylene glycol monomethyl ether). Alkane, 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.

[0507] Examples of ether ester solvents 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, ethyl 2-ethoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, ethyl 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 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.

[0508] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0509] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycidol.

[0510] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0511] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0512] The solvent (J) preferably comprises one or more selected from propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and aromatic hydrocarbon solvents.

[0513] As solvent (J), preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, 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.

[0514] Solvent (J) refers to components other than solid components, such as solvents contained in dispersions of semiconductor particles (A) and solutions of resins (C).

[0515] The solvent (J) content in the curable composition is the ratio of the total mass of all solvents contained in the curable composition to the total mass of the curable composition, and is, for example, 40% to 95% by mass, preferably 50% to 90% by mass relative to the total mass of the curable composition. In other words, the solid content of the curable composition is, for example, 5% to 60% by mass, preferably 10% to 50% by mass. When the solvent (J) content is within the above range, the flatness of the cured composition layer during coating becomes better, and there is a tendency to easily form a wavelength conversion layer of appropriate thickness.

[0516] <Other Ingredients>

[0517] The curable composition may be further contained, as needed, additives known in the art such as polymerization inhibitors, fillers, other polymeric compounds, adhesion promoters, and chain transfer agents.

[0518] <<Method for Manufacturing Curable Compositions>>

[0519] The curable composition can be manufactured by a method including a step of mixing the specified components and other components to be used as needed. The method of manufacturing the curable composition may further include a step of preparing a resin (C). Among the components contained in the curable composition, the semiconductor particles (A) and the light scattering agent (B) may be pre-mixed with some or all of the solvent (J) before being mixed with the other components.

[0520] <<Method for Manufacturing Cured Film>>

[0521] A cured film can be obtained by performing a manufacturing method that includes a step of coating the curable composition of the present invention and a thermal curing step of thermally curing the coated film of the curable composition (hereinafter also referred to as the "composition layer"). After the step of coating the curable composition, a further exposure step of irradiating the coated film of the curable composition with light is generally included, and the thermal curing step is performed after the exposure step.

[0522] The above-mentioned method for manufacturing a cured film further includes: a drying step for drying the composition layer formed by the coating step, and a developing step for the composition layer after the exposure step.

[0523] The coating process is a process of applying a curable composition to a substrate to form a composition layer. Examples of coating methods include spin coating, slot coating, slot spin coating, and printing. In the printing process, the curable composition is applied through a mask placed on the substrate. After the mask is peeled off from the substrate, the composition layer formed by the coating process is cured, thereby forming a cured film as a curing pattern on a portion of the substrate surface.

[0524] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass with a surface coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed. Preferred substrates are glass plates and silicon substrates.

[0525] The substrate can be a substrate that has undergone pretreatment to adjust the wettability of its surface. Examples of pretreatment include solvent cleaning with alcohols or acetone, acid treatment, alkali treatment, plasma treatment, and corona treatment. By selecting an appropriate pretreatment, the coatability of the curable composition can be improved compared to an untreated substrate for substrates to be laminated and cured.

[0526] When the curable composition contains a solvent (J), a drying process is performed after the coating process to remove volatile components such as the solvent (J) from the composition layer. The drying process may include heat drying (pre-drying), reduced pressure drying, or both.

[0527] The curable composition of the present invention can suppress the decrease in the residual film rate of the cured film when the heating drying (pre-baking) temperature is low.

[0528] The preferred temperature for heating and drying is 30°C or higher and less than 100°C, more preferably 50°C to 95°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0529] When performing vacuum drying, it is preferable to carry out the process at a pressure of 50 Pa to 150 Pa and a temperature range of 20 °C to 25 °C.

[0530] The thickness of the composite layer after the coating or drying process is not particularly limited, and can be appropriately selected according to the thickness of the target cured film, for example, 0.5 μm to 10 μm, preferably 1 μm to 9 μm, more preferably 1.5 μm to 7 μm, and even more preferably 2 μm to 5 μm. The thickness of the final cured film can also be the same as described above.

[0531] Next, an exposure process is performed on the composition layer after the coating and drying processes. The exposed composition layer is then cured by polymerization of a polymerizable compound (D) or the like contained in the composition layer, including in a preferred manner. As the light source used for exposure, a light source that generates light with wavelengths of 250 nm to 450 nm is preferred. When the curable composition contains a photopolymerization initiator (E), light around 436 nm, 408 nm, or 365 nm can be selectively extracted from the light of the aforementioned wavelengths using a bandpass filter, depending on the absorption wavelength of the polymerization initiator (E). Specifically, examples of light sources include mercury lamps, light-emitting diodes (LEDs), metal halide lamps, and halogen lamps.

[0532] The preferred exposure amount X in the exposure process is 50 mJ / cm. 2 The above, more preferably 80 mJ / cm 2 The above is further preferred to be 100 mJ / cm. 2 The above is further optimized to 150 mJ / cm. 2 That's all. Exposure X is typically 1000 mJ / cm². 2 The preferred value is 800 mJ / cm. 2 The following is more preferably 700 mJ / cm 2 The exposure amount X in the exposure process is 1000 mJ / cm². 2 The following measures prevent excessive shrinkage of the cured film, thus preventing the approach of semiconductor particles (A) in the film caused by the shrinkage of the cured film and preventing a decrease in the intensity of emitted light. The exposure amount X is the exposure amount at a wavelength of 365nm, which can be measured using an ultraviolet cumulative photometer (UIT-250, manufactured by Ushio Electric Co., Ltd.).

[0533] As an example of a method for forming a cured pattern of a cured film, photolithography can be cited. Photolithography is a method of exposing and developing a composition layer using a photomask used to form the target cured pattern. In this case, since parallel light can be uniformly irradiated onto the entire exposed surface, and precise alignment of the photomask with the substrate on which the composition layer is formed is possible, exposure apparatus such as a mask aligner and a stepper is preferred.

[0534] By subjecting the composition layer after the exposure process to a developing process in which it comes into contact with a developing solution, the unexposed portions of the composition layer dissolve in the developing solution and are removed, thereby imparting a pattern to the composition layer. Examples of developing solutions include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, as well as organic solvents. The concentration of the alkaline compound in the aqueous solution is preferably 0.01% to 10% by mass, more preferably 0.03% to 5% by mass. Examples of organic solvents are substances similar to the solvents mentioned above (J). The developing solution may contain a surfactant. The developing method can be any of the following: spin-dip method, immersion method, and spray method. Furthermore, the substrate can be tilted to any angle during developing.

[0535] The composition layer after the exposure and development processes is heat-cured (post-baked) in a heat-curing process. The heat-curing process can further polymerize resins (C), polymeric compounds (D), etc., including those in preferred forms.

[0536] The heat curing temperature in the heat curing process performed after the exposure and development processes is preferably below 150°C, more preferably below 120°C, even more preferably below 100°C, and particularly preferably below 95°C. The heat curing temperature is preferably above 70°C, more preferably above 80°C, and even more preferably above 85°C.

[0537] The heat curing time in the heat curing process is preferably 0.1 hours or more, more preferably 0.2 hours or more, even more preferably 0.4 hours or more, and even more preferably 0.5 hours or more. The heat curing time is usually 2 hours or less, preferably 1.5 hours or less, and more preferably 1.2 hours or less.

[0538] The thermosetting process can be carried out in an atmospheric atmosphere or in a vacuum atmosphere. A vacuum atmosphere refers to a pressure range of 150 Pa or less, preferably 120 Pa or less, more preferably 100 Pa or less, and may also be 50 Pa or more.

[0539] The temperatures in the aforementioned drying process (especially heat drying) and heat curing process are preferably less than 100°C, and more preferably less than 95°C.

[0540] When the cured film manufactured at the preferred heating and drying (pre-baking) temperature described above, or when the cured film manufactured at the preferred heating and drying temperature and heat curing temperature described above, is measured according to the "determination of residual film rate" in the embodiments described below, the residual film rate (residual film rate of low-temperature curing) is, for example, greater than 75%, preferably more than 80%, more preferably more than 90%, and the upper limit can be 100%. Furthermore, when the cured film is evaluated according to the "evaluation of patternability" in the embodiments described below, the minimum linewidth of the exposed pattern portion or completely remaining can be 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. In addition, when the cured film is evaluated according to the "determination of fluorescence intensity of the cured film" in the embodiments described below, the fluorescence intensity can be 400 (mW•sr) when the film thickness of the cured film is, for example, 0.5 μm to 10 μm (particularly 2 μm to 5 μm). ―1 •m ―2 ) or above, preferably 500 (mW•sr) ―1 •m ―2 ) or higher, more preferably 700 (mW•sr) ―1 •m ―2 The upper limit is not specifically limited and can also be 1500 (mW•sr). ―1 •m ―2 )the following.

[0541] <<Display Device>>

[0542] The cured film obtained from the curable composition of the present invention has the function of converting the wavelength of irradiated light, and therefore can be used as a color conversion layer (wavelength conversion film) for display devices. Examples of such display devices include those described in Japanese Patent Application Publication Nos. 2006-309219, 2006-310303, 2013-15812, 2009-251129, and 2014-2363. The cured film according to the present invention is useful as a color conversion layer (wavelength conversion film) for display devices, particularly liquid crystal display devices, organic EL display devices, or inorganic EL display devices.

[0543] Example

[0544] The following examples illustrate the present invention in more detail. However, the present invention is not limited to the following examples, and appropriate modifications can be made to implement it within the scope suitable for the foregoing and following spirit. All such modifications are included within the technical scope of the present invention. Unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts, respectively.

[0545] [Thickness of the cured film]

[0546] The film thickness was measured using a film thickness measuring device (DEKTAKXT; manufactured by Bruker).

[0547] [Weight-average molecular weight]

[0548] The weight-average molecular weight (Mw) of resin (C) was determined by GPC under the following conditions.

[0549] Device: K2479 (manufactured by Shimadzu Corporation)

[0550] Pillar: SHIMADZU Shim-pack GPC-80M

[0551] Column temperature: 40℃

[0552] Solvent: Tetrahydrofuran

[0553] Flow rate: 1.0 mL / min

[0554] Detector: RI

[0555] Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0556] [Acid Value]

[0557] Accurately weigh 3g of resin (C) solution and dissolve it in a mixed solvent of 90g acetone and 10g water. Use 0.1 equivalent of KOH aqueous solution as titrant and determine the acid value of resin (C) solution using an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555). Calculate the acid value (AV) per 1g of solid component from the acid value of the solution and the solid component of the solution.

[0558] [Double bond equivalent]

[0559] The double bond equivalent is determined by dividing the total mass of the cured resin by the number of moles of free radical polymerizable double bonds introduced into the cured resin.

[0560] [Solid composition]

[0561] Approximately 1 g of resin (C) solution was measured in an aluminum cup, dried at 180°C for 1 hour, and its mass was determined. The solid content (mass %) of the resin (C) solution was calculated based on the amount of mass reduction.

[0562] (Synthesis Example 1: Synthesis of Resin (C1))

[0563] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 276.8 g of propylene glycol monomethyl ether acetate was added. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 120°C. Then, over a period of 2 hours, 35.3 g of tert-butylperoxy-2-ethylhexanoate (a polymerization initiator) was added dropwise to the flask through a dropping funnel to obtain a mixture consisting of a monomer mixture of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentyl methacrylate. After the addition was complete, the mixture was stirred further at 120°C for 30 minutes to carry out a copolymerization reaction, generating an addition copolymer.

[0564] Then, the flask was purged with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of p-methoxyphenol (polymerization inhibitor) were added to the above addition copolymer solution. The reaction was continued at 110 °C for 10 hours, during which the epoxy groups from glycidyl methacrylate reacted with acrylic acid to open the epoxy ring, and polymerizable unsaturated bonds were introduced onto the polymer side chains. Next, 53.5 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110 °C for 1 hour, allowing the hydroxyl groups generated by the epoxy ring opening to react with the succinic anhydride, introducing carboxyl groups onto the side chains to obtain the polymer (resin (C1)).

[0565] Finally, 436.0 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C1) solution with a polymer solid content of 40%.

[0566] The weight-average molecular weight (Mw) of the resulting resin (C1) is 6.7 × 10⁻⁶. 3 The acid value converted from solid components is 70 mg-KOH / g, and the double bond equivalent is 336 g / eq.

[0567] (Synthesis Example 2: Synthesis of Resin (C2))

[0568] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 276.8 g of propylene glycol monomethyl ether acetate was added. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 120°C. Then, over a period of 2 hours, 35.3 g of tert-butylperoxy-2-ethylhexanoate (a polymerization initiator) was added dropwise to the flask through a dropping funnel to obtain a mixture consisting of a monomer mixture of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentyl methacrylate. After the addition was complete, the mixture was stirred further at 120°C for 30 minutes to carry out a copolymerization reaction, generating an addition copolymer.

[0569] Then, the flask was purged with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of p-methoxyphenol (polymerization inhibitor) were added to the above addition copolymer solution. The reaction was continued at 110 °C for 10 hours, during which the epoxy groups from glycidyl methacrylate reacted with acrylic acid to open the epoxy ring, and polymerizable unsaturated bonds were introduced onto the polymer side chains. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110 °C for 1 hour, allowing the hydroxyl groups generated by the epoxy ring opening to react with the succinic anhydride, introducing carboxyl groups onto the side chains to obtain the polymer (resin (C2)).

[0570] Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C2) solution with a polymer solid content of 40%.

[0571] The weight-average molecular weight (Mw) of the resulting copolymer is 6.2 × 10⁻⁶. 3 The acid value converted from solid components is 35 mg-KOH / g, and the double bond equivalent is 313 g / eq.

[0572] (Synthesis Example 3: Synthesis of Resin (C3))

[0573] By adjusting the amount of raw material monomers in the same manner as the above resin (C1), a polymer (resin (C3)) is obtained. Finally, 383.3 g of propylene glycol monomethyl ether acetate is added to the reaction solution to obtain a resin (C3) solution with a polymer solid content of 40%.

[0574] The weight-average molecular weight (Mw) of the resulting copolymer is 4.96 × 10⁻⁶. 3 The acid value converted from solid components is 37 mg-KOH / g, and the double bond equivalent is 344 g / eq.

[0575] (Synthesis Example 4: Synthesis of Resin (C4))

[0576] By adjusting the amount of raw material monomers in the same manner as the above resin (C1), a polymer (resin (C4)) is obtained. Finally, 383.3 g of propylene glycol monomethyl ether acetate is added to the reaction solution to obtain a resin (C4) solution with a polymer solid content of 40%.

[0577] The weight-average molecular weight (Mw) of the resulting copolymer is 4.91 × 10⁻⁶. 3 The acid value converted from solid components is 42 mg-KOH / g, and the double bond equivalent is 514 g / eq.

[0578] (Preparation Example 1: Preparation of dispersion b of semiconductor particles (A))

[0579] Prepare a toluene dispersion a containing semiconductor particles (A) [InP / ZnSeS quantum dots emitting green light] with oleic acid as an organic ligand (G). After removing toluene from the toluene dispersion a by vacuum distillation, add 70 parts of cyclohexyl acetate relative to 30 parts of the total amount of solid components (semiconductor particles (A) and organic ligand (G)) to obtain a dispersion b of semiconductor particles (A).

[0580] For the composition ratio of semiconductor particles (A) to organic ligands (G), the residue of the mixture after removing toluene was determined by TG-DTA when heated to 550°C at a heating rate of 5°C / min, and this residue was used as the weight of semiconductor particles (A) for calculation.

[0581] (Preparation Example 2: Preparation of dispersion c of light scattering agent (B))

[0582] Add 3 parts of BYK-LPN21116 (manufactured by BYK-Chemie Japan) based on solid content to 70 parts of titanium dioxide nanoparticles, and add propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA") to make the total amount 100 parts. Stir the mixture using a coating shaker until it is fully dispersed to obtain a dispersion c of light scattering agent (B1) (73% solid content).

[0583] (Example 1: Preparation of Curable Composition 1)

[0584] A dispersion b of semiconductor particles (A), a dispersion c of light scattering agent (B), and other components were mixed to prepare a curable composition 1 having the composition shown in Table 1. In Table 1, the parts of components other than solvent (J) are shown as solid component conversion values.

[0585] [Table 1]

[0586]

[0587] Polymer compound (D1): Carboxyl-containing polyfunctional (meth)acrylate (trade name "Aronix (registered trademark) M-510" manufactured by Toa Synthetic Co., Ltd.)

[0588] Polymerizable compound (D2): Ethylene oxide-modified bisphenol A diacrylate, with an average molecular weight (Mw) of 512.

[0589] Polymerization initiator (E1): A compound represented by the following formula (EA-1)

[0590]

[0591] Antioxidant (Fb1): Manufactured by Sumitomo Chemical Co., Ltd. under the trade name "Sumilizer (registered trademark) GP".

[0592] Leveling agent (H1): Polyether-modified silicone oil (trade name "ToraySilicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

[0593] Dispersant (I1): BYK-LPN21116 (manufactured by BYK-Chemie Japan)

[0594] Solvent (J1): A mixture of PGMEA (propylene glycol monomethyl ether acetate) and cyclohexyl acetate.

[0595] (Example 2: Preparation of Curable Composition 2)

[0596] Resin (C2) is used instead of resin (C1), and otherwise, curable composition 2 is prepared in the same manner as curable composition 1.

[0597] (Example 3: Preparation of curable composition 3)

[0598] As the polymerizable compound (D), only the polymerizable compound (D2) is used instead of the polymerizable compound (D1), and the amount of (D2) is 6.3 parts. Otherwise, the curable composition 3 is prepared in the same manner as the curable composition 1.

[0599] (Example 4: Preparation of curable composition 4)

[0600] As the polymerizable compound (D), only the polymerizable compound (D1) is used instead of the polymerizable compound (D2), and the amount of (D1) is 6.3 parts. Otherwise, the curable composition 4 is prepared in the same manner as the curable composition 1.

[0601] (Example 5: Preparation of curable composition 5)

[0602] Resin (C3) is used instead of resin (C1), and otherwise, curable composition 5 is prepared in the same manner as curable composition 1.

[0603] (Example 6: Preparation of curable composition 6)

[0604] Resin (C4) is used instead of resin (C1), and otherwise, curable composition 6 is prepared in the same manner as curable composition 1.

[0605] (Example 7: Preparation of curable composition 7)

[0606] The curable composition 7 is prepared in the same manner as curable composition 1, except that a polymerizable compound (D3) that is a dipentaerythritol polyacrylate (5-6 functional) is used instead of polymerizable compound (D2).

[0607] (Example 8: Preparation of curable composition 8)

[0608] The polymerization initiator (E2) represented by the following formula (EB-1) is used instead of the polymerization initiator (E1), otherwise the curable composition 8 is prepared in the same manner as the curable composition 1.

[0609]

[0610] (Example 9: Preparation of curable composition 9)

[0611] The polymerizable compound (D3), which is a dipentaerythritol polyacrylate (5-6 functional), is used instead of the polymerizable compound (D2), and the polymerization initiator (E2) represented by the above formula (EB-1) is used instead of the polymerization initiator (E1). Otherwise, the curable composition 9 is prepared in the same manner as the curable composition 1.

[0612] (Comparative Example 1: Preparation of Curable Composition 10)

[0613] The material used has a different structure from resin (C1) and a weight-average molecular weight (Mw) of 6.2 × 10⁻⁶. 3 A resin (C5) with an acid value of 99 mg-KOH / g and a double bond equivalent of 0 was used to replace resin (C1). Otherwise, curable composition 10 was prepared in the same manner as curable composition 1.

[0614] (Comparative Example 2: Preparation of Curable Composition 11)

[0615] The above-mentioned resin (C5) is used instead of resin (C1), and a polymerizable compound (D3) as dipentaerythritol polyacrylate (5-6 functional) is used instead of polymerizable compound (D2). Furthermore, the polymerization initiator (E2) represented by the above formula (EB-1) is used instead of polymerization initiator (E1). Otherwise, the curable composition 11 is prepared in the same manner as the curable composition 1.

[0616] Using curing compositions 1 to 11, evaluate the residual film rate and patterning properties according to the following guidelines.

[0617] [Determination of residual film ratio]

[0618] (i) Using spin coating, any one of the curable compositions 1 to 11 is coated onto a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning) with a pre-baked film thickness of 5 μm, and then dried at 70°C for 1 minute (pre-baking) to form a film of the curable composition. Then, without exposure, development is performed using a developing apparatus (Actes Kyosan Co., Ltd., ADE-3000S) with a developing solution (0.12% tetramethylammonium hydroxide aqueous solution), and the time until the coating is completely removed is measured.

[0619] (ii) After coating and pre-baking the curable composition according to the same steps as in (i) above, use an exposure machine (UPE-1255MA; manufactured by Ushio Lighting Co., Ltd.) at 200 mJ / cm² in an atmospheric atmosphere. 2 The exposure process was performed by irradiating the light with an exposure amount (wavelength 365nm reference). Then, development was performed under the same conditions and time as in (i) above, followed by washing with distilled water and heat curing at 95°C for 30 minutes (post-baking), and the film thickness t1 was measured.

[0620] (iii) Without performing the development process, except for preparing the post-baked film (exposure film) according to the same procedure as (ii) above, and measuring the film thickness t0.

[0621] (iv) The ratio of the above film thickness t1 to t0 (t1 / t0) is taken as the residual film rate.

[0622] [Evaluation of the pattern depiction]

[0623] The pattern used to evaluate the patternability is prepared by the following method. Any one of the curable compositions 1 to 11 is spin-coated onto a 5cm square glass substrate (EAGLE 2000; Corning Incorporated) to a pre-baked film thickness of 5μm. A drying process (pre-baking) at 70°C for 1 minute is then performed to form a film of the curable composition. After cooling the pre-baked film of the curable composition, the distance between the substrate with the film and a quartz glass photomask is set to 150μm. An exposure machine (UPE-1255MA; Ushio Lighting Co., Ltd.) is used under atmospheric conditions at 200mJ / cm². 2The film was irradiated with light at an exposure level (based on a wavelength of 365 nm). A photomask was used to form a pattern of lines and spaces with a linewidth of 3–30 μm and a pattern spacing of 30 μm. The irradiated film was developed using a developing apparatus (Actes Kyosan Co., Ltd., ADE-3000S) with a developing solution (an aqueous solution containing 0.12% tetramethylammonium hydroxide). The development time was the time until the separately prepared unexposed film was completely removed while developing it under the same conditions. After washing with water, the film was dried in an oven at 95°C for 30 minutes to obtain a pattern formed by the cured film, with 10 lines and 10 spaces for each linewidth of 3 μm, 5 μm, 10 μm, 20 μm, or 30 μm.

[0624] The obtained pattern was observed using a microscope (200x magnification; VHX-2000; manufactured by Keyence Co., Ltd.), and the minimum line width of the exposed pattern that was partially or completely retained was used as an indicator of the patternability of the composition.

[0625] [Determination of fluorescence intensity of the cured film]

[0626] Any one of the curable compositions 1 to 11 was spin-coated onto a 5 cm square glass substrate (EAGLE 2000; Corning Incorporated) to a thickness of 5 μm after baking. A pre-baking process (drying) at 70°C for 1 minute was then performed to form a film of curable compositions 1 to 11. After cooling, the film was exposed to atmospheric pressure at 200 mJ / cm² using an exposure machine (UPE-1255MA; Ushio Illumination Co., Ltd.). 2 The exposure process is carried out by irradiating with light at an exposure level (based on wavelength 365nm), and the thermal curing process is carried out by thermal curing at 95°C for 30 minutes (post-baking) to obtain a substrate with a cured film.

[0627] Next, a surface-emitting backlight (OPSM series: Optex FA) with an LED lamp having a peak emission wavelength of 450nm and a diffuser plate was prepared as the backlight. The backlight was positioned with the diffuser plate facing upwards, and a spectroradiometer (SR-UL1R: TOPCON TECHNOHOUSE) was placed at a height of 60cm above the surface of the diffuser plate. A glass substrate (EAGLE 2000: Corning) was placed on the surface of the backlight's diffuser plate as a control. With the backlight illuminated in this state, the cumulative value of the spectroradiant illuminance in the wavelength range of 380nm to 480nm, separated by the glass substrate, was 2.69 W·sr. －1 •m －2The amount of light from the backlight was adjusted in a certain way. Next, the glass substrate used as a control was removed, and a 5 cm square substrate having a cured film obtained from the curable compositions 1 to 11 described above was placed on the surface of the backlight's diffuser plate. The backlight was then turned on in this state, and the luminous intensity (unit: mW•sr) of the light emitted from the cured film was measured. ―1 •m ―2 ) is the cumulative spectral irradiance in the wavelength range of 480nm to 780nm.

[0628] The results of the determination of residual film rate, evaluation of patterning properties, and determination of fluorescence intensity of cured film are shown in Table 2.

[0629] [Table 2]

[0630]

[0631] In addition, for Examples 1, 2, and Comparative Example 1, the pre-drying conditions were set at 100°C for 3 minutes, and the post-drying conditions were set at 180°C for 30 minutes. Otherwise, the residual film rate was measured according to the same procedure. The results are shown in Table 3.

[0632] [Table 3]

[0633]

[0634] According to Table 2, in Examples 1 to 9 that satisfy the requirements of the present invention, the residual film rate when the curable composition is cured at low temperature is good. In contrast, in Comparative Examples 1 and 2, the residual film rate when cured at low temperature is lower compared to Examples 1 to 9. According to Table 3, it can be seen that Comparative Example 1 also has a good residual film rate when cured at high temperature, indicating that the issue of reduced residual film rate does not arise when curing conventional curable compositions at high temperatures.

Claims

1. A curable composition comprising semiconductor particles A and resin C, The value X, calculated from the acid value and weight-average molecular weight Mw of the resin C using the following formula (1), is 10–59.

75. The double bond equivalent of resin C is greater than 100 g / eq and less than 600 g / eq. X = {acid value × weight-average molecular weight Mw} / 10000 … (1) The unit of the acid value is mg-KOH / g.

2. The curable composition according to claim 1, wherein, The acid value of resin C is less than 85 mg-KOH / g.

3. The curable composition according to claim 1, wherein, The weight-average molecular weight (Mw) of the resin C is above 5000.

4. The curable composition according to claim 1, wherein, The mass ratio of the semiconductor particle A to the resin C, A / C, is 0.65 or higher.

5. The curable composition according to claim 1, wherein, It further comprises a polymerizable compound D, wherein the mass ratio of the resin C to the polymerizable compound D, C / D, is 2 or more.

6. The curable composition according to claim 1, wherein, It further includes a polymeric compound D, which comprises a polymeric compound having one or more cyclic hydrocarbon groups and two olefinic unsaturated bonds within one molecule.

7. The curable composition according to claim 6, wherein, The polymeric compound D further comprises a polymeric compound having an acidic functional group and three or more olefinic unsaturated bonds within one molecule.

8. The curable composition according to claim 1, wherein, It further contains light scattering agent B.

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