Curable composition

Abstract

To provide a curable composition containing semiconductor particles, the composition being capable of suppressing a decrease in the residual film ratio of a cured product when cured at a low temperature.SOLUTION: The present invention is a curable composition containing semiconductor particles (A) and a resin (C), wherein the value X calculated using the following formula (1) from the acid value and the weight-average molecular weight Mw of the resin (C) is 10 or more and 59.75 or less, and the double bond equivalent of the resin (C) is at least 100 g / eq and less than 600 g / eq. X={acid value (mg-KOH / g)×weight-average molecular weight Mw} / 10,000 (1).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes that a curable composition containing quantum dots (A) and a photopolymerizable compound (B) is subjected to a drying process (pre-baking) at 100°C for 3 minutes to form a film, and then an exposure process is carried out by irradiating light. After development, a heat curing process is carried out by performing a heat curing treatment (post-baking) at 180°C for 1 hour to obtain a cured film.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] A curable composition containing semiconductor particles such as quantum dots is preferable because the energy cost can be reduced if it can be cured at a low temperature. As a result of investigations by the present inventors, it has been clarified that when the curable composition is cured at a low temperature, the development remaining film rate of the cured film may be poor.

[0005] Therefore, an object of the present invention is to provide a curable composition containing semiconductor particles, which can suppress a decrease in the development remaining film rate of a cured product when cured at a low temperature.

Means for Solving the Problems

[0006] The present invention that has achieved the above problems is as follows. [1] A curable composition containing semiconductor particles (A) and a resin (C), The value X calculated by the following formula (1) from the acid value and weight average molecular weight Mw of the resin (C) is 10 or more and 59.75 or less, A curable composition in which 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) × weight average molecular weight Mw} / 10,000 …(1) [2] The curable composition according to [1], wherein the acid value of the resin (C) is less than 85 mg-KOH / g. [3] The curable composition according to [1] or [2], wherein the weight average molecular weight Mw of the resin (C) is 5000 or more. [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. [5] The curable composition according to any one of [1] to [4], further comprising a polymerizable compound (D), wherein the mass ratio (C / D) of the resin (C) to the polymerizable compound (D) is 2 or more. [6] The curable composition according to any one of [1] to [5], further comprising a polymerizable compound (D), wherein the polymerizable compound (D) includes a polymerizable compound having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule. [7] The curable composition according to [6], wherein the polymerizable compound (D) further includes a polymerizable compound having an acidic functional group and three or more ethylenically unsaturated bonds in one molecule. [8] The curable composition according to any one of [1] to [7], further comprising a light scattering agent (B).

Advantages of the Invention

[0007] According to the present invention, it is possible to suppress a decrease in the development residual film rate of a cured product obtained by curing a curable composition containing semiconductor particles at a low temperature.

Embodiments for Carrying Out the Invention

[0008] <<Curable Composition>> The curable composition preferably contains, in addition to semiconductor particles (A) and resin (C), at least one selected from an organic ligand (G), a light-scattering agent (B), a polymerizable compound (D), a polymerization initiator (E), a light stabilizer (F), a leveling agent (H), and a solvent (J) as required.

[0009] In the present specification, the compounds exemplified as each component can be used alone or in combination of two or more unless otherwise specified. When a plurality of types of each component are used, the content can be adjusted by the total amount of the plurality of types unless otherwise specified.

[0010] <Semiconductor particles (A)> The semiconductor particles (A) are preferably luminescent inorganic semiconductor particles that absorb primary light and emit light having a wavelength different from that of the primary light. More preferably, the luminescent inorganic semiconductor particles absorb primary light and emit green or red light, and still more preferably, convert the wavelength of blue light, which is the primary light, into the wavelength of red light or green light.

[0011] In the present specification, "blue" refers to all light visually recognized as blue (all light having intensity in the blue wavelength range, for example, 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light visually recognized as green (all light having intensity in the green wavelength range, for example, 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to all light visually recognized as red (all light having intensity in the red wavelength range, for example, 585 nm to 780 nm), and is not limited to light of a single wavelength.

[0012] Examples of the semiconductor particles (A) include particles composed of quantum dots and compounds having a perovskite crystal structure (hereinafter also referred to as "perovskite compounds"), and quantum dots are preferred. Quantum dots are luminescent inorganic semiconductor fine particles having a particle diameter of 1 nm or more and 100 nm or less, and are fine particles that utilize the bandgap of a semiconductor and absorb ultraviolet light or visible light (for example, blue light) to emit light.

[0013] Examples of quantum dots include compounds of Group 12 elements and Group 16 elements such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; compounds of Group 13 elements and Group 15 elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs; compounds of Group 14 elements and Group 16 elements such as PdS, PbSe, etc.

[0014] When the quantum dots contain S or Se, quantum dots surface-modified with metal oxides or organic substances may be used. By using surface-modified quantum dots, it is possible to prevent S or Se from being extracted by reaction components contained or that may be contained in the curable composition.

[0015] Also, the quantum dots may form a core-shell structure by combining the above compounds. Examples of such combinations include fine particles with a core of CdSe and a shell of ZnS, and fine particles with a core of InP and a shell of ZnSeS.

[0016] Since the energy state of quantum dots depends on their size, it is possible to freely select the emission wavelength by changing the particle size. Also, since the emission light from quantum dots has a narrow spectral width, it is advantageous for widening the color gamut of display devices. Furthermore, since quantum dots have high responsiveness, they are also advantageous in terms of the utilization efficiency of primary light.

[0017] A perovskite compound is a compound having a perovskite crystal structure and containing A, B, and X as components.

[0018] A is a component located at each vertex of an octahedron centered on B in the perovskite crystal structure and is a monovalent cation.

[0019] X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure and is at least one ion selected from the group consisting of halide ions and thiocyanate ions.

[0020] B is a component located at the center of an octahedron having A at its vertices and an octahedron having X at its vertices in the perovskite crystal structure and is a metal ion.

[0021] The perovskite compound containing A, B, and X as components is not particularly limited and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a pseudo-two-dimensional structure.

[0022] In the case of a three-dimensional structure, the perovskite compound is represented by ABX (3+δ) as shown.

[0023] In the case of a two-dimensional structure, the perovskite compound is represented by A2BX (4+δ) as shown.

[0024] Here, δ is a number that can be appropriately changed according to the charge balance of B and is from -0.7 to 0.7.

[0025] Preferred specific examples of a perovskite compound having a three-dimensional perovskite crystal structure represented by ABX (3+δ) include CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbI3, CH3NH3PbBr (3-y) I y (0 < y < 3), CH3NH3PbBr (3-y) Cly (0 < y < 3), (H2N=CH-NH2)PbBr3, (H2N=CH-NH2)PbCl3, (H2N=CH-NH2)PbI3, CH3NH3Pb (1-a) 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), 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), 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), 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 aBr (3+δ-y) Cl y (0 < a ≤ 0.7, -0.7 ≤ δ < 0, 0 < y < 3), (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), 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), 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), 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) Coa 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), 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) Mg a Br (3-y) Cl y (0 < a ≤ 0.7, 0 < y < 3), (H2N=CH-NH2)Zn aBr3(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. can be mentioned.

[0026] A perovskite compound, A2BX (4+δ) As a preferred specific example of a compound having a two-dimensional perovskite crystal structure represented by (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), (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), (C4H9NH3)2Pb(1-a) Na 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), (C4H9NH3)2Pb (1-a) Na 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), (C4H9NH3)2PbBr4, (C7H 15 NH3)2PbBr4, (C4H9NH3)2PbBr (4-y) Cl y (0 < y < 4), (C4H9NH3)2PbBr (4-y) I y (0 < y < 4), (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), (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), (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), (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. can be mentioned.

[0027] The content rate of the semiconductor particles (A) in the curable composition is preferably 3 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 55 mass% or less, still more preferably 20 mass% or more and 50 mass% or less, and particularly preferably 30 mass% or more and 50 mass% or less with respect to 100 mass% of the solid content of the curable composition.

[0028] In this specification, the total amount of the solid content in the curable composition means the total of the components excluding the solvent (J) among the components contained in the curable composition. The content rate in the solid content of the curable composition can be measured by known analysis means such as liquid chromatography or gas chromatography. The content rate of each component in the solid content of the curable composition may be calculated from the formulation at the time of preparing the curable composition.

[0029] <(organic ligand (G))> The semiconductor particles (A) may be present in the curable composition in a state where the organic ligand (G) is coordinated. The organic ligand (G) is, for example, an organic compound having a polar group exhibiting a coordination ability with respect to the semiconductor particles (A). The organic ligand (G) can be coordinated, for example, on the surface of the semiconductor particles (A). The curable composition can contain one or more organic ligands (G).

[0030] It is preferable that at least a part of the molecules of the organic ligand (G) are coordinated to the semiconductor particles (A), and all or almost all of the molecules thereof may be coordinated to the semiconductor particles (A). Containing the organic ligand (G) coordinated to the semiconductor particles (A) can be advantageous from the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer.

[0031] The polar group of the organic ligand (G) is, for example, at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH2). The polar group selected from this group can be advantageous in enhancing the coordination ability to the semiconductor particles (A). The high coordination ability can contribute to improving the stability and dispersibility of the semiconductor particles (A) in the curable composition, and improving the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer. Among them, it is more preferable that the polar group is at least one group selected from the group consisting of a thiol group and a carboxy group. The organic ligand (G) can have one or more polar groups.

[0032] The organic ligand (G) is, for example, the following formula (x): X A -R X (x) It can be an organic compound represented by. In the formula, X A is the above polar group, and R X is a monovalent hydrocarbon group which may contain a hetero atom (N, O, S, halogen atom, etc.). The hydrocarbon group may have one or more unsaturated bonds such as a carbon-carbon double bond. The hydrocarbon group may have a linear, branched or cyclic structure. The number of carbon atoms of the hydrocarbon group is, for example, 1 or more and 40 or less, and may be 1 or more and 30 or less. The methylene group contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc.

[0033] Group R X may contain a polar group. For specific examples of the polar group, the above description regarding the polar group X A is cited.

[0034] Polar group X ASpecific examples of the organic ligand having a carboxy group include formic acid, acetic acid, propionic acid, and saturated or unsaturated fatty acids. Specific examples of the saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenoic acid, erucic acid, nervonic acid; and polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, adrenic acid (eicosatetraenoic acid).

[0035] Polar group X A Specific examples of the organic ligand having a thiol group or an amino group include the polar group X exemplified above A and include an organic ligand in which the carboxy group of the organic ligand having a carboxy group is replaced with a thiol group or an amino group.

[0036] In addition to the above, examples of the organic ligand represented by the above formula (x) include compound (G-1) and compound (G-2).

[0037] [Compound (G-1)] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxy group (-COOH), and the second functional group is a carboxy group or a thiol group (-SH). Since compound (G-1) has a carboxy group and / or a thiol group, it can be a ligand that coordinates to semiconductor particles (A). The curable composition may contain only one kind of compound (G-1) or two or more kinds thereof.

[0038] An example of compound (G-1) is a compound represented by the following formula (G-1a). Compound (G-1) may be an acid anhydride of the compound represented by formula (G-1a).

[0039] [Chemical formula]

[0040] [In the formula, R B represents a divalent hydrocarbon group. When there are a plurality of R B s, they may be the same or different. The above hydrocarbon group may have one or more substituents. When there are a plurality of substituents, they may be the same or different, and they may be bonded to each other to form a ring together with the atoms to which they are respectively bonded. -CH2- contained in the above hydrocarbon group may be replaced by at least one of -O-, -S-, -SO2-, -CO- and -NH-. p represents an integer of 1 to 10.]

[0041] Examples of the divalent hydrocarbon group represented by R B include, for example, a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., and groups combining these.

[0042] Examples of the chain hydrocarbon group include a linear or branched alkanediyl group, and the number of its carbon atoms is usually 1 to 50, preferably 1 to 20, more preferably 1 to 10. Examples of the alicyclic hydrocarbon group include a monocyclic or polycyclic cycloalkanediyl group, and the number of its carbon atoms is usually 3 to 50, preferably 3 to 20, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include a monocyclic or polycyclic arenediyl group, and the number of its carbon atoms is usually 6 to 20.

[0043] Examples of the substituent that the above hydrocarbon group may have include, for example, an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxy group, an amino group, a halogen atom, etc. The substituent that the above hydrocarbon group may have is preferably a carboxy group, an amino group or a halogen atom.

[0044] When -CH2- contained in the hydrocarbon group is replaced by at least one of -O-, -CO- and -NH-, the -CH2- is preferably replaced by at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0045] Examples of the compound represented by the formula (G-1a) include compounds represented by the following formulas (1-1) to (1-9).

[0046]

Chemical formula

[0047] Specific examples of the compound represented by the formula (G-1a) shown by chemical names include, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-mercaptopropionic acid 3-methoxybutyl, 3-mercapto-2-methylpropionic acid and the like. Among them, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0048] Another example of the compound (G-1) is a polycarboxylic acid compound, preferably a compound (G-1b) in which -SH in the formula (G-1a) is replaced by a carboxy group (-COOH) in the compound represented by the above formula (G-1a).

[0049] Examples of the compound (G-1b) include the following compounds.

[0050] Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecafluorosuberic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecafluorosebacic acid, acetylenedicarboxylic 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-furandicarboxylic acid, benzophenone-2,4'-dicarboxylic acid monohydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbenedicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, keldonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorendic acid, 1H-imidazole-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,1,10-bis(4-carboxyphenoxy)decane, dipropyl malonic acid, dithiodiglycolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiobutanoic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidenediphenoxyacetic acid, 1,3-acetonedicarboxylic acid, methylenedisalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl) isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid, 1,3,5-benzenetricarboxylic acid, etc.,

[0051] From the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer, the molecular weight of the compound (G-1) is preferably 3,000 or less, more preferably 2,500 or less, still more preferably 2,000 or less, even more preferably 1,000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of the compound (G-1) is usually 100 or more.

[0052] The above molecular weight may be a number average molecular weight or a weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC), respectively.

[0053] When the curable composition contains the compound (G-1), the content ratio of the compound (G-1) to the semiconductor particles (A) in the curable composition is preferably 0.001 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, still more preferably 0.02 or more and 0.45 or less, by mass ratio. When the content ratio is within this range, it can be advantageous from the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film is used as a wavelength conversion layer.

[0054] When the curable composition contains the compound (G-1), the content of the compound (G-1) in the curable composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 20% by mass or less, still more preferably 0.2% by mass or more and 10% by mass or less, even more preferably 0.5% by mass or more and 10% by mass or less, particularly preferably 0.5% by mass or more and 8% by mass or less, from the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film is used as a wavelength conversion layer, based on the total amount of the solid content of the curable composition.

[0055] 〔Compound (G-2)〕 Compound (G-2) is a compound different from compound (G-1), which contains a polyalkylene glycol structure and has a polar group at the molecular terminal. The molecular terminal is preferably the terminal of the longest carbon chain (the carbon atoms in the carbon chain may be replaced by other atoms such as oxygen atoms) in compound (G-2).

[0056] The curable composition may contain only one kind of compound (G-2) or may contain two or more kinds. The curable composition may contain compound (G-1) or compound (G-2), or may contain both compound (G-1) and compound (G-2).

[0057] In addition, a compound containing a polyalkylene glycol structure and having the above first functional group and second functional group shall belong to compound (G-1).

[0058] The polyalkylene glycol structure refers to the following formula:

[0059]

Chemical formula

[0060] represents the structure shown (n is an integer of 2 or more). In the formula, R C is an alkylene group, and examples thereof include an ethylene group and a propylene group.

[0061] As a specific example of the compound (G-2), a polyalkylene glycol compound represented by the following formula (G-2a) can be mentioned.

[0062] [Chemical formula]

[0063] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z C is a divalent or trivalent group. n is an integer of 2 or more. m is 1 or 2. R C is an alkylene group.

[0064] The polar group X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH2). The polar group selected from this group can be advantageous in enhancing the coordination property to the semiconductor particles (A). Among them, from the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission 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 the group consisting of a thiol group and a carboxy group.

[0065] The group Y is a monovalent group. The group Y is not particularly limited, and examples thereof include a monovalent hydrocarbon group which may have substituents (such as N, O, S, halogen atoms, etc.). -CH2- contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The carbon number of the above hydrocarbon group is, for example, 1 or more and 12 or less. The hydrocarbon group may have an unsaturated bond.

[0066] Examples of the group Y include an alkyl group having a linear, branched or cyclic structure and having 1 to 12 carbon atoms; an alkoxy group having a linear, branched or cyclic structure and having 1 to 12 carbon atoms, etc. The number of carbon atoms of the alkyl group and the alkoxy group is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. The -CH2- contained in the alkyl group and the alkoxy group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. Among them, the group Y is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and more preferably a linear alkoxy group having 1 to 4 carbon atoms.

[0067] The group Y may contain a polar group. Examples of the polar group include at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH2). However, as described above, a compound containing a polyalkylene glycol structure and having the above first functional group and second functional group shall belong to the compound (G-1). The polar group is preferably located at the terminal of the group Y.

[0068] Group Z C is a divalent or trivalent group. Group Z C is not particularly limited, and examples thereof include a divalent or trivalent hydrocarbon group which may contain a hetero atom (N, O, S, halogen atom, etc.). The number of carbon atoms of the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond.

[0069] Group Z which is a divalent group CExamples include an alkylene group having a linear, branched or cyclic structure and having 1 to 24 carbon atoms; an alkenylene group having a linear, branched or cyclic structure and having 1 to 24 carbon atoms, etc. The number of carbon atoms of the alkyl group and the alkenylene group is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less. The —CH2— contained in the alkyl group and the alkenylene group may be substituted with —O—, —S—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —C(═O)—NH—, —NH—, etc. Group Z which is a trivalent group C Examples of C include a group obtained by removing one hydrogen atom from the above divalent group Z

[0070] Group Z C may have a branched structure. Group Z having a branched structure C may have a polyalkylene glycol structure different from the polyalkylene glycol structure shown in the above formula (G-2a) in a branched chain different from the branched chain containing the polyalkylene glycol structure shown in the above formula (G-2a).

[0071] Among them, group Z C is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

[0072] R C is an alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

[0073] n in the formula (G-2a) is an integer of 2 or more, preferably 2 or more and 540 or less, more preferably 2 or more and 120 or less, and even more preferably 2 or more and 60 or less.

[0074] The molecular weight of the compound (G-2) can be, for example, about 150 or more and 10,000 or less. However, from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer, it is preferably 150 or more and 5,000 or less, and more preferably 150 or more and 4,000 or less. This molecular weight may be a number average molecular weight or a weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are respectively the number average molecular weight and the weight average molecular weight in terms of standard polystyrene measured by GPC.

[0075] When the curable composition contains the compound (G-2), the content ratio of the compound (G-2) to the semiconductor particles (A) in the curable composition is preferably 0.001 or more and 2 or less, more preferably 0.01 or more and 1.5 or less, and still more preferably 0.1 or more and 1 or less, in terms of mass ratio. When the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer.

[0076] When the curable composition contains the compound (G-2), the content rate of the compound (G-2) in the curable composition is preferably 0.1 mass% or more and 40 mass% or less, more preferably 0.1 mass% or more and 20 mass% or less, still more preferably 1 mass% or more and 15 mass% or less, and even more preferably 2 mass% or more and 12 mass% or less, with respect to the total amount of the solid content of the curable composition, from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer.

[0077] When the curable composition contains the 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 or more and 1 or less, more preferably 0.01 or more and 0.8 or less, and still more preferably 0.02 or more and 0.5 or less, in terms of mass ratio. When the content ratio is within this range, it can be advantageous from the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission 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 is the total content of all the organic ligands contained in the curable composition.

[0078] From the viewpoints of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity when the cured film of the curable composition is used as a wavelength conversion layer, the total content ratio of the semiconductor particles (A) and the organic ligand (G) in the curable composition is preferably 10% by mass or more and 75% by mass or less, more preferably 12% by mass or more and 70% by mass or less, based on the total amount of the solid content of the curable composition.

[0079] <Resin (C)> Examples of the resin (C) include the following resins [K1] to [K6] and the like.

[0080] Resin [K1]; A copolymer having a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as "(a)") and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a)) (hereinafter also referred to as "(c)"); Resin [K2]; A copolymer having a structural unit derived from the above (a), a structural unit derived from the above (c), and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(b)"); Resin [K3]; A copolymer having a structural unit obtained by adding the above (b) to the structural unit derived from the above (a) and a structural unit derived from the above (c); Resin [K4]: A copolymer having a structural unit obtained by adding (b) to the structural unit derived from (a) and further having a structural unit obtained by ester-bonding a carboxylic anhydride, and a structural unit derived from (c). Resin [K5]; A copolymer having a structural unit obtained by adding (a) to the structural unit derived from (b) and a structural unit derived from (c); Resin [K6]; A copolymer having a structural unit obtained by adding (a) to the structural unit derived from (b) and further having a structural unit obtained by ester-bonding a carboxylic anhydride, and a structural unit derived from (c).

[0081] Examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, etc.; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc.; Bicyclic unsaturated compounds containing a carboxy group such as 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, etc.; Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc.; Unsaturated mono-[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with two or more valences, such as succinic acid mono-[2-(meth)acryloyloxyethyl], phthalic acid mono-[2-(meth)acryloyloxyethyl], etc.; Unsaturated (meth)acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid etc. may be mentioned.

[0082] Among these, from the viewpoints of copolymerization reactivity and the like, (meth)acrylic acid, succinic acid mono-[2-(meth)acryloyloxyethyl], maleic anhydride, etc. are preferable.

[0083] In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid. The same applies to "(meth)acryloyl", "(meth)acrylate", etc.

[0084] (b) is a monomer having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0085] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

[0086] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0087] 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(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0088] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), the compound represented by formula (BI), and the compound represented by formula (BII).

[0089] [Chemical formula]

[0090] [In formula (BI) and formula (BII), R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X e and X f is a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-. R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0091] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like. Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like. R e and R f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and more preferably a hydrogen atom, a methyl group.

[0092] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, and the like. X e and X f are preferably a single bond, a methylene group, an ethylene group, *-CH2-O- and *-CH2CH2-O-, and more preferably a single bond, *-CH2CH2-O- (* represents a bond to O).

[0093] Examples of the compound represented by formula (BI) include compounds represented by any of formula (BI-1) to formula (BI-15). Among them, compounds represented by formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9), or formula (BI-11) to formula (BI-15) are preferred, and compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15) are more preferred.

[0094]

Chem.

[0095] Examples of the compound represented by formula (BII) include compounds represented by any of formula (BII-1) to formula (BII-15). Among them, compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formula (BII-11) to formula (BII-15) are preferred, and compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15) are more preferred.

[0096]

Chem.

[0097] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratios [compound represented by formula (BI): compound represented by formula (BII)] are preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0098] (b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. 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.

[0099] (b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Specifically, examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0100] (b) is preferably (b1) in terms of being able to further enhance the reliability such as chemical resistance.

[0101] Since the monomers having an oxirane ring and an ethylenically unsaturated bond have high reactivity during the production of Resins [K3] to [K6] and it is difficult for unreacted (b) to remain, (b) is preferably such a monomer.

[0102] (c) includes, for example, 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[5.2.1.0 2,6Decan-8-yl (meth)acrylate (in the art, it is commonly known as "dicyclopentanyl (meth)acrylate". It may also be referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 2,6 Decen-8-yl (meth)acrylate (in the art, it is commonly known as "dicyclopentenyl (meth)acrylate".), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylic acid esters; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyrate, N-succinimidyl 6-maleimidocaproate, N-succinimidyl 3-maleimidopropionate, N-(9-acridinyl)maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene isoprene, 2,3-dimethyl-1,3-butadiene etc. can be mentioned.

[0103] Among the above, from the viewpoint of copolymerization reactivity, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable.

[0104] In resin [K1], the ratio of the structural units derived therefrom is among all the structural units constituting resin [K1], (a) the structural unit derived therefrom; 2 mol% or more and 60 mol% or less (c) the structural unit derived therefrom; 40 mol% or more and 98 mol% or less it is preferably that, (a) the structural unit derived therefrom; 10 mol% or more and 50 mol% or less (c) the structural unit derived therefrom; 50 mol% or more and 90 mol% or less it is more preferably that.

[0105] When the ratio of the structural units of resin [K1] is within the above range, it tends to be excellent in storage stability and solvent resistance.

[0106] Resin [K1] can be produced, for example, with reference to the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Publishing Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the cited references described in the literature.

[0107] Specifically, a method may be mentioned in which a predetermined amount of (a) and (c), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is made oxygen-free, for example, by replacing oxygen with nitrogen, and heating and heat preservation are carried out while stirring.

[0108] The polymerization initiator, solvent, etc. used are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.) may be mentioned. As the solvent, any solvent that can dissolve each monomer may be used, and examples include the solvents described later as solvent (J).

[0109] The obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. If the solvent (J) described later is used as the solvent during polymerization, the reaction solution can be used as it is for the preparation of the composition, so the manufacturing process of the composition can be simplified.

[0110] In resin [K2], the ratio of the structural units derived from each is among all the structural units constituting resin [K2], Structural unit derived from (a); 2 to 45 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (c); 1 to 65 mol% It is preferably, Structural unit derived from (a); 5 to 40 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (c); 5 to 60 mol% It is more preferably.

[0111] When the ratio of the structural units of resin [K2] is within the above range, the storage stability of the composition and the developability when forming a coloring pattern tend to be excellent.

[0112] Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

[0113] Resin [K3] can be produced by adding the cyclic ether having 2 to 4 carbon atoms of (b) to the copolymer of (a) and (c) to the carboxylic acid and / or carboxylic anhydride having (a).

[0114] First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio described for resin [K1].

[0115] Next, a cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0116] Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and in the presence of (b), a carboxylic acid or carboxylic anhydride, a reaction catalyst for the cyclic ether (for example, an organic phosphorus compound, a metal complex, an amine compound, etc.) and a polymerization inhibitor (for example, hydroquinone, methoxyquinone, etc.), etc., for example, at 60 ° C or higher and 130 ° C or lower, for 1 hour or more and 10 hours or less, resin [K3] can be produced.

[0117] The usage amount of (b) is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more and 75 mol or less, per 100 mol of (a). By setting it within this range, it is possible to suppress a decrease in the development residue film ratio of the cured film when the curable composition is cured at a low temperature.

[0118] Examples of the organic phosphorus compound as the reaction catalyst include triphenylphosphine and the like. As the amine compound as the reaction catalyst, for example, an aliphatic tertiary amine compound or an aliphatic quaternary ammonium salt compound can be used. Specific examples thereof include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, tetrabutylammonium chloride and the like. The reaction catalyst is preferably an organic phosphorus compound.

[0119] The amount of the reaction catalyst used is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).

[0120] The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).

[0121] The charging method, reaction conditions such as reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. In addition, similar to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

[0122] Resin [K4] is a resin obtained by further reacting resin [K3] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the carboxylic acid or carboxylic anhydride and the cyclic ether. Examples of the carboxylic anhydride 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of the carboxylic anhydride used is preferably 0.5 mol or more and 1 mol or less with respect to 1 mol of the amount of (b) used.

[0123] As a first step, the resin [K5] is obtained by obtaining a copolymer of (b) and (c) in the same manner as the method for producing the resin [K1] described above. Similar to the above, the obtained copolymer may be used as the solution after the reaction as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.

[0124] (b) and the ratio of the structural units derived from (c) are, respectively, based on the total number of moles of all the structural units constituting the copolymer, (b) Structural units derived from; 5 mol% or more and 95 mol% or less (c) Structural units derived from; 5 mol% or more and 95 mol% or less It is preferably that, (b) Structural units derived from; 10 mol% or more and 90 mol% or less (c) Structural units derived from; 10 mol% or more and 90 mol% or less It is more preferably that.

[0125] The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride of (a) with the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as the method for producing the resin [K3].

[0126] The amount of (a) used for reacting with the copolymer is preferably 5 mol or more and 120 mol or less, more preferably 20 mol or more and 110 mol or less, per 100 mol of (b).

[0127] The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

[0128] Examples of the carboxylic acid anhydride 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like.

[0129] The amount of the carboxylic acid anhydride used is preferably 0.1 to 1 mol, more preferably 0.2 to 1 mol, and still more preferably 0.3 to 1 mol, per 1 mol of the amount of (a) used.

[0130] Examples of the resins [K1], [K2], [K3], [K4], [K5] and [K6] include resin [K1] such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / dicyclopentanyl (meth)acrylate / methyl (meth)acrylate copolymer; resin [K2] such as glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / methyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate copolymer; Resins such as a resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K3]; Resins such as a resin obtained by ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate / methyl (meth)acrylate / (meth)acrylic acid copolymer, a resin obtained by ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / (meth)acrylic acid copolymer [K4]; Resins such as a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K5]; Examples include resins such as a resin obtained by ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, a resin obtained by ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding (meth)acrylic acid to a copolymer of dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / glycidyl (meth)acrylate [K6], etc.

[0131] The resin (C) contained in the curable composition preferably contains at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5], and resin [K6], more preferably contains at least one selected from the group consisting of resin [K3], resin [K4], resin [K5], and resin [K6], still more preferably contains at least one selected from the group consisting of resin [K4] and resin [K6], and particularly preferably resin [K6].

[0132] As a further example of the resin (C), the resin described in JP-A-2018-123274 can be mentioned. As the resin, a polymer having a double bond in the side chain and containing a structural unit (α) represented by the following formula (I) and a structural unit (β) represented by the following formula (II) in the main chain and further containing an acid group (hereinafter, also referred to as "resin (Ca)") can be mentioned.

[0133] The acid group can be introduced into the resin, for example, by the resin (Ca) containing a structural unit (γ) derived from an acid group-containing monomer (for example, (meth)acrylic acid, etc.). The resin (Ca) preferably contains the structural units (α), (β), and (γ) in the main chain skeleton.

[0134] [Chemical formula]

[0135] [In the formula, R A and R B represent the same or different hydrogen atoms or hydrocarbon groups having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by formula (I) and is a number of 1 or more.]

[0136] [Chemical formula]

[0137] [In the formula, R C represent the same or different hydrogen atoms or methyl groups. R Dis the same or different and represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by formula (II) and is a number of 1 or more.] In the resin (Ca), from the viewpoint of the storage stability of the resin (Ca), the content ratio of the structural unit (α) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca). n in formula (I) represents the average number of repeating units of the structural unit (α) in the resin (Ca), and n can be set so that the content ratio of the structural unit (α) is within the above range.

[0138] From the viewpoint of solvent resistance, the content ratio of the structural unit (β) is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 75% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca). m in formula (II) represents the average number of repeating units of the structural unit (β) in the resin (Ca), and m can be set so that the content ratio of the structural unit (β) is within the above-mentioned range.

[0139] From the viewpoints such as the solubility of the resin (Ca) in the solvent (J), the content ratio of the structural unit (γ) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca).

[0140] In the present invention, it is important that the value X calculated by the following formula (1) from the acid value and the weight average molecular weight Mw of the resin (C) is 10 or more and 59.75 or less. By setting the value X within this range, it is possible to suppress a decrease in the development remaining film ratio of the cured film (hereinafter, may be simply referred to as the remaining film ratio) when the curable composition is cured at a low temperature. The value X is preferably 12.50 or more, more preferably 16.50 or more, and preferably 58 or less, more preferably 56.25 or less. The value X is preferably 12.50 or more and 56.25 or less, more preferably 16.50 or more and 56.25 or less. X = {acid value (mg-KOH / g) × weight average molecular weight Mw} / 10,000 …(1)

[0141] The acid value of the resin (C) is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (C), and can be determined, for example, by titration using an aqueous potassium hydroxide solution. Specifically, it can be measured according to the measurement method described in the Examples section below. Alternatively, for the resin (C) contained in the composition, the acid value may be determined, for example, by performing its structural analysis.

[0142] The weight average molecular weight Mw of the resin (C) is the weight average molecular weight in terms of standard polystyrene measured by GPC, and can be measured according to the measurement method described in the Examples section below. Alternatively, for the resin (C) contained in the curable composition, Mw may be measured using GPC.

[0143] The weight average molecular weight Mw of the resin (C) is not particularly limited as long as it can satisfy the above-mentioned value X. For example, it is 1,000 or more, preferably 3,000 or more, more preferably 5,000 or more, still more preferably 5,500 or more. Also, for example, it is 100,000 or less, preferably 50,000 or less, more preferably 20,000 or less, still more preferably 8,000 or less, and even more preferably 7,500 or less. The weight average molecular weight Mw of the resin (C) is preferably 5,000 or more and 8,000 or less, and more preferably 5,500 or more and 7,500 or less. In particular, from the viewpoint of improving the patterning property after exposure and development, it is preferable that Mw is 5,000 or more. The Mw of the resin (C) can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the charging method, the reaction temperature, and the reaction time.

[0144] The acid value of the resin (C) is not particularly limited as long as it can satisfy the above-mentioned value X. However, it is preferably 150 mg-KOH / g or less, more preferably 110 mg-KOH / g or less, still more preferably 85 mg-KOH / g or less, particularly preferably 80 mg-KOH / g or less, and most preferably 75 mg-KOH / g or less. Also, it is preferably 20 mg-KOH / g or more, more preferably 25 mg-KOH / g or more, and still more preferably 30 mg-KOH / g or more. The acid value of the resin (C) is preferably 25 mg-KOH / g or more and 80 mg-KOH / g or less, and more preferably 30 mg-KOH / g or more and 75 mg-KOH / g or less. The acid value of the resin (C) can be adjusted by the content of the monomer component having an acid group (for example, the above (a)) and the content of the carboxylic acid anhydride.

[0145] Also, it is important that the double bond equivalent of the resin (C) is 100 g / eq or more and less than 600 g / eq. By the double bond equivalent being within the above range, a decrease in the residual film rate of the cured film when the curable composition is cured at a low temperature can be suppressed. The double bond equivalent of the resin (C) is preferably 200 g / eq or more, more preferably 250 g / eq or more, still more preferably 300 g / eq or more, and preferably 500 g / eq or less, more preferably 450 g / eq or less, still more preferably 400 g / eq or less. The double bond equivalent of the resin (C) is preferably 250 g / eq or more and 450 g / eq or less, more preferably 300 g / eq or more and 400 g / eq or less. Examples of the resin having the above-described double bond equivalent include (meth)acrylic resins. The resin (C) preferably consists of a (meth)acrylic resin.

[0146] The content of the resin (C) in the curable composition is, for example, 5% by mass or more and 80% by mass or less, preferably 10% by mass or more and 70% by mass or less, more preferably 13% by mass or more and 60% by mass or less, still more preferably 17% by mass or more and 55% by mass or less, based on the total amount of the solid content of the curable composition. When the content of the resin (C) is within the above range, a decrease in the residual film rate of the cured film obtained by curing the coating film of the curable composition at a low temperature can be suppressed.

[0147] 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, still more preferably 1.5 or more, and preferably less than 10, more preferably 8 or less, still more preferably 5 or less.

[0148] <Light scattering agent (B)> Examples of the light scattering agent (B) include inorganic particles such as metal or metal oxide particles and glass particles. Examples of the metal oxide include TiO2, SiO2, BaTiO3, ZnO, etc., and TiO2 particles are preferred because they efficiently scatter light. The particle diameter of the light scattering agent (B) is, for example, about 0.03 μm or more and 20 μm or less, preferably 0.05 μm or more and 1 μm or less, more preferably 0.05 μm or more and 0.5 μm or less.

[0149] As the light scattering agent (B), a light scattering agent dispersed in part or all of the solvent (J) in advance using a dispersant (I) may be used. As the dispersant (I), commercially available products can be used. Examples of commercially available products include DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 manufactured by BYK-Chemie Japan; ANTI-TERRA-U, U100, 203, 204, 250; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.; 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. manufactured by Lubrizol Japan; 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. manufactured by BASF; Examples include Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc.

[0150] The content ratio of the light-scattering agent (B) in the curable composition is, for example, 0.001% by mass or more and 50% by mass or less with respect to the total amount of the solid content of 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% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, still more preferably 5% by mass or more and 30% by mass or less, and even more preferably 8% by mass or more and 30% by mass or less.

[0151] <Polymerizable compound (D)> The polymerizable compound (D) is a compound that can be polymerized by active radicals, acids, etc. generated from a polymerization initiator (E) described later. Examples of the polymerizable compound (D) include photopolymerizable compounds such as compounds having an ethylenically unsaturated bond, for example, (meth)acrylic acid ester compounds. Another example of the polymerizable compound (D) is a thermopolymerizable compound. The curable composition may contain two or more kinds of the polymerizable compound (D).

[0152] Examples of the polymerizable compound (D) include a photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule and a photopolymerizable compound (Dβ) having three or more ethylenically unsaturated bonds in the molecule. In the photopolymerizable compound (Dβ), the number of ethylenically unsaturated bonds in the molecule is preferably 6 or less. The ethylenically unsaturated bond is preferably a (meth)acryloyloxy group. The weight average molecular weight of the polymerizable compound (D) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less. The polymerizable compound (D) preferably contains one or more selected from the photopolymerizable compound (Dα) and the photopolymerizable compound (Dβ), and more preferably contains one or more of the photopolymerizable compound (Dβ). It is also preferable that the photopolymerizable compound (D) contains one or more of the photopolymerizable compound (Dα) and one or more of the photopolymerizable compound (Dβ).

[0153] Examples of the photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule include bifunctional (meth)acrylic compounds, such as alkylene glycol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, halogen-substituted alkylene glycol di(meth)acrylate, di(meth)acrylate of aliphatic polyol, di(meth)acrylate of hydrogenated dicyclopentadiene or tricyclodecane dialkanol, di(meth)acrylate of dioxane glycol or dioxane dialkanol, di(meth)acrylate of alkylene oxide adduct of bisphenol A or bisphenol F, epoxy di(meth)acrylate of bisphenol A or bisphenol F, and the like.

[0154] More specific examples of the bifunctional (meth)acrylic compound include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 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 hydroxypivalic acid neopentyl glycol ester, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,3-dioxane-2,5-diyl di(meth)acrylate [alias: dioxane glycol di(meth)acrylate], di(meth)acrylate of an acetal compound of hydroxypivalaldehyde and trimethylolpropane [chemical name: 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane], tris(hydroxyethyl)isocyanurate di(meth)acrylate, 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, and the like.

[0155] The photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule is preferably a photopolymerizable compound (Dα1) having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule, and it is preferable that the polymerizable compound (D) contains one or more of the 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 a phenylene group. Also, in the photopolymerizable compound (Dα1), the number of cyclic hydrocarbon groups in one molecule is preferably two. Specific examples of the photopolymerizable compound (Dα1) include di(meth)acrylates of ethoxylated bisphenol A, di(meth)acrylates of propoxylated bisphenol A, di(meth)acrylates of ethoxylated bisphenol F, di(meth)acrylates of propoxylated bisphenol F, and the like.

[0156] Examples of the polymerizable compound (Dβ) having three or more ethylenically unsaturated bonds in the molecule include a compound (Dβ1) having three or more ethylenically unsaturated bonds (particularly (meth)acryloyloxy groups) in the molecule and having an acidic functional group, and a compound (Dβ2) having three or more ethylenically unsaturated bonds (particularly (meth)acryloyloxy groups) in the molecule and not having an acidic functional group. The polymerizable compound (D) preferably contains at least one of the compounds (Dβ1) and (Dβ2), and more preferably contains at least one of the compounds (Dβ1). Examples of the above acidic functional group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like. Among them, the acidic functional group is preferably a carboxy group.

[0157] The number of ethylenically unsaturated bonds (particularly (meth)acryloyloxy groups) in one molecule of the compound (Dβ1) is, for example, 3 or more and 6 or less, preferably 3 or more and 5 or less, and more preferably 3. The number of acidic functional groups in one molecule of the compound (Dβ1) is 1 or more, and preferably 1. When having two or more acidic functional groups, each acidic functional group may be different or the same, but it preferably has at least one carboxy group.

[0158] Examples of the compound (Dβ1) include compounds obtained by esterifying a compound having three or more (meth)acryloyloxy groups and hydroxy groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid or dicarboxylic anhydride. Examples of such compounds include a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Among them, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

[0159] Examples of commercially available products of the compound (Dβ1) include "Aronix M-510" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate as the main component, and "Aronix M-520D" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate as the main component. These commercially available products have a carboxy group as an acidic functional group.

[0160] The number of ethylenically unsaturated bonds (particularly (meth)acryloyloxy groups) possessed by the compound (Dβ2) is preferably 3 to 6, more preferably 4 to 6.

[0161] Examples of the compound (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, tris(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, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferable.

[0162] The polymerizable compound (D) in the curable composition preferably contains the compound (Dα) (particularly the compound (Dα1)) because it can suppress a decrease in the residual film ratio of the cured film obtained by curing the coating film of the curable composition at a low temperature and can reduce the residue after development of the curable composition. The polymerizable compound (D) preferably contains the compound (Dβ) because it can suppress a decrease in the residual film ratio of the cured film obtained by curing the coating film of the curable composition at a low temperature, can improve the curability during exposure and the patternability during development, can further improve the dispersibility of the semiconductor particles (A), and can improve the emission intensity when the cured film is used as a wavelength conversion layer.

[0163] In 100% by mass of the polymerizable compound (D) contained in the curable composition, it is preferable that the compound (Dα) (compound (Dα1)) is 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and may be 70% by mass or less. In 100% by mass of the polymerizable compound (D) contained in the curable composition, it is preferable that the compound (Dβ) is 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and may be 100% by mass or 60% by mass or less.

[0164] When the polymerizable compound (D) in the curable composition contains both the compound (Dα) and the compound (Dβ), it preferably contains the compounds (Dα1) and (Dβ1), and the total content of the compounds (Dα1) and (Dβ1) with respect to 100% by mass of the polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may be 100% by mass. The content of the compound (Dα1) with respect to 100% by mass of the total amount of the compounds (Dα1) and (Dβ1) is preferably more than 50% by mass, more preferably 53% by mass or more, still more preferably 55% by mass or more, and may be 70% by mass or less.

[0165] When the polymerizable compound (D) in the curable composition contains both the compound (Dβ1) and the compound (Dβ2), the total content of the compounds (Dβ1) and (Dβ2) with respect to 100% by mass of the polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may be 100% by mass. The content of the compound (Dβ2) with respect to 100% by mass of the total amount of the compounds (Dβ1) and (Dβ2) is preferably more than 50% by mass, more preferably 53% by mass or more, still more preferably 55% by mass or more, and may be 70% by mass or less.

[0166] The content rate (total amount in case of multiple types) of the polymerizable compound (D) in the curable composition is preferably 3 mass% or more and 30 mass% or less, more preferably 4 mass% or more and 20 mass% or less, still more preferably 5 mass% or more and 15 mass% or less, based on 100 mass% of the total solid content of the curable composition. When the content rate of the polymerizable compound (D) is within the above range, a decrease in the remaining film rate of the cured film obtained by curing the coating film of the curable composition at a low temperature can be suppressed.

[0167] The mass ratio (C / D) of the resin (C) to the polymerizable compound (D) in the curable composition is preferably 2 or more, more preferably 2.3 or more, still more preferably 2.5 or more, and preferably 8 or less, more preferably 7 or less, still more preferably 6 or less, from the viewpoint of suppressing a decrease in the remaining film rate of the cured film. When the mass ratio (C / D) of the resin (C) to the polymerizable compound (D) satisfies the above range, it is preferable that the photopolymerizable compound (D) contains one or more of the photopolymerizable compounds (Dα1), and more preferably that the photopolymerizable compound (D) contains one or more of the photopolymerizable compounds (Dα1) and one or more of the photopolymerizable compounds (Dβ1).

[0168] <Polymerization initiator (E)> The polymerization initiator (E) is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate the polymerization of the polymerizable compound (D). The curable composition can contain one or more polymerization initiators (E).

[0169] Examples of the polymerization initiator (E) include oxime compounds, and for example, compounds represented by the formula (EA). By the polymerization initiator (E) containing the compound represented by the formula (EA), a decrease in the remaining film rate of the cured film when the curable composition is cured at a low temperature can be suppressed, and it is also advantageous from the viewpoint of improving the patterning after exposure and development. Further, by containing the compound represented by the formula (EA), the effect of improving the emission intensity (fluorescence emission intensity) evaluated in the examples described later can also be exhibited.

[0170]

Chemical formula

[0171] R ea1 Examples of the branched hydrocarbon group having 3 to 20 carbon atoms represented by

[0172] R ea1Examples of the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1,1-dimethylethyl group (tert-butyl group), a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylpentyl group, a 2,2-dimethylpentyl group, a 3,3-dimethylpentyl group, a 1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a 2,3-dimethylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 1,1-dimethylhexyl group, a 2,2-dimethylhexyl group, a 3,3-dimethylhexyl group, a 1,2-dimethylhexyl group, a 1,3-dimethylhexyl group, a 2,3-dimethylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 4-methylheptyl group, a 1,1-dimethylheptyl group, a 2,2-dimethylheptyl group, a 3,3-dimethylheptyl group, a 1,2-dimethylheptyl group, a 1,3-dimethylheptyl group, a 2,3-dimethylheptyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, a 3-ethylheptyl group, a 1-methyloctyl group, a 2-methyloctyl group, a 3-methyloctyl group, a 4-methyloctyl group, a 1,1-dimethyloctyl group, a 2,2-dimethyloctyl group, a 3,3-dimethyloctyl group, a 1,2-dimethyloctyl group, a 1,3-dimethyloctyl group, 2,Branched alkyl groups such as 3-dimethyloctyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, dimethylnonyl group, ethylnonyl group, methyldecyl group, dimethyldecyl group, ethyldecyl group, methylundecyl group, dimethylundecyl group, ethylundecyl group, methyldodecyl group, etc.; may be mentioned., R ea1 The branched alkyl group represented by may be any of a primary branched alkyl group, a secondary branched alkyl group, or a tertiary branched alkyl group., R ea1 The number of carbon atoms of the branched saturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.,

[0173] R ea1 Examples of the branched unsaturated hydrocarbon group represented by include groups in which at least one carbon-carbon single bond contained in the branched saturated hydrocarbon group represented by the aforementioned R ea1 is replaced by a carbon-carbon double bond or a carbon-carbon triple bond., R ea1 Examples of the branched unsaturated hydrocarbon group represented by include alkenyl groups such as isopropenyl group, isobutenyl group, isopentenyl group, isohexenyl group, isoheptenyl group, isooctenyl group, isononyl group, isodecenyl group; alkynyl groups such as isopropynyl group, isobutinyl group, isopentynyl group, isohexynyl group, isoheptynyl group, isooctynyl group, isononynyl group, isodecynyl group; etc., R ea1 The number of carbon atoms of the branched unsaturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.,

[0174] R ea2 R ea3 R ea4 and R ea5Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by include a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. R ea2 、R ea3 、R ea4 and R ea5 The hydrocarbon groups represented by may be the same or different from each other.

[0175] Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group; branched-chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, still more preferably 1 to 10, and even more preferably 1 to 8.

[0176] Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, hexadecenyl group, octadecenyl group, and icosenyl group; alkynyl groups such as ethynyl group, propynyl group, hexynyl group, decynyl group, and icosenyl group; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group; and the like. The number of carbon atoms of the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and still more preferably 2 to 10.

[0177] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and further preferably 6 to 12.

[0178] R ea1 , R ea2 , R ea3 , R ea4 and R ea5 Examples of the substituent that the hydrocarbon group represented by the formula (I) may have include a halogen atom, a cyano group, and a nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom.

[0179] The -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-, provided that adjacent -CH2- are not simultaneously replaced by the same type of group, and the terminal -CH2- is not replaced.

[0180] n represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably an integer of 0 or 1, and even more preferably 0.

[0181] *-OCO-R ea4 The bonding position of the group (* represents a bond to the phenyl group) is the *-OCO-R ea4 The group may be bonded to any of the 2-, 3- or 4-positions of the phenyl group, but is preferably bonded to the 3- or 4-position, more preferably to the 4-position.

[0182] R ea1 The branched hydrocarbon group having 3 to 20 carbon atoms represented by the formula: A branched saturated hydrocarbon group having 3 to 20 carbon atoms is preferred. A branched alkyl group having 3 to 20 carbon atoms is more preferable. A branched alkyl group having 3 to 10 carbon atoms is more preferable. At least one selected from the group consisting of 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group and 3-ethylheptyl group is preferable.

[0183] R ea2 , R ea3 , R ea4 and R ea5 The hydrocarbon group having 1 to 20 carbon atoms represented by a saturated hydrocarbon group having 1 to 20 carbon atoms and an unsaturated hydrocarbon group having 2 to 20 carbon atoms are preferable, a saturated hydrocarbon group having 1 to 20 carbon atoms is more preferable, a linear saturated hydrocarbon group having 1 to 10 carbon atoms is still more preferable, a linear alkyl group having 1 to 8 carbon atoms is even more preferable. R ea2 is preferably a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 6 carbon atoms. R ea3 is preferably a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms. R ea4 is preferably a linear alkyl group having 1 to 8 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms. R ea5 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0184] Further, as the polymerization initiator (E) which is an oxime compound, a compound represented by the formula (EB) can be mentioned. By including the compound represented by the formula (EB) in the polymerization initiator (E), it is possible to suppress the decrease in the residual film ratio of the cured film when the curable composition is cured at a low temperature.

[0185] [Chemical formula] [wherein, R eb1 represents a branched hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. R eb2 ~R eb4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. m represents any integer from 0 to 4. -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-.

[0186] R eb1 Examples of the branched hydrocarbon group having 3 to 20 carbon atoms represented by include branched saturated hydrocarbon groups having 3 to 20 carbon atoms, branched unsaturated hydrocarbon groups having 3 to 20 carbon atoms, and the like.

[0187] R eb1 Examples of the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by are the same as those exemplified above for the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ea1 . R eb1 The branched alkyl group represented by may be any of a primary branched alkyl group, a secondary branched alkyl group, or a tertiary branched alkyl group. R eb1 The number of carbon atoms of the branched saturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0188] R eb1 Examples of the branched unsaturated hydrocarbon group represented by include groups in which at least one carbon-carbon single bond contained in the branched saturated hydrocarbon group represented by the aforementioned R eb1 is replaced by a carbon-carbon double bond or a carbon-carbon triple bond. R eb1Examples of the branched unsaturated hydrocarbon group represented by the formula (I) include alkenyl groups such as an isopropenyl group, an isobutenyl group, an isopentenyl group, an isohexenyl group, an isoheptenyl group, an isooctenyl group, an isononyl group, and an isodecenyl group; and alkynyl groups such as an isopropynyl group, an isobutynyl group, an isopentynyl group, an isohexynyl group, an isoheptynyl group, an isooctynyl group, an isononynyl group, and an isodecynyl group. R eb1 The branched unsaturated hydrocarbon group represented by the formula (I) has preferably 4 or more, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

[0189] R eb2 , R eb3 and R eb4 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. eb2 , R eb3 and R eb4 The hydrocarbon groups represented by the following formula may be the same or different.

[0190] Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8.

[0191] Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, hexadecenyl group, octadecenyl group, and icosenyl group; alkynyl groups such as ethynyl group, propynyl group, hexynyl group, decynyl group, and icosenyl group; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group; etc. 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.

[0192] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and further preferably 6 to 12.

[0193] R eb1 , R eb2 , R eb3 and R eb4 Examples of the substituent that the hydrocarbon group represented by the formula (I) may have include a halogen atom, a cyano group, and a nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom, and more preferably a fluorine atom.

[0194] The -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-, in particular may be replaced by -O-, provided that adjacent -CH2- are not simultaneously replaced by the same group, and the terminal -CH2- is not replaced.

[0195] m represents an integer of 0 to 4, preferably an integer of 1 to 3, more preferably an integer of 2 or 3, and further preferably 3.

[0196] If m is 1 or more, then *-R eb4At least one of the 2-position, 4-position, and 6-position of the phenyl group to which it is bonded has *-R eb4 (* represents a bond to the phenyl group) is preferably bonded, and *-R eb4 is bonded to at least two of the 2-position, 4-position, and 6-position of the phenyl group to which *-R eb4 is bonded is more preferable, and *-R eb4 is bonded to all of the 2-position, 4-position, and 6-position of the phenyl group to which *-R eb4 is bonded is even more preferable.

[0197] R eb1 The branched hydrocarbon group having 3 to 20 carbon atoms represented by is preferably a branched saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably a branched-chain alkyl group having 3 to 20 carbon atoms, even more preferably a branched-chain alkyl group having 3 to 10 carbon atoms, One or more selected from the group consisting of 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group and 3-ethylheptyl group are preferred.

[0198] R eb2 The hydrocarbon group having 1 to 20 carbon atoms represented by is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 17 carbon atoms, even more preferably an aromatic hydrocarbon group having 7 to 15 carbon atoms, particularly preferably an aromatic hydrocarbon group having 8 to 13 carbon atoms. In any of these preferred embodiments, it preferably has 1 to 8 (particularly 1 to 5) fluorine atoms as substituents and has a structure in which 1 to 2 -CH2- are replaced by -O-.

[0199] R eb2In a preferred embodiment, the aromatic hydrocarbon group having 8 to 13 carbon atoms is preferably any one of the following (eb2-1) to (eb2-6).

[0200]

Chemical formula

[0201] R eb3 and R eb4 The hydrocarbon groups having 1 to 20 carbon atoms represented by are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms is preferred, a saturated hydrocarbon group having 1 to 20 carbon atoms is more preferred, a linear saturated hydrocarbon group having 1 to 10 carbon atoms is even more preferred, a linear alkyl group having 1 to 8 carbon atoms is still more preferred, and a linear alkyl group having 1 to 3 carbon atoms is particularly preferred.

[0202] In addition, when -CH2- contained in the hydrocarbon group in formula (EB) is replaced by -O-, -S-, -CO- or -OCO-, the carbon number of this replaced part shall be counted as the carbon number of -CH2- before replacement.

[0203] Examples of the polymerization initiator (E) other than the compounds represented by formula (EA) and formula (EB) include photopolymerization initiators such as oxime compounds (excluding the compounds represented by formula (EA) and formula (EB)), alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphine compounds, and thermal polymerization initiators such as azo compounds and organic peroxides.

[0204] An example of the oxime compound (excluding the compounds represented by formula (EA) and formula (EB)) is an oxime compound having the first molecular structure represented by the following formula (1). Hereinafter, this oxime compound is also referred to as "oxime compound (1)".

[0205]

Chemical formula

[0206] It may be advantageous from the viewpoint of improving the emission intensity to include the oxime compound (1) as the polymerization initiator (E). One reason why such an effect can be achieved is that due to the specific molecular structure of the oxime compound (1), when the oxime compound (1) initiates photopolymerization, the absorption wavelength of the oxime compound (1) changes significantly before and after the cleavage (decomposition) of the oxime compound (1) required for the initiation of photopolymerization. Therefore, it is presumed that the oxime compound (1) has a high ability to initiate photoradical polymerization.

[0207] In formula (1), R 1 represents R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN.

[0208] R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0209] R 11 , R 12 or R 13 The hydrogen atom of the group represented by may be substituted with 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, a halogen atom, or COOR 21 and may be substituted.

[0210] R 21 、R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0211] R 21 、R 22 or R 23 the hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group, or a carboxy group.

[0212] R 11 、R 12 、R 13 、R 21 、R 22 or R 23 when the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO-.

[0213] R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0214] R 11 、R 12 、R 13 、R 21 、R 22 or R 23 when the group represented by has an alkyl moiety, the alkyl moiety may be branched, cyclic, and also, R 12 and R 13 and R 22 and R 23 may together form a ring.

[0215] * represents a bond with a second molecular structure, which is a molecular structure other than the first molecular structure possessed by the oxime compound (1).

[0216] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the alkyl group having 1 to 20 carbon atoms represented by R, R, R, R, R, R, R, and R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, etc.

[0217] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms represented by R, R, R, R, R, R, R, and R include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group, phenyl group substituted with one or more of the above alkyl groups, biphenylyl group, naphthyl group, anthryl group, etc.

[0218] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aralkyl group having 7 to 30 carbon atoms represented by R, R, R, R, R, R, R, and R include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, etc.

[0219] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms represented by include a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazol-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolidyl group, a pyrazolidyl group, a thiazolidyl group, an isothiazolidyl group, an oxazolidyl group, an isoxazolidyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, etc., and preferably a 5- to 7-membered heterocycle.

[0220] R in formula (1) 12 and R 13 and R 22 and R 23 may each combine together to form a ring, which means that R 12 and R 13 and R 22 and R 23 may each combine together to form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0221] R in formula (1) 12 and R 13 and R 22 and R 23 Examples of the ring that can be formed by combining include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, a lactam ring, etc., and preferably a 5- to 7-membered ring.

[0222] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of the halogen atom that may be possessed as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0223] R in formula (1) 1 is preferably R 11 and more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0224] An example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (2). The second molecular structure means another molecular structure part other than the above first molecular structure that the oxime compound (1) has.

[0225] In formula (2), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring having "-*" in formula (2) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0226]

Chemical formula

[0227] In formula (2), R 2 and R 3 each independently represent R 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 a halogen atom.

[0228] When there are a plurality of R 2 they may be the same or different.

[0229] R 3 When there are a plurality of them, they may be the same or different.

[0230] R 11 、R 12 and R 13 have the same meaning as described above.

[0231] s and t each independently represent an integer from 0 to 4.

[0232] L represents a sulfur atom, CR 31 R 32 、CO or NR 33 represents.

[0233] R 31 、R 32 and R 33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.

[0234] R 31 、R 32 or R 33 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 31 、R 32 and R 33 may each independently form a ring together with either adjacent benzene ring.

[0235] R 4 is a hydroxy group, a carboxy group or the following formula (2-1)

[0236]

Chemical formula

[0237] (In formula (2-1), L 1 represents -O-, -S-, -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0238] R 22 represents the same meaning as described above.

[0239] L 2 represents 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.

[0240] L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 22 -, -NR 22 COO-, -OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic.

[0241] R 4a is 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 a halogen atom.

[0242] R 4a When there are a plurality of them, they may be the same or different.

[0243] R 41 、R 42 and R 43 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, R 41 、R 42 and R43 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 42 and R 43 may together form a ring.

[0244] v represents an integer from 1 to 3.) represents a group represented by.

[0245] * represents a bond to the first molecular structure of the oxime compound (1).

[0246] R in formula (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 the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, and aralkyl group having 7 to 30 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in formula (1).

[0247] R in formula (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 the heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R24 is the same as the example for

[0248] R in formula (2) 31 , R 32 and R 33 each independently may form a ring together with either adjacent benzene ring, which means that R 31 , R 32 and R 33 each independently may form a ring together with either adjacent benzene ring and the nitrogen atom connecting therewith.

[0249] R in formula (2) 31 , R 32 and R 33 Examples of the ring that may be formed together with either adjacent benzene ring are the same as the examples of the ring that may be formed by R 12 and R 13 and R 2 and R 23 together in formula (1).

[0250] L in the above formula (2-1) 2 represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0251] Examples of the group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, when v is 1, methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, ethane-1,1-diyl group, propane-2,2-diyl group, and other alkylene groups.

[0252] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v is 1, an arylene group such as a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 2,6-naphthylene group, a 1,4-naphthylene group, a 2,5-dimethyl-1,4-phenylene group, a diphenylmethane-4,4'-diyl group, a 2,2-diphenylpropane-4,4'-diyl group, a diphenylsulfide-4,4'-diyl group, and a diphenylsulfone-4,4'-diyl group.

[0253] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, when v is 1, a group represented by the following formula (a) and a group represented by the following formula (b).

[0254] [Chemical formula]

[0255] [In formulas (a) and (b), L 3 and L 5 represent an alkylene group having 1 to 10 carbon atoms, and L 4 and L 6 represent a single bond or an alkylene group having 1 to 10 carbon atoms.] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,2-dimethylpropylene group, a 1,3-dimethylpropylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 4-methylbutylene group, a 2,4-dimethylbutylene group, a 1,3-dimethylbutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

[0256] Examples of the group obtained by removing v hydrogen atoms from a complex ring group having 2 to 20 carbon atoms include, for example, when v is 1, divalent complex ring groups such as 2,5-pyridinediyl group, 2,6-pyridinediyl group, 2,5-pyrimidinediyl group, 2,5-thiophenediyl group, 3,4-tetrahydrofurandiyl group, 2,5-tetrahydrofurandiyl group, 2,5-furandiyl group, 3,4-thiazoldiyl group, 2,5-benzofurandiyl group, 2,5-benzothiophenediyl group, N-methylindole-2,5-diyl group, 2,5-benzothiazoldiyl group, 2,5-benzoxazoldiyl group, etc.

[0257] R in formula (2) 2 and R 3 , and examples of the halogen atom represented by R in the above formula (2-1) 4a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0258] From the viewpoint of solubility in the solvent (J) and / or developability of the curable composition, a preferred example of the structure represented by formula (2) is the structure represented by the following formula (2a).

[0259]

Chemical formula

[0260] [In formula (2a), L’ represents a sulfur atom or NR 50 , R 50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R 2 , R 3 , R 4 , s and t represent the same meanings as described above.] From the same viewpoint as above, another preferred example of the structure represented by formula (2) is the structure represented by the following formula (2b).

[0261]

Chemical formula

[0262] [In formula (2b), R 44 represents a hydroxy group, a carboxy group or the following formula (2-2)

[0263] [Chemical formula]

[0264] (In formula (2-2), L 11 represents *-O- or *-OCO-, where * represents the bond with L 12 and L 12 represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be interrupted by 1 to 3 -O-'s, and R 44a represents OR 55 or COOR 55 and R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) represents a group represented by. R 44 is preferably a group represented by formula (2-2). 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.

[0265] The alkylene group represented by L 12 preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.

[0266] R 44a is preferably a hydroxy group or a carboxy group, more preferably a hydroxy group.

[0267] The method for producing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited, but for example, it can be produced by the method described in JP-A-2011-132215.

[0268] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (3).

[0269] In formula (3), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring having "-*" in formula (3) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0270]

Chemical formula

[0271] In formula (3), R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0272] R 5 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0273] R 5 The hydrogen atom of the group represented by is 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 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 and may be substituted.

[0274] R 21 、R 22 and R 23 have the same meaning as described above.

[0275] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted with a CN, halogen atom, hydroxy group or carboxy group.

[0276] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -,-SCO-,-COS-,-OCS- or -CSO-.

[0277] R 24 has the same meaning as described above.

[0278] R 21 、R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may combine together to form a ring.

[0279] R 6 、R 7 、R 8 and R 9 each independently represents R 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 , represents a hydroxyl group, nitro group, CN or halogen atom.

[0280] R 61 , R 62 , R 63 , R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0281] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is 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 may be substituted.

[0282] R 6 and R 7 , R 7 and R 8 and R 8 and R 9 may together form a ring.

[0283] * represents a bond with the first molecular structure possessed by the oxime compound (1).

[0284] R in formula (3) 5, R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 are the same as those for.

[0285] R 22 and R 23 in formula (3) may together form a ring, which means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0286] Examples of the ring that R 22 and R 23 in formula (3) can form together are the same as the examples of the rings that R 12 and R 13 and R 22 and R 23 in formula (1) can form together.

[0287] Examples of the halogen atom represented by R 6 , R 7 , R 8 and R 9 in formula (3) that may substitute the hydrogen atom of R 5 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 include fluorine atom, chlorine atom, bromine atom and iodine atom.

[0288] From the viewpoints of solubility in the solvent (J) and / or developability of the curable composition, in one preferred embodiment, R 5 is a group represented by the following formula (3-1).

[0289] [Chemical formula]

[0290] [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. When the group represented by Z has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR -, -NR 24 -, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic. R R 21 , R 22 and R 24 represent the same meaning as described above.] From the same viewpoints as above, in formula (3-1), Z is preferably a methylene group, an ethylene group or a phenylene group.

[0291] In formula (3-1), R 21 and R 22 are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms from the same viewpoints as above, and more preferably a methyl group, an ethyl group or a phenyl group.

[0292] From the same viewpoints as above, in another preferred embodiment, R 7 is a nitro group.

[0293] The production method of the oxime compound (1) having the second molecular structure represented by the formula (3) is not particularly limited. For example, it can be produced by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0294] Still another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is a structure represented by the following formula (4).

[0295] In the formula (4), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is a structure represented by the formula (4), the benzene ring having "-*" in the formula (4) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0296]

Chemical formula

[0297] In the formula (4), R 71 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0298] R 71 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0299] R 71 The hydrogen atom of the group represented by is 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 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 may be substituted therewith.

[0300] R 21 , R 22 and R 23 represent the same meaning as described above.

[0301] R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group.

[0302] R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-.

[0303] R 24 represents the same meaning as described above.

[0304] R 21 , R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched, cyclic, and R 22 and R 23 may combine together to form a ring.

[0305] R72 、R 73 and three Rs 74 are each independently R 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 、represent a hydroxyl group, nitro group, CN or halogen atom.

[0306] R 61 、R 62 、R 63 、R 64 and R 65 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0307] R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atom of the group represented by is 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 and may be substituted.

[0308] R 72 and R73 and two Rs 74 may combine together to form a ring, respectively.

[0309] * represents a bond with the first molecular structure of the oxime compound (1).

[0310] R in formula (4) 71 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in formula (1).

[0311] R in formula (4) 22 and R 23 may combine together to form a ring means that R 22 and R 23 may combine together with the connecting nitrogen atom, carbon atom or oxygen atom to form a ring.

[0312] R in formula (4) 22 and R 23 Examples of the ring that can be formed by combining together are the same as the examples for the ring that can be formed by combining R 12 and R 13 and R 22 and R 23 in formula (1).

[0313] R in formula (4) 72 , R 73 and R 74 represented by the halogen atom, R 71 , R 21 , R22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of halogen atoms that may replace the hydrogen atoms of R include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0314] The method for producing the oxime compound (1) having the second molecular structure represented by the formula (4) is not particularly limited. For example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0315] Another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is the structure represented by the following formula (5).

[0316] In the formula (5), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is the structure represented by the formula (5), the pyrrole ring having "-*" in the formula (5) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0317]

Chemical formula

[0318] In the formula (5), R 81 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0319] R 81 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0320] R 81 The hydrogen atom of the group represented by is 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 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 may be substituted.

[0321] R 21 , R 22 and R 23 have the same meaning as described above.

[0322] R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group.

[0323] R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -,-SCO-,-COS-,-OCS- or -CSO-.

[0324] R 24 has the same meaning as described above.

[0325] R 21 、R 22 and R 23 when the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and also, R 22 and R 23 may combine together to form a ring.

[0326] R 82 、R 83 、R 84 、R 85 and R 86 each independently represents R 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 、a hydroxyl group, a nitro group, CN or a halogen atom.

[0327] R 61 、R 62 、R 63 、R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0328] R 61 、R 62 、R 63 、R 64 or R 65 the hydrogen atom of the group represented by is OR 21 、COR 21 、SR 21 、NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, a halogen atom, or COOR 21 may be substituted.

[0329] R 83 and R 84 , R 84 and R 85 and R 85 and R 86 may together form a ring.

[0330] * represents a bond with the first molecular structure of the oxime compound (1).

[0331] R in formula (5) 81 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in formula (1).

[0332] R in formula (5) 22 and R 23 may together form a ring means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0333] R in formula (5)22 and R 23 Examples of rings that can be formed by combining R in formula (1) with 12 and R 13 and R 22 and R 23 are the same as the examples of rings that can be formed by combining them together.

[0334] R in formula (5) 82 , R 83 , R 84 , R 85 and R 86 represent halogen atoms, and examples of halogen atoms that may replace the hydrogen atoms of R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0335] The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0336] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (6).

[0337] In formula (6), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (6), the benzene ring having "-*" in formula (6) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0338]

Chemical formula

[0339] In formula (6), the four Rs 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 each independently represents R 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 , a hydroxyl group, a nitro group, CN or a halogen atom.

[0340] R 61 , R 62 , R 63 , R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0341] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is 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, a halogen atom, or COOR 21may be substituted with.

[0342] R 21 , R 22 and R 23 has the same meaning as above.

[0343] R 92 and R 93 , R 94 and R 95 , R 95 and R 96 and R 96 and R 97 may be joined together to form a ring.

[0344] * represents a bond to the first molecular structure of the oxime compound (1).

[0345] R in Equation (6) 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms, which are represented by the formula (1), are R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The example for is similar.

[0346] R in Equation (6) 22 and R 23 may be joined together to form a ring, R 22 and R 23 means that they may be taken together to form a ring with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0347] R in Equation (6) 22 and R 23 Examples of rings that may be formed by combining with each other include R 12 and R 13and R 22 and R 23 is the same as the example of the ring that can be formed by combining them together.

[0348] R in formula (6) 91 R 92 R 93 R 94 R 95 R 96 and R 97 and the halogen atoms represented by R 21 R 22 R 23 R 61 R 62 R 63 R 64 and R 65 Examples of the halogen atoms that may substitute the hydrogen atoms of R, R, R, R, R, R, R, R, R, R, R, R, R, R, and R include fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0349] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0350] Examples of the oxime compound that is other than the compound represented by formula (EA), other than the compound represented by formula (EB), and other than the oxime compound (1) include the oxime compound having the partial structure represented by the following formula (d1). * represents a bond.

[0351]

Chemical formula

[0352] Examples of the oxime compound having the partial structure represented by the formula (d1) include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in JP-A-2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, International Publication No. 2012 / 132558, etc. may be mentioned. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine), OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (manufactured by BASF), N-1919 (manufactured by ADEKA), etc. may be used.

[0353] Among them, the oxime compound having the partial structure represented by the formula (d1) is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine.

[0354] The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the following formula (d3). In these partial structures, the benzene ring may have a substituent. * represents a bond.

[0355] [Chemical formula]

[0356] Examples of the compound having the structure represented by the formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl]butan-1-one, and the like. Commercially available products such as OMNIRAD (registered trademark) 369, 907, 379 (manufactured by IGM Resins) may also be used.

[0357] Examples of the compound having the structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, benzyldimethyl ketal, and the like.

[0358] In terms of sensitivity, as the alkylphenone compound, a compound having the structure represented by the formula (d2) is preferable.

[0359] Examples of the biimidazole compound include, for example, the compound represented by the formula (d5).

[0360] [Chemical formula]

[0361] [In the formula (d5), R E ~R J each represents an aryl group having 6 to 10 carbon atoms which may have a substituent.] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like, and a phenyl group is preferable.

[0362] Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, and a methoxy group is preferable.

[0363] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-06-75372 and JP-A-06-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboxyalkoxy groups (see, for example, JP-A-7-10913), and the like. Among them, compounds represented by the following formula or mixtures thereof are preferred.

[0364] [Chemical formula]

[0365] Examples of the triazine compound 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-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-dimethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferable.

[0366] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, etc.

[0367] Another example of the photopolymerization initiator includes, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc.

[0368] The content of the polymerization initiator (E) in the curable composition is preferably 0.1 part by mass or more and 300 parts by mass or less, more preferably 0.1 part by mass or more and 200 parts by mass or less, still more preferably 3 parts by mass or more and 150 parts by mass or less, and even more preferably 5 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the polymerizable compound (D). Further, the content of the polymerization initiator (E) in the curable composition is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.5 part by mass or more and 20 parts by mass or less, still more preferably 1 part by mass or more and 10 parts by mass, based on 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiator (E) is within the above range, it is possible to suppress a decrease in the residual film ratio of the cured film when the curable composition is cured at a low temperature, and it is also advantageous from the viewpoint of improving patterning after exposure and development.

[0369] The content ratio of the polymerization initiator (E) in the curable composition is, for example, 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.2% by mass or more and 10% by mass or less, still more preferably 0.3% by mass or more and 8% by mass or less, even more preferably 0.5% by mass or more and 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the solid content of the curable composition.

[0370] The polymerization initiator (E) preferably contains at least one oxime compound, more preferably contains at least one of the compound represented by formula (EA), the compound represented by formula (EB), and the oxime compound (1), still more preferably contains at least one of the compound represented by formula (EA) and the compound represented by formula (EB), even more preferably contains at least one of the compound represented by formula (EA), and most preferably contains the compound represented by formula (EA-1) described below. 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 a low temperature. Further, the compound represented by formula (EA) can further improve the fluorescence emission intensity of the cured film. The content of the compound represented by formula (EA) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 100% by mass (that is, the polymerization initiator (E) contains the compound represented by formula (EA) and does not contain the compound represented by formula (EB)) with respect to 100% by mass of the total amount of the compound represented by formula (EA) and the compound represented by formula (EB).

[0371] When the polymerization initiator (E) contains at least one of the compound represented by formula (EA) and the compound represented by formula (EB), the total content of the compound represented by formula (EA) and the compound represented by formula (EB) in the polymerization initiator (E) is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, still more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, particularly preferably 90% by mass or more and 100% by mass or less, most preferably 95% by mass or more and 100% by mass or less, and may be 100% by mass.

[0372] <Light stabilizer (F)> The light stabilizer (F) may be any additive that has the effect of stabilizing components against light, including known light stabilizers (Fa), and the light stabilizer (F) of the present invention also includes an antioxidant (Fb) and an ultraviolet absorber (Fc) that absorbs light and renders it harmless. The curable composition may contain two or more types of light stabilizers (F).

[0373] <Light stabilizer (Fa)> Examples of the light stabilizer (Fa) include hindered amine-based light stabilizers, acrylate-based light stabilizers, nickel-based light stabilizers, and oxamide-based light stabilizers.

[0374] <Antioxidants (Fb)> The antioxidant (Fb) is not particularly limited as long as it is an antioxidant generally used industrially, and may be a phenol-based antioxidant, a phosphorus-based antioxidant, a phosphorus / phenol complex type antioxidant, a sulfur-based antioxidant, etc. The curable composition may contain two or more types of antioxidants (Fb).

[0375] The phosphorus / phenol complex type antioxidant is, for example, a compound having one or more phosphorus atoms and one or more phenol structures in the molecule. Among them, from the viewpoint of the developability and luminescence intensity of the curable composition, it is preferable that the antioxidant (Fb) contains a phosphorus / phenol complex type antioxidant.

[0376] Examples of phenolic antioxidants include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), 1076 (Irganox 1076: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 1330 (Irganox 1330: 3,3’,3’’,5,5’,5’’-hexa-tert-butyl-a,a’,a’’-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), 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), 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl benzenepropanoate, manufactured by BASF Corporation), 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), 3125 (Irganox 3125, manufactured by BASF Corporation), 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3’,5’-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), Adeka Stab (registered trademark) AO-80 (Adeka Stab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5) Undecane (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT, Sumilizer GA-80, and Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.).

[0377] Examples of phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Co., Ltd.), Adeka STAB (registered trademark) 329K, Adeka STAB PEP36, Adeka STAB PEP-8 (all manufactured by ADEKA Co., Ltd.), Sandstab Examples of such antibacterial agents include P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (all manufactured by GE), and Ultranox 626 (manufactured by GE).

[0378] Examples of phosphorus / phenol complex antioxidants include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

[0379] Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl, dimyristyl, and distearyl thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0380] <Ultraviolet absorber (Fc)> Examples of the ultraviolet absorber (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-octyloxybenzophenone; benzoate compounds such as 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol; and the like.

[0381] The content of the light stabilizer (F) in the curable composition (total amount in the case of multiple types) is, for example, 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin (C), and from the viewpoint of emission intensity, preferably 5 parts by mass or more and 40 parts by mass or less, more preferably 7 parts by mass or more and 30 parts by mass or less.

[0382] When the curable composition contains the light stabilizer (F), the light stabilizer (F) is preferably an antioxidant (Fb) and / or an ultraviolet absorber (Fc).

[0383] <Leveling agent (H)> Examples of the leveling agent (H) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain. The leveling agent (H) preferably contains a silicone surfactant. The curable composition may contain two or more kinds of the leveling agent (H).

[0384] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc.

[0385] Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, F575, R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

[0386] Examples of silicone surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation), etc.

[0387] When the curable composition contains a leveling agent (H), the content of the leveling agent (H) in the curable composition is, based on the total amount of the curable composition, for example, 0.001% by mass or more and 1.0% by mass or less, preferably 0.005% by mass or more and 0.75% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less. 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 made better when the cured film is used as a wavelength conversion layer.

[0388] <Solvent (J)> The solvent (J) dissolves the resin (C) and the polymerizable compound (D) and the polymerization initiator (E) used in a preferred embodiment. Examples of the solvent (J) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0389] Examples of the ester solvent 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, cyclohexyl acetate, and γ-butyrolactone.

[0390] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole and the like.

[0391] Examples of the ether ester solvent 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, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate and the like.

[0392] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

[0393] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

[0394] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

[0395] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.

[0396] The solvent (J) preferably contains one or more selected from the group consisting of 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.

[0397] The solvent (J) is 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 thereof.

[0398] The solvent (J) is a component other than the solid content. For example, solvents contained in a dispersion of semiconductor particles (A) or a solution of resin (C) are also included in the solvent (J).

[0399] The content rate of the solvent (J) in the curable composition is the ratio of the total mass of all solvents contained in the curable composition to the total amount of the curable composition, and is, for example, 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less with respect to the total amount of the curable composition. In other words, the solid content of the curable composition is, for example, 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less. When the content rate of the solvent (J) is within the above range, the flatness of the curable composition layer during coating becomes better, and it tends to be easier to form a wavelength conversion layer with an appropriate thickness.

[0400] <Other components> The curable composition may further contain additives known in the art, such as a polymerization inhibitor, a filler, other polymer compounds, an adhesion promoter, a chain transfer agent, etc., if necessary.

[0401] <<Method for producing curable composition>> The curable composition can be produced by a method including a step of mixing predetermined components and other components used if necessary. The method for producing the curable composition may further include a step of preparing the resin (C). Among the components contained in the curable composition, the semiconductor particles (A) and the light scattering agent (B) may be mixed with a part or all of the solvent (J) in advance and then mixed with other components.

[0402] <<Method for producing cured film>> A cured film can be obtained by carrying out a production method including a step of coating the curable composition of the present invention and a thermal curing step of thermally curing the coating film of the curable composition (hereinafter also referred to as "composition layer"). After the step of coating the curable composition, usually, an exposure step of irradiating light on the coating film of the curable composition is further included, and the thermal curing step is carried out after the exposure step.

[0403] The manufacturing method of the cured film described above further includes a drying step of drying the composition layer formed by the coating step, and a development step performed on the composition layer after the exposure step.

[0404] The coating step is a step of coating a curable composition on a substrate to form a composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, a printing method, etc. In the printing method, the curable composition is applied through a mask provided on the substrate, and after peeling the mask from the substrate, the composition layer formed by the coating step is cured, so that a cured film can be formed as a cured pattern on a part of the substrate surface.

[0405] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass with a silica-coated surface, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and those with an aluminum, silver, silver / copper / palladium alloy thin film, etc. formed on the above substrate. The substrate is preferably a glass plate, a silicon substrate, etc.

[0406] The substrate may be one that has undergone a pretreatment capable of adjusting the wettability of the substrate surface. Examples of the pretreatment include solvent cleaning with alcohol or acetone, acid treatment, alkali treatment, plasma treatment, corona treatment, etc. By selecting an appropriate pretreatment for the substrate on which the cured film is to be laminated, the coatability of the curable composition can be improved compared to an untreated substrate.

[0407] When the curable composition contains a solvent (J), a drying step of removing volatile components such as the solvent (J) from the composition layer is performed after the coating step. The drying step may include a heat drying (pre-bake) treatment, a reduced pressure drying treatment, or both of these.

[0408] The curable composition of the present invention can suppress a decrease in the residual film rate of the cured film when the heat drying (pre-bake) temperature is lowered. When performing heat drying, the temperature is preferably 30°C or higher and lower than 100°C, more preferably 50°C or higher and 95°C or lower. The heating time is preferably 10 seconds or longer and 60 minutes or shorter, more preferably 30 seconds or longer and 30 minutes or shorter. When performing vacuum drying, it is preferably performed under a pressure of 50 Pa or higher and 150 Pa or lower and in a temperature range of 20°C or higher and 25°C or lower.

[0409] The film thickness of the composition layer after the coating step or the drying step is not particularly limited and may be appropriately selected according to the film thickness of the target cured film. For example, it is 0.5 μm or more and 10 μm or less, preferably 1 μm or more and 9 μm or less, more preferably 1.5 μm or more and 7 μm or less, and still more preferably 2 μm or more and 5 μm or less. The film thickness of the finally obtained cured film may be the same as above.

[0410] Next, an exposure step is performed on the composition layer after the coating step and the drying step. The exposed composition layer cures by polymerization of the polymerizable compound (D) etc. contained in the composition layer including the preferred embodiments. As the light source used for exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferred. When the curable composition contains a photoinitiator (E), light near 436 nm, near 408 nm, or near 365 nm may be selectively extracted by a band-pass filter from the light of the above wavelength according to the absorption wavelength of the photoinitiator (E). Specific examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc.

[0411] The exposure amount X in the exposure step is preferably 50 mJ / cm 2 or more, more preferably 80 mJ / cm 2 or more, still more preferably 100 mJ / cm 2 or more, and even more preferably 150 mJ / cm 2 or more. The exposure amount X is usually 1000 mJ / cm 2 or less, preferably 800 mJ / cm 2 or less, more preferably 700 mJ / cm 2is as follows. When the exposure amount X in the exposure process is 1000 mJ / cm 2 or less, it is possible to prevent the cured film from shrinking too much, so that the proximity of the semiconductor particles (A) in the film due to the shrinkage of the cured film can be prevented, and the decrease in the emission light intensity can be prevented. The exposure amount X is the exposure amount based on a wavelength of 365 nm and can be measured using an ultraviolet integrated light quantity meter (UIT-250, manufactured by USHIO INC.).

[0412] As an example of a method for forming a cured pattern, which is one aspect of the cured film, a photolithography method can be mentioned. The photolithography method is a method of exposing and developing a composition layer through a photomask for forming a target cured pattern. In this case, since it is possible to irradiate the entire exposure surface with parallel light rays uniformly or to perform accurate alignment between the photomask and the substrate on which the composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

[0413] By subjecting the composition layer after the exposure process to a development process in which it is brought into contact with a developer and developed, the unexposed portion of the composition layer is dissolved and removed by the developer, and a pattern is imparted to the composition layer. Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents. The concentration in the aqueous solution of the alkaline compound is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Examples of the organic solvent include the same ones as the above-mentioned solvent (J). The developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, a spray method, etc. Further, the substrate may be tilted at an arbitrary angle during development.

[0414] The composition layer after the exposure process and after the development process is thermally cured (post-baked) in the thermal curing process. By the thermal curing process, the polymerization of the resin (C), the polymerizable compound (D), etc. including the preferred embodiments can be further advanced.

[0415] The thermosetting temperature in the thermosetting process carried out after the exposure process and after the development process is preferably 150 °C or lower, more preferably 120 °C or lower, still more preferably less than 100 °C, and particularly preferably 95 °C or lower. The thermosetting temperature is preferably 70 °C or higher, more preferably 80 °C or higher, and still more preferably 85 °C or higher.

[0416] The thermosetting time in the thermosetting process is preferably 0.1 hr or more, more preferably 0.2 hr or more, still more preferably 0.4 hr or more, and even more preferably 0.5 hr or more. The thermosetting time is usually 2 hr or less, preferably 1.5 hr or less, and more preferably 1.2 hr or less.

[0417] The thermosetting process can be carried out in an air atmosphere or in a vacuum atmosphere. The vacuum atmosphere refers to a pressure range of 150 Pa or lower, preferably 120 Pa or lower, more preferably 100 Pa or lower, and may be 50 Pa or higher.

[0418] The temperatures in the above-mentioned drying process (especially heat drying) and thermosetting process are both preferably less than 100 °C, and more preferably both are 95 °C or lower.

[0419] The residual film ratio (residual film ratio of low-temperature curing) when measuring the cured film produced at the above-mentioned preferred heat drying (pre-bake) temperature or the cured film produced at the above-mentioned preferred heat drying temperature and thermosetting temperature according to the "measurement of residual film ratio" in the following examples is, for example, more than 75%, preferably 80% or more, more preferably 90% or more, and the upper limit may be 100%. Also, the minimum line width at which the exposed pattern remains partially or completely when evaluating the cured film according to the "evaluation of patterning property" in the following examples can be 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. Furthermore, the emission intensity when evaluating the cured film according to the "measurement of fluorescence emission intensity of cured film" in the following examples is, when the film thickness of the cured film is, for example, 0.5 μm or more and 10 μm or less (especially 2 μm or more and 5 μm or less), 400 (mW·sr -1 ·m-2 ) It can be set as above, and 500 (mW·sr -1 ·m -2 ) or more is preferable, and 700 (mW·sr -1 ·m -2 ) or more is more preferable. The upper limit is not particularly limited, but it may be 1500 (mW·sr -1 ·m -2 ) or less.

[0420] <<Display device>> Since the cured film obtained from the curable composition of the present invention has the function of converting the wavelength of the irradiated light, it can be used as a color conversion layer (wavelength conversion film) of a display device. Examples of such display devices include those described in, for example, JP-A-2006-309219, JP-A-2006-310303, JP-A-2013-15812, JP-A-2009-251129, JP-A-2014-2363, etc. The cured film according to the present invention is useful as a color conversion layer (wavelength conversion film) of a display device, particularly a liquid crystal display device, an organic EL display device, or an inorganic EL display device.

Examples

[0421] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and it is of course possible to appropriately modify and implement it within the range that can conform to the above-mentioned and following gists, and all of them are included in the technical scope of the present invention. In the examples, “%” and “parts” are mass% and parts by mass, respectively, unless otherwise specified.

[0422] [Thickness of cured film] It was measured with a film thickness measuring device (DEKTAKXT; manufactured by Bruker).

[0423] [Weight average molecular weight] The weight average molecular weight (Mw) of the resin (C) was measured by the GPC method under the following conditions. Device: K2479 (manufactured by Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40 °C Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0424] [Acid value] Accurately weigh 3 g of the resin (C) solution, dissolve it in a mixed solvent of 90 g of acetone and 10 g of water, and use 0.1 N aqueous KOH solution as the titrant. Measure the acid value of the resin (C) solution with an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555), and calculate the acid value (AV) per gram of solid content from the acid value of the solution and the solid content of the solution.

[0425] [Double bond equivalent] The double bond equivalent was determined by dividing the total mass of the curable resin by the number of moles of radically polymerizable double bonds introduced into the curable resin.

[0426] [Solid content] Weigh approximately 1 g of the resin (C) solution into an aluminum cup, dry it at 180 °C for 1 hour, and then measure the mass. Calculate the solid content (mass %) of the resin (C) solution from the mass reduction amount.

[0427] (Synthesis Example 1: Synthesis of Resin (C1)) Place 276.8 g of propylene glycol monomethyl ether acetate in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. Stir while purging with nitrogen and heat to 120 °C. Next, add 35.3 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) to the monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentanyl methacrylate, and drop the resulting mixture into the flask from the dropping funnel over 2 hours. After completion of the dropping, stir at 120 °C for an additional 30 minutes to carry out a copolymerization reaction to produce an addition copolymer.

[0428] Thereafter, the inside of the flask was replaced with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of methoquinone (polymerization inhibitor) were added into the above addition copolymer solution. The reaction was continued at 110 °C for 10 hours. The epoxy group derived from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy group, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 53.5 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110 °C for 1 hour. The hydroxy group generated by the cleavage of the epoxy group reacted with succinic anhydride to introduce a carboxyl group into the side chain, and a polymer (resin (C1)) was obtained.

[0429] 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%.

[0430] The weight average molecular weight Mw of the produced resin (C1) was 6.7×10 3 , and the acid value in terms of solid content was 70 mg-KOH / g, and the double bond equivalent was 336 g / eq.

[0431] (Synthesis Example 2: Synthesis of Resin (C2)) 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While stirring and purging with nitrogen, the temperature was raised to 120 °C. Next, a monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentanyl methacrylate, to which 35.3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator) was added, was dropped into the flask from the dropping funnel over 2 hours. After the dropping was completed, the mixture was further stirred at 120 °C for 30 minutes to carry out a copolymerization reaction to produce an addition copolymer.

[0432] Thereafter, the inside of the flask was replaced with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of methoquinone (polymerization inhibitor) were added into the above addition copolymer solution, and the reaction was continued at 110 °C for 10 hours. The epoxy group derived from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy group and simultaneously introduce a polymerizable unsaturated bond into the side chain of the polymer. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110 °C for 1 hour. The hydroxyl group generated by the cleavage of the epoxy group reacted with succinic anhydride to introduce a carboxyl group into the side chain, and a polymer (resin (C2)) was obtained.

[0433] 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%.

[0434] The weight average molecular weight Mw of the produced copolymer was 6.2×10 3 , the acid value in terms of solid content was 35 mg-KOH / g, and the double bond equivalent was 313 g / eq.

[0435] (Synthesis Example 3: Synthesis of Resin (C3)) In the same manner as the above resin (C1), the amount of the raw material monomer was adjusted to obtain a polymer (resin (C3)). Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C3) solution with a polymer solid content of 40%.

[0436] The weight average molecular weight Mw of the produced copolymer was 4.96×10 3 , the acid value in terms of solid content was 37 mg-KOH / g, and the double bond equivalent was 344 g / eq.

[0437] (Synthesis Example 4: Synthesis of Resin (C4)) In the same manner as the above resin (C1), the amount of the raw material monomer was adjusted to obtain a polymer (resin (C4)). Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C4) solution with a polymer solid content of 40%.

[0438] The weight-average molecular weight Mw of the produced copolymer was 4.91×10 3 , the acid value in terms of solid content was 42 mg-KOH / g, and the double bond equivalent was 514 g / eq.

[0439] (Preparation Example 1: Preparation of Dispersion Liquid b of Semiconductor Particles (A)) A toluene dispersion liquid a of semiconductor particles (A) [InP / ZnSeS quantum dots emitting green light] containing oleic acid as the organic ligand (G) was prepared. After removing toluene from the above toluene dispersion liquid a by vacuum distillation, 70 parts of cyclohexyl acetate was added to 30 parts in total of the solid content (semiconductor particles (A) and organic ligand (G)) to obtain a dispersion liquid b of semiconductor particles (A).

[0440] The composition ratio of the semiconductor particles (A) and the organic ligand (G) was measured for the mixture after removing toluene by measuring the remaining amount when heated to 550 °C at a heating rate of 5 °C / min by TG-DTA measurement, and the remaining amount was calculated as the weight of the semiconductor particles (A).

[0441] (Preparation Example 2: Preparation of Dispersion Liquid c of Light Scattering Agent (B)) To 70 parts of titanium oxide nanoparticles, 3 parts of BYK-LPN21116 (manufactured by BYK-Chemie Japan) in terms of solid content and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added so that the total amount became 100 parts, and then stirred with a paint shaker until sufficiently dispersed to obtain a dispersion liquid c (solid content 73%) of the light scattering agent (B1).

[0442] (Example 1: Preparation of Curable Composition 1) The dispersion liquid b of semiconductor particles (A) and the dispersion liquid c of the light scattering agent (B) were mixed with each component to prepare a curable composition 1 having the composition shown in Table 1. In Table 1, the number of parts of components other than the solvent (J) represents the value in terms of solid content.

[0443]

Table 1

[0444] Coincidence compound (D1): Polyfunctional (meth)acrylate containing carboxy group (trade name "ARONIX (registered trademark) M-510" manufactured by Toagosei Co., Ltd.) Polymerizable compound (D2): Ethylene oxide-modified bisphenol A diacrylate, average molecular weight Mw is 512 Polymerization initiator (E1): Compound represented by the following formula (EA-1)

[0445] [Chemical formula]

[0446] Antioxidant (Fb1): Trade name "Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd. Leveling agent (H1): Polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.) Dispersant (I1): BYK-LPN21116 (manufactured by BYK-Chemie Japan) Solvent (J1): Mixture of PGMEA (propylene glycol monomethyl ether acetate) and cyclohexyl acetate

[0447] (Example 2: Preparation of curable composition 2) A curable composition 2 was prepared in the same manner as curable composition 1, except that resin (C2) was used instead of resin (C1).

[0448] (Example 3: Preparation of curable composition 3) A curable composition 3 was prepared in the same manner as curable composition 1, except that only polymerizable compound (D2) was used as the polymerizable compound (D) and the amount of (D2) was 6.3 parts.

[0449] (Example 4: Preparation of curable composition 4) A curable composition 4 was prepared in the same manner as curable composition 1, except that only polymerizable compound (D1) was used as the polymerizable compound (D) and the amount of (D1) was 6.3 parts.

[0450] (Example 5: Preparation of curable composition 5) A curable composition 5 was prepared in the same manner as curable composition 1, except that resin (C3) was used instead of resin (C1).

[0451] (Example 6: Preparation of curable composition 6) A curable composition 6 was prepared in the same manner as curable composition 1, except that resin (C4) was used instead of resin (C1).

[0452] (Example 7: Preparation of curable composition 7) A curable composition 7 was prepared in the same manner as curable composition 1, except that a polymerizable compound (D3), which is dipentaerythritol polyacrylate (5 - 6 functional groups), was used instead of the polymerizable compound (D2).

[0453] (Example 8: Preparation of curable composition 8) A curable composition 8 was prepared in the same manner as curable composition 1, except that a polymerization initiator (E2) represented by the following formula (EB - 1) was used instead of the polymerization initiator (E1).

[0454] [Chemical formula]

[0455] (Example 9: Preparation of curable composition 9) A curable composition 9 was prepared in the same manner as curable composition 1, except that a polymerizable compound (D3), which is dipentaerythritol polyacrylate (5 - 6 functional groups), was used instead of the polymerizable compound (D2), and a polymerization initiator (E2) represented by the above formula (EB - 1) was used instead of the polymerization initiator (E1).

[0456] (Comparative Example 1: Preparation of curable composition 10) Instead of resin (C1), a resin having a structure different from that of resin (C1) and a weight - average molecular weight Mw of 6.2×10 3A curable composition 10 was prepared in the same manner as curable composition 1, except that a resin (C5) having an acid value in terms of solid content of 99 mg-KOH / g and a double bond equivalent of 0 was used.

[0457] (Comparative Example 2: Preparation of Curable Composition 11) A curable composition 11 was prepared in the same manner as curable composition 1, except that the above resin (C5) was used instead of resin (C1), a polymerizable compound (D3) which is dipentaerythritol polyacrylate (5 to 6 functional) was used instead of polymerizable compound (D2), and a polymerization initiator (E2) represented by the above formula (EB-1) was used instead of polymerization initiator (E1).

[0458] Using curable compositions 1 to 11, the development residue ratio and the patterning property were evaluated in the following manner.

[0459] [Measurement of Residue Ratio] (i) On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), any one of curable compositions 1 to 11 was applied by the spin coating method so that the film thickness after pre-baking became 5 μm, and then a drying step (pre-baking) at 70°C for 1 minute was performed to form a film of the curable composition. Thereafter, without exposure, development was carried out using a developer (0.12% aqueous solution of tetramethylammonium hydroxide) in a developing apparatus (manufactured by Actes Kyosan Co., Ltd., ADE-3000S), and the time until the coating film was completely removed was measured. (ii) After applying and pre-baking the curable composition in the same procedure as in (i) above, using an exposure machine (UPE-1255MA; manufactured by Ushio Lighting Co., Ltd.), in an air atmosphere, an exposure step was carried out by irradiating light with an exposure amount of 200 mJ / cm 2 (based on a wavelength of 365 nm). Thereafter, development was carried out under the same conditions and for the same time as in (i) above, washed with distilled water, and then heat curing treatment (post-baking) at 95°C for 30 minutes was performed, and the film thickness t1 was measured. (iii) A post-baked film (exposed film) was prepared in the same manner as in (ii) above except that the development step was not performed, and the film thickness t0 was measured. (iv) The ratio of the film thickness t1 to t0 (t1 / t0) was defined as the residue ratio.

[0460] [Evaluation of Patterning Property] Patterns for the evaluation of patterning property were prepared by the following method. On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.), any one of the curable compositions 1 to 11 was applied by spin coating so that the film thickness after pre-baking was 5 μm, and then a drying process (pre-baking) at 70 °C for 1 minute was performed to form a film of the curable composition. After cooling the film of the curable composition after pre-baking, with the distance between the substrate on which the film was formed and a photomask made of quartz glass being 150 μm, using an exposure machine (UPE-1255MA; manufactured by Ushio Inc.), in an air atmosphere, light irradiation was performed at an exposure dose of 200 mJ / cm 2 (based on a wavelength of 365 nm). As the photomask, one for forming a line and space pattern with a line width of 3 to 30 μm and a pattern pitch of 30 μm was used. The film after light irradiation was developed using a developing solution (an aqueous solution containing 0.12% of tetramethylammonium hydroxide) in a developing apparatus (ADE-3000S; manufactured by Actes Co., Ltd.). The developing time was set to the time until the film was completely removed when an unexposed film prepared separately was developed under the same conditions. After washing with water, post-baking was performed in an oven at 95 °C for 30 minutes to obtain a pattern composed of a cured film in which a line and space pattern (having 10 lines and spaces each for each line width of 3 μm, 5 μm, 10 μm, 20 μm, or 30 μm) was formed. Regarding the obtained pattern, observation was performed using a microscope (magnification: 200 times; VHX-2000; manufactured by Keyence Corporation), and the minimum line width at which the exposed pattern remained partially or completely was used as an index of the patterning property of the composition.

[0461] [Measurement of Fluorescence Emission Intensity of Cured Film] On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.), any one of curable compositions 1 to 11 was applied by spin coating so that the film thickness after post-baking would be 5 μm, and then a drying process (pre-baking) at 70 °C for 1 minute was performed to form a film of curable compositions 1 to 11. After cooling, using an exposure machine (UPE-1255MA; manufactured by Ushio Inc.), in an air atmosphere, an exposure process was carried out by irradiating light with an exposure dose of 200 mJ / cm 2 (with a reference wavelength of 365 nm), and a heat curing process was carried out by performing a heat curing treatment (post-baking) at 95 °C for 30 minutes to obtain a substrate having a cured film. Next, a surface-emitting backlight illumination (OPSM series; manufactured by Optrex Corporation) equipped with an LED lamp having an emission peak wavelength of 450 nm and a diffusion plate was prepared as a backlight. The backlight was installed with the diffusion plate facing upward, and a spectro-radiometer (SR-UL1R; manufactured by Topcon Technology House) was installed at a position 60 cm above the surface of the diffusion plate. A glass substrate (Eagle 2000: manufactured by Corning Inc.) as a reference was placed on the surface of the diffusion plate of the backlight. In this state, the backlight was turned on, and the integrated value of the spectral irradiance in the range of 380 nm or more and 480 nm or less of the backlight wavelength was 2.69 W·sr through the glass substrate as a reference -1 ·m -2 , and the light amount of the backlight was adjusted accordingly. Next, the glass substrate as a reference was removed, and a 5 cm square substrate having a cured film obtained from the above-described curable compositions 1 to 11 was placed on the surface of the diffusion plate of the backlight. In this state, the backlight was turned on, and for the light emitted from the cured film, the emission intensity (unit: mW·sr -1 ·m -2 ) was measured as the integrated spectral irradiance in the range of 480 nm or more and 780 nm or less of the wavelength.

[0462] Table 2 shows the results of the measurement of the remaining film ratio, the evaluation of the patterning property, and the measurement of the fluorescence emission intensity of the cured film described above.

[0463]

Table 2

[0464] Also, for Example 1, Example 2, and Comparative Example 1, the residual film rate was measured in the same manner except that the pre-baking condition was 100°C for 3 minutes and the post-baking condition was 180°C for 30 minutes. The results are shown in Table 3.

[0465]

Table 3

[0466] According to Table 2, in Examples 1 to 9 that satisfied the requirements of the present invention, the residual film rate was good when the curable composition was cured at a low temperature. In contrast, in Comparative Examples 1 and 2, the residual film rate decreased when cured at a low temperature compared to Examples 1 to 9. From Table 3, it can be seen that the residual film rate of Comparative Example 1 was also good when cured at a high temperature, and it can be understood that there was no problem of a decrease in the residual film rate when cured at a high temperature in the conventional curable composition.

Claims

1. A curable composition containing semiconductor particles (A) and a resin (C), wherein a value X calculated by the following formula (1) from the acid value and weight average molecular weight Mw of the resin (C) is 10 or more and 59.75 or less, and the curable composition wherein 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) × weight average molecular weight Mw} / 10,000 …(1)

2. The curable composition according to Claim 1, wherein the acid value of the 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 5000 or more.

4. The curable composition according to Claim 1, wherein the mass ratio (A / C) of the semiconductor particles (A) to the resin (C) is 0.65 or more.

5. The curable composition according to Claim 1, further containing a polymerizable compound (D), wherein the mass ratio (C / D) of the resin (C) to the polymerizable compound (D) is 2 or more.

6. The curable composition according to Claim 1, further containing a polymerizable compound (D), wherein the polymerizable compound (D) contains a polymerizable compound having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule.

7. The curable composition according to Claim 6, wherein the polymerizable compound (D) further contains a polymerizable compound having an acidic functional group and three or more ethylenically unsaturated bonds in one molecule.

8. The curable composition according to Claim 1, further containing a light scattering agent (B).

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