Curable composition, cured film, and display device

Abstract

The present invention provides a curable composition containing light-emitting semiconductor particles, which is capable of suppressing a reduction in weight associated with storage. The present invention provides a curable composition containing semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C), and an antioxidant (D), and the polymerizable compound (B) contains 40 mass% or more of a polymerizable compound having a dipole moment of 3D or more with respect to the total amount of the polymerizable compound (B).

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured film formed therefrom, and a display device including the cured film. Background Art

[0002] Patent Document 1 describes a curable composition capable of forming a cured film by an inkjet method as a curable composition for forming a cured film such as a wavelength conversion film included in a display device.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-105710 Summary of the Invention

[0006] Conventional ink compositions containing semiconductor particles may experience a significant weight loss during storage.

[0007] One object of the present invention is to provide a curable composition containing light-emitting semiconductor particles that can suppress weight loss during storage. Another object of the present invention is to provide a cured film formed from the curable composition and a display device including the cured film.

[0008] The present invention provides the following curable composition, cured film, and display device.

[0009] [1] A curable composition comprising semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C), and an antioxidant (D),

[0010] The polymerizable compound (B) contains 40% by mass or more of a polymerizable compound having a dipole moment of 3D or more relative to the total amount of the polymerizable compound (B).

[0011] [2] The curable composition according to [1], wherein the polymerizable compound (B) contains 40% by mass or more of a bifunctional polymerizable compound having a dipole moment of 3D or more relative to the total amount of the polymerizable compound (B).

[0012] [3] A curable composition comprising semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C) and an antioxidant (D),

[0013] The polymerizable compound (B) contains 20% by mass or more of a polymerizable compound having a dipole moment of 3D or more based on the total amount of the curable composition.

[0014] [4] The curable composition according to [3], wherein the polymerizable compound (B) contains 20% by mass or more of a bifunctional polymerizable compound having a dipole moment of 3D or more, relative to the total amount of the curable composition.

[0015] [5] The curable composition according to any one of [1] to [4], wherein the polymerizable compound (B) comprises a trifunctional polymerizable compound having a dipole moment of 3D to 4D.

[0016] [6] The curable composition according to any one of [1] to [5], further comprising a light scattering agent (E).

[0017] [7] The curable composition according to any one of [1] to [6], wherein the content of the solvent (F) is 1% by mass or less relative to the total amount of the curable composition.

[0018] [8] The curable composition according to any one of [1] to [7], wherein the content of the resin (I) is 1% by mass or less relative to the total amount of the curable composition.

[0019] [9] The curable composition according to any one of [1] to [8], wherein the viscosity at 40°C is 20 cP or less.

[0020]

[10] A cured film formed from the curable composition according to any one of [1] to [9].

[0021]

[11] A display device comprising the cured film described in

[10] .

[0022] The present invention provides a curable composition containing light-emitting semiconductor particles, which can suppress weight loss during storage, a cured film formed from the curable composition, and a display device including the cured film. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 1 is a schematic cross-sectional view showing an example of a display component. DETAILED DESCRIPTION

[0024] <Curable composition>

[0025] The curable composition of the present invention (hereinafter also referred to as "curable composition") comprises semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C), and an antioxidant (D). The components contained or optionally contained in the curable composition are described below.

[0026] In addition, in this specification, unless otherwise specified, the compounds exemplified as the components contained or may be contained in the curable composition may be used alone or in combination of two or more.

[0027] [1] Semiconductor particles (A)

[0028] The semiconductor particles (A) emit light of a different wavelength from the primary light, preferably converting the wavelength of blue light as the primary light into a wavelength of light of a different color. The semiconductor particles (A) preferably emit green or red light, more preferably absorbing blue light and emitting green or red light.

[0029] In this specification, "blue" refers to all light that is perceived as blue (all light with intensity in the blue wavelength region, such as 380nm to 495nm), and is not limited to light of a single wavelength. "Green" refers to all light that is perceived as green (all light with intensity in the green wavelength region, such as 495nm to 585nm), and is not limited to light of a single wavelength. "Red" refers to all light that is perceived as red (all light with intensity in the red wavelength region, such as 585nm to 780nm), and is not limited to light of a single wavelength. "Yellow" refers to all light that is perceived as yellow (all light with intensity in the yellow wavelength region, such as 560nm to 610nm), and is not limited to light of a single wavelength.

[0030] The emission spectrum of the semiconductor particles (A) emitting green light preferably includes a peak having a maximum value in the wavelength range of 500nm to 560nm, more preferably includes a peak having a maximum value in the wavelength range of 520nm to 545nm, and further preferably includes a peak having a maximum value in the wavelength range of 525nm to 535nm. Thus, the color gamut that can be displayed by the green light of the display device can be expanded. The half-peak width of the peak is preferably 15nm to 80nm, more preferably 15nm to 60nm, further preferably 15nm to 50nm, and particularly preferably 15nm to 45nm. Thus, the color gamut that can be displayed by the green light of the display device can be expanded.

[0031] The emission spectrum of the semiconductor particles (A) emitting red light preferably includes a peak having a maximum value in the wavelength region of 610nm to 750nm, more preferably includes a peak having a maximum value in the wavelength region of 620nm to 650nm, and further preferably includes a peak having a maximum value in the wavelength region of 625nm to 645nm. Thus, the color gamut that can be displayed by the red light of the display device can be expanded. The half-peak width of the peak is preferably 15nm to 80nm, more preferably 15nm to 60nm, further preferably 15nm to 50nm, and particularly preferably 15nm to 45nm. Thus, the color gamut that can be displayed by the red light of the display device can be expanded.

[0032] The emission spectrum of the semiconductor particles (A) is measured by the method described in the Examples section below.

[0033] Examples of semiconductor particles (A) include particles composed of quantum dots and compounds having a perovskite crystal structure (hereinafter also referred to as "perovskite compounds"), with quantum dots being preferred. Quantum dots are light-emitting semiconductor particles with a particle size of 1 nm to 100 nm that emit light by absorbing ultraviolet light or visible light (e.g., blue light) using the band gap of the semiconductor.

[0034] Examples of quantum dots include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe , CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS , HgZnSeTe, HgZnSTe and other group 12 elements and group 16 elements; compounds of group 13 elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs and other group 15 elements; compounds of group 14 elements such as PdS, PbSe and other group 16 elements, etc.

[0035] When the quantum dots contain S and Se, the surface of the quantum dots can be modified with metal oxides or organic substances. By using surface-modified quantum dots, it is possible to prevent the reaction components contained in or that may be contained in the composition I from taking away S and Se.

[0036] Furthermore, quantum dots can be formed by combining the aforementioned compounds to form a core-shell structure. Examples of such a combination include microparticles having a CdSe core and a ZnS shell, and microparticles having an InP core and a ZnSeS shell.

[0037] The energy level of quantum dots depends on their size, so the ability to adjust the particle size allows for flexible selection of emission wavelengths. Furthermore, the spectral width of the light emitted by quantum dots is narrow, facilitating the development of a wide color gamut for display devices. Furthermore, quantum dots' high responsiveness improves the efficiency of primary light utilization.

[0038] The perovskite compound is a compound having A, B, and X as components and having a perovskite-type crystal structure.

[0039] A is a component located at each vertex of a hexahedron centered around B in the perovskite crystal structure and is a monovalent cation.

[0040] X represents a component located at each vertex of an octahedron centered at B in a perovskite crystal structure, and is at least one ion selected from a halide ion and a thiocyanate ion.

[0041] B is a component located at the center of a hexahedron having A at its vertices and an octahedron having X at its vertices in the perovskite crystal structure, and is a metal ion.

[0042] 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 quasi-two-dimensional structure.

[0043] In the case of three-dimensional structure, perovskite compounds are composed of ABX (3+δ) express.

[0044] In the case of two-dimensional structures, perovskite compounds are composed of A2BX (4+δ) express.

[0045] Here, δ is a value that can be appropriately changed according to the charge balance of B, and is within a range of -0.7 to 0.7.

[0046] As a perovskite compound and composed of ABX (3+δ) Preferred specific examples of the compound having a three-dimensional perovskite-type crystal structure include:

[0047] CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbI3, CH3NH3PbBr (3-y) I y (0<y<3), CH3NH3PbBr (3-y) Cl y (0<y<3), (H2N=CH-NH2)PbBr3, (H2N=CH-NH2)PbCl3, (H2N=CH-NH2)PbI3,

[0048] CH3NH3Pb (1-a) Ca a<h2 style=";text-align:left;direction:ltr">Br3(0<a≤0.7)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Sr<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br3(0<a≤0.7)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> No<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、0<δ≤0.7)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Ba<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br3(0<a≤0.7),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0049] <h2 style=";text-align:left;direction:ltr"> CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Dy<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、0<δ≤0.7)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0050] <h2 style=";text-align:left;direction:ltr"> CsPb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0)、CsPb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0051] <h2 style=";text-align:left;direction:ltr"> CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ-y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0、0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ-y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0、0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ-y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0、0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1-a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ-y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7、-0.7≤δ<0、0<y<3),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0052] <h2 style=";text-align:left;direction:ltr"> (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),

[0053] 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),

[0054] 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),

[0055] CsPb (1-a) Zn a Br3(0<a≤0.7)、CsPb (1-a) Al a Br (3+δ) (0<a≤0.7、0<δ≤0.7)、CsPb (1-a) Co a Br3(0<a≤0.7)、CsPb (1-a) Mna Br3(0<a≤0.7)、CsPb (1-a) Mg a Br3(0<a≤0.7),

[0056] 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),

[0057] (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.

[0058] As a perovskite compound and composed of A2BX (4+δ) Preferred specific examples of the compound having a two-dimensional perovskite-type crystal structure include:

[0059] (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),

[0060] (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) RbBr (4+δ) (0<a≤0.7, -0.7≤δ<0),

[0061] (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),

[0062] (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),

[0063] (C4H9NH3)2PbBr4、(C7H 15 NH3)2PbBr4,

[0064] (C4H9NH3)2PbBr (4-y) Cl y (0<y<4)、(C4H9NH3)2PbBr (4-y) I y (0<y<4),

[0065] (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) Mna Br4(0<a≤0.7),

[0066] (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),

[0067] (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),

[0068] (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 aBr (4-y) Cl y (0<a≤0.7, 0<y<4), etc.

[0069] The curable composition may contain two or more types of semiconductor particles (A). For example, the curable composition may contain only one type of semiconductor particles (A) that absorb primary light and emit green light, or may contain a combination of two or more types. The curable composition may contain only one type of semiconductor particles (A) that absorb primary light and emit red light, or may contain a combination of two or more types.

[0070] Semiconductor particles (A) can be ligand-containing semiconductor particles containing organic ligands (G) coordinated to semiconductor particles. Organic ligands (G) are, for example, organic compounds having polar groups that exhibit coordination capabilities to semiconductor particles (A). Organic ligands (G) can, for example, be coordinated to the surface of semiconductor particles (A). When organic ligands (G) are organic compounds having polar groups, organic ligands (G) are typically coordinated to semiconductor particles via the polar groups. Semiconductor particles (A) can include one or more organic ligands (G). From the perspective of improving the stability and dispersibility of semiconductor particles (A) and the luminous intensity of curable compositions and cured films, it is advantageous for semiconductor particles (A) to include organic ligands (G). The situation in which organic ligands (G) are coordinated to semiconductor particles is confirmed by uniformly dispersing semiconductor particles in a dispersion medium suitable for organic ligands.

[0071] The above-mentioned polar group of organic ligand (G) is, for example, at least one group selected from thiol group (-SH), carboxyl group (-COOH) and amino group (-NH2). The polar group selected from these is advantageous in improving the coordination property to semiconductor particles. High coordination property helps the stability and dispersibility of the semiconductor particles (A) in the curable composition to improve, as well as the luminous intensity of the curable composition and the cured film to improve. Among them, the polar group is more preferably at least one group selected from thiol group and carboxyl group. Organic ligand (G) can have one or more polar groups.

[0072] The organic ligand (G) may be, for example, an organic compound represented by the following formula (x).

[0073] X A -R X (x)

[0074] Where, X A is the polar group mentioned above, R XIt is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds. The hydrocarbon group may have a linear, branched, or cyclic structure. The number of carbon atoms in the hydrocarbon group is, for example, 1 to 40, or 1 to 30. The methylene group contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0075] Group R X A polar group may be included. Specific examples of the polar group include polar group X A The above description involved.

[0076] As a polar group X having a carboxyl group A Specific examples of the organic ligand include, in addition to formic acid, acetic acid, and propionic acid, saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, and tetradecanoic acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, octadecatetraenoic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenic acid (docosatetraenoic acid).

[0077] As a polar group X having a thiol group or an amino group A Specific examples of the organic ligand include the above-mentioned organic ligands having a carboxyl group as a polar group X A The carboxyl group of the organic ligand is substituted with a thiol group or an amino group.

[0078] In addition to the above, examples of the organic ligand represented by the above formula (x) include compound (G-1) and compound (G-2).

[0079] [Compound (G-1)]

[0080] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). Since compound (G-1) has a carboxyl group and / or a thiol group, it can serve as a ligand coordinated to semiconductor particles. Semiconductor particles (A) may contain only one compound (G-1) or two or more.

[0081] 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).

[0082]

[0083] [Where R B Represents a divalent hydrocarbon group. B When , they may be the same or different. The above-mentioned hydrocarbon group may have one or more substituents. When there are multiple 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 bonded. The -CH2- contained in the above-mentioned hydrocarbon group may be substituted with at least one of -O-, -S-, -SO2-, -CO-, and -NH-. p represents an integer of 1 to 10.

[0084] As R B Examples of the divalent hydrocarbon group represented by include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0085] Examples of the chain hydrocarbon group include linear or branched alkanediyl groups, which usually have 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of the alicyclic hydrocarbon group include monocyclic or polycyclic cycloalkanediyl groups, which usually have 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include monocyclic or polycyclic arenediyl groups, which usually have 6 to 20 carbon atoms.

[0086] Examples of the substituent that the hydrocarbon group may have include 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 carboxyl group, an amino group, and a halogen atom. The substituent that the hydrocarbon group may have is preferably a carboxyl group, an amino group, or a halogen atom.

[0087] When -CH2- contained in the above hydrocarbon group is substituted with at least one of -O-, -CO-, and -NH-, the group replacing -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0088] Examples of the compound represented by formula (G-1a) include compounds represented by the following formulae (1-1) to (1-9).

[0089]

[0090] Specific examples of the compound represented by formula (G-1a) are exemplified by chemical names such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionate, and 3-mercapto-2-methylpropionic acid. Among these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0091] Another example of compound (G-1) is a polycarboxylic acid compound, preferably a compound (G-1b) in which -SH in formula (G-1a) is replaced with a carboxyl group (-COOH) in the compound represented by formula (G-1a).

[0092] Examples of the compound (G-1b) include the following compounds.

[0093] Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecafluorooctanedioic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecafluorodecanedioic acid, acetylene dicarboxylic 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-naphthalene dicarboxylic acid, 2,3-norbornane dicarboxylic 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-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,1'-ferrocene dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2,5-furan dicarboxylic 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'-stilbene dicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorendic acid, 1H-imidazole-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1, 10-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiglycolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidene diphenoxyacetic 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.

[0094] From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film, the molecular weight of the compound (G-1) is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, even more preferably 1000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of the compound (G-1) is usually 100 or more.

[0095] The 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 gel permeation chromatography (GPC).

[0096] When the ligand-containing semiconductor particles contain compound (G-1), the content ratio of compound (G-1) to the semiconductor particles is preferably 0.001 to 1, more preferably 0.01 to 0.5, and even more preferably 0.02 to 0.45, by mass. Within this range, the content ratio is advantageous from the perspective of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film.

[0097] When the ligand-containing semiconductor particles contain compound (G-1), from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film, the content of compound (G-1) in the curable composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.2% by mass to 10% by mass, further preferably 0.5% by mass to 10% by mass, and particularly preferably 0.5% by mass to 8% by mass, relative to the total amount of the solid content of the curable composition.

[0098] [Compound (G-2)]

[0099] Compound (G-2) is a compound different from compound (G-1) and is a compound containing a polyalkylene glycol structure and having a polar group at the molecular end. The molecular end is preferably the end of the longest carbon chain in compound (G-2) (carbon atoms in the carbon chain may be substituted with other atoms such as oxygen atoms).

[0100] The semiconductor particles (A) may contain only one compound (G-2) or two or more. The semiconductor particles (A) may contain the compound (G-1) or the compound (G-2), or may contain the compound (G-1) and the compound (G-2).

[0101] In addition, the compound which contains a polyalkylene glycol structure and has the said 1st functional group and 2nd functional group belongs to compound (G-1).

[0102] The polyalkylene glycol structure refers to a structure represented by the following formula (n is an integer greater than or equal to 2):

[0103]

[0104] Where R C The alkylene group includes, for example, an ethylene group and a propylene group.

[0105] Specific examples of the compound (G-2) include polyalkylene glycol compounds represented by the following formula (G-2a).

[0106]

[0107] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z is C is a divalent or trivalent group. n is an integer greater than 2. m is 1 or 2. R C It is an alkylene group.

[0108] The polar group X is preferably at least one group selected from a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2). Polar groups selected from these are advantageous in improving coordination with semiconductor particles. Among them, from the perspective of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film, the polar group X is more preferably at least one group selected from a thiol group and a carboxyl group.

[0109] The group Y is a monovalent group. Group Y is not particularly limited, and examples thereof include monovalent hydrocarbon groups that may have substituents (N, O, S, halogen atoms, etc.). -CH2- contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-. The number of carbon atoms in the above hydrocarbon group is, for example, 1 to 12. The hydrocarbon group may have an unsaturated bond.

[0110] Examples of the group Y include an alkyl group having 1 to 12 carbon atoms and a linear, branched, or cyclic structure; and an alkoxy group having 1 to 12 carbon atoms and a linear, branched, or cyclic structure. The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The -CH2- contained in the alkyl and alkoxy groups may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-. 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.

[0111] The group Y may contain a polar group. As the polar group, at least one group selected from a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2) can be cited. Among them, as mentioned above, a compound containing a polyalkylene glycol structure and having the first and second functional groups is included in compound (G-1). The polar group is preferably disposed at the end of the group Y.

[0112] Group Z C is a divalent or trivalent group. C The hydrocarbon group is not particularly limited and may be a divalent or trivalent hydrocarbon group that may contain a heteroatom (N, O, S, a halogen atom, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond.

[0113] As a group Z belonging to a divalent group C , examples include alkylene groups having 1 to 24 carbon atoms and having a linear, branched or cyclic structure; alkenylene groups having 1 to 24 carbon atoms and having a linear, branched or cyclic structure, etc. The number of carbon atoms in the alkyl and alkenylene groups is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. -CH2- in the alkyl and alkenylene groups may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. As a trivalent group, group Z C Examples of the group Z include the group Z belonging to the above-mentioned divalent group C A group formed by removing one hydrogen atom from a molecule.

[0114] Group Z C It may have a branched structure. Group Z having a branched structure C A branch chain different from the branch chain containing the polyalkylene glycol structure represented by the above formula (G-2a) may have a polyalkylene glycol structure different from the polyalkylene glycol structure represented by the above formula (G-2a).

[0115] Among them, group Z C It 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.

[0116] R C It 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.

[0117] In formula (G-2a), n is an integer of 2 or greater, preferably 2-540, more preferably 2-120, and even more preferably 2-60.

[0118] The molecular weight of compound (G-2) can be, for example, about 150 to 10,000. From the perspective of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film, it is preferably 150 to 5,000, and more preferably 150 to 4,000. The molecular weight can be either 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 calculated based on standard polystyrene as measured by GPC.

[0119] When the ligand-containing semiconductor particles contain compound (G-2), the content ratio of compound (G-2) to the semiconductor particles is preferably 0.001 to 2, more preferably 0.01 to 1.5, and even more preferably 0.1 to 1. When the content ratio is within this range, it is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the curable composition and the cured film.

[0120] When the ligand-containing semiconductor particles contain compound (G-2), from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the curable composition and the cured film, the content of compound (G-2) in the curable composition is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 20% by mass, further preferably 1% by mass to 15% by mass, and further preferably 2% by mass to 12% by mass relative to the total amount of the solid content of the curable composition.

[0121] When the semiconductor particles (A) are ligand-containing semiconductor particles containing organic ligands (G), the content ratio of the organic ligands (G) in the curable composition to the semiconductor particles is preferably 0.001 to 1, more preferably 0.01 to 0.8, and even more preferably 0.02 to 0.5, by mass ratio. If the content ratio is within this range, it is advantageous from the perspective of improving the stability and dispersibility of the semiconductor particles (A) and the luminous intensity of the curable composition and the cured film. The content of the organic ligand (G) mentioned herein refers to the total content of all organic ligands contained in the curable composition.

[0122] The content ratio M of the semiconductor particles (A) relative to the total amount of the curable composition is A It is preferably 10% by mass or more, more preferably 16% by mass or more, further preferably 17% by mass or more, further preferably 18% by mass or more, particularly preferably 20% by mass or more, most preferably 25% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less. If the content M of the semiconductor particles (A) is AIn the above range, it is advantageous from the viewpoint of improving the luminous intensity of the curable composition and the cured film. In this specification, when the semiconductor particles (A) are ligand-containing semiconductor particles containing organic ligands (G), the content ratio M of the semiconductor particles (A) is A It refers to the content of semiconductor particles containing ligands.

[0123] From the viewpoint of improving the emission intensity of the curable composition and the cured film, the content of the semiconductor particles (A) relative to the total solid content of the curable composition is preferably within the same range as described above.

[0124] In this specification, the total amount of solid content of the curable composition refers to the total amount of components contained in the curable composition excluding the solvent (F). The content of the solid content of the curable composition can be measured by a known analytical method such as liquid chromatography or gas chromatography. The content of each component in the solid content of the curable composition can be calculated based on the formulation when preparing the curable composition.

[0125] As described above, the curable composition may contain two or more semiconductor particles (A). In this case, the above content of the semiconductor particles (A) refers to the total content of the two or more semiconductor particles (A). The same applies to the components other than the semiconductor particles (A) that are included or may be included in the curable composition. When the curable composition contains two or more, the content or content of the component refers to the total content or total content.

[0126] [2] Polymerizable compound (B)

[0127] The curable composition contains a polymerizable compound (B). The polymerizable compound (B) is a compound that can be polymerized by active radicals, acids, etc. generated by a polymerization initiator (C) described below. The curable composition may contain two or more polymerizable compounds (B).

[0128] Examples of the polymerizable compound (B) include photopolymerizable compounds that are cured by irradiation with light and thermally polymerizable compounds that are cured by heat. Examples of the photopolymerizable compound include photoradical polymerizable compounds that are cured by free radical polymerization reaction by irradiation with light and photocationic polymerizable compounds that are cured by cationic polymerization reaction by irradiation with light. The photopolymerizable compound is preferably a photoradical polymerizable compound.

[0129] The weight average molecular weight of the photopolymerizable compound is, for example, 150 to 3000, preferably 150 to 2900, and more preferably 250 to 1500.

[0130] Examples of the photoradical polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond, with (meth)acrylate compounds being preferred. Examples of the (meth)acrylate compound include a monofunctional (meth)acrylate compound having one (meth)acryloyloxy group in the molecule (hereinafter also referred to as "compound (B-1)"), a difunctional (meth)acrylate compound having two (meth)acryloyloxy groups in the molecule (hereinafter also referred to as "compound (B-2)"), and a polyfunctional (meth)acrylate compound having three or more (meth)acryloyloxy groups in the molecule (hereinafter also referred to as "compound (B-3)").

[0131] In this specification, "(meth)acrylate" means acrylate and / or methacrylate. The same applies to "(meth)acryloyl" and "(meth)acrylic acid".

[0132] Examples of the compound (B-1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and (meth)acrylate. isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, ethyl carbitol (meth)acrylate (ethoxyethoxyethyl (meth)acrylate), 3,3,5-trimethylcyclohexyl (meth)acrylate, and the like.

[0133] Examples of the compound (B-2) include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and neopentyl glycol. Hydroxypivalate di(meth)acrylate, di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl)isocyanurate are substituted with (meth)acryloyloxy groups, di(meth)acrylate in which two hydroxyl groups of a diol are substituted with (meth)acryloyloxy groups, obtained by adding 1 mol of neopentyl glycol to 4 mol or more of ethylene oxide or propylene oxide, di(meth)acrylate in which two hydroxyl groups of a diol are substituted with (meth)acryloyloxy groups, obtained by adding 1 mol of bisphenol A to 2 mol of ethylene oxide or propylene oxide, di(meth)acrylate in which two hydroxyl groups of a triol are substituted with (meth)acryloyloxy groups, obtained by adding 1 mol of trimethylolpropane to 3 mol or more of ethylene oxide or propylene oxide, di(meth)acrylate in which two hydroxyl groups of a diol are substituted with (meth)acryloyloxy groups, and the like.

[0134] Examples of the compound (B-3) include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified trimethylolpropane tris(meth)acrylate, and the like. acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, and the like.

[0135] The number of the (meth)acryloyloxy groups contained in one molecule of the compound (B-3) is, for example, 3 to 6, preferably 3 to 5, and more preferably 3.

[0136] Other examples of photoradical polymerizable compounds include (meth)acrylate compounds having a vinyl ether group and a (meth)acryloyl group (preferably a (meth)acryloyloxy group) in the same molecule (hereinafter also referred to as "compound (B-4)"). Compound (B-4) may be any of compounds (B-1) to (B-3).

[0137] The number of vinyl ether groups in compound (B-4) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. The number of (meth)acryloyl groups in compound (B-4) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0138] Examples of compound (B-4) include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 1-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 3-vinyloxybutyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, and 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, (4-vinyloxymethylcyclohexyl)methyl (meth)acrylate, (3-vinyloxymethylcyclohexyl)methyl (meth)acrylate, (2-vinyloxymethylcyclohexyl)methyl (meth)acrylate, (4-vinyloxymethylphenyl)methyl (meth)acrylate, (3-vinyloxymethylphenyl)methyl (meth)acrylate, 2-vinyloxymethylphenyl methyl (meth)acrylate, 2-(2-vinyloxymethyl)methoxy)acrylate isopropyloxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)propyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)propyl (meth)acrylate, 2-(2-vinyloxyethoxy)isopropyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}ethyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}ethyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)ethoxy}ethyl (meth)acrylate, {2-(2-vinyloxyisopropoxy)isopropoxy}ethyl ester, 2-{2-(2-vinyloxyethoxy)ethoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)isopropoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)isopropoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}isopropyl (meth)acrylate, ethoxy)isopropoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)isopropoxy}isopropyl (meth)acrylate, 2-[2-{2-(2-vinyloxyethoxy)ethoxy}ethoxy]ethyl (meth)acrylate, 2-[2-{2-(2-vinyloxyisopropoxy)ethoxy}ethoxy]ethyl (meth)acrylate, 2-(2-[2-{2-(2-vinyloxyethoxy)ethoxy}ethoxy]ethoxy)ethyl (meth)acrylate, etc.

[0139] As compound (B-4), vinyloxy (meth)acrylate C 1-6 Alkyl ester or (meth) acrylic acid (ethyleneoxy C 1-4 Alkoxy) C 1-4 Alkyl esters, more preferably (meth) acrylic acid (ethyleneoxy C 1-4 Alkoxy) C 1-4 The alkyl ester is particularly preferably 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0140] In the polymerizable compound (B), the content of the photoradical polymerizable compound, which is an amine compound or an amide compound, relative to the total amount of the curable composition is preferably less than 20% by mass, more preferably less than 10% by mass, further preferably less than 5% by mass, and even more preferably not contained. The inclusion of such a radical polymerizable compound may deteriorate the light-emitting properties of the semiconductor particles (A) in the curable composition or in the cured film.

[0141] Examples of photocationically polymerizable compounds include compounds having at least one oxetane ring (four-membered cyclic ether) in the molecule (hereinafter also referred to as "oxetane compound"), compounds having at least one ethylene oxide ring (three-membered cyclic ether) in the molecule (hereinafter also referred to as "epoxy compound"), and vinyl ether compounds.

[0142] Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and phenol novolac oxetane. These oxetane compounds are readily available as commercial products, and examples of commercial products include "ARON OXETANE (registered trademark) OXT-101," "ARON OXETANE (registered trademark) OXT-121," "ARON OXETANE (registered trademark) OXT-211," "ARON OXETANE (registered trademark) OXT-221," and "ARON OXETANE (registered trademark) OXT-212," all sold by Toagosei Co., Ltd.

[0143] Examples of the epoxy compound include aromatic epoxy compounds, glycidyl ethers of polyols having an alicyclic ring, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0144] Examples of the aromatic epoxy compound include bisphenol-type epoxy resins such as the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, and the diglycidyl ether of bisphenol S; novolac-type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; and multifunctional epoxy resins such as the glycidyl ether of tetrahydroxyphenylmethane, the glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyethylene phenol.

[0145] Examples of glycidyl ethers of polyols having alicyclic rings include those obtained by glycidyl etherifying a core-hydrogenated polyol obtained by selectively hydrogenating the aromatic rings of an aromatic polyol in the presence of a catalyst under pressure. Examples of aromatic polyols include bisphenol-type compounds such as bisphenol A, bisphenol F, and bisphenol S; novolac-type resins such as phenol novolac resins, cresol novolac resins, and hydroxybenzaldehyde phenol novolac resins; and polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, and polyvinylphenol. Glycidyl ethers can be prepared by reacting alicyclic polyols obtained by hydrogenating the aromatic rings of these aromatic polyols with epichlorohydrin. Among these glycidyl ethers of polyols having alicyclic rings, diglycidyl ether of hydrogenated bisphenol A is a preferred example.

[0146] Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof. Specific examples include diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerol; triglycidyl ether of trimethylolpropane; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; diglycidyl ether of neopentyl glycol; and polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to an aliphatic polyol such as ethylene glycol, propylene glycol, or glycerol.

[0147] The alicyclic epoxy compound is a compound having at least one structure forming an oxirane ring together with carbon atoms of an alicyclic ring in the molecule, and examples thereof include "Celloxide" series and "CYCLOMER" (both manufactured by Daicel Corporation), and "CYRACURE UVR" series (manufactured by Dow Chemical).

[0148] Examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

[0149] The content ratio M of the polymerizable compound (B) relative to the total amount of the curable composition is B It is preferably 20% to 90% by mass, more preferably 30% to 88% by mass, further preferably 40% to 86% by mass, further preferably 45% to 84% by mass, particularly preferably 50% to 82% by mass, and can be 80% by mass or less, 75% by mass or less, or 70% by mass or less.

[0150] The content of the polymerizable compound (B) relative to the total solid content of the curable composition is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 88% by mass, further preferably 40% by mass to 86% by mass, further preferably 45% by mass to 84% by mass, particularly preferably 50% by mass to 82% by mass, and may be 80% by mass or less, 75% by mass or less, or 70% by mass or less.

[0151] The curable composition satisfies at least one of the following (i) or (ii).

[0152] (i) The polymerizable compound (B) contains 40% by mass or more of a polymerizable compound having a dipole moment of 3D (Debye) or more (hereinafter also referred to as "polymerizable compound (Bx)") relative to the total amount of the polymerizable compound (B).

[0153] (ii) The polymerizable compound (B) contains 20% by mass or more of the polymerizable compound (Bx) based on the total amount of the curable composition.

[0154] By satisfying at least one of the above-mentioned (i) or (ii), the weight loss (hereinafter also referred to as "weight loss") caused by the storage of the curable composition can be suppressed. In addition, by satisfying at least one of the above-mentioned (i) or (ii), a curable composition can be provided, which can suppress the weight loss caused by storage and has good film-forming properties, and as a result, a cured film that suppresses the generation of wrinkles can be formed, and further, a cured film with good luminous intensity can be formed. In addition, by satisfying at least one of the above-mentioned (i) or (ii), a curable composition can be provided, which can suppress the weight loss caused by storage and has a low viscosity, and can form a cured film that suppresses the generation of wrinkles, and further, a cured film with good luminous intensity can be formed. From the viewpoint of suppressing weight loss, and further, improving film-forming properties and luminous intensity, and from the viewpoint of low viscosity of the curable composition, the curable composition preferably satisfies both of the above-mentioned (i) and (ii).

[0155] The polymerizable compound (B) may contain two or more polymerizable compounds (Bx). In this case, the content of the polymerizable compound (Bx) in (i) and (ii) above is the total content of the two or more polymerizable compounds (Bx) relative to the total amount of the polymerizable compound (B) and the total amount of the curable composition, respectively.

[0156] From the viewpoint of suppressing weight loss, the dipole moment of the polymerizable compound (Bx) is preferably 3.2 D or more, more preferably 3.4 D or more, and even more preferably 3.6 D or more. The dipole moment of the polymerizable compound (Bx) is usually 10 D or less, and may be 8.0 D or less, 7.0 D or less, 6.5 D or less, 6.0 D or less, or 5.5 D or less.

[0157] The weight loss rate of the curable composition measured by the method described in the Examples section below is preferably 4.0 mass% or less, more preferably 3.0 mass% or less, further preferably 2.0 mass% or less, further preferably 1.0 mass% or less, particularly preferably 0.5 mass% or less, and most preferably 0.1 mass% or less (e.g., 0.0 mass%).

[0158] The dipole moment of a polymerizable compound can be calculated based on its molecular structure by DFT (Density Functional Theory; B3LYP / 6-31G+g(d)) calculation using general calculation software. Examples of calculation software include the quantum chemical calculation program "Gaussian Series" manufactured by HULINKS. The dipole moment of a polymerizable compound depends on the electronegativity and steric structure of the atoms constituting the polymerizable compound.

[0159] From the perspective of suppressing weight loss, thereby improving film-forming properties and luminous intensity, and reducing the viscosity of the curable composition, the content of the polymerizable compound (Bx) relative to the total amount of the polymerizable compound (B) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and even more preferably 95% by mass or more (e.g., 100% by mass). This content may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.

[0160] From the perspective of suppressing weight loss, thereby improving film-forming properties and luminous intensity, and reducing the viscosity of the curable composition, the content of the polymerizable compound (Bx) relative to the total amount of the curable composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 65% ​​by mass or more. This content may be 90% by mass or less, or 85% by mass or less.

[0161] From the viewpoint of suppressing weight loss, and further improving film-forming properties and luminous intensity, as well as the viewpoint of reducing the viscosity of the curable composition, the polymerizable compound (B) preferably contains a difunctional polymerizable compound having a dipole moment of 3D or more (hereinafter also referred to as "polymerizable compound (Bx-2)".). A difunctional polymerizable compound refers to a compound having two polymerizable groups in the molecule. As a difunctional polymerizable compound, for example, the above-mentioned difunctional (meth)acrylate compound can be cited. The polymerizable compound (Bx-2) is preferably a difunctional (meth)acrylate compound having a dipole moment of 3D or more.

[0162] From the viewpoint of suppressing weight loss, the dipole moment of the polymerizable compound (Bx-2) is preferably 3.2 D or greater, more preferably 3.4 D or greater, even more preferably 3.6 D or greater, even more preferably 3.8 D or greater, particularly preferably 4.0 D or greater, and most preferably 4.2 D or greater. The dipole moment of the polymerizable compound (Bx-2) is generally 8.0 D or less, and may be 7.0 D or less, 6.5 D or less, 6.0 D or less, or 5.0 D or less.

[0163] From the perspective of suppressing weight loss, thereby improving film-forming properties and luminous intensity, and reducing the viscosity of the curable composition, the content of the polymerizable compound (Bx-2) relative to the total amount of the polymerizable compound (B) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, particularly preferably 90% by mass or more, and even more preferably 95% by mass or more (e.g., 100% by mass). This content may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0164] From the perspective of suppressing weight loss, thereby improving film-forming properties and luminous intensity, and reducing the viscosity of the curable composition, the content of the polymerizable compound (Bx-2) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of the curable composition. This content may be 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0165] The polymerizable compound (B) may contain two or more polymerizable compounds (Bx-2). In this case, the above content of the polymerizable compound (Bx-2) is the total content of the two or more polymerizable compounds (Bx-2) relative to the total amount of the polymerizable compound (B) and the total amount of the curable composition.

[0166] The polymerizable compound (B) may contain a polyfunctional polymerizable compound in addition to the polymerizable compound (Bx-2). The polyfunctional polymerizable compound mentioned here refers to a compound having three or more polymerizable groups in the molecule. Examples of the polyfunctional polymerizable compound include the above-mentioned polyfunctional (meth)acrylate compounds. The number of (meth)acryloyloxy groups possessed by one molecule of the polyfunctional (meth)acrylate compound is, for example, 3 to 6, preferably 3 to 5, and more preferably 3.

[0167] By using a polyfunctional polymerizable compound together with the polymerizable compound (Bx-2), weight loss can sometimes be further suppressed. From the viewpoint of suppressing weight loss, the polyfunctional polymerizable compound preferably includes a polyfunctional polymerizable compound having a dipole moment of 3D or greater (hereinafter also referred to as "polymerizable compound (Bx-3)"). The polymerizable compound (Bx-3) is preferably a trifunctional polymerizable compound having a dipole moment of 3D or greater, and more preferably a trifunctional (meth)acrylate compound having a dipole moment of 3D or greater.

[0168] From the viewpoint of suppressing weight loss, the dipole moment of the polymerizable compound (Bx-3) is preferably 3.2 D or more, more preferably 3.4 D or more, and even more preferably 3.6 D or more. The dipole moment of the polymerizable compound (Bx-3) is usually 10 D or less, and may be 8.0 D or less, 7.0 D or less, 6.0 D or less, 5.5 D or less, 5.0 D or less, or 4.0 D or less.

[0169] In one embodiment, the polymerizable compound (B) includes a polymerizable compound (Bx-3) which is a trifunctional polymerizable compound having a dipole moment of 3D to 5D or 3D to 4D.

[0170] In another embodiment, the polymerizable compound (B) includes a polymerizable compound (Bx-2) and a polymerizable compound (Bx-3), wherein the polymerizable compound (Bx-2) is a difunctional polymerizable compound having a dipole moment of 3D to 8D or 3D to 7D, and the polymerizable compound (Bx-3) is a trifunctional polymerizable compound having a dipole moment of 3D to 5D or 3D to 4D.

[0171] When the polymerizable compound (B) further contains a polyfunctional polymerizable compound (preferably a polymerizable compound (Bx-3)), from the viewpoint of suppressing weight loss, the content of the polyfunctional polymerizable compound (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, particularly preferably 3.0% by mass or more, particularly preferably 4.0% by mass or more, and most preferably 5.0% by mass or more, relative to the total amount of the polymerizable compound (B). From the viewpoint of reducing the viscosity of the curable composition, the content of the polyfunctional polymerizable compound (B) is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 8.0% by mass or less.

[0172] When the polymerizable compound (B) further contains a multifunctional polymerizable compound (preferably a polymerizable compound (Bx-3)), from the viewpoint of suppressing weight loss, the content thereof is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, particularly preferably 2.0% by mass or more, particularly preferably 3.0% by mass or more, and most preferably 4.0% by mass or more, relative to the total amount of the curable composition. From the viewpoint of reducing the viscosity of the curable composition, the content thereof is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8.0% by mass or less, and even more preferably 6.0% by mass or less, relative to the total amount of the curable composition.

[0173] The polymerizable compound (B) may contain two or more polyfunctional polymerizable compounds (preferably the polymerizable compound (Bx-3)). In this case, the above-mentioned content of the polyfunctional polymerizable compound is the total content of the two or more polyfunctional polymerizable compounds relative to the total amount of the polymerizable compound (B) and the total amount of the curable composition.

[0174] When the polymerizable compound (B) further contains a polyfunctional polymerizable compound, from the viewpoint of suppressing weight loss, the polyfunctional polymerizable compound is preferably the polymerizable compound (Bx-3). In this case, from the viewpoint of suppressing weight loss, the absolute value of the difference between the dipole moment of the polymerizable compound (Bx-2) and the dipole moment of the polymerizable compound (Bx-3) is preferably 2.0 D or less, more preferably 1.5 D or less, and even more preferably 1.0 D or less. The absolute value of this difference may be 0 D.

[0175] The polymerizable compound (B) may include a polymerizable compound having a dipole moment less than 3D (hereinafter also referred to as "polymerizable compound (By)"). The content of the polymerizable compound (By) relative to the total amount of the polymerizable compound (B) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less. This content may be 0% by mass, or may be 1% by mass or more, 2% by mass or more, or 3% by mass or more.

[0176] The content of the polymerizable compound (By) relative to the total amount of the curable composition is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and even more preferably 5% by mass or less. This content may be 0% by mass, or may be 1% by mass or more, 2% by mass or more, or 3% by mass or more.

[0177] The polymerizable compound (B) may contain two or more polymerizable compounds (By). In this case, the above content of the polymerizable compound (By) is the total content of the two or more polymerizable compounds (By) relative to the total amount of the polymerizable compound (B) and the total amount of the curable composition.

[0178] The dipole moment of the polymerizable compound (By) may be, for example, 2.8 D or less, 2.5 D or less, or 2.0 or less, and may be greater than 0 or 0.0001 D or more.

[0179] [3]Polymerization initiator (C)

[0180] The curable composition contains a polymerization initiator (C). The polymerization initiator (C) is a compound that can generate active radicals, acids, etc. under the action of light or heat to initiate polymerization of the polymerizable compound (B). The curable composition may contain one or more polymerization initiators (C).

[0181] Examples of the polymerization initiator (C) include photopolymerization initiators such as oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds; and thermal polymerization initiators such as azo compounds and organic peroxides.

[0182] An example of the oxime compound is an oxime compound having a first molecular structure represented by the following formula (1). Hereinafter, this oxime compound is also referred to as "oxime compound (1)".

[0183]

[0184] Inclusion of an oxime compound (1) as a polymerization initiator (C) is advantageous from the viewpoint of increasing the luminescence intensity of the curable composition and the cured film. It is presumed that one reason for this effect is that the unique molecular structure of the oxime compound (1) significantly changes the absorption wavelength of the oxime compound (1) before and after the cleavage (decomposition) of the oxime compound (1), which is required for the oxime compound (1) to initiate photopolymerization, resulting in a high photoradical polymerization initiation ability of the oxime compound (1).

[0185] In formula (1), R 1 Represents R 11 , OR 11 、COR 11 SR 11 、CONR 12 R 13 Or CN.

[0186] R 11 、R 12 and R 13 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.

[0187] R 11 、R 12 or R 13 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 Ra 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 atoms or COOR 21 replace.

[0188] 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.

[0189] R 21 、R 22 or R23 The hydrogen atom of the group represented may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0190] 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 replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- is interrupted 1 to 5 times.

[0191] 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.

[0192] R 11 、R 12 、R 13 、R 21 、R 22 or R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 12 With R 13 and R 22 With R 23 They can each form a ring together.

[0193] * represents a bonding site to the second molecular structure which is another molecular structure other than the first molecular structure of the oxime compound (1).

[0194] As 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 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0195] As 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 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0196] As 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 include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0197] As R in formula (1) 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The heterocyclic group having 2 to 20 carbon atoms represented by the present invention includes, for example, pyridyl, pyrimidinyl, furyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzo oxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolyl, Oxazolidinyl, isocyanate oxazolyl, piperidinyl, piperazinyl, morpholinyl, etc., preferably a 5- to 7-membered heterocyclic ring.

[0198] R in formula (1) 12 With R 13 and R 22 With R 23 can form a ring together, which means R 12 With R 13 and R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected, respectively.

[0199] As Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23Examples of the ring that can be formed together include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, and a 5- to 7-membered ring is preferred.

[0200] As R in formula (1) 11 、R 12 、R 13 、R 21 、R 22 and R 23 Examples of the halogen atom which may be a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0201] R in formula (1) 1 Preferably R 11 , more preferably an alkyl group having 1 to 20 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms.

[0202] An example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (2): The second molecular structure refers to a molecular structure portion other than the first molecular structure possessed by the oxime compound (1).

[0203] The bonding site represented by "*" in formula (2) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having "-*" in formula (1).

[0204]

[0205] In formula (2), R 2 and R 3 Each independently represents 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 halogen atoms.

[0206] There are multiple R 2 They can be the same or different.

[0207] There are multiple R3 They can be the same or different.

[0208] R 11 、R 12 and R 13 Means the same as above.

[0209] s and t each independently represent an integer of 0-4.

[0210] L represents a sulfur atom, CR 31 R 32 , CO or NR 33 .

[0211] R 31 、R 32 and R 33 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.

[0212] R 31 、R 32 or R 33 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 31 、R 32 and R 33 Each independently may form a ring together with any adjacent benzene ring.

[0213] R 4 represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-1).

[0214] (R 4a ) v -L 2 -L 1 - (2-1)

[0215] (In formula (2-1), L 1 Indicates -O-, -S-, and -NR 22 -、-NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0216] R 22 Means the same as above.

[0217] L 2 It 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.

[0218] L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 22 -、-NR 22 COO-、-OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted 1 to 5 times, and the alkylene portion may be branched or cyclic.

[0219] R 4a Indicates OR 41 SR 41 、CONR 42 R 43 NR 42 COR 43 , OCOR 41 、COOR 41 SCOR 41 , OCSR 41 、COSR 41 , CSOR 41 , CN or halogen atoms.

[0220] There are multiple R 4a They can be the same or different.

[0221] 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, and R 41 、R 42 and R 43 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 42 With R 43 Can form a ring together.

[0222] v represents an integer from 1 to 3. )

[0223] * represents a bonding site with the first molecular structure of the oxime compound (1).

[0224] R in formula (2) 11 、R 12 、R 13 、R 21 、R 22 、R 23 、R 24 、R 31 、R 32 and R33 , and R in the above formula (2-1) 22 、R 41 、R 42 and R 43 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms are the same as those in R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The examples involved are the same.

[0225] 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 heterocyclic groups having 2 to 20 carbon atoms are the same as those of R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The examples involved are the same.

[0226] R in formula (2) 31 、R 32 and R 33 Each independently can form a ring with any adjacent benzene ring means R 31 、R 32 and R 33 Each independently can form a ring together with any adjacent benzene ring and the nitrogen atom to which it is connected.

[0227] R in formula (2) 31 、R 32 and R 33 Examples of rings that can be formed together with any adjacent benzene ring are the same as Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same examples are involved in the rings that can be formed together.

[0228] L in the above formula (2-1) 2It 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.

[0229] Examples of the group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, 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, a decylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, an ethane-1,1-diyl group, and a propane-2,2-diyl group.

[0230] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, for example, arylene groups such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenylsulfide-4,4'-diyl, and diphenylsulfone-4,4'-diyl when v is 1.

[0231] 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).

[0232]

[0233] [In formulas (a) and (b), L 3 and L 5 represents an alkylene group having 1 to 10 carbon atoms, L 4 and L 6 represents a single bond or an alkylene group having 1 to 10 carbon atoms.]

[0234] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0235] Examples of the group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms include, for example, when v is 1, 2,5-pyridinediyl, 2,6-pyridinediyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazoldiyl, 2,5-benzofurandiyl, 2,5-benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolediyl, 2,5-benzothiazoldiyl, and 2,5-benzothiazoldiyl. A divalent heterocyclic group such as oxadiyl.

[0236] As R in formula (2) 2 and R 3 , and R in the above formula (2-1) 4a Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0237] From the viewpoint of solubility in the solvent (F) and / or developability of the curable composition, a preferred example of the structure represented by formula (2) is a structure represented by the following formula (2a).

[0238]

[0239] [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 have the same meanings as above.]

[0240] From the same viewpoint as above, another preferred example of the structure represented by formula (2) is a structure represented by the following formula (2b).

[0241]

[0242] [In formula (2b), R 44 represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-2).

[0243] R 44a -L 12 -L 11 - (2-2)

[0244] (In formula (2-2), L 11 Indicates -O- or *-OCO-, * indicates L 12 The bonding site, L 12 represents an alkylene group having 1 to 20 carbon atoms, which may be interrupted by 1 to 3 -O- groups, R 44a Indicates OR55 or COOR 55 , R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )]

[0245] R 44 The group represented by the formula (2-2) is preferred. In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (F) and the developability of the curable composition.

[0246] L 12 The number of carbon atoms of the alkylene group represented by is preferably 1 to 10, more preferably 1 to 4.

[0247] R 44a It is preferably a hydroxy group or a carboxyl group, and more preferably a hydroxy group.

[0248] The method for producing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited, and it can be produced, for example, by the method described in JP-A-2011-132215.

[0249] 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).

[0250] The bonding site represented by "*" in formula (3) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having "-*" in formula (1).

[0251]

[0252] 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.

[0253] R 5 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0254] R 5 The hydrogen atoms of the group represented by R 21 , OR 21 、COR 21 SR 21 NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR22 )-OCOR 23 NR 22 COR 21 , OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 , CSOR 21 , hydroxyl, nitro, CN, halogen atoms or COOR 21 replace.

[0255] R 21 、R 22 and R 23 Means the same as above.

[0256] R 21 、R 22 or R 23 The hydrogen atom of the group represented may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0257] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- is interrupted 1 to 5 times.

[0258] R 24 Means the same as above.

[0259] R 21 、R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0260] R 6 、R 7 、R 8 and R 9 Each independently represents R 61 , OR 61SR 61 、COR 62 、CONR 63 R 64 NR 65 COR 61 , OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 , CSOR 61 , hydroxyl, nitro, CN or halogen atoms.

[0261] 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.

[0262] R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 Ra 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 atoms or COOR 21 replace.

[0263] R 6 With R 7 、R 7 With R 8 and R 8 With R 9 They can each form a ring together.

[0264] * represents a bonding site with the first molecular structure of the oxime compound (1).

[0265] 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 alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those in R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The examples involved are the same.

[0266] R in formula (3) 22 With R 23 Can form a ring together means R 22 With R 23 Together with the nitrogen atom, carbon atom or oxygen atom to which they are attached, they may form a ring.

[0267] R in formula (3) 22 With R 23 Examples of rings that can be formed together are the same as Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The same examples are involved in the rings that can be formed together.

[0268] As R in formula (3) 6 、R 7 、R 8 and R 9 The halogen atom represented by R 5 、R 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the halogen atom in place of a hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0269] From the viewpoint of solubility in the solvent (F) and / or developability of the curable composition, in one preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0270]

[0271] [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,

[0272] When the group represented by Z has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted 1 to 5 times, and the alkylene portion may be branched or cyclic,

[0273] R 21 、R 22 and R 24 Means the same as above.]

[0274] From the same viewpoint as above, Z in formula (3-1) is preferably a methylene group, an ethylene group, or a phenylene group.

[0275] From the same viewpoint as above, R in formula (3-1) 21 and R 22 It is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably a methyl group, an ethyl group or a phenyl group.

[0276] From the same viewpoint as above, in another preferred embodiment, R 7 For nitro.

[0277] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and it can be produced, for example, by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0278] 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 (4).

[0279] The bonding site represented by "*" in formula (4) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (4), the benzene ring having "-*" in formula (4) is directly bonded to the carbonyl group having "-*" in formula (1).

[0280]

[0281] In 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.

[0282] R 71 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0283] R 71 The hydrogen atoms of the group represented by R 21 , OR 21 、COR 21 SR 21 NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 NR 22 COR 21 , OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 , CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0284] R 21 、R 22 and R 23 Means the same as above.

[0285] R 21 、R 22 or R 23 The hydrogen atom of the group represented may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0286] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24-、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- is interrupted 1 to 5 times.

[0287] R 24 Means the same as above.

[0288] R 21 、R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0289] R 72 、R 73 and 3 R's 74 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 , hydroxyl, nitro, CN or halogen atoms.

[0290] 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.

[0291] R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 Ra 23 、CONR 22 R23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms or COOR 21 replace.

[0292] R 72 With R 73 and 2 R 74 They can each form a ring together.

[0293] * represents a bonding site with the first molecular structure of the oxime compound (1).

[0294] 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 alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those in R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The examples involved are the same.

[0295] R in formula (4) 22 With R 23 Can form a ring together means R 22 With R 23 Together with the nitrogen atom, carbon atom or oxygen atom to which they are attached, they may form a ring.

[0296] R in formula (4) 22 With R 23 Examples of rings that can be formed together are the same as Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The same examples are involved in the rings that can be formed together.

[0297] As R in formula (4)72 、R 73 and R 74 The halogen atom represented by R 71 、R 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the halogen atom in place of a hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0298] The method for producing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, and for example, it can be produced by the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0299] 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 (5).

[0300] The bonding site represented by "*" in formula (5) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (5), the pyrrole ring having "-*" in formula (5) is directly bonded to the carbonyl group having "-*" in formula (1).

[0301]

[0302] In 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.

[0303] R 81 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0304] R 81 The hydrogen atoms of the group represented by 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 COR21 , OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 , CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0305] R 21 、R 22 and R 23 Means the same as above.

[0306] R 21 、R 22 or R 23 The hydrogen atom of the group represented may be substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0307] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be replaced by -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- is interrupted 1 to 5 times.

[0308] R 24 Means the same as above.

[0309] R 21 、R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0310] 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 , hydroxyl, nitro, CN or halogen atoms.

[0311] 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.

[0312] R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 Ra 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 atoms or COOR 21 replace.

[0313] R 83 With R 84 、R 84 With R 85 and R 85 With R 86 They can each form a ring together.

[0314] * represents a bonding site with the first molecular structure of the oxime compound (1).

[0315] R in formula (5) 81 、R 21 、R22 、R 23 、R 24 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those in R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R 24 The examples involved are the same.

[0316] R in formula (5) 22 With R 23 Can form a ring together means R 22 With R 23 Together with the nitrogen atom, carbon atom or oxygen atom to which they are attached, they may form a ring.

[0317] R in formula (5) 22 With R 23 Examples of rings that can be formed together are the same as Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The same examples are involved in the rings that can be formed together.

[0318] As R in formula (5) 82 、R 83 、R 84 、R 85 and R 86 The halogen atom represented by R 81 、R 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the halogen atom in place of a hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0319] 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 Nos. 2017 / 051680 and 2020 / 004601.

[0320] 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 (6).

[0321] The bonding site represented by "*" in formula (6) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having "-*" in formula (1).

[0322]

[0323] In formula (6), the four R 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 , hydroxyl, nitro, CN or halogen atoms.

[0324] 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.

[0325] R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 Ra 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 atoms or COOR 21 replace.

[0326] R 21 、R 22 and R 23 Means the same as above.

[0327] R 92 With R 93 、R 94 With R 95 、R 95 With R 96 and R 96 With R 97 They can each form a ring together.

[0328] * represents a bonding site with the first molecular structure of the oxime compound (1).

[0329] R in formula (6) 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, and heterocyclic groups having 2 to 20 carbon atoms are the same as those in R in formula (1). 11 、R 12 、R 13 、R 21 、R 22 and R 23 The examples involved are the same.

[0330] R in formula (6) 22 With R 23 Can form a ring together means R 22 With R 23 Together with the nitrogen atom, carbon atom or oxygen atom to which they are attached, they may form a ring.

[0331] R in formula (6) 22 With R 23 Examples that can be formed together are the same as Ra in formula (1) 12 With Ra 13 and Ra22 With Ra 23 The same examples are involved in the rings that can be formed together.

[0332] As R in formula (6) 91 、R 92 、R 93 、R 94 、R 95 、R 96 and R 97 The halogen atom represented by R 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the halogen atom in place of a hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0333] 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 Nos. 2017 / 051680 and 2020 / 004601.

[0334] Other examples of the photopolymerization initiator include other photopolymerization initiators other than the oxime compound (1). Examples of other photopolymerization initiators include oxime compounds other than the oxime compound (1), alkyl phenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0335] Examples of oxime compounds other than the oxime compound (1) include oxime compounds having a partial structure represented by the following formula (d1): * represents a bonding site.

[0336]

[0337] Examples of the oxime compound having a partial structure represented by 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-dimethyl)propane-1-one-2-imine, oxacyclopentylmethyloxy)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, WO-2008 / 78678, WO-2008 / 78686, and WO-2012 / 132558, etc. Commercially available products such as Irgacure (registered trademark) OXE01, Irgacure OXE02, Irgacure OXE03 (all manufactured by BASF), N-1919, NCI-930, and NCI-831 (all manufactured by ADEKA) can be used.

[0338] Among them, the oxime compound having a partial structure represented by formula (d1) is preferably at least one selected from N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine.

[0339] The alkyl phenone 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.

[0340]

[0341] Examples of the compound having a structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as OMNIRAD (registered trademark) 369, OMNIRAD 907, and OMNIRAD 379 (all manufactured by IGM Resins) can be used.

[0342] Examples of the compound having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0343] From the viewpoint of sensitivity, the alkyl phenone compound is preferably a compound having a structure represented by formula (d2).

[0344] Examples of the biimidazole compound include compounds represented by formula (d5).

[0345]

[0346] [In formula (d5), R E ~R J represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

[0347] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluoyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

[0348] Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, with a methoxy group being preferred.

[0349] 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, Japanese Patent Application Laid-Open No. 06-75372 and Japanese Patent Application Laid-Open No. 06-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. (Alkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Among them, compounds represented by the following formulas or mixtures thereof are preferred.

[0350]

[0351] 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-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferred.

[0352] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. Commercially available products such as OMNIRAD (registered trademark) 819 (manufactured by IGM Resins Co., Ltd.) can be used.

[0353] Other examples of photopolymerization initiators other than the oxime compound (1) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

[0354] From the perspective of increasing the luminescence intensity of the curable composition and the cured film, the photopolymerization initiator is preferably at least one selected from the group consisting of oxime compounds, alkyl phenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds. In a preferred embodiment, the photopolymerization initiator comprises an acylphosphine oxide compound.

[0355] The content of the polymerization initiator (C) relative to the total amount of the curable composition is C For example, it is 0.1% by mass to 20% by mass. From the viewpoint of improving the sensitivity of the curable composition and improving the luminous intensity and heat resistance of the curable composition and the cured film (making it less likely to deteriorate the luminous properties due to heat), it is preferably 0.2% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, further preferably 1% by mass to less than 10% by mass, further preferably 1% by mass to 9% by mass, particularly preferably 1% by mass to 8% by mass, and may be 6% by mass or less or 5% by mass or less.

[0356] The content of the polymerization initiator (C) relative to the total solid content of the curable composition is, for example, 0.1% by mass to 20% by mass. From the viewpoint of improving the sensitivity of the curable composition and improving the luminous intensity and heat resistance of the curable composition and the cured film, it is preferably 0.2% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, further preferably 1% by mass to less than 10% by mass, further preferably 1% by mass to 9% by mass, particularly preferably 1% by mass to 8% by mass, and may be 6% by mass or less or 5% by mass or less.

[0357] [4]Polymerization initiator (C1)

[0358] The curable composition may further contain a polymerization initiation aid (C1) together with the polymerization initiator (C). The polymerization initiation aid (C1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (B) initiated by the polymerization initiator (C). Examples of the polymerization initiation aid (C1) include photopolymerization initiation aids such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, as well as thermal polymerization initiation aids. The curable composition may contain two or more polymerization initiation aids (C1).

[0359] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0360] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0361] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0362] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

[0363] When the curable composition contains a polymerization initiator (C1), the content of the polymerization initiator (C1) in the curable composition is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 200 parts by mass, relative to 100 parts by mass of the polymerizable compound (B). When the content of the polymerization initiator (C1) is within this range, higher sensitivity of the curable composition can be achieved.

[0364] [5] Antioxidants (D)

[0365] The curable composition contains an antioxidant (D). The antioxidant (D) is not particularly limited as long as it is an antioxidant commonly used in industry, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. can be used. The curable composition may contain two or more antioxidants (D).

[0366] 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), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), and Irganox 3114 (Irganox 1330: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation). 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of phenylpropionic acid, manufactured by BASF Corporation), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylphenylamino)-1,3,5-triazine, manufactured by BASF Corporation), ADK STAB (registered trademark) AO-80 (ADK 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 Corporation), SUMILIZER (registered trademark) BHT, SUMILIZER GA-80, SUMILIZER GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by Scitec Corporation), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0367] As the phenolic antioxidant, an antioxidant having a hindered phenol structure in which a bulky organic group is bonded to the ortho position of at least one of the phenolic hydroxyl groups is preferred. The bulky organic group is preferably a secondary or tertiary alkyl group, and specific examples thereof include isopropyl, sec-butyl, tert-butyl, sec-pentyl, and tert-pentyl. Among them, tertiary alkyl groups are preferred, and tert-butyl and tert-pentyl groups are particularly preferred.

[0368] Examples of phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Corporation), ADK STAB (registered trademark) 329K, ADK STAB PEP36, and ADK STAB PEP-8 (all manufactured by ADEKA Corporation), and Sandstab. P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (all manufactured by GE), Ultranox 626 (manufactured by GE) and SUMILIZER (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphine) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

[0369] As the phosphorus-based antioxidant, an antioxidant having a group represented by the following formula (e1) is preferred.

[0370]

[0371] [In formula (e1), R e1 ~R e5 Each independently represents a hydrogen atom or an alkyl group, and * represents a bonding site.]

[0372] R e1 It is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, or a tert-butyl group.

[0373] R e2 and R e4 It is preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom.

[0374] R e5and R e3 Each independently is preferably an alkyl group, more preferably a secondary or tertiary alkyl group, further preferably a tert-butyl group or a tert-pentyl group.

[0375] The two units enclosed by brackets can be represented by R e1 Bonded to each other to form a ring. e1 Bonding to each other means from R e1 The groups obtained by removing hydrogen atoms from the two R e1 When all are hydrogen atoms, it refers to R on a benzene ring. e1 The carbon atom bonded to the other benzene ring R e1 The bonded carbon atoms are directly bonded to each other.

[0376] Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and β-alkylmercaptopropionate compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0377] As the antioxidant (D), a phenolic antioxidant or a phosphorus antioxidant is more preferred, an antioxidant having at least one of the above-mentioned hindered phenol structure and the group represented by formula (e1) is more preferred, an antioxidant having both the above-mentioned hindered phenol structure and the group represented by formula (e1) is further preferred, and SUMILIZER (registered trademark) GP is particularly preferred.

[0378] The content ratio M of the antioxidant (D) relative to the total amount of the curable composition is D For example, it is 0.01% by mass to 60% by mass. From the viewpoint of improving the luminous intensity and heat resistance of the curable composition and the cured film (less prone to degradation of the luminous properties due to heat), it is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 40% by mass, and even more preferably 0.5% by mass to 30% by mass. It may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 2% by mass or less.

[0379] The content of the antioxidant (D) relative to the total solid content of the curable composition is, for example, 0.01% by mass to 60% by mass. From the viewpoint of improving the luminous intensity and heat resistance of the curable composition and the cured film, it is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 40% by mass, and even more preferably 0.5% by mass to 30% by mass. It may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 2% by mass or less.

[0380] [6] Light scattering agent (E)

[0381] The curable composition may further contain a light scattering agent (E). By containing a light scattering agent (E), the scattering property of light from a light source irradiated on the cured film formed by the curable composition is improved. The curable composition may contain two or more light scattering agents (E).

[0382] As the light scattering agent (E), inorganic particles such as particles of metal or metal oxides and glass particles can be cited. As metal oxides, TiO2, SiO2, BaTiO3, ZnO and the like can be cited. From the perspective of effectively scattering light, TiO2 particles are preferred.

[0383] The volume-based median diameter of the light scattering agent (E) is, for example, 0.03 μm or more, preferably 0.10 μm or more, more preferably 0.15 μm or more, further preferably 0.20 μm or more, and for example, 20 μm or less, preferably 5 μm or less, further preferably 1 μm or less.

[0384] The content of the light scattering agent (E) in the curable composition is, for example, 0.001% by mass to 50% by mass, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, relative to the total amount of the curable composition or the total amount of the solid content of the curable composition. From the viewpoint of improving the light scattering energy and luminous intensity of the curable composition and the cured film, the content is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0385] [7]Solvent (F)

[0386] Curable composition can include solvent (F). When including solvent (F), its content is as little as possible. When curable composition includes solvent (F), its content is relative to the total amount of curable composition, preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 3 mass % or less, further preferably 2 mass % or less, particularly preferably 1 mass % or less, in addition, it can be 0 mass %, or it can be more than 0.5 mass %. By reducing the content of solvent (F), it is easy to control the film thickness when forming cured film, and it is possible to reduce manufacturing cost or the load that solvent brings to earth environment or working environment. Curable composition can include two or more solvents (F).

[0387] Examples of the solvent (F) include ester solvents (solvents containing -C(=O)-O-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -C(=O)-O- and -O-), ketone solvents other than ester solvents (solvents containing -C(=O)-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0388] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and γ-butyrolactone.

[0389] 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-dihydrofuran, 1,4-di ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0390] 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, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0391] 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, and isophorone.

[0392] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0393] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0394] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0395] As the solvent (F), an ester solvent, an ether ester solvent, an alcohol solvent or an amide solvent is preferred, and an ether ester solvent is more preferred.

[0396] [8] Leveling agent (H)

[0397] The curable composition may further include a leveling agent (H). Examples of the leveling agent (H) include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms. These may have polymerizable groups in their side chains. The curable composition may include two or more leveling agents (H).

[0398] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0399] Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC F575, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.).

[0400] Examples of the organosilicon-based surfactant having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0401] When the curable composition contains a leveling agent (H), the content of the leveling agent (H) in the curable composition is, for example, 0.001% by mass to 1.0% by mass, preferably 0.005% by mass to 0.75% by mass, more preferably 0.01% by mass to 0.5% by mass, and even more preferably 0.05% by mass to 0.5% by mass, relative to the total amount of the curable composition. When the content of the leveling agent (H) is within this range, the flatness of the cured film can be further improved.

[0402] [9] Resin (I)

[0403] Curable composition can include resin (I), and when including resin (I), its content is as little as possible. When curable composition includes resin (I), its content is relative to the total amount of curable composition, preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 3 mass % or less, more preferably 2 mass % or less, particularly preferably 1 mass % or less, in addition, it can be 0 mass %, or it can be more than 0.5 mass %. By reducing the content of resin (I), the viscosity of curable composition can be reduced, and then the ejection property, especially the ejection property when ejecting from the nozzle of inkjet printer is improved. Curable composition can include two or more resins (I).

[0404] Examples of the resin (I) include the following resins [K1] to [K4].

[0405] Resin [K1]: a copolymer of at least one (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(a)") and a monomer (c) copolymerizable with (a) (which is different from (a)) (hereinafter also referred to as "(c)");

[0406] Resin [K2]: A resin obtained by reacting a copolymer of (a) and (c) with 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)");

[0407] Resin [K3]: a resin obtained by reacting a copolymer of (b) and (c) with (a);

[0408] Resin [K4]: A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic anhydride.

[0409] Examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0410] 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, and 1,4-cyclohexenedicarboxylic acid;

[0411] Bicyclic unsaturated compounds containing a carboxyl 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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0412] 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0413] Unsaturated mono-(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono-(2-(meth)acryloyloxyethyl) succinate and mono-(2-(meth)acryloyloxyethyl phthalate;

[0414] Unsaturated (meth)acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl) (meth)acrylate, and the like.

[0415] Among these, (meth)acrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and the like.

[0416] (b) For example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferably, a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0417] Examples of (b) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (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-dimethyl- - Monomers having an ethylene oxide ring and an ethylenically unsaturated bond, such as 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, and 2,4,6-tris(glycidyloxymethyl)styrene;

[0418] Monomers having an oxetane ring and an ethylenically unsaturated bond, such as 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, and 3-ethyl-3-acryloyloxyethyloxetane;

[0419] Monomers having a tetrahydrofuran ring and an ethylenically unsaturated bond, such as tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate, etc.

[0420] From the viewpoint of high reactivity during production of resins [K2] to [K4] and less likelihood of unreacted (b) remaining, (b) is preferably a monomer having an ethylene oxide ring and an ethylenically unsaturated bond.

[0421] Examples of (c) include 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](meth)acrylate, 2,6] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes referred to as "tricyclodecyl (meth)acrylate".), tricyclo (meth)acrylate [5.2.1.0 2,6 (Meth)acrylates such as decen-8-yl acrylate (also commonly known as "dicyclopentenyl (meth)acrylate" in the art), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0422] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0423] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0424] 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclic unsaturated compounds such as bicyclo[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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0425] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0426] 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.

[0427] Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance of the resin (C).

[0428] In the resin [K1], the ratio of the structural units derived from each monomer in all the structural units constituting the resin [K1] is preferably:

[0429] Structural units derived from (a): 2 mol% to 60 mol%,

[0430] Structural units derived from (c): 40 mol% to 98 mol%,

[0431] More preferably:

[0432] Structural units derived from (a): 10 mol% to 50 mol%,

[0433] Structural unit derived from (c): 50 mol% to 90 mol%.

[0434] When resin (I) contains a structural unit derived from (a), it may contain two or more types of structural units derived from (a). In this case, the ratio (content on a molar basis) of the structural unit derived from (a) is the sum of the ratios of the respective structural units. The same applies to structural units derived from other monomers such as (b) and (c).

[0435] Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu and published by Kagaku Doujin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document.

[0436] Specifically, a method is exemplified in which a predetermined amount of (a) and (c), a polymerization initiator, and a solvent are placed in a reaction vessel, oxygen is replaced with nitrogen, for example, to create a deoxygenated atmosphere, and heating and heat-maintaining are performed while stirring.

[0437] The polymerization initiator and solvent used are not particularly limited, and those commonly used in the art can be used. For example, polymerization initiators include azo compounds (such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). Solvents that can dissolve the monomers may be used, and examples thereof include the solvents mentioned above as the solvent (F) included in the curable composition.

[0438] The obtained copolymer may be used as a solution after the reaction, or may be used after concentration or dilution, or may be used after being collected as a solid (powder) by a method such as reprecipitation.

[0439] Resin [K2] can be produced by adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a) to a copolymer of (a) and (c).

[0440] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each monomer is preferably the same as that described for resin [K1].

[0441] Next, a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms contained in (b).

[0442] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and the mixture is reacted at 60° C. to 130° C. for 1 to 10 hours in the presence of (b), a reaction catalyst (e.g., an organic phosphorus compound, a metal complex, an amine compound, etc.) of a carboxylic acid or a carboxylic anhydride and a cyclic ether, and a polymerization inhibitor (e.g., hydroquinone, etc.), to produce resin [K2].

[0443] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a).

[0444] Examples of the organic phosphorus compound serving as the reaction catalyst include triphenylphosphine, etc. Examples of the amine compound serving as the reaction catalyst include aliphatic tertiary amine compounds or aliphatic quaternary ammonium salt compounds, and specific examples thereof include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride.

[0445] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0446] The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0447] The reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, etc. It should be noted that the feeding method and reaction temperature can also be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, etc., similarly to the polymerization conditions.

[0448] As a first step, resin [K3] is subjected to the same method as for producing resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as is after the reaction, or after a concentrated or diluted solution, or after being obtained as a solid (powder) by a method such as reprecipitation.

[0449] The ratios of the structural units derived from (b) and (c) relative to the total number of moles of all structural units constituting the copolymer are preferably:

[0450] Structural units derived from (b): 5 mol% to 95 mol%,

[0451] Structural units derived from (c): 5 mol% to 95 mol%,

[0452] More preferably:

[0453] Structural units derived from (b): 10 mol% to 90 mol%,

[0454] Structural unit derived from (c): 10 mol% to 90 mol%.

[0455] Resin [K3] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a) under the same conditions as those for producing resin [K2].

[0456] The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol relative to 100 mol of (b).

[0457] Resin [K4] is a resin obtained by further reacting resin [K3] with carboxylic anhydride. The hydroxyl groups generated by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride are reacted with the carboxylic anhydride.

[0458] Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0459] The amount of carboxylic anhydride used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a) used.

[0460] Examples of the resin [K1], resin [K2], resin [K3], and resin [K4] include resin [K1] such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer;

[0461] 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, and a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K2];

[0462] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K3];

[0463] Resins [K4] and the like, such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride.

[0464] As another example of resin (I), the resin described in Japanese Patent Application Laid-Open No. 2018-123274 can be given. As such resin, a polymer having a double bond in a side chain and comprising 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 comprising an acid group (hereinafter also referred to as "resin (Ba)").

[0465] Acid groups can be introduced into the resin by, for example, including a structural unit (γ) derived from an acid group-containing monomer (e.g., (meth)acrylic acid) in the resin (Ba). The resin (Ba) preferably includes structural units (α), (β), and (γ) in the main chain skeleton.

[0466]

[0467] [Where R A and R B They may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. n represents the average number of repeating units of the constituent unit represented by formula (I) and is a number greater than 1.]

[0468]

[0469] [Where R C R may be the same or different and represents a hydrogen atom or a methyl group. D They may be the same or different and represent a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the constituent unit represented by formula (II) and is a number greater than 1.]

[0470] In resin (Ba), from the viewpoint of heat resistance and storage stability of resin (Ba), the content ratio of constitutional unit (α) relative to the total amount (100 mass%) of all monomer units providing the main chain skeleton of resin (Ba) is, for example, 0.5 mass% to 50 mass%, preferably 1 mass% to 40 mass%, and more preferably 5 mass% to 30 mass%. In formula (I), n represents the average number of repeating units of constitutional unit (α) in resin (Ba), and n can be set so that the content ratio of constitutional unit (α) is within the above range.

[0471] From the viewpoint of solvent resistance of the cured film, the content ratio of the structural unit (β) relative to 100 mass% of the total amount of all monomer units providing the main chain skeleton of the resin (Ba) is, for example, 10 mass% to 90 mass%, preferably 20 mass% to 80 mass%, and more preferably 30 mass% to 75 mass%. In formula (II), m represents the average number of repeating units of the structural unit (β) in the resin (Ba), and m can be set so that the content ratio of the structural unit (β) is within the above range.

[0472] From the viewpoint of the solubility of the resin (Ba), etc., the content ratio of the structural unit (γ) relative to 100 mass% of the total amount of all monomer units providing the main chain skeleton of the resin (Ba) is, for example, 0.5 mass% to 50 mass%, preferably 2 mass% to 50 mass%, and more preferably 5 mass% to 45 mass%.

[0473] The resin (I) may be one or more selected from the group consisting of the resin [K1], the resin [K2], the resin [K3], the resin [K4], and the resin (Ba).

[0474]

[10] Other ingredients

[0475] The curable composition may contain additives such as a dispersant, a plasticizer, and a filler as other components as necessary.

[0476] Examples of dispersants include, but are not limited to, cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. A dispersant is preferably used in conjunction with the curable composition when it contains a light scattering agent (E). The inclusion of a dispersant in the curable composition improves the dispersibility of the light scattering agent (E) in the curable composition.

[0477] When the curable composition contains a dispersant, its content is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less, relative to the total amount of the curable composition. Alternatively, it may be 0% by mass, 0.1% by mass or more, or 0.3% by mass or more. Furthermore, from the viewpoint of reducing viscosity, it is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0478] The content of the additives relative to the total amount of the curable composition is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 1% by mass or less, and may be 0% by mass.

[0479] <Production Method and Viscosity of Curable Composition>

[0480] The curable composition can be produced by a method including a step of mixing predetermined components and, if necessary, other components.

[0481] The order of mixing the components is not particularly limited. For example, after obtaining a dispersion of semiconductor particles (A) and a polymerizable compound (B), the dispersion can be mixed with a polymerization initiator (C), an antioxidant (D) and other components to prepare a curable composition.

[0482] The ligand-containing semiconductor particles as semiconductor particles (A) can be, for example, prepared or produced by preparing semiconductor particles coordinated with organic ligands, followed by a ligand reduction treatment to reduce the amount of coordination of the organic ligands relative to the semiconductor particles. The ligand reduction treatment can be, for example, a treatment to extract the organic ligand coordinated to the semiconductor particles into an appropriate solvent.

[0483] The viscosity of the curable composition at 40°C is preferably 20 cP or less, more preferably 15 cP or less, even more preferably 12 cP or less, and even more preferably 10 cP or less. The lower limit is not particularly limited and may be 2 cP or more, 3 cP or more, or 5 cP or more. By setting the viscosity of the curable composition within the above range, ejection properties are improved. In particular, by setting the viscosity of the curable composition within the above range, the curable composition can be smoothly ejected from the nozzle of an inkjet printer, making it suitable for use as an inkjet printer ink.

[0484] When used as an inkjet printer ink, the curable composition can be ejected from the inkjet printer's nozzle at a temperature of 40°C or higher. Because the curable composition has excellent heat resistance, even when ejected at a temperature of 40°C or higher, the resulting cured film exhibits excellent physical properties (particularly, light conversion efficiency). The temperature of the curable composition when ejected from the inkjet printer's nozzle can be 50°C or higher, 60°C or higher, or 80°C or lower.

[0485] <Cured film, patterned cured film, wavelength conversion film, and display device>

[0486] A cured film can be obtained by curing a film (layer) composed of a curable composition. Specifically, a cured film can be obtained by coating a curable composition on a substrate to form a coating film, and then exposing the obtained coating film to light.

[0487] As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, and substrates on which thin films of aluminum, silver, or silver / copper / palladium alloy are formed can be used.

[0488] The curable composition can be applied by, for example, various printing methods such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, electrostatic printing, and plateless printing; coating methods such as gravure coating, roll coating, doctor blade coating, air knife coating, rod coating, dip coating, kiss coating, spray coating, die coating, comma coating, inkjet coating, spin coating, and slit coating; and combinations thereof.

[0489] As the light source used in the exposure, a light source that generates light with a wavelength of 250nm to 450nm is preferably used. For example, a filter that cuts off this wavelength region can be used to cut off light less than 350nm, or a bandpass filter that extracts these wavelength regions can be used to selectively extract light near 436nm, near 408nm, and near 365nm. As light sources, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. can be mentioned. Exposure can be carried out in an air atmosphere or in an inert gas (nitrogen, argon, etc.) atmosphere, preferably in an inert gas atmosphere.

[0490] Alternatively, a patterned cured film can be formed from the curable composition by patterning using methods such as photolithography, inkjet printing, etc. However, photolithography results in loss of expensive composition materials, so inkjet printing is preferred from the perspective of reducing material loss.

[0491] An example of a method for producing a patterned cured film using an inkjet method is a method in which, after forming banks on a substrate, a curable composition is selectively deposited on the substrate in the areas defined by the banks using an inkjet method, and then exposed to light to cure the curable composition. The substrates exemplified in the description of the method for producing a cured film can be used.

[0492] Examples of methods for forming the bank include photolithography and inkjet, with inkjet being preferred. Examples of inkjet include the Bubble Jet (registered trademark) method using an electrothermal converter as an energy generating element and the piezoelectric inkjet method using a piezoelectric element.

[0493] As the light source used for exposure, the light source exemplified in the description of the method for producing the cured film can be used.

[0494] Unpatterned or patterned cured films can be suitably used as wavelength conversion films (wavelength conversion filters) that emit light of a wavelength different from the wavelength of light incident from a light-emitting portion such as an LED. In particular, the patterned cured film is preferably positioned above a light-emitting element such as an LED corresponding to each pattern. By independently performing wavelength conversion on each light-emitting element, the shape of the emission spectrum, such as red, green, and blue, can be appropriately formed, enabling high color reproducibility. Display components having wavelength conversion films are suitable for display devices such as liquid crystal displays and organic EL devices.

[0495] Figure 1 This is a schematic cross-sectional view of one embodiment of a display component formed by an inkjet method. Figure 1The display component 10 includes banks 2 formed on a substrate 1 and light-emitting elements 3, such as LEDs, disposed between the banks 2. Furthermore, the display component 10 includes a cured film 4 (wavelength conversion film) formed by applying the curable composition of the present invention to the light-emitting elements 3 between the banks 2 by an inkjet method and then curing the cured film (hereinafter, each cured film patterned to the dimensions between the banks 2 is also referred to as a "cured film pixel"). A color filter 5, a gas barrier layer 6, and the like may be disposed on each cured film pixel 4.

[0496] By forming the cured film pixels 4 by the inkjet method, patterning can be performed in a larger size, and the cured film pixels 4 can be applied to large displays such as digital signage.

[0497] When using an inkjet method, the vertical dimension (L1) of the pixel 4 of the cured film formed from the curable composition of the present invention is preferably 9 μm or greater, more preferably 12 μm or greater, and even more preferably 15 μm or greater. It can be 40 μm or less, or 30 μm or less. The vertical dimension (L1) can be the same length as the horizontal dimension (L3) of the light-emitting element.

[0498] When the inkjet method is used, the horizontal dimension (L2) of the pixel 4 of the cured film formed from the curable composition of the present invention is preferably 10 μm or more, more preferably 30 μm or more, further preferably 50 μm or more, further preferably 80 μm or more, and particularly preferably 100 μm or more. It may be 900 μm or less, 800 μm or less, or 700 μm or less.

[0499] The vertical dimension (L1) of the cured film pixel 4 refers to the dimension in the substrate thickness direction of a cross section cut in a direction perpendicular to the substrate. The cross section is cut at the position where the vertical dimension of the cured film pixel 4 is the largest. Figure 1 The cross section is shown, which is cut in a direction perpendicular to the substrate at a position where the vertical dimension of the cured film pixel 4 is the largest.

[0500] The horizontal dimension ( L2 ) of the cured film pixel 4 is the maximum dimension of the cured film pixel 4 in a direction horizontal to the substrate, and refers to the dimension when the substrate is viewed from a vertical direction (a dimension in plan view).

[0501] The horizontal dimension (L3) of the light emitting element is the maximum dimension of the light emitting element in a direction horizontal to the substrate, and refers to the dimension when the substrate is viewed from a vertical direction (planar dimension).

[0502] Example

[0503] The present invention will be described in more detail below with reference to the following examples. However, the present invention is not limited to the following examples. It is understood that the present invention can be implemented with appropriate modifications within the scope of the above and following descriptions, and all such modifications are encompassed within the technical scope of the present invention. Hereinafter, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0504] <Measurement and Evaluation>

[0505] (1) Thickness of cured film

[0506] The thickness (μm) of the cured film was measured using a film thickness measuring device (“DEKTAKXT” manufactured by Bruker Corporation).

[0507] (2) Dipole moment of polymerizable compounds

[0508] The dipole moment (D: Debye) of the polymerizable compound was calculated based on its molecular structure by DFT (Density Functional Theory; B3LYP / 6-31G+g(d)) calculation using the quantum chemical calculation program "Gaussian 16" manufactured by HULINKS. The results are shown in Table 1.

[0509] (3) Viscosity of curable composition (40°C)

[0510] The viscosity (cP) of the curing composition at 40° C. was measured using a Brookfield rotational viscometer at a constant temperature of 40° C. and a rotation speed of 7 rpm. The results are shown in Table 1.

[0511] (4) Weight reduction rate of curable composition

[0512] The curable composition just prepared was placed in a sealed container and allowed to stand at 25°C for 1 day. Thereafter, 0.5 g of the curable composition was measured and placed in a 6 mL screw tube, covered, and placed on a hot plate set at 40°C for 4 days. The weight reduction rate (mass %) of the curable composition was calculated according to the following formula from the weight of the curable composition before storage at 40°C for 4 days (W0) and the weight after storage at 40°C for 4 days (W1). The results are shown in Table 1.

[0513] Weight reduction rate (mass %) = 100 × (W0 - W1) / W0

[0514] (5) Film-forming properties of curable composition

[0515] The curable composition was applied by spin coating onto a 5 cm square glass substrate ("EAGLE XG" manufactured by CORNING) so that the thickness of the layer after post-baking was 10 μm. The curable composition was then exposed to light at 200 mJ / cm2 in a nitrogen atmosphere using an exposure machine ("UVH-1500M" manufactured by USHIO INC.). 2 The film was irradiated with light at an exposure dose of 100 nm (based on 365 nm) and post-baked at 180°C for 30 minutes to produce a cured film with a thickness of 10 μm. The resulting cured film was visually observed, and the film-forming properties of the curable composition were evaluated according to the following criteria. The results are shown in Table 1.

[0516] A: No wrinkles were observed in the cured film.

[0517] B: Wrinkles were observed in the cured film.

[0518] (6) Luminous intensity of the cured film

[0519] A cured film was produced on a glass substrate by the same method as in (5) above.

[0520] A light diffuser was placed on a backlight using a blue LED with a peak wavelength of 450nm as a point light source to form the backlight unit. The backlight unit was placed with the light diffuser facing upward, and a spectroradiometer ("SR-UL1R" manufactured by TOPCON Co., Ltd.) was set up at a height of 60cm from the surface of the light diffuser. A cured film formed on the aforementioned glass substrate was used as a measurement sample, and this measurement sample was placed on the surface of the light diffuser with the cured film facing upward. In this state, the backlight was turned on, and the spectroradiometer was used to measure the spectral luminance spectrum of the light emitted from the cured film. The luminous intensity EI (μW) at the maximum peak wavelength of the luminous peak was calculated from this spectrum. The results are shown in Table 1.

[0521] <Preparation of ingredients>

[0522] In order to prepare the curable composition, the following materials were prepared.

[0523] Semiconductor particles (A1): Dried quantum dots obtained by removing toluene from a toluene dispersion of ligand-containing quantum dots having an InP / ZnSeS structure (emission spectrum with a maximum peak wavelength of 530 nm and a half-peak width of 42 nm) containing an organic ligand (G) of oleic acid by vacuum distillation.

[0524] Polymerizable compound (B1): Monofunctional methacrylate compound corresponding to the above-mentioned compound (B-1) with a dipole moment of 2.1144

[0525] Polymerizable compound (B2): Difunctional acrylate compound corresponding to the above-mentioned compound (B-2) with a dipole moment of 4.5854

[0526] Polymerizable compound (B3): Difunctional acrylate compound corresponding to the above-mentioned compound (B-4) with a dipole moment of 1.7481

[0527] Polymerizable compound (B4): A multifunctional acrylate compound corresponding to the above-mentioned compound (B-3) with a dipole moment of 4.5374

[0528] Polymerizable compound (B5): A multifunctional acrylate compound corresponding to the above-mentioned compound (B-3) with a dipole moment of 3.7115

[0529] Polymerizable compound (B6): A multifunctional acrylate compound corresponding to the above-mentioned compound (B-3) with a dipole moment of 5.0332

[0530] Polymerizable compound (B7): A multifunctional acrylate compound corresponding to the above-mentioned compound (B-3) with a dipole moment of 3.7927

[0531] Polymerizable compound (B8): A multifunctional acrylate compound corresponding to the above-mentioned compound (B-2) with a dipole moment of 6.19

[0532] Polymerization initiator (C1): OMNIRAD (registered trademark) 819 manufactured by IGM Resins

[0533] Polymerization initiator (C2): OMNIRAD (registered trademark) 907 manufactured by IGM Resins

[0534] Antioxidant (D1): SUMILIZER (registered trademark) GP manufactured by Sumitomo Chemical Co., Ltd.

[0535] The emission spectrum of the semiconductor particles (A1) was measured as follows: using an absolute PL quantum yield measuring apparatus ("C9920-02" manufactured by Hamamatsu Photonics, excitation light 450 nm, room temperature, atmospheric pressure), a dispersion of the semiconductor particles (A) diluted so that the absorbance at a wavelength of 450 nm was 0.4 was used as a measurement sample.

[0536] <Examples 1 to 9, Comparative Examples 1 to 3>

[0537] The polymerizable compound (B) listed in Table 1 was added to the semiconductor particles (A) and stirred using an ultrasonic cleaner and a touch stirrer until the solid matter disappeared, thereby obtaining a quantum dot monomer dispersion. A polymerization initiator (C) and an antioxidant (D) were added to the resulting dispersion to achieve the formulation listed in Table 1, and stirred using a touch stirrer to obtain a curable composition. In Table 1, the number of parts of each component is expressed as a solids content conversion value.

[0538] Table 1

[0539]

[0540] Explanation of symbols

[0541] 1 substrate, 2 bank, 3 light-emitting element, 4 cured film (wavelength conversion film), 5 color filter, 6 gas barrier layer, 10 display component, L1 vertical dimension, L2 horizontal dimension, L3 horizontal dimension of the light-emitting element.

Claims

1. A curable composition comprising semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C), and an antioxidant (D). The polymerizable compound (B) comprises a polymerizable compound having a dipole moment of 3 D or more and accounting for 40% by mass or more of the total amount of the polymerizable compound (B).

2. The curable composition according to claim 1, wherein, the polymerizable compound (B) comprises a bifunctional polymerizable compound having a dipole moment of 3 D or more and accounting for 40% by mass or more of the total amount of the polymerizable compound (B).

3. A curable composition comprising semiconductor particles (A), a polymerizable compound (B), a polymerization initiator (C), and an antioxidant (D), wherein the polymerizable compound (B) comprises a polymerizable compound having a dipole moment of 3 D or more and accounting for 20% by mass or more of the total amount of the curable composition.

4. The curable composition according to claim 3, wherein, the polymerizable compound (B) comprises a bifunctional polymerizable compound having a dipole moment of 3 D or more and accounting for 20% by mass or more of the total amount of the curable composition.

5. The curable composition according to any one of claims 1 to 4, wherein, the polymerizable compound (B) comprises a trifunctional polymerizable compound having a dipole moment of 3 D to 4 D.

6. The curable composition according to any one of claims 1 to 4, wherein, it further comprises a light scattering agent (E).

7. The curable composition according to any one of claims 1 to 4, wherein, the content rate of the solvent (F) is 1% by mass or less relative to the total amount of the curable composition.

8. The curable composition according to any one of claims 1 to 4, wherein, the content rate of the resin (I) is 1% by mass or less relative to the total amount of the curable composition.

9. The curable composition according to any one of claims 1 to 4, having a viscosity of 20 cP or less at 40 °C.

10. A cured film formed from the curable composition according to any one of claims 1 to 4.

11. A display device comprising the cured film according to claim 10.

Images