Composition, cured film, and display device

Abstract

The present invention addresses the problem of providing a composition capable of forming a cured film having an excellent residual film rate while reducing film reduction during development. The composition contains semiconductor particles (A) and a polymerizable compound (C), and the polymerizable compound (C) contains a polymerizable compound (C-1) having a molecular volume of 450 cm < 3 > / mol or less.

Description

Technical Field

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

[0002] Patent Document 1 describes a curable resin composition comprising quantum dots, a resin, a photopolymerizable compound, and a photopolymerization initiator having a specific structural unit, and a cured film formed using the curable resin composition.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-161392 Summary of the Invention

[0006] However, in the aforementioned curable resin compositions, the cured films formed using the curable resin compositions sometimes fail to achieve a satisfactory residual film rate during development. An object of the present invention is to provide a composition that reduces film loss during development and can form a cured film with a superior residual film rate. Another object of the present invention is to provide a cured film formed from the composition and a display device comprising the cured film.

[0007] The gist of the present invention is as follows.

[0008] [1] A composition comprising semiconductor particles (A) and a polymerizable compound (C),

[0009] The polymerizable compound (C) comprises a molecular volume of 450 cm 3 / mol or less polymerizable compound (C-1).

[0010] [2] The composition according to [1], further comprising a polymerization initiator (D).

[0011] [3] The composition according to [1] or [2], further comprising a resin (B).

[0012] [4] The composition according to any one of [1] to [3], further comprising a light scattering agent (E).

[0013] [5] The composition according to any one of [1] to [4], further comprising a solvent (I).

[0014] [6] The composition according to any one of [1] to [5], wherein the polymerizable compound (C-1) is a compound having a cyclic hydrocarbon group in its structure.

[0015] [7] The composition according to any one of [1] to [6], wherein the polymerizable compound (C-1) is a compound having two or more polymerizable functional groups.

[0016] [8] The composition according to [3], wherein the content ratio of the semiconductor particles (A) to the resin (B) (semiconductor particles (A) / resin (B)) is 0.3 to 4.0 on a mass basis.

[0017] [9] The composition according to [3] or [8], wherein the content ratio of the resin (B) to the polymerizable compound (C) (resin (B) / polymerizable compound (C)) is 0.5 to 10 on a mass basis.

[0018]

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

[0019]

[11] The cured film according to

[10] , wherein the absorbance per 1 μm of film thickness at a wavelength of 300 nm or more is 0.5 or less.

[0020]

[12] A display device comprising the cured film according to

[10] or

[11] .

[0021]

[13] A cured film formed from a composition comprising semiconductor particles (A) and a polymerizable compound (C),

[0022] The absorbance per 1 μm of film thickness at a wavelength of 300 nm or longer is 0.5 or less.

[0023] According to the present invention, there can be provided a composition capable of forming a cured film having a more excellent residual film ratio during development, a cured film formed from the composition, and a display device including the cured film. DETAILED DESCRIPTION

[0024] <Composition>

[0025] The composition of the present invention (hereinafter also referred to as "composition") comprises semiconductor particles (A) and a polymerizable compound (C), and has a molecular volume of 450 cm 3 / mol or less of a polymerizable compound (C-1) as the above-mentioned polymerizable compound (C). According to the composition of the present invention, a cured film having a more excellent residual film rate during development can be formed. In addition, as a composition capable of forming a cured film, it is important not only that the residual film rate during development is good, but also that the luminous intensity of the film after development is good. The composition of the present invention can form a cured film that can improve the residual film rate during development while preferably suppressing the decrease in luminous intensity, and more preferably has a better luminous intensity.

[0026] The composition of the present invention preferably further contains a polymerization initiator (D).

[0027] The composition of the present invention preferably further contains a resin (B).

[0028] The composition of the present invention preferably further comprises a light scattering agent (E).

[0029] The composition of the present invention may further contain an antioxidant (F).

[0030] The composition of the present invention may further contain a leveling agent (J).

[0031] The components contained or may be contained in the composition are described below. It should be noted that the compounds exemplified as the components contained or may be contained in the composition in this specification may be used alone or in combination of two or more unless otherwise specified.

[0032] Semiconductor particles (A)

[0033] The semiconductor particles (A) are preferably luminescent (fluorescent) semiconductor particles, more preferably semiconductor particles that convert the wavelength of blue light, which is primary light, into a wavelength of light of a different color. The semiconductor particles (A) preferably emit green or red light, more preferably absorb blue light and emit green or red light. A cured film such as a wavelength conversion film formed from a composition containing luminescent semiconductor particles can be a film that exhibits excellent color reproducibility of fluorescent light in a desired wavelength range.

[0034] The semiconductor particles (A) can be, for example, red light-emitting semiconductor particles that emit light having a luminescence peak wavelength in the wavelength region of 605nm to 665nm, green light-emitting semiconductor particles that emit light having a luminescence peak wavelength in the wavelength region of 500nm to 560nm, or blue light-emitting semiconductor particles that emit light having a luminescence peak wavelength in the wavelength region of 420nm to 480nm. The semiconductor particles (A) are preferably red light-emitting semiconductor particles and / or green light-emitting semiconductor particles. In addition, the light absorbed by the semiconductor particles (A) can be, for example, light in a wavelength region of 400nm or more and less than 500nm (blue light) or light in a wavelength region of 200nm to 400nm (ultraviolet light). It should be noted that the luminescence peak wavelength of the semiconductor particles (A) can be confirmed in a luminescence spectrum measured, for example, using an ultraviolet-visible spectrophotometer.

[0035] The half-peak width of the luminescence spectrum of the semiconductor particles (A) is preferably less than 60nm, more preferably less than 55nm, further preferably less than 50nm, and particularly preferably less than 45nm. Thus, light with higher color purity can be emitted. The lower limit of the half-peak width of the luminescence spectrum of the semiconductor particles (A) is not particularly limited and can be more than 5nm or more than 15nm.

[0036] The semiconductor particles (A) are particles composed of semiconductor crystals, preferably nanoparticles composed of semiconductor crystals. Preferred examples of the semiconductor particles (A) include semiconductor quantum dots (hereinafter also referred to as "quantum dots") and particles of compounds having a perovskite crystal structure (hereinafter also referred to as "perovskite compounds"), with quantum dots being more preferred.

[0037] The average particle size of the quantum dots is, for example, 0.5 nm to 20 nm, preferably 1 nm to 15 nm (e.g., 2 nm to 15 nm). Since the energy state of the quantum dots depends on their size, the emission wavelength can be freely selected by changing the particle size. For example, in the case of quantum dots consisting only of CdSe, the peak wavelengths of the emission spectra when the particle sizes are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. The average particle size of the semiconductor particles (A) can be measured using a scanning transmission electron microscope.

[0038] Quantum dots can be composed of semiconductor materials containing one or more elements selected from, for example, Group IIA elements, Group IB elements, Group IIB elements, Group IIIA elements, Group IVA elements, Group VA elements, and Group VIA elements of the periodic table.

[0039] Specific examples of semiconductor materials that can constitute quantum dots include: compounds of Group IVA elements and Group VIA elements such as SnS2, SnS, SnSe, SnTe, PbS, PbSe, PbTe; compounds of Group IIIA elements and Group VA elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, InGaP; compounds of Group IIIA elements and Group VIA elements such as Ga2O3, Ga2S3, Ga2Se3, Ga2Te3, In2O3, In2S3, In2Se3, In2Te3; compounds of Group IIIA elements and Group VIA elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, ZnST Compounds of Group IIB elements such as e, ZnSeS, ZnSeTe, CdSTe, CdSeTe, HgSTe, HgSeS, HgSeTe and Group VIA elements; compounds of Group VA elements such as As2O3, As2S3, As2Se3, As2Te3, Sb2O3, Sb2S3, Sb2Se3, Sb2Te3, Bi2O3, Bi2S3, Bi2Se3, Bi2Te3 and Group VIA elements; compounds of Group IIA elements such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe and Group IIA elements; simple substances of Group IVA elements, Group VA elements or Group VIA elements such as Si and Ge.

[0040] Quantum dots can be a single-layer structure consisting of a single semiconductor material, or a core-shell structure in which the surface of a core particle (core layer) consisting of a single semiconductor material is coated with a coating layer (shell layer) consisting of one or more semiconductor materials different therefrom. In the latter case, as the semiconductor material constituting the shell layer, a material having a band gap energy greater than that of the semiconductor material constituting the core layer is generally used. Quantum dots can have more than two shell layers. The shape of the quantum dots is not particularly limited, for example, it can be spherical or roughly spherical, rod-shaped, disc-shaped, etc.

[0041] Perovskite compounds are composed of A, B and X A A compound having a perovskite crystal structure.

[0042] A is a component located at each vertex of a hexahedron centered around B in the perovskite crystal structure and is a monovalent cation.

[0043] X A The component located at each vertex of the octahedron centered at B in the perovskite crystal structure is at least one ion selected from the group consisting of a halide ion and a thiocyanate ion.

[0044] B is a hexahedron with A at the vertices and X at the vertices in the perovskite crystal structure. A The component at the center of the octahedron arranged at the vertex is a metal ion.

[0045] From the perspective of maintaining a good crystal structure, the average particle size of the semiconductor particles composed of the perovskite compound is preferably 3 nm or more, more preferably 4 nm or more, and even more preferably 5 nm or more. In addition, from the perspective of suppressing the precipitation of the perovskite compound in the composition, the average particle size of the semiconductor particles composed of the perovskite compound is preferably 5 μm or less, more preferably 500 nm or less, even more preferably 100 nm or less, and typically 50 nm or less.

[0046] As A, B and X A The perovskite compound as a component 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.

[0047] In the case of three-dimensional structures, perovskite compounds are composed of ABX A (3+δ) express.

[0048] In the case of two-dimensional structures, perovskite compounds are composed of A2BX A (4+δ) express.

[0049] Here, δ is a number that can be appropriately changed according to the charge balance of B, and is in the range of −0.7 to 0.7.

[0050] As a perovskite compound and composed of ABX A (3+δ) Preferred specific examples of the compound having a three-dimensional perovskite crystal structure include:

[0051] 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,

[0052] CH3NH3Pb (1－a) Ca a Br3(0<a≤0.7), CH3NH3Pb (1－a) Sr aBr3(0<a≤0.7)、CH3NH3Pb (1－a) La a Br (3+δ) (0<a≤0.7,0<δ≤0.7)、CH3NH3Pb (1－a) Ba a Br3(0<a≤0.7)、CH3NH3Pb (1－a) Dy a Br (3+δ) (0<a≤0.7,0<δ≤0.7),

[0053] CH3NH3Pb (1－a) Na a Br (3+δ) (0<a≤0.7,-0.7≤δ<0)、CH3NH3Pb (1－a) Li a Br (3+δ) (0<a≤0.7,-0.7≤δ<0),

[0054] CsPb (1－a) Na a Br (3+δ) (0<a≤0.7,-0.7≤δ<0)、CsPb (1－a) Li a Br (3+δ) (0<a≤0.7,-0.7≤δ<0),

[0055] CH3NH3Pb (1－a) Na a Br (3+δ－y) I y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb (1－a) Li a Br (3+δ－y) I y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb (1－a) Na a Br (3+δ－y) Cl y (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb (1－a) Li a Br (3+δ－y) Cl y (0<a≤0.7,-0.7≤δ<0,0<y<3)、

[0056] (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)、

[0057] 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)、

[0058] 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)、

[0059] CsPb (1－a) Zn a Br3(0<a≤0.7)、CsPb (1－a) Al a Br (3+δ) (0<a≤0.7,0<δ≤0.7)、CsPb (1－a) CO a Br3(0<a≤0.7)、CsPb (1－a) Mn a Br3(0<a≤0.7)、CsPb (1－a)Mg a Br3(0<a≤0.7)、

[0060] 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 x 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)、

[0061] (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.

[0062] 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:

[0063] (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),

[0064] (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),

[0065] (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)、

[0066] (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)、

[0067] (C4H9NH3)2PbBr4、(C7H 15 NH3)2PbBr4、

[0068] (C4H9NH3)2PbBr (4－y) Cl y (0<y<4)、(C4H9NH3)2PbBr (4－y) I y (0<y<4)、

[0069] (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)、

[0070] (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)、

[0071] (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)、

[0072] (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.

[0073] The semiconductor particles (A) may be ligand-containing semiconductor particles containing an organic ligand (G) coordinated to the semiconductor particles. The organic ligand (G) may be, for example, an organic compound having a polar group that exhibits coordination ability with the semiconductor particles. The organic ligand (G) may be, for example, coordinated to the surface of the semiconductor particles.

[0074] Organic ligand (G) can be one kind of ligand, or it can be more than two kinds of ligands. When organic ligand (G) is an organic compound with a polar group, organic ligand (G) is usually coordinated to semiconductor particles via its polar group. It can be confirmed that organic ligand (G) has been coordinated by semiconductor particles (A) being uniformly dispersed in a dispersion medium suitable for organic ligand (G). From the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and luminous intensity, it can be advantageous to use ligand-containing semiconductor particles as semiconductor particles (A).

[0075] The polar group of the organic ligand (G) is preferably at least one group selected from the group consisting of, for example, a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2). The polar group selected from this group is advantageous in that it can improve the coordination with the semiconductor particles. High coordination can contribute to the improvement of the color unevenness of the cured film and / or the improvement of the pattern depiction of the photosensitive composition. Among them, from the viewpoint of improving the luminous intensity, the polar group is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group. The organic ligand (G) may have one or more polar groups.

[0076] The organic ligand (G) may be, for example, an organic compound represented by the following formula (y).

[0077] Y-Z a (y)

[0078] Wherein, Y is the polar group mentioned above, Z a It 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 by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. From the perspective of the simplicity of preparation of ligand-containing semiconductor particles, the hydrocarbon group usually does not contain heteroatoms.

[0079] Group Z aIt may contain a polar group. The specific example of the polar group is cited above for the polar group Y. From the perspective of the ease of preparation of the ligand-containing semiconductor particles, the group Z a Most of them usually do not contain polar groups.

[0080] Specific examples of organic ligands having a carboxyl group as the polar group Y 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 lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenic acid (docosatetraenoic acid).

[0081] Specific examples of the organic ligand having a thiol group or an amino group as the polar group Y include organic ligands in which the carboxyl group of the organic ligand having a carboxyl group as the polar group Y exemplified above is substituted with a thiol group or an amino group.

[0082] In addition to the above, examples of the organic ligand represented by the above formula (y) include compound (G-1) and compound (G-2).

[0083] [Compound (G-1)]

[0084] 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 (A). The composition may contain only one compound (G-1) or two or more.

[0085] 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).

[0086]

[0087] [Where R b Represents a divalent hydrocarbon group. There are multiple R bWhen , they may be the same or different. The above 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 and form a ring together with the atoms to which they are bonded. The -CH2- contained in the above hydrocarbon group may be substituted with at least one of -O-, -S-, -SO2-, -CO-, and -NH-. p represents an integer from 1 to 10.

[0088] As R b Examples of the divalent hydrocarbon group represented by include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0089] 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.

[0090] 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.

[0091] When -CH2- contained in the above hydrocarbon group is substituted with at least one of -O-, -CO-, and -NH-, the substitution for -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0092] Examples of the compound represented by formula (G-1a) include compounds represented by the following formulae (1-1) to (1-9).

[0093]

[0094] Specific examples of the compound represented by formula (G-1a) are represented 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 them, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0095] Another example of compound (G-1) is a polycarboxylic acid compound, and preferably, compound (G-1b) is a compound represented by formula (G-1a) above, wherein -SH in formula (G-1a) is replaced with a carboxyl group (-COOH).

[0096] Examples of the compound (G-1b) include the following compounds.

[0097] 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, hexadecanedicarboxylic 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 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, 1,1 0-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'-isopropyldiphenoxyacetic 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.

[0098] From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity, 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, even more preferably 800 or less, and even more preferably 500 or less. The molecular weight of the compound (G-1) is usually 100 or more.

[0099] 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).

[0100] When the ligand-containing semiconductor particles contain compound (G-1), the content ratio of compound (G-1) to semiconductor particles is preferably 0.001 to 1, more preferably 0.01 to 0.5, and even more preferably 0.02 to 0.45, in terms of mass ratio. When the content ratio is within this range, it is advantageous from the perspective of improving the stability and dispersibility of the semiconductor particles (A), as well as the emission intensity.

[0101] When the composition contains compound (G-1), from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminous intensity of the wavelength conversion layer, the content of compound (G-1) in the composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 20% by mass, and even more preferably 0.5% by mass to 15% by mass relative to the total amount of the solid content of the composition.

[0102] In this specification, the total amount of solid content refers to the total amount of components obtained by excluding the solvent (I) from the components contained in the composition. The content of the solid content of the composition can be measured using known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid content of the composition can also be calculated based on the formulation during the preparation of the composition.

[0103] [Compound (G-2)]

[0104] Compound (G-2) is a compound different from compound (G-1) and comprises a polyalkylene glycol structure and has a polar group at a molecular terminal. The molecular terminal is preferably the terminus of the longest carbon chain (carbon atoms in the carbon chain may be substituted with other atoms such as oxygen atoms) in compound (G-2).

[0105] 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).

[0106] In addition, the polycarboxylic acid compound containing a polyalkylene glycol structure belongs to compound (G-1).

[0107] The polyalkylene glycol structure refers to a structure represented by the following formula.

[0108]

[0109] [Where R a is an alkylene group, and e is an integer greater than or equal to 2.]

[0110] As R a Examples of the alkylene group represented by include ethylene and propylene.

[0111] Specific examples of the compound (G-2) include polyalkylene glycol compounds represented by the following formula (G-2a).

[0112]

[0113] [In formula (G-2a), Y E is a polar group, L E is a monovalent group, M E is a divalent or trivalent group, and b is 1 or 2. a is an alkylene group, and e is an integer greater than or equal to 2.]

[0114] Polar group Y E Preferably, it is at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2). Polar groups selected from this group are advantageous in terms of improving the coordination with semiconductor particles. Among them, from the perspective of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity, the polar group Y E More preferably, it is at least one group selected from a thiol group (—SH) and a carboxyl group.

[0115] Group L E Is a monovalent group. As group L E , but not particularly limited, include monovalent hydrocarbon groups that may have substituents (N, O, S, halogen atoms, etc.). The -CH2- contained in the hydrocarbon group may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the above hydrocarbon group is, for example, 1 to 12. The hydrocarbon group may have an unsaturated bond.

[0116] As the group L E, examples include alkyl groups with 1 to 12 carbon atoms in a straight chain, branched chain, or cyclic structure; alkoxy groups with 1 to 12 carbon atoms in a straight chain, branched chain, or cyclic structure, etc. 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- in the alkyl and alkoxy groups can be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. Among them, the group L E It 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.

[0117] Group L E It 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 polycarboxylic acid compound containing a polyalkylene glycol structure belongs to compound (G-1). The polar group is preferably arranged in group L E The end of .

[0118] Group M E is a divalent or trivalent group. E The hydrocarbon group is not particularly limited and may be a divalent or trivalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond.

[0119] For the group M as a divalent group E , examples include alkylene groups having 1 to 24 carbon atoms in a linear, branched, or cyclic structure; alkenylene groups having 1 to 24 carbon atoms in a linear, branched, or cyclic structure. 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. The -CH2- in the alkyl and alkenylene groups may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. For the group M as a trivalent group E Examples of the divalent group M include the group E A group obtained by removing one hydrogen atom from a molecule.

[0120] Group M E It may have a branched structure. E 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).

[0121] Among them, the group M E 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.

[0122] R a 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.

[0123] e in formula (G-2a) is an integer of 2 or greater, preferably 2-540, more preferably 2-120, and even more preferably 2-60.

[0124] 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, it is preferably 150 to 5,000, and more preferably 150 to 4,000. The molecular weight can 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 measured by GPC in terms of standard polystyrene.

[0125] When the ligand-containing semiconductor particles contain the compound (G-2), the content ratio of the 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.

[0126] When the composition contains compound (G-2), from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminous intensity of the wavelength conversion layer, the content of compound (G-2) in the composition is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 20% by mass, and even more preferably 1% by mass to 15% by mass relative to the total amount of the solid content of the composition.

[0127] When the semiconductor particles (A) are ligand-containing semiconductor particles, the ratio of the organic ligand content 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, calculated as a mass ratio. This range of content is advantageous from the perspective of improving the stability and dispersibility of the semiconductor particles (A), as well as the luminescence intensity. The organic ligand content referred to herein refers to the total content of all organic ligands.

[0128] The content of the semiconductor particles (A) in the composition (wherein, in the case of ligand-containing semiconductor particles containing an organic ligand (G), the organic ligand (G) is not included) is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 17% by mass or more, still more preferably 20% by mass or more, still more preferably 22% by mass or more, and still more preferably 25% by mass or more, relative to the total amount of the solid components of the composition. In addition, the above content is preferably 70% by mass or less, more preferably 65% ​​by mass or less, further preferably 60% by mass or less, further preferably 55% by mass or less, further preferably 50% by mass or less, and further preferably 45% by mass or less, relative to the total amount of the solid components of the composition.

[0129] Resin (B)

[0130] The resin (B) may contain one or more resins. Examples of the resin (B) include the following resins [K1] to [K6].

[0131] Resin [K1]: A copolymer comprising a structural unit derived from at least one monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(a)") and a structural unit derived from a monomer (c) copolymerizable with (a) (which is different from (a)) (hereinafter also referred to as "(c)");

[0132] Resin [K2]: A copolymer comprising structural units derived from the above-mentioned (a), structural units derived from the above-mentioned (c), and structural units derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(b)");

[0133] Resin [K3]: a copolymer comprising a structural unit obtained by adding a structural unit derived from the above-mentioned (a) to the above-mentioned (b) and a structural unit derived from the above-mentioned (c);

[0134] Resin [K4]: A copolymer comprising a structural unit obtained by adding a structural unit derived from the above-mentioned (a) to the above-mentioned (b) and further forming an ester bond with a carboxylic anhydride, and a structural unit derived from the above-mentioned (c);

[0135] Resin [K5]: a copolymer comprising a structural unit obtained by adding a structural unit derived from the above-mentioned (b) to the above-mentioned (a) and a structural unit derived from the above-mentioned (c);

[0136] Resin [K6]: A copolymer having a structural unit obtained by adding a structural unit derived from the above-mentioned (b) to the above-mentioned (a) and further forming an ester bond with a carboxylic acid anhydride, and a structural unit derived from the above-mentioned (c).

[0137] Examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0138] 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;

[0139] 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;

[0140] 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;

[0141] Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;

[0142] Unsaturated (meth)acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl) (meth)acrylic acid, and the like.

[0143] Among them, (meth)acrylic acid, mono[2-(meth)acryloyloxyethyl]succinate, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and the like.

[0144] In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid, and the same applies to "(meth)acryloyl" and "(meth)acrylate".

[0145] (b) is, 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) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0146] As (b), for example, a monomer (b1) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)"), etc. can be cited.

[0147] Examples of (b1) include monomers (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and monomers (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0148] Examples of (b1-1) 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(glycidyl)acrylate, styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

[0149] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0150]

[0151] [In formula (BI) and formula (BII), R e and R f It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxy group.

[0152] X e and X f Indicates a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-.

[0153] R g It represents an alkanediyl group having 1 to 6 carbon atoms.

[0154] *Indicates the bonding site with O.]

[0155] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

[0156] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0157] As R e and R f , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0158] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0159] As X e and X f , preferably, a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O- are mentioned, and more preferably, a single bond and *-CH2CH2-O- (* represents a bonding site with O) are mentioned.

[0160] Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), or formulas (BI-11) to (BI-15) are preferred, and compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15) are more preferred.

[0161]

[0162] Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among them, compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formulas (BII-11) to (BII-15) are preferred, and compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15) are more preferred.

[0163]

[0164] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the ratio of their content [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0165] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0166] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0167] As (b), (b1) is preferred because reliability such as chemical resistance can be further improved.

[0168] Since the reactivity during production of resins [K3] to [K6] is high and unreacted (b) is less likely to remain, a monomer having an oxirane ring and an ethylenically unsaturated bond is preferred as (b).

[0169] 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 this technical field, it is commonly known as "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 (Meth)acrylates such as decen-8-yl acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), 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;

[0170] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0171] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0172] 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;

[0173] 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;

[0174] 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.

[0175] Among them, from the viewpoint of copolymerization reactivity and heat resistance of the resin (B), preferred as (c) are methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, tricyclo[5.2.1.0 2,6 ]Decan-8-yl ester, bicyclo[2.2.1]hept-2-ene, etc.

[0176] In the resin [K1], the ratio of the structural units derived from each unit is preferably 2 mol% to 60 mol% of the structural units derived from (a) and 40 mol% to 98 mol% of the structural units derived from (c) in all the structural units constituting the resin [K1]. More preferably, the structural units derived from (a) are 10 mol% to 50 mol% and the structural units derived from (c) are 50 mol% to 90 mol%.

[0177] When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the composition and the solvent resistance of the cured film tend to be excellent.

[0178] 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, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document.

[0179] Specifically, a method is exemplified in which predetermined amounts of (a) and (c), a polymerization initiator, and a solvent are placed in a reaction vessel, oxygen is replaced with nitrogen to create a deoxygenated atmosphere, and the mixture is heated and maintained while stirring.

[0180] The polymerization initiator and solvent used are not particularly limited, and those commonly used in this field 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 and t-butyl peroxy-2-ethylhexanoate). The solvent can be any solvent that dissolves the monomers, and examples thereof include the solvents described below as solvent (I) that can be included in the composition.

[0181] The obtained copolymer may be used directly as a post-reaction solution, after concentration or dilution, or in a solid (powder) form by reprecipitation or the like. If the solvent (I) described later is used as a solvent during polymerization, the post-reaction solution can be used directly to prepare the composition, thereby simplifying the composition production process.

[0182] In the resin [K2], the ratio of the structural units derived from each unit is preferably 2 to 45 mol% of the structural units derived from (a), 2 to 95 mol% of the structural units derived from (b), and 1 to 65 mol% of the structural units derived from (c) in all the structural units constituting the resin [K2]. More preferably, the structural units derived from (a) are 5 to 40 mol%, the structural units derived from (b) are 5 to 80 mol%, and the structural units derived from (c) are 5 to 60 mol%.

[0183] When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the composition and the developability when forming a colored pattern tend to be excellent.

[0184] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0185] The resin [K3] can be produced by adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a) to the copolymer of (a) and (c).

[0186] 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 unit is preferably the same as the ratio described for resin [K1].

[0187] 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).

[0188] After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and the reaction is carried out at, for example, 60°C to 130°C for 1 to 10 hours in the presence of (b), a reaction catalyst (e.g., an organophosphorus compound, a metal complex, an amine compound, etc.) for a carboxylic acid or a carboxylic anhydride and a cyclic ether, and a polymerization inhibitor (e.g., hydroquinone, p-methoxyphenol, etc.), to produce resin [K2].

[0189] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). Within this range, the storage stability of the composition and the balance between solvent resistance, heat resistance, and mechanical strength of the cured film tend to be improved.

[0190] Examples of organophosphorus compounds used as reaction catalysts include triphenylphosphine. Examples of amine compounds used as reaction catalysts include aliphatic tertiary amine compounds and aliphatic quaternary ammonium salt compounds. Specific examples include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride. From the perspective of the luminescence intensity of the resulting cured film, the reaction catalyst is preferably an organophosphorus compound.

[0191] 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).

[0192] 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).

[0193] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. In addition, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0194] Resin [K4] is obtained by further reacting resin [K3] with carboxylic anhydride. The hydroxyl groups generated by the reaction of carboxylic acid or carboxylic anhydride with cyclic ether are reacted with the carboxylic anhydride.

[0195] Examples of the carboxylic anhydride include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0196] The amount of the carboxylic anhydride used is preferably 0.5 mol to 1 mol relative to 1 mol of the amount of (b) used.

[0197] As a first step, resin [K5] is subjected to the same method as for producing resin [K1] to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, after concentration or dilution, or after being obtained as a solid (powder) by reprecipitation or the like.

[0198] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 mol% to 95 mol% for the structural units derived from (b) and 5 mol% to 95 mol% for the structural units derived from (c), and more preferably 10 mol% to 90 mol% for the structural units derived from (b) and 10 mol% to 90 mol% for the structural units derived from (c).

[0199] Resin [K5] 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 [K3].

[0200] The amount of (a) to be reacted with the copolymer is preferably 5 mol to 120 mol, more preferably 20 mol to 110 mol, based on 100 mol of (b).

[0201] Resin [K6] is a resin obtained by further reacting resin [K5] with carboxylic anhydride under the same conditions as those for producing resin [K4]. The hydroxyl groups generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride are reacted with the carboxylic anhydride.

[0202] The amount of the carboxylic anhydride used is preferably 0.1 to 1 mol, more preferably 0.2 to 1 mol, further preferably 0.3 to 1 mol, and even more preferably 0.5 to 1 mol, relative to 1 mol of (a).

[0203] Examples of the resin [K1], resin [K2], resin [K3], resin [K4], resin [K5], and resin [K6] include:

[0204] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, (meth)acrylate / mono-[2-(meth)acryloyloxyethyl]succinate / dicyclopentanyl (meth)acrylate / methyl (meth)acrylate copolymer [K1];

[0205] Glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / methyl (meth) acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl ester / (meth) acrylic acid / benzyl (meth) acrylate copolymer resin [K2];

[0206] Resins obtained by adding benzyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate, resins obtained by adding tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer to glycidyl (meth)acrylate, resins obtained by adding tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate, resins obtained by adding dicyclopentanyl (meth)acrylate / methyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate, etc. [K3];

[0207] Resins obtained by esterifying a resin obtained by adding a benzyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate with tetrahydrophthalic anhydride or succinic anhydride; resins obtained by esterifying a resin obtained by adding a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate with tetrahydrophthalic anhydride or succinic anhydride; resins obtained by esterifying a resin obtained by adding a dicyclopentanyl (meth)acrylate / methyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate with tetrahydrophthalic anhydride or succinic anhydride; and resins obtained by esterifying a resin obtained by adding a dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / (meth)acrylic acid copolymer to glycidyl (meth)acrylate with tetrahydrophthalic anhydride or succinic anhydride [K4];

[0208] Resins obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, and resins obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K5];

[0209] Resins such as a resin obtained by adding a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate to (meth)acrylic acid and further forming an ester bond with tetrahydrophthalic anhydride or succinic anhydride, and a resin obtained by adding a copolymer of dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / glycidyl (meth)acrylate to (meth)acrylic acid and further forming an ester bond with tetrahydrophthalic anhydride or succinic anhydride [K6].

[0210] The resin (B) contained in the composition preferably comprises at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5], and resin [K6]. From the viewpoint of improving the residual film rate during development of the cured film, the resin (B) more preferably comprises resin [K4], resin [K5], and / or resin [K6]. It is further preferred that the resin (B) comprises resin [K4] and / or resin [K6]. It is further preferred that the resin (B) comprises resin [K6].

[0211] Another example of resin (B) includes the resin described in Japanese Patent Application Laid-Open No. 2018-123274. Examples of such resins include polymers having a double bond in the side chain, a main chain comprising a structural unit (α) represented by the following formula (I) and a structural unit (β) represented by the following formula (II), and further containing an acid group (hereinafter also referred to as "resin (Ba)").

[0212] Acid groups can be introduced into the resin by, for example, allowing the resin (Ba) to contain a structural unit (γ) derived from an acid group-containing monomer (e.g., (meth)acrylic acid). The resin (Ba) preferably contains structural units (α), (β), and (γ) in its main chain skeleton.

[0213]

[0214] [Where R A and R B are 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 or equal to 1.]

[0215]

[0216] [Where R C are the same or different and represent a hydrogen atom or a methyl group. D are 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.]

[0217] In the resin (Ba), from the viewpoint of heat resistance and storage stability of the resin (Ba), the content ratio of the structural unit (α) is, for example, 0.5% by mass to 50% by mass, preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, relative to 100% by mass of the total amount of all monomer units providing the main chain skeleton of the resin (Ba). In formula (I), n represents the average number of repeating units of the structural unit (α) in the resin (Ba), and n can be set so that the content ratio of the structural unit (α) is within the above range.

[0218] From the viewpoint of solvent resistance of the cured film, the content ratio of the structural unit (β) relative to the total amount (100 mass%) 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.

[0219] From the viewpoint of the solubility of the resin (Ba) in the solvent (I), the content ratio of the structural unit (γ) is, for example, 0.5% by mass to 50% by mass, preferably 2% by mass to 50% by mass, and more preferably 5% by mass to 45% by mass, relative to 100% by mass of the total amount of all monomer units providing the main chain skeleton of the resin (Ba).

[0220] Another example of the resin (B) is a polyalkylene glycol compound. Examples of the polyalkylene glycol compound include polyethylene glycol and polypropylene glycol.

[0221] The weight average molecular weight (Mw) of the resin (B) measured by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably 9000 or less. By making the resin (B) have the above-mentioned Mw, there is a tendency to easily improve the luminous intensity of the obtained cured film. The Mw of the resin (B) in terms of standard polystyrene is, for example, 1000 to 9000, and from the viewpoint of the strength of the cured film, it is preferably 2000 to 8500, and more preferably 3000 to 8500. The smaller the Mw of the resin (B), the more likely it is that the film will be reduced during development, but in the present invention, since the composition contains a molecular volume of 450 cm 3 Since the polymerizable compound (C-1) contains 100 Å / mol or less of the polymerizable compound (C), the film loss can be reduced and a high residual film rate can be achieved.

[0222] In order to adjust the Mw of the resin (B) to the above range, the reaction conditions such as the selection of raw materials to be used, the charging method, the reaction temperature and time can be adjusted in appropriate combination.

[0223] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) measured by GPC is, for example, 1.0 to 6.0, and preferably 1.2 to 4.0 from the viewpoint of reducing film loss during development and increasing the emission intensity of the resulting cured film.

[0224] From the perspective of reducing film loss during development and improving the luminescence intensity and solvent resistance of the resulting cured film, the acid value of resin (B) is preferably 30 mgKOH / g or greater, more preferably 90 mgKOH / g to 150 mgKOH / g, even more preferably 95 mgKOH / g to 140 mgKOH / g, and even more preferably 100 mgKOH / g to 130 mgKOH / g. The acid value of resin (B) can be adjusted by, for example, the content of monomer components having acid groups (e.g., (a) above), the content of carboxylic anhydride that reacts with the hydroxyl groups generated by the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether, and the like.

[0225] The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B). It can be determined, for example, by titration using an aqueous potassium hydroxide solution. Specifically, it can be measured according to the measurement method described in the Examples section below. Alternatively, the acid value of the resin (B) contained in the composition can be determined, for example, by performing a structural analysis thereof.

[0226] From the perspective of reducing film loss during development and increasing the luminescence intensity of the resulting cured film, resin (B) preferably comprises a resin having a double bond equivalent weight of 300 to 2000 g / eq, more preferably 320 to 1800 g / eq, even more preferably 340 to 1600 g / eq, and even more preferably 500 to 1500 g / eq. Examples of resins having a double bond equivalent weight of 300 to 2000 g / eq include (meth)acrylic resins. Resin (B) is preferably composed of a (meth)acrylic resin.

[0227] When the composition contains a resin (B), the content of the resin (B) in the composition is, for example, 5% to 80% by mass, preferably 10% to 70% by mass, more preferably 15% to 60% by mass, and even more preferably 15% to 50% by mass, relative to the total solid content of the composition. When the content of the resin (B) is within the above range, film loss during development is reduced, and the semiconductor particles (A) are easily dispersed, which tends to increase the luminescence intensity of the resulting cured film.

[0228] When the composition contains a resin (B), the content ratio of the semiconductor particles (A) to the resin (B) in the composition (semiconductor particles (A) / resin (B)) is, on a mass basis, for example, 4.0 or less, preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.2 or less, even more preferably 2.0 or less, and even more preferably 1.8 or less. Furthermore, from the viewpoint of increasing the luminous intensity of the resulting cured film, the above ratio is preferably 0.3 or greater, more preferably 0.35 or greater, even more preferably 0.4 or greater, and even more preferably 0.5 or greater.

[0229] When the composition contains a resin (B), from the viewpoint of reducing film reduction during development, the content ratio of the resin (B) to the polymerizable compound (C) in the composition (resin (B) / polymerizable compound (C)) is preferably 0.5 or more, more preferably 0.7 or more, further preferably 1.0 or more, and even more preferably 1.2 or more, and is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, and even more preferably 4 or less, on a mass basis.

[0230] <Polymerizable compound (C)>

[0231] The polymerizable compound (C) is a compound that can be polymerized by active radicals, acids, etc., and in particular, a compound that can be polymerized by active radicals, acids, etc. generated by the polymerization initiator (D) described below. The composition may contain one or more polymerizable compounds (C), and as the polymerizable compound (C), at least one 3 The polymerizable compound (C-1) contains a polymerizable compound (C-1) at a concentration of 1 mol or less. The composition contains the polymerizable compound (C-1), which reduces film loss during development, allows formation of a cured film having a more excellent residual film rate, and preferably also a cured film having excellent luminous intensity.

[0232] <<Polymerizable compound (C-1)>>

[0233] The molecular volume of the polymerizable compound (C-1) is 450 cm 3 / mol or less, preferably 430cm 3 / mol or less or 410cm 3 / mol or less, more preferably 400cm 3 / mol or below or 390cm 3 / mol or less, more preferably 380cm 3 / mol or below or 370cm 3 / mol or less, more preferably 360cm 3 / mol or below or 350cm 3 / mol or less, more preferably 340cm 3 / mol or less, and more preferably 330cm 3 / mol or less. In addition, the molecular volume of the polymerizable compound (C-1) is preferably 70 cm 3 / mol or above or 90cm 3 / mol or more, more preferably 100cm 3 / mol or above, 110cm 3 / mol or above or 120cm 3 / mol or more, more preferably 130cm 3 / mol or above, 140cm 3 / mol or above or 150cm 3 / mol or more, more preferably 160cm 3 / mol or above, 170cm 3 / mol or above or 180cm 3 / mol or more, more preferably 190cm 3 / mol and above, 200cm 3 / mol or above or 210cm 3 / mol or more, and more preferably 220cm 3 / mol or more, and more preferably 250cm 3 When the molecular volume of the polymerizable compound (C-1) is within the above range, a composition capable of forming a cured film having a high residual film rate during development and excellent luminescence intensity can be obtained.

[0234] The molecular volume is a value that varies depending on the size of atoms constituting a compound, the three-dimensional structure, the intermolecular force, and the like.

[0235] The molecular volume of the polymerizable compound (C) can be determined based on its molecular structure by DFT (Density Functional Theory; B3LYP / 6-31G) calculation using general calculation software. Examples of calculation software include the quantum chemical calculation program "Gaussian Series" manufactured by HULINKS.

[0236] From the perspective of improving the residual film rate during development and forming a cured film with good luminous intensity, the absorbance of the polymerizable compound (C-1) at a wavelength of 300 nm when prepared as a solution with a concentration of 1 mg / 100 mL is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less. As the solvent used in the above absorbance measurement, it is preferred to use a solvent that dissolves the polymerizable compound (C-1) and has good transparency. Such a solvent is preferably used. As the solvent, for example, the solvents described below as solvent (I) that can be contained in the composition can be preferably mentioned. From the perspective of solubility, propylene glycol monomethyl ether acetate is particularly preferred. The above absorbance is preferably satisfied also at wavelengths greater than 300 nm. For example, it is preferably satisfied over the entire wavelength range of 300 nm to 500 nm (i.e., the absorbance is 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less), and more preferably satisfied over the entire wavelength range of 300 nm to 700 nm.

[0237] From the perspective of improving the residual film rate during development, the polymerizable compound (C-1) preferably has one or more polymerizable functional groups in the molecule, and more preferably has two or more polymerizable functional groups. The upper limit of the polymerizable functional groups is not particularly limited, and for example, it is 6 or less, preferably 4 or less, and more preferably 3 or less. In addition, the polymerizable compound (C-1) preferably has 2, 4, or 6 polymerizable functional groups in the molecule, more preferably has 2 or 4 polymerizable functional groups, and particularly preferably has 2 polymerizable functional groups.

[0238] When the polymerizable compound (C-1) has two or more polymerizable functional groups in the molecule, it may have only one type of polymerizable functional group or may have two or more types, but preferably has only one type.

[0239] Examples of the polymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a (meth)acryloyloxy group, an oxirane group, and an oxetane group. From the viewpoint of improving the residual film rate during development and forming a cured film having good luminescence intensity, the polymerizable functional group possessed by the polymerizable compound (C-1) is preferably a (meth)acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxirane group, and an oxetane group, more preferably a (meth)acryloyloxy group, and still more preferably an acryloyloxy group.

[0240] From the perspective of improving the residual film rate during development and forming a cured film with good luminescence intensity, the polymerizable compound (C-1) preferably has one or more cyclic hydrocarbon groups in the molecule. The cyclic hydrocarbon group is a group obtained by removing the same number of hydrogen atoms as the number of bonding sites from a cyclic hydrocarbon. Examples of the cyclic hydrocarbon include aromatic hydrocarbons and alicyclic hydrocarbons.

[0241] The aromatic hydrocarbons may be monocyclic or polycyclic. Examples of the aromatic hydrocarbons include benzene, indene, naphthalene, azulene, fluorene, anthracene, tetracene, and biphenyl. The number of carbon atoms in the aromatic hydrocarbon is preferably 4 to 25, more preferably 4 to 20, even more preferably 6 to 14, and even more preferably 6 to 12. From the perspective of improving the residual film rate during development and forming a cured film with good luminescence intensity, the aromatic hydrocarbons are preferably benzene, naphthalene, and biphenyl, with benzene being particularly preferred.

[0242] The above-mentioned alicyclic hydrocarbons may be saturated or unsaturated, and may be monocyclic or polycyclic. Examples of saturated monocyclic hydrocarbons include cycloalkanes such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, and cyclooctane. Examples of unsaturated monocyclic hydrocarbons include cycloalkenes such as cyclopentene, cyclohexene, and cyclooctene; cycloadienes such as cyclooctadiene; and cycloalkynes such as cyclooctyne. Examples of saturated polycyclic hydrocarbons include bicyclo[2.1.0]pentane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, decahydronaphthalene, adamantane, tricyclo[3.2.1.0 2,7 ]Octane, tricyclic [5.2.1.0 2,6 ] decane and other bridged ring hydrocarbons; spiro ring hydrocarbons such as spiro [4.5] decane and dispiro [4.2.4.2] tetradecane. Examples of unsaturated polycyclic hydrocarbons include bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6]dec-3,8-diene, etc. The number of carbon atoms in the alicyclic hydrocarbon is preferably 3 to 25, more preferably 4 to 20, even more preferably 5 to 15, and even more preferably 7 to 12. From the viewpoint of improving the residual film rate during development and forming a cured film with good luminescence intensity, the alicyclic hydrocarbon is preferably a saturated alicyclic hydrocarbon, more preferably a saturated polycyclic hydrocarbon, and particularly preferably a saturated bridged ring hydrocarbon having 7 to 12 carbon atoms.

[0243] From the viewpoint of improving the residual film rate during development and forming a cured film with good luminous intensity, the polymerizable compound (C-1) preferably has in the molecule at least one aromatic hydrocarbon group (a group obtained by removing hydrogen atoms having the same number as the number of bonding sites from an aromatic hydrocarbon) and in the molecule at least one six-membered ring monocyclic hydrocarbon group (a group obtained by removing hydrogen atoms having the same number as the number of bonding sites from a monocyclic hydrocarbon) or both, and in particular preferably has in the molecule at least one six-membered ring aromatic hydrocarbon group.

[0244] The above-mentioned aromatic hydrocarbon group, six-membered ring monocyclic hydrocarbon group, etc. are preferably included in the polymerizable compound (C-1) together with the hydrocarbon chain. Examples of the hydrocarbon chain include alkanes such as ethane, propane, butane, and pentane, which may be linear or branched, preferably linear. In addition, the number of carbon atoms in the hydrocarbon chain is, for example, 2 to 20, preferably 3 to 10, and more preferably 3 to 5. When the hydrocarbon chain is regarded as the main chain, the aromatic hydrocarbon group, six-membered ring monocyclic hydrocarbon group, etc., together with the polymerizable functional group, constitute a side chain, and the side chain is bonded to the above-mentioned main chain.

[0245] In addition, the molecular volume is suppressed to 450 cm 3 From the viewpoint of the number of cyclic hydrocarbon groups in the polymerizable compound (C-1) being less than 3 / mol, the number of cyclic hydrocarbon groups in the molecule is preferably 3 or less, more preferably 2 or less. In the present specification, when counting the number of rings, for cyclic hydrocarbon groups having a condensed ring structure (e.g., naphthalene, tricyclic [5.2.1.0 2,6 ] decane, etc., by removing the number of hydrogen atoms that constitute the bonding sites, and the fused ring is counted as 1 ring. Therefore, a compound such as a spiro compound, in which two rings are bonded together sharing one carbon atom, has 2 rings.

[0246] When the polymerizable compound (C-1) contains two or more cyclic hydrocarbon groups, the two or more cyclic hydrocarbon groups are preferably linked by a hydrocarbon group. Examples of such hydrocarbon groups include groups obtained by removing a number of hydrogen atoms equal to the number of linked cyclic hydrocarbon groups from an alkane such as methane, ethane, or propane. The number of carbon atoms in such hydrocarbon group is, for example, 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

[0247] The polymerizable compound (C-1) preferably has a symmetrical structure. Here, a symmetrical structure refers to a structure having a molecular center and two identical structural parts bonded to the above-mentioned center. The center of a molecule is usually on an atom, or on a bond connecting atoms, and a ring (including a condensed ring) can also be regarded as a center. When the center is a ring (including a condensed ring), the ring (including a condensed ring) itself may not have symmetry. The two or more structural parts bonded to the center are respectively composed of one or more monovalent groups bonded to the above-mentioned center. In this case, since the structural parts are identical to each other, for example, when the structural part has two or more monovalent groups A and B, the two structural parts bonded to the center will have the same monovalent groups A and B. When one structural part has two or more organic groups, they may be bonded to each other.

[0248] The structural portion bonded to the center preferably has one monovalent group. Furthermore, when the structural portion has two or more monovalent groups, the molecular weight of one group is 100 or more, preferably 120 or more, more preferably 130 or more, and the molecular weights of the remaining groups are preferably less than 100. Polymerizable compounds having such structural portions tend to form rod-shaped molecules, which is preferred from the perspective of achieving a good residual film rate during development. It should be noted that when two or more monovalent groups contained in one structural portion are bonded to each other, the molecular weight of the group is the value obtained by dividing the molecular weight after bonding by the number of bonded groups.

[0249] The polymerizable compound (C-1) is preferably a compound without a quaternary carbon atom (C-1a), or a compound with a quaternary carbon atom in which at least one, preferably two, of the four groups bonded to the quaternary carbon atom has a molecular weight of 50 or less, and the remaining groups have a molecular weight of greater than 50 (C-1b). Such a polymerizable compound also tends to form rod-shaped molecules, which is preferred from the perspective of achieving a good residual film rate during development. When two or more groups bonded to a quaternary carbon atom are bonded to each other, the molecular weight of the group is the value obtained by dividing the molecular weight after bonding by the number of bonded groups.

[0250] The polymerizable compound (C-1) preferably has 1 to 3 cyclic hydrocarbon groups in the molecule, more preferably has 1 to 3 cyclic hydrocarbon groups in the molecule and has two or more polymerizable functional groups in the molecule, and even more preferably has 1 to 3 cyclic hydrocarbon groups in the molecule and has two polymerizable functional groups in the molecule.

[0251] As the polymerizable compound (C-1), for example, tricyclic [5.2.1.0 2,6] decanedimethanol diacrylate (specifically, trade name "IRR214-K"; manufactured by Daicel Allnex, etc.), ethylene oxide-modified bisphenol diacrylate (specifically, trade name "EBECRYL150"; manufactured by Daicel Allnex, etc.). In addition, as the polymerizable compound (C-1), a compound that does not have a cyclic hydrocarbon group in the molecule, for example, 1,6-hexanediol diacrylate is preferred.

[0252] From the viewpoint of improving the residual film rate and luminous intensity of the film, the content of the polymerizable compound (C) in the composition is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 40% by mass, further preferably 5% by mass to 30% by mass, and even more preferably 10% by mass to 25% by mass relative to the total amount of solid components of the composition.

[0253] From the viewpoint of improving the residual film rate during development, the content of the polymerizable compound (C-1) in the composition is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, further preferably 3% by mass to 30% by mass, further preferably 5% by mass to 25% by mass, and even more preferably 5% by mass to 20% by mass, relative to the total solid content of the composition.

[0254] From the viewpoint of improving the residual film rate during development, the content of the polymerizable compound (C-1) in the polymerizable compound (C) is preferably 35% by mass to 100% by mass, more preferably 40% by mass to 95% by mass, further preferably 45% by mass to 90% by mass, further preferably 50% by mass to 80% by mass, and even more preferably 55% by mass to 70% by mass, relative to the total amount of the polymerizable compound (C).

[0255] The polymerizable compound (C) preferably contains at least one compound having three or more polymerizable functional groups (for example, a group having an ethylenically unsaturated bond, preferably a (meth)acryloyloxy group, more preferably an acryloyloxy group) in the molecule and having an acidic functional group (hereinafter also referred to as "polymerizable compound (C-2)").

[0256] Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among them, the acidic functional group is preferably a carboxyl group.

[0257] When the polymerizable compound (C) in the composition includes the polymerizable compound (C-2), the dispersibility of the semiconductor particles (A) can be improved, thereby increasing the luminescence intensity of the wavelength conversion layer. Furthermore, when the polymerizable compound (C) includes the polymerizable compound (C-2), the curability and heat resistance of the composition can be improved.

[0258] The number of polymerizable functional groups (particularly (meth)acryloyloxy groups) possessed by one molecule of the polymerizable compound (C-2) is, for example, 3 to 6, preferably 3 to 5, and more preferably 3. The number of acidic functional groups possessed by one molecule of the polymerizable compound (C-2) is 1 or more, preferably 1. When the polymerizable compound (C-2) has two or more acidic functional groups, the acidic functional groups may be different or the same, and preferably have at least one carboxyl group.

[0259] The polymerizable compound (C-2) preferably does not have a cyclic hydrocarbon group in the molecule.

[0260] Examples of the polymerizable compound (C-2) include compounds obtained by esterifying a compound having three or more (meth)acryloyloxy groups and hydroxyl groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid. Examples of such compounds include compounds obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, compounds obtained by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, compounds obtained by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and compounds obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Among these, compounds obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid are preferred.

[0261] Examples of commercially available polymerizable compounds (C-2) include "Aronix M-510" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate as a main component, and "Aronix M-520D" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate as a main component. These commercially available products have a carboxyl group as an acidic functional group.

[0262] When the polymerizable compound (C) contains the polymerizable compound (C-2), the content thereof is preferably 1% by mass to 65% by mass, more preferably 5% by mass to 60% by mass, further preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass, relative to the total amount of the polymerizable compound (C).

[0263] When the polymerizable compound (C) contains the polymerizable compound (C-2), the content ratio of the polymerizable compound (C-2) to the polymerizable compound (C-1) (polymerizable compound (C-2) / polymerizable compound (C-1)) is preferably 0.10 to 1.0, more preferably 0.20 to 0.90, further preferably 0.30 to 0.85, and even more preferably 0.40 to 0.80 on a mass basis.

[0264] The total content of the polymerizable compound (C-1) and the polymerizable compound (C-2) in 100 parts by mass of the polymerizable compound (C) is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, further preferably 90 to 100 parts by mass, and particularly preferably 100 parts by mass.

[0265] From the viewpoint of film curability, the content of the monofunctional polymerizable compound having one polymerizable functional group in the molecule of the polymerizable compound (C) is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less, relative to the total amount of the polymerizable compound (C). It can also be 0% by mass.

[0266] <Polymerization initiator (D)>

[0267] The polymerization initiator (D) is a compound that generates active radicals, acids, etc. under the action of light or heat to initiate polymerization of the polymerizable compound (C). The composition may contain one or more polymerization initiators (D).

[0268] Examples of the polymerization initiator (D) 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.

[0269] 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)".

[0270]

[0271] [In formula (1), R 1 Represents R 11 , OR 11 、COR 11 SR 11 、CONR 12 R 13 or CN. * represents a bonding site with the second molecular structure, which is another molecular structure other than the first molecular structure of the oxime compound (1).]

[0272] From the perspective of increasing the luminescence intensity of the cured film, it is advantageous to include an oxime compound (1) as the polymerization initiator (D). One factor contributing to this effect is presumably that 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, changes significantly due to the unique molecular structure of the oxime compound (1), resulting in a high photoradical polymerization initiation ability of the oxime compound (1).

[0273] 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.

[0274] By R 11 、R 12 or R 13 The hydrogen atoms of the group represented by OR 21 、COR 21 SR 21 NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms or COOR 21 replace.

[0275] 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.

[0276] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0277] 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 can be represented 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.

[0278] 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.

[0279] 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 form a ring together.

[0280] 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.

[0281] 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 represented by phenyl include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthrenyl, and phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0282] 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 represented by alkyl include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0283] 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, isothiazolidinyl, Oxazolidinyl, isocyanate oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, etc., preferably a five- to seven-membered heterocyclic ring.

[0284] R in formula (1) 12 With R 13 and R 22 With R 23 can form a ring together R 12 With R 13 and R 22 With R 23 They can form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

[0285] As R in formula (1) 12 With R 13 and R 22 With R 23 Examples 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 five- to seven-membered ring is preferred.

[0286] 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 present as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0287] 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.

[0288] 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).

[0289] 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).

[0290]

[0291] [In formula (2),

[0292] 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 atom.

[0293] There are multiple R 2 When , they may be the same or different.

[0294] There are multiple R 3 When , they may be the same or different.

[0295] R 11 、R 12 and R 13 Means the same as above.

[0296] s and t each independently represent an integer of 0-4.

[0297] L represents a sulfur atom, CR 31 R 32 , CO or NR 33 .

[0298] R 31 、R 32 and R 33Each 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.

[0299] 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 of them can independently form a ring together with an adjacent benzene ring.

[0300] R 4 It represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-1).

[0301] (R 4a ) v -L 2 -L 1 - (2-1)

[0302] [In formula (2-1),

[0303] L 1 Indicates -O-, -S-, and -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0304] R 22 Means the same as above.

[0305] 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.

[0306] L 2 When the group represented by has an alkylene moiety, the alkylene moiety can be represented 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.

[0307] R 4a Indicates OR 41 SR 41 、CONR42 R 43 NR 42 COR 43 , OCOR 41 、COOR 41 SCOR 41 , OCSR 41 、COSR 41 , CSOR 41 , CN or halogen atom.

[0308] There are multiple R 4a When , they may be the same or different.

[0309] 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.

[0310] v represents an integer from 1 to 3.]

[0311] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0312] R in formula (2) 11 、R 12 、R 13 、R 21 、R 22 、R 23 、R 24 、R 31 、R 32 and R 33 , and R in the above formula (2-1) 22 、R 41 、R 42 and R 43 Examples of 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 Same as the example.

[0313] 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 Same as the example.

[0314] R in formula (2) 31 、R 32 and R 33 Each of the R rings can independently form a ring with an adjacent benzene ring. 31 、R 32 and R 33 Each of them can independently form a ring together with an adjacent benzene ring and the nitrogen atom to which it is connected.

[0315] R in formula (2) 31 、R 32 and R 33 Examples of rings that can be formed together with an adjacent benzene ring are the same as R in formula (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0316] L in the above formula (2-1) 2 It represents 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 group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms.

[0317] 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.

[0318] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v is 1, 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.

[0319] 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).

[0320]

[0321] [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.]

[0322] 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.

[0323] 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. divalent heterocyclic groups such as oxadiyl and the like.

[0324] 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.

[0325] From the viewpoint of solubility in the solvent (I) and developability of the composition, a preferred example of the structure represented by formula (2) is a structure represented by the following formula (2a).

[0326]

[0327] [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. * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0328] 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).

[0329]

[0330] [In formula (2b), R 44 represents a hydroxyl group, a carboxyl group, or a group represented by the following formula (2-2).

[0331] R 44a -L 12 -L 11 - (2-2)

[0332] [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 OR 55 or COOR 55 , R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0333] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0334] R 44 The group represented by formula (2-2) is preferred. In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (I) and the developability of the composition.

[0335] L 12 The number of carbon atoms of the alkylene group represented by is preferably 1 to 10, more preferably 1 to 4.

[0336] R 44aIt is preferably a hydroxy group or a carboxyl group, and more preferably a hydroxy group.

[0337] 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.

[0338] 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).

[0339] 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).

[0340]

[0341] [In formula (3),

[0342] 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.

[0343] R 5 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0344] 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(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 , CSOR21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0345] R 21 、R 22 and R 23 Means the same as above.

[0346] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0347] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety can be represented 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.

[0348] R 24 Means the same as above.

[0349] 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.

[0350] R 6 、R 7 、R 8 and R 9 Each independently represents R 61 , OR 61 SR 61 、COR 62 、CONR 63 R 64 NR 65 COR 61 , OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 , CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0351] 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.

[0352] 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 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms or COOR 21 replace.

[0353] R 6 With R 7 、R 7 With R 8 and R 8 With R 9 They can form a ring together.

[0354] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0355] 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 Same as the example.

[0356] 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 it is connected, they can form a ring.

[0357] R in formula (3) 22 With R 23 Examples of rings that can be formed together are the same as R in formula (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0358] 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.

[0359] From the viewpoint of solubility in the solvent (I) and developability of the composition, in one preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0360]

[0361] [In formula (3-1),

[0362] 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,

[0363] When the group represented by Z has an alkylene moiety, the alkylene moiety can be represented 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.

[0364] R 21 、R 22 and R 24 Means the same as above.]

[0365] From the same viewpoint as described above, Z in formula (3-1) is preferably a methylene group, an ethylene group, or a phenylene group.

[0366] 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.

[0367] From the same viewpoint as above, in another preferred embodiment, R 7 For nitro.

[0368] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and for example, it can be produced by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0369] 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).

[0370] 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).

[0371]

[0372] [In formula (4),

[0373] 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.

[0374] R 71When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0375] R 71 The hydrogen atom 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.

[0376] R 21 、R 22 and R 23 Means the same as above.

[0377] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0378] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety can be represented 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.

[0379] R 24 Means the same as above.

[0380] 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.

[0381] 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 atom.

[0382] 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.

[0383] 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 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R22 , CN, halogen atoms or COOR 21 replace.

[0384] R 72 With R 73 and 2 R 74 They can form a ring together.

[0385] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0386] 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 Same as the example.

[0387] R in formula (4) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0388] R in formula (4) 22 With R 23 Examples of rings that can be formed together are the same as R in formula (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0389] 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.

[0390] 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.

[0391] 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).

[0392] 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).

[0393]

[0394] [In formula (5),

[0395] 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.

[0396] R 81 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0397] 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 COR 21 , OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22SCOR 21 , OCSR 21 、COSR 21 , CSOR 21 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0398] R 21 、R 22 and R 23 Means the same as above.

[0399] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0400] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety can be represented 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.

[0401] R 24 Means the same as above.

[0402] 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.

[0403] 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 , OCSR61 、COSR 62 , CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0404] 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.

[0405] 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 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms or COOR 21 replace.

[0406] R 83 With R 84 、R 84 With R 85 and R 85 With R 86 They can form a ring together.

[0407] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0408] R in formula (5) 81 、R 21 、R 22 、R 23 、R 24 、R 61 、R 62 、R 63 、R 64 and R 65Examples 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 Same as the example.

[0409] R in formula (5) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0410] R in formula (5) 22 With R 23 Examples of rings that can be formed together are the same as R in formula (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0411] 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.

[0412] 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.

[0413] 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).

[0414] 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).

[0415]

[0416] [In formula (6),

[0417] 4 Rs 91 、R 92 、R 93 、R 94 、R 95 、R 96 and R 97 Each independently represents R 61 , OR 61 SR 61 、COR 62 、CONR 63 R 64 NR 65 COR 61 , OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 , CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0418] 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.

[0419] 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 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms or COOR 21 replace.

[0420] R 21 、R 22 and R 23 Means the same as above.

[0421] R 92 With R 93 、R 94 With R 95 、R 95 With R 96 and R 96 With R 97 They can form a ring together.

[0422] * represents the bonding site with the first molecular structure of the oxime compound (1).]

[0423] 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 Same as the example.

[0424] R in formula (6) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0425] R in formula (6) 22 With R 23 Examples of rings that can be formed together are the same as R in formula (1). 12 With R 13 and R 22 With R 23 The same applies to examples of rings that can be formed together.

[0426] 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.

[0427] 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.

[0428] As one example of the oxime compound (excluding the oxime compound (1)), there is a compound represented by the following formula (DA).

[0429]

[0430] [Where,

[0431] R d1 It represents a branched hydrocarbon group having 3 to 20 carbon atoms which may have a substituent.

[0432] R d2 ~R d5 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0433] n represents any integer from 0 to 4.

[0434] The -CH2- contained in the above hydrocarbon group may be substituted with -O-, -S-, -CO- or -OCO-.]

[0435] As R d1 Examples of the branched hydrocarbon group having 3 to 20 carbon atoms include a branched saturated hydrocarbon group having 3 to 20 carbon atoms and a branched unsaturated hydrocarbon group having 3 to 20 carbon atoms.

[0436] As R d1The branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by butyl includes, for example, 1-methylethyl (isopropyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl), 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl 1-Methylhexyl, 2-Methylhexyl, 3-Methylhexyl, 4-Methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 2,3-dimethylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3 ,3-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 2,3-dimethylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 1,1-dimethylheptyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 2,3-dimethylheptyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 1-methyloctyl, 2-methyloctyl, 3 branched-chain alkyl groups such as 1-methyloctyl, 4-methyloctyl, 1,1-dimethyloctyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 1,2-dimethyloctyl, 1,3-dimethyloctyl, 2,3-dimethyloctyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, dimethylnonyl, ethylnonyl, methyldecyl, dimethyldecyl, ethyldecyl, methylundecyl, dimethylundecyl, ethylundecyl, and methyldodecyl.

[0437] R d1 The branched alkyl group represented by may be any of a branched primary alkyl group, a branched secondary alkyl group, and a branched tertiary alkyl group.

[0438] R d1 The number of carbon atoms in the branched saturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

[0439] As R d1 The branched unsaturated hydrocarbon group represented by d1A group in which at least one carbon-carbon single bond contained in a branched saturated hydrocarbon group represented by is substituted with a carbon-carbon double bond or a carbon-carbon triple bond.

[0440] As R d1 The branched unsaturated hydrocarbon group represented by , for example, can include alkenyl groups such as isopropenyl, isobutenyl, isopentenyl, isohexenyl, isoheptenyl, isooctenyl, isononenyl, and isodecenyl; and alkynyl groups such as isopropynyl, isobutynyl, isopentenyl, isohexynyl, isoheptynyl, isooctynyl, isononynyl, and isodecenyl.

[0441] R d1 The number of carbon atoms in the branched unsaturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

[0442] As R d2 、R d3 、R d4 and R d5 The hydrocarbon group having 1 to 20 carbon atoms represented by R includes saturated hydrocarbon groups having 1 to 20 carbon atoms, unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. d2 、R d3 、R d4 and R d5 The hydrocarbon groups represented by may be the same or different.

[0443] Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The saturated hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8 carbon atoms.

[0444] Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and eicosenyl; alkynyl groups such as ethynyl, propynyl, hexynyl, decynyl, and eicosynyl; and cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl. The unsaturated hydrocarbon group preferably has 2 to 18 carbon atoms, more preferably 2 to 15, and even more preferably 2 to 10 carbon atoms.

[0445] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, xylyl, trimethylphenyl, dipropylphenyl, di(2,2-dimethylpropyl)phenyl, naphthyl, benzyl, phenylethyl, and phenylbutyl. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 15, and even more preferably 6 to 12 carbon atoms.

[0446] As R d1 、R d2 、R d3 、R d4 and R d5 The substituents that the hydrocarbon group represented by may have include a halogen atom, a cyano group, a nitro group, etc. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom.

[0447] The -CH2- contained in the above hydrocarbon group can be substituted by -O-, -S-, -CO- or -OCO-, the adjacent -CH2- will not be substituted by the same group at the same time, and the terminal -CH2- will not be substituted.

[0448] n represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and even more preferably 0.

[0449] *-OCO-R d4 The bonding position of the group (* represents the bonding site to the phenyl group) can be the *-OCO-R d4 The phenyl group to which the phenyl group is bonded is at any of the 2-position, 3-position, or 4-position, preferably the 3-position or the 4-position, and more preferably the 4-position.

[0450] R d1 The branched hydrocarbon group having 3 to 20 carbon atoms represented by is preferably a branched saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 3 to 20 carbon atoms, further preferably a branched alkyl group having 3 to 10 carbon atoms, and preferably one or more members selected from the group consisting of 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 1-ethylheptyl, 2-ethylheptyl and 3-ethylheptyl.

[0451] R d2 、R d3 、R d4 and R d5The hydrocarbon group having 1 to 20 carbon atoms represented by is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, further preferably a chain saturated hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a chain alkyl group having 1 to 8 carbon atoms.

[0452] R d2 A chain alkyl group having 1 to 8 carbon atoms is preferred, and a chain alkyl group having 1 to 6 carbon atoms is more preferred.

[0453] R d3 A chain alkyl group having 1 to 8 carbon atoms is preferred, and a chain alkyl group having 1 to 3 carbon atoms is more preferred.

[0454] R d4 A chain alkyl group having 1 to 8 carbon atoms is preferred, and a chain alkyl group having 1 to 3 carbon atoms is more preferred.

[0455] R d5 It is preferably a chain or branched alkyl group having 1 to 8 carbon atoms, and more preferably a chain or branched alkyl group having 1 to 6 carbon atoms.

[0456] Other examples of photopolymerization initiators include photopolymerization initiators other than the oxime compound (1) and the compound represented by formula (DA). Examples of other photopolymerization initiators include oxime compounds other than the oxime compound (1) and the compound represented by formula (DA), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0457] Examples of oxime compounds other than the oxime compound (1) and the compound represented by formula (DA) include oxime compounds having a partial structure represented by the following formula (d1): * represents a bonding site.

[0458]

[0459] Examples of the oxime compound having a partial structure represented by formula (d1) include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-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-dioxolane)-1-imine,

[0014] Examples of the present invention include N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in Japanese Patent Application Laid-Open No. 2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, and International Publication No. 2012 / 132558. Commercially available products such as Irgacure (registered trademark) OXE01, Irgacure OXE02, and Irgacure OXE03 (all manufactured by BASF), N-1919, NCI-930, and NCI-831 (all manufactured by ADEKA) can also be used.

[0460] Among them, the oxime compound having a partial structure represented by formula (d1) is preferably at least one selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine.

[0461] The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the following formula (d3). In these partial structures, the benzene ring may have a substituent. * represents a bonding site.

[0462]

[0463] Examples of the compound having a structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butan-1-one. Commercially available products such as OMNIRAD (registered trademark) 369, OMNIRAD 907, and OMNIRAD 379 (all manufactured by IGM Resins) can also be used.

[0464] 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 benzyl dimethyl ketal.

[0465] In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

[0466] Examples of the biimidazole compound include compounds represented by formula (d5).

[0467]

[0468] [In formula (d5), R E ~R J represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

[0469] Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.

[0470] 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.

[0471] 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 Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (for example, see JP-A-48-38403 and JP-A-62-174204), and the like. Among them, compounds represented by the following formulas or mixtures thereof are preferred.

[0472]

[0473] 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.

[0474] 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) can also be used.

[0475] Examples of other photopolymerization initiators other than the oxime compound (1) and the compound represented by the formula (DA) 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 benzoylformate, and titanocene compounds.

[0476] As the polymerization initiator (D), an oxime compound having a second molecular structure represented by the above-mentioned formula (2) bonded to the first molecular structure represented by the above-mentioned formula (1), in particular an oxime compound having a structure represented by the above-mentioned formula (2b), and / or a compound represented by the above-mentioned formula (EA) are preferred. An oxime compound having a second molecular structure represented by the above-mentioned formula (2) bonded to the first molecular structure represented by the above-mentioned formula (1), in particular an oxime compound having a structure represented by the above-mentioned formula (2b), is more preferred.

[0477] When the composition contains a polymerization initiator (D), the content of the polymerization initiator (D) in the composition is, for example, 0.01% by mass to 20% by mass relative to the total amount of the solid content of the composition. From the viewpoint of improving the sensitivity of the composition and improving the luminous intensity and heat resistance of the film, it is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, further preferably 0.3% by mass to 8% by mass, and even more preferably 0.5% by mass or more and 5% by mass or less or 3% by mass or less.

[0478] The content of the polymerization initiator (D) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the polymerizable compound (C), and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, a composition capable of forming a cured film having a further improved residual film rate can be obtained, and a composition capable of forming a cured film having excellent heat resistance can also be obtained.

[0479] Light scattering agent (E)

[0480] The composition may contain a light scattering agent (E). A film formed from the composition can exhibit light scattering properties. In a film containing a light scattering agent (E) in addition to semiconductor particles (A), the light scattering agent (E) can enhance the luminous intensity by scattering light emitted by the semiconductor particles (A). The composition may contain one or more light scattering agents (E).

[0481] As light scattering agents (E), inorganic particles such as particles of metals or metal oxides, and glass particles can be mentioned. As metal oxides, TiO2, SiO2, BaTiO3, ZnO, etc. can be mentioned. Since they effectively scatter light, particles of TiO2 are preferred. The average particle size (D50) of the light scattering agent (E) is, for example, about 0.03 μm to 20 μm, preferably 0.05 μm to 1 μm, and more preferably 0.05 μm to 0.5 μm. The average particle size of the light scattering agent (E) can be measured using a centrifugal sedimentation dispersion stability particle size distribution device to measure the particle size distribution, and is measured as a volume-based median particle size (D50).

[0482] As the light scattering agent (E), a dispersion obtained by preliminarily dispersing the light scattering agent in a part or all of the solvent (I) using a dispersant can be used. As the dispersant, a commercially available product can be used. Examples of commercially available dispersants include:

[0483] BYK-Chemie Japan's DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250; BYK- P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.;

[0484] SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Japan Lubrizol;

[0485] EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF;

[0486] Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Precision Technology Co., Ltd.

[0487] The content of the light scattering agent (E) in the composition is, for example, 0.001 to 50% by mass, and from the viewpoint of improving the light scattering energy and luminous intensity of the cured film, preferably 1 to 30% by mass, and more preferably 2 to 15% by mass, relative to the total solid content of the composition.

[0488] <Antioxidant (F)>

[0489] The composition may contain an antioxidant (F). The antioxidant (F) is not particularly limited as long as it is an antioxidant commonly used in industry, and phenolic antioxidants, phosphorus-based antioxidants, phosphorus / phenol composite antioxidants, and sulfur-based antioxidants can be used. Two or more antioxidants (F) may be used in combination.

[0490] The phosphorus / phenol complex antioxidant may be a compound having one or more phosphorus atoms and a phenol structure in each molecule. From the viewpoint of the luminescence intensity of the cured film, the antioxidant (F) preferably contains a phosphorus / phenol complex antioxidant.

[0491] Examples of the phenolic antioxidant include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox (registered trademark) 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), and Irganox (registered trademark) 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), Irganox (registered trademark) 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF), Irganox (registered trademark) 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF), Irganox (registered trademark) 1035 (Irganox 1035: diethylene sulfide bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox (registered trademark) 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of phenylpropionic acid, manufactured by BASF), Irganox (registered trademark) 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF), Irganox (registered trademark) (Irgano X3125, manufactured by BASF), Irganox (registered trademark) 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF), ADKSTAB (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 (registered trademark) GA-80, Sumilizer (registered trademark) GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by Sitech Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0492] Examples of phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos (registered trademark) 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 (registered trademark) 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Corporation), ADKSTAB (registered trademark) 329K, ADKSTAB (registered trademark) PEP36, and ADKSTAB (registered trademark) PEP-8 (all manufactured by ADEKA Corporation), and Sandstab P-EPQ (manufactured by Clariant AG), Weston (registered trademark) 618, Weston (registered trademark) 619G (all manufactured by GE), Ultranox 626 (manufactured by GE), and the like.

[0493] Examples of phosphorus / phenol composite antioxidants include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphopeptane) (manufactured by Sumitomo Chemical Co., Ltd.).

[0494] Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and β-alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0495] When the composition contains an antioxidant (F), the content of the antioxidant (F) in the composition is, for example, 0.05% by mass to 20% by mass, preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and even more preferably 0.5% by mass to 5% by mass, relative to the total amount of solids in the composition.

[0496] <Solvent (I)>

[0497] The composition may contain a solvent (I). Examples of the solvent (I) include ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (solvents containing OH and no -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide. Two or more solvents (I) may be used in combination.

[0498] Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0499] 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-dimethoxy-1-butanol, 3-methoxy-3-methylbutanol ... 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.

[0500] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0501] 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.

[0502] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycidol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0503] The solvent (I) is preferably propylene glycol monomethyl ether acetate, cyclohexyl acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone or toluene, or a mixture of two or more thereof.

[0504] The content of solvent (I) in the composition is the ratio of the total mass of all solvents contained in the composition to the total amount of the composition, and is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 100 parts by mass or more, and even more preferably 120 parts by mass or more, relative to 100 parts by mass of the solid content of the composition, and is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. When the content of solvent (I) is within the above range, the flatness of the composition layer during coating tends to be improved, and a cured film of an appropriate film thickness tends to be easily formed.

[0505] The solid content concentration of the composition is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass.

[0506] <Leveling agent (J)>

[0507] The composition may contain a leveling agent (J). Examples of the leveling agent (J) include silicone surfactants, fluorine-based surfactants, and silicone surfactants containing fluorine atoms. These may have polymerizable groups in their side chains. The composition may contain two or more leveling agents (J).

[0508] Examples of the silicone 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 names: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0509] Examples of fluorine-based surfactants 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 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.), etc.

[0510] 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).

[0511] When the composition contains a leveling agent (J), the content of the leveling agent (J) in the composition is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.3% by mass, and even more preferably 0.01 to 0.2% by mass, relative to the total solid content of the composition.

[0512] <Other ingredients>

[0513] The composition may further contain additives known in the art, such as a polymerization inhibitor, a filler, other polymer compounds, an adhesion promoter, a light stabilizer, and a polymerization initiation aid, as needed.

[0514] The composition of the present invention comprises semiconductor particles (A) and a polymerizable compound (C), and contains a molecular volume of 450 cm 3 The polymerizable compound (C-1) having a concentration of 100 mol or less as the polymerizable compound (C) can reduce film loss during development and form a cured film with an excellent residual film rate. In addition, the composition of the present invention can form a cured film with excellent luminescence intensity.

[0515] <Method for producing composition>

[0516] The composition can be produced by a method comprising the step of mixing predetermined components and, if necessary, other components. The method for producing the composition may further comprise the step of preparing the resin (B).

[0517] The method for producing the composition preferably comprises a first step of preparing a dispersion of semiconductor particles (A) as ligand-containing semiconductor particles, and a second step of mixing the dispersion with other predetermined components (and other components used as needed).

[0518] The viscosity of the composition at 25°C (viscosity at the time of composition preparation) is, for example, 1 cP to 3000 cP. From the perspective of improving the coating properties of the composition and the appearance of the formed film, it is preferably 2 cP to 2000 cP, more preferably 5 cP to 1000 cP, even more preferably 10 cP to 500 cP, and even more preferably 10 cP to 100 cP. The viscosity of the composition can be measured using a Brookfield rotational viscometer.

[0519] <Film and its manufacturing method>

[0520] The film of the present invention is a film formed from the composition of the present invention. The film production method includes, for example, the following steps.

[0521] a step of forming a composition layer by applying the composition to a substrate or spraying the composition onto a region partitioned by the bank on a substrate having the bank formed thereon, and

[0522] A step of heat-treating the composition layer.

[0523] The film may be formed on the entire surface of the substrate, or may be formed on a portion of the substrate surface (for example, in a pattern).

[0524] The film production method may include other steps in addition to the above-mentioned steps. Examples of the other steps include an exposure step of irradiating the composition layer with light and a development step of the composition layer after the exposure step.

[0525] In the step of forming the composition layer, methods for applying the composition to the substrate include spin coating, slit coating, and slit and spin coating. The step of forming the composition layer by spraying the composition may be a step of selectively spraying the composition onto the area defined by the bank using, for example, an inkjet method. A patterned composition layer may also be formed by stencil printing, screen printing, or printing and coating using an applicator.

[0526] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and substrates having thin films of aluminum, silver, or silver / copper / palladium alloy formed thereon.

[0527] A patterned film can be formed on a substrate, for example, by the following method: First, a patterned composition layer is formed by applying the composition onto the substrate through a mask or spraying the composition onto regions partitioned by banks.

[0528] Next, the composition layer is heat-treated to obtain a film. The heat treatment may include a drying step (a step of removing volatile components such as a solvent) of the composition layer. Examples of drying methods include heating drying, reduced-pressure drying, and a combination thereof. The temperature for heating drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When reduced-pressure drying is performed, it is preferably performed under a pressure of 50 Pa to 150 Pa. The drying of the composition layer may be carried out in multiple steps, for example, by performing multiple drying steps with different drying temperatures.

[0529] The step of heat-treating the composition layer may include the aforementioned drying step (pre-baking) followed by a subsequent post-baking step. The heating temperature in the baking step is preferably 30°C to 120°C, more preferably 50°C to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0530] Since the composition contains a polymerizable compound (C) and has curability, it is preferred to include the above-mentioned exposure step. For a patterned cured film formed by a photocurable composition, when a method using photolithography is cited as an example, for example, it can be formed on a substrate by the following operation. First, a composition layer is formed on a substrate, and a drying step of heating and drying (pre-baking) and / or drying under reduced pressure is implemented. As a method for forming and drying the composition layer, the same method as described above can be cited.

[0531] Next, the composition layer is exposed through a photomask formed into the desired pattern. The light source used for exposure is preferably one that generates light with a wavelength of 250 nm to 450 nm. For example, a bandpass filter can be used to selectively extract light near 436 nm, 408 nm, or 365 nm from this wavelength, depending on the absorption wavelength of the photopolymerization initiator. Specific examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0532] In order to uniformly irradiate the entire exposure surface with parallel light and accurately align the photomask with the substrate on which the composition layer is formed, it is preferred to use an exposure device such as a mask aligner and a stepper. The exposed composition layer is cured by polymerization of the polymerizable compound contained in the composition layer.

[0533] The exposed composition layer is brought into contact with a developer to carry out the above-mentioned development step, whereby the unexposed portion of the composition layer is dissolved in the developer and removed to obtain a patterned cured film. Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents. The concentration of the alkaline compound in the aqueous solution is preferably 0.01% to 10% by mass, more preferably 0.02% to 5% by mass. Examples of the organic solvent include the same solvents as those in the above-mentioned solvent (I). The developer may contain a surfactant.

[0534] The development method may be any of a spin immersion method, a dipping method, a spray method, etc. Furthermore, the substrate may be tilted at any angle during development.

[0535] It is preferred to further heat (post-bake) the patterned cured film obtained by development. The heating temperature is preferably 150°C to 250°C, more preferably 160°C to 235°C. The heating time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes. By heating after development, unreacted photopolymerizable compounds contained in the cured film can be polymerized, thereby obtaining a cured film with better chemical resistance. Even when development is not performed, it is preferred to further heat (post-bake) the exposed composition layer.

[0536] On the other hand, as a method for forming a cured film on the entire surface of a substrate, there is mentioned a method of forming a composition layer on a substrate, drying it as needed, heating the composition layer, and / or exposing the entire surface of the composition layer to light.

[0537] The thickness of the cured film (film thickness) is not particularly limited and can be appropriately selected depending on the intended purpose. For example, it is 1 μm to 30 μm, preferably 1 μm to 20 μm, more preferably 1.5 μm to 18 μm, further preferably 1.5 μm to 15 μm, further preferably 1.8 μm to 14 μm, further preferably 1.8 μm to 12 μm, and even more preferably 2 μm to 10 μm. The shape and size of the patterned cured film are not particularly limited. For example, the patterned cured film has a square shape when viewed from above.

[0538] The cured film of the present invention comprises semiconductor particles (A) and a polymerizable compound (C) having a molecular volume of 450 cm 3 Since the polymerizable compound (C-1) having an % content of 1 mol or less is formed as a composition of the polymerizable compound (C), the residual film rate is excellent, and further, a decrease in luminous intensity is suppressed, and preferably, the luminous intensity can be improved.

[0539] The cured film of the present invention preferably has an absorbance of 0.5 or less per unit film thickness (specifically, per 1 μm film thickness) at a wavelength of 300 nm, more preferably 0.3 or less. By setting this absorbance within the above range, the residual film rate of the cured film is improved, thereby suppressing the decrease in luminous intensity, and preferably increasing the luminous intensity. The above absorbance is preferably exhibited also at wavelengths greater than 300 nm, and in general, it is preferably exhibited at wavelengths of 300 nm or more. The upper limit of the wavelength required to exhibit the above absorbance is not particularly limited, and for example, it can be any of less than 800 nm, less than 780 nm, less than 700 nm, less than 600 nm, less than 500 nm, or less than 400 nm, or less than 350 nm.

[0540] The cured film obtained from the composition of the present invention preferably has a residual film rate after development of 5 μm in thickness, compared to that before development, of preferably 70% or more, more preferably 72% or more, even more preferably 74% or more, and even more preferably 75% or more. Specifically, it is preferred that the residual film rate after development at 25°C for 30 seconds be within the above range using a developer comprising a 0.02% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).

[0541] Furthermore, the cured film of the present invention preferably exhibits good luminescence intensity. Specifically, the luminescence intensity (unit luminescence intensity calculated according to the following formula) measured according to the measurement method described in the Examples section below is preferably 100 μW / μm or greater, more preferably 200 μW / μm or greater, even more preferably 300 μW / μm or greater, even more preferably 400 μW / μm or greater, even more preferably 500 μW / μm or greater, and even more preferably 540 μW / μm or greater or 560 μW / μm or greater.

[0542] Unit luminous intensity (μW / μm) = luminous intensity of cured film (μW) / average film thickness of cured film (μm)

[0543] <Display device>

[0544] The display device of the present invention includes at least a light source and the above-mentioned cured film. Examples of the display device include liquid crystal display devices, organic EL display devices, and inorganic EL display devices. Specific examples include display devices described in Japanese Patent Application Laid-Open Nos. 2006-309219, 2006-310303, 2013-15812, 2009-251129, and 2014-2363.

[0545] A display device according to one embodiment includes a backlight serving as a blue light source and multiple patterns disposed on the viewing side of the backlight. The multiple patterns may be a red pattern, a green pattern, and a white (transparent, achromatic) pattern, and at least one of the red and green patterns may be the cured film of the present invention. The red or green colored pattern containing semiconductor particles (A) has the function of converting the wavelength of incident light and emitting the light.

[0546] Example

[0547] 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 aforementioned and subsequent descriptions, and such modifications are encompassed within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0548] <Measurement and Evaluation>

[0549] (1) Weight average molecular weight Mw of resin (B)

[0550] The weight average molecular weight Mw of the resin (B) was measured by GPC method under the following conditions.

[0551] Device: K2479 (manufactured by Shimadzu Corporation)

[0552] Column: SHIMADZU Shim-pack GPC-80M

[0553] Column temperature: 40°C

[0554] Solvent: tetrahydrofuran

[0555] Flow rate: 1.0 mL / min

[0556] Detector: RI

[0557] Calibration standard substances: TSKSTANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0558] (2) Acid value of resin (B)

[0559] 3 g of the resin (B) solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. A 0.1-N aqueous KOH solution was used as a titrant. The acid value of the resin (B) solution was measured using an automatic titrator (manufactured by Hiranuma Industries, trade name: COM-555). The acid value Av (mgKOH / g) per 1 g of solid content was calculated based on the acid value of the solution and the solid content of the solution.

[0560] (3) Double bond equivalent of resin (B)

[0561] The double bond equivalent of the resin (B) is determined by dividing the total mass of the resin by the number of moles of radically polymerizable double bonds introduced into the resin.

[0562] (4) Solid content of resin (B) solution

[0563] About 1 g of the resin (B) solution was weighed in an aluminum cup, dried at 180°C for 1 hour, and then the mass was measured. The solid content (mass %) of the resin (B) solution was calculated based on the mass loss.

[0564] (5) Molecular volume of polymerizable compound (C)

[0565] The molecular volume of the polymerizable compound (C) was determined based on its molecular structure by DFT (Density Functional Theory; B3LYP / 6-31G) calculation using a quantum chemical calculation program “Gaussian16” manufactured by HULINKS.

[0566] (6) Evaluation of film luminescence intensity

[0567] A narrow-angle sensor detection backlight (OPF series; manufactured by Optex FA) equipped with a 444nm LED and a scratch-resistant cover was prepared as the backlight. The backlight was placed with the scratch-resistant cover facing upward, and an optical fiber connected to the spectrometer described below for detecting the light emission was placed 4 cm above the scratch-resistant cover. A glass substrate (EAGLE 2000; manufactured by Corning Incorporated) was placed on the surface of the scratch-resistant cover as a control. The backlight was illuminated in this state, and the backlight intensity was adjusted so that the total radiant flux (μW) of the backlight passing through the control glass substrate (EAGLE 2000; manufactured by Corning Incorporated) reached 5000 μW.

[0568] Next, a substrate having a cured film made from the composition was placed on the surface of the glass substrate. In this state, a backlight was turned on, and the luminous intensity (unit: μW) of the light emitted from the cured film was measured using a cumulative radiant flux meter within a wavelength range of 485 nm to 780 nm. A spectrometer (manufactured by Ocean Optics) was used to measure the luminous intensity.

[0569] The thickness of the cured film was measured by measuring the height difference of the surface scratch of the cured film using a probe-type surface profiler (DektakXT, manufactured by Bluker Corporation).

[0570] A substrate with a cured film was prepared as follows. The composition was applied to a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Incorporated) by spin coating to a film thickness of 5 μm, and then pre-baked at 100°C for 3 minutes to form a composition layer. The substrate with the composition layer formed thereon was exposed to a light source at 80 mJ / cm in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2 The film was irradiated with light at an exposure dose of 100 nm (365 nm basis), developed, and then post-baked at 180° C. for 60 minutes to obtain a substrate having a cured film.

[0571] (7) Evaluation of the residual film rate before and after development

[0572] The composition was applied to a 5 cm square glass substrate (EAGLE2000; manufactured by Corning Incorporated) by spin coating to a film thickness of 5 μm, and then pre-baked at 100°C for 3 minutes to form a composition layer. The substrate with the composition layer formed was exposed to a light source at 80 mJ / cm in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2After irradiation with light at an exposure dose of 100 nm (365 nm reference), the substrate was immersed in a developer consisting of a 0.02% by mass TMAH aqueous solution at 25°C for 30 seconds for development, and then post-baked at 180°C for 60 minutes to obtain a substrate having a cured film. The residual film rate was measured according to the following formula. The film thickness of the exposed portion after exposure and the film thickness after post-baking were measured by measuring the height difference of the surface scratch of the film using a probe-type surface profiler (DektakXT, manufactured by Bluker).

[0573] Residual film rate (%) = 100 × (film thickness after post-baking) / (film thickness after exposure)

[0574] (Production Example 1: Preparation of a Dispersion Liquid of Semiconductor Particles (A1))

[0575] A toluene dispersion of InP / ZnSeS quantum dots coordinated with oleic acid as an organic ligand (G1) was prepared. The dispersion was subjected to reduced pressure distillation to remove toluene. 70 parts of cyclohexyl acetate was added to 30 parts of the solid content to obtain a dispersion of semiconductor particles (A1) (solid content 30%).

[0576] (Production Example 2: Preparation of a Dispersion of a Light Scattering Agent (E1))

[0577] To 70 parts of titanium oxide nanoparticles, 3 parts of DISPERBYK 21116 (manufactured by BYK-Chemie Japan) were added in terms of solid content, and propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA") was added to make a total of 100 parts. The mixture was then stirred using a paint shaker until fully dispersed to obtain a dispersion of the light scattering agent (E1) (solid content 73%).

[0578] (Production Example 3: Preparation of Resin (B1) Solution)

[0579] 110 parts of PGMEA were placed in a flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel, and a nitrogen inlet tube. The mixture was stirred while nitrogen substitution was performed and the temperature was raised to 80°C. 25 parts of dicyclopentanyl methacrylate, 23 parts of methyl methacrylate, 19 parts of methacrylic acid, and 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were dissolved in 110 parts of PGMEA. The resulting solution was added dropwise to the flask from the dropping funnel and stirred at 80°C for 3 hours.

[0580] Next, 16 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts of triphenylphosphine were placed in a flask, heated to 110°C, and stirred for 8 hours to react the carboxylic acid in the polymer with the epoxy groups, introducing polymerizable unsaturated bonds. Subsequently, 17 parts of 1,2,3,6-tetrahydrophthalic anhydride was added and the reaction continued for 3 hours to introduce carboxylic acid groups into the side chains. The reaction solution was cooled to room temperature to obtain a resin (B1) solution.

[0581] The weight average molecular weight of the resin (B1) in terms of standard polystyrene was 8400, the acid value was 120 mgKOH / g, and the solid content in the resin (B1) solution was 40% by mass.

[0582] (Manufacturing Example 4: Preparation of Resin (B2) Solution)

[0583] PGMEA was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred while nitrogen substitution was performed and the temperature was raised to 120°C. Next, a solution containing t-butyl peroxy-2-ethylhexanoate (polymerization initiator) added to a monomer mixture consisting of 2-ethylhexyl acrylate, glycidyl methacrylate, and dicyclopentanyl methacrylate was added dropwise to the flask from the dropping funnel over two hours. After the addition was complete, the mixture was stirred at 120°C for a further 30 minutes to allow for a copolymerization reaction, producing an addition copolymer.

[0584] The flask was then purged with air, and acrylic acid, triphenylphosphine (catalyst), and p-methoxyphenol (polymerization inhibitor) were added to the addition copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups derived from glycidyl methacrylate reacted with the acrylic acid, cleaving the epoxy groups and introducing polymerizable unsaturated bonds into the side chains of the polymer. Succinic anhydride was then added to the reaction system, and the reaction was continued at 110°C for 1 hour. The hydroxyl groups generated by the cleavage of the epoxy groups reacted with the succinic anhydride, introducing carboxylic acid groups into the side chains, thereby obtaining a polymer (resin (B2)).

[0585] Finally, PGMEA was added to the reaction solution to obtain a resin (B2) solution having a polymer solid content of 40% by mass.

[0586] The resin (B2) had a standard polystyrene-equivalent weight average molecular weight of 4960, an acid value of 37 mgKOH / g, and a double bond equivalent of 344 g / eq. The weight average molecular weight, acid value, and double bond equivalent were adjusted to desired values ​​by adjusting the amounts of the raw monomers.

[0587] (Manufacturing Example 5: Preparation of Resin (B3) Solution)

[0588] The amounts of raw monomers were adjusted in the same manner as for the resin (B2) to obtain a polymer (resin (B3)). Finally, PGMEA was added to the reaction solution to obtain a resin (B3) solution having a polymer solid content of 40%.

[0589] The resin (B3) had a weight average molecular weight of 4910 in terms of standard polystyrene, an acid value of 42 mg-KOH / g, and a double bond equivalent of 514 g / eq.

[0590] <Examples 1 to 9, Comparative Examples 1 and 2>

[0591] (1) Preparation of composition

[0592] The dispersion of semiconductor particles (A1) obtained in Production Example 1, the dispersion of light scattering agent (E1) obtained in Production Example 2, the solutions of resins (B1) to (B3) obtained in Production Examples 3 to 5, and other components shown in Table 1 were mixed in predetermined amounts to prepare a composition.

[0593] The content of each component in the composition calculated based on the addition amount is shown in Table 1. In Table 1, the components other than the solvent (I) are the contents converted to solid content (unit: mass parts). The unit of the content of the solvent (I) is mass parts. For example, the semiconductor particles (A1) are formulated in the form of a dispersion of the semiconductor particles (A1) in the preparation of the composition, but the content shown in Table 1 is the amount of the semiconductor particles (A1) itself contained in the dispersion. The solvent (I) in Table 1 includes the solvent contained in the dispersion or solution used in the preparation of the composition. The content of the light scattering agent (E1) in Table 1 includes the dispersant.

[0594] The content of the organic ligand (G1) in the composition shown in Table 1 was calculated based on the concentration of the organic ligand (G1) in the dispersion of semiconductor particles (A1) obtained in Production Example 1, measured by the following method. Specifically, the dispersion of semiconductor particles (A1) was vacuum-dried at 150°C to remove the solvent. The weight change of the remaining solids was measured using a thermogravimetric analyzer "TGDTA6200" at a heating rate of 5°C / min from 50°C to 550°C. The weight change from 50°C to 500°C was used as the weight of the organic ligand (G1), and the concentration of the organic ligand (G1) in the dispersion of semiconductor particles (A1) was calculated.

[0595] The molecular volumes of the polymerizable compounds (C1) to (C4) and (C6) were determined according to (4) of the above <Measurement and Evaluation>. The results are shown in Table 1.

[0596] (2) Film preparation

[0597] Cured films were prepared according to (6) and (7) of the above-mentioned <Measurement and Evaluation>, and the emission intensity and the residual film ratio before and after development were evaluated. The evaluation results are shown in Table 1.

[0598] [Table 1]

[0599]

[0600] The details of the abbreviations of the components shown in Table 1 are as follows.

[0601] Polymerizable compound (C1): A-9550 (dipentaerythritol polyacrylate; hexafunctional, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., solid content 100%)

[0602] Polymerizable compound (C2): A-BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate; bifunctional, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: NK ESTERA-BPEF, solid content 100%)

[0603] Polymerizable compound (C3): EBECRYL 150 (ethylene oxide-modified bisphenol diacrylate; bifunctional, manufactured by Daicel Allnex, solid content 100%)

[0604] Polymerizable compound (C4): IRR-214K (tricyclodecane dimethanol diacrylate; bifunctional, manufactured by Daicel Allnex, solid content 100%)

[0605] Polymerizable compound (C5): Carboxyl group-containing polyfunctional (meth)acrylate (trade name "Aronix (registered trademark) M-510" manufactured by Toagosei Co., Ltd.)

[0606] Polymerizable compound (C6): 1,6-hexanediol diacrylate (bifunctional, solid content 100%)

[0607] Polymerization initiator (D1): a photopolymerization initiator represented by the following formula (solid content 100%).

[0608] It was produced by the method described in Japanese Patent Application Laid-Open No. 2011-132215.

[0609]

[0610] Antioxidant (F1): Sumilizer-GP (phosphorus / phenol complex antioxidant, manufactured by Sumitomo Chemical Co., Ltd., solid content 100%)

[0611] Leveling agent (J1): SH8400 (silicone-based leveling agent, manufactured by Dow Corning Toray, solid content 100%)

[0612] Solvent (I1): PGMEA (propylene glycol monomethyl ether acetate)

[0613] Solvent (I2): Cyclohexyl acetate

[0614] For the above-mentioned polymerizable compounds (C1) to (C4) and (C6), the absorbance of a 0.01% PGMEA solution was measured using an ultraviolet-visible spectrophotometer UV-3600 (Shimadzu Corporation). As a result, the absorbance at wavelengths of 250 to 500 nm was less than 0.5 for polymerizable compounds (C1) and (C2), respectively, at any wavelength, while the absorbance at wavelengths exceeding 0.5 was observed for polymerizable compounds (C3), (C4) and (C6).

[0615] Cured films were prepared in the same manner as in (6) of <Measurement and Evaluation> above, except that the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were applied to a film thickness of 3.0 μm. The absorbance of these cured films at wavelengths of 300 to 780 nm (measurement wavelength interval of 0.5 nm) was measured using an ultraviolet-visible spectrophotometer UV-3600 (Shimadzu Corporation). The results showed that the absorbance per unit film thickness (specifically, per 1 μm) of the cured films using the compositions of Examples 1 to 9 was 0.23 or less at any wavelength, while the absorbance of the cured films using the compositions of Comparative Examples 1 and 2 exceeded 0.5 at each wavelength.

Claims

1. A composition comprising semiconductor particles (A) and a polymerizable compound (C), The polymerizable compound (C) comprises a molecular volume of 450 cm 3 / mol or less polymerizable compound (C-1).

2. The composition according to claim 1, wherein The composition further comprises a polymerization initiator (D).

3. The composition according to claim 1, wherein The composition further comprises a resin (B).

4. The composition according to claim 1, wherein The composition further comprises a light scattering agent (E).

5. The composition according to claim 1, wherein The composition further comprises a solvent (I).

6. The composition according to claim 1, wherein The polymerizable compound (C-1) is a compound having a cyclic hydrocarbon group in its structure.

7. The composition according to claim 1, wherein The polymerizable compound (C-1) is a compound having two or more polymerizable functional groups.

8. The composition according to claim 3, wherein The content ratio of the semiconductor particles (A) to the resin (B), that is, semiconductor particles (A) / resin (B), is 0.3 to 4.0 on a mass basis.

9. The composition according to claim 3, wherein The content ratio of the resin (B) to the polymerizable compound (C), that is, resin (B) / polymerizable compound (C), is 0.5 to 10 on a mass basis. 10 . A cured film formed from the composition according to claim 1 . The cured film according to claim 10 , wherein The absorbance per 1 μm of film thickness at a wavelength of 300 nm or longer is 0.5 or less. 12 . A display device comprising the cured film according to claim 10 .

13. A cured film formed from a composition comprising semiconductor particles (A) and a polymerizable compound (C), The absorbance per 1 μm of film thickness at a wavelength of 300 nm or longer is 0.5 or less.

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