Semiconductor nanoparticle-containing composition, color filter, and image display device

Abstract

The present invention provides a composition containing semiconductor nanoparticles, said composition being capable of forming a wavelength conversion layer that efficiently converts the wavelength of excitation light and exhibits a sufficient luminous intensity. This composition containing semiconductor nanoparticles contains semiconductor nanoparticles (A), a (meth)acrylate compound (D) and a fluorescent dye (C), and is characterized in that: the semiconductor nanoparticles (A) have a maximum emission wavelength within the range of from 500 nm to 670 nm at a wavelength within the range of from 300 nm to 780 nm; the fluorescent dye (C) has a substituent that performs a function of linking to the semiconductor nanoparticles (A); and the content of the (meth)acrylate compound (D) in this composition containing semiconductor nanoparticles is 20% by mass or more.

Description

[Technical Field]

[0001] The present invention relates to a semiconductor nanoparticle-containing composition, a color filter, and an image display device. This application claims priority based on Japanese Patent Application No. 2020-145534, filed on August 31, 2020, and Japanese Patent Application No. 2020-218441, filed on December 28, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] 2. Description of the Related Art Displays such as liquid crystal display devices are becoming more and more popular year by year as they consume little power and are space-saving image display devices. However, in recent years, there has been a demand for further power saving and improved color reproducibility.

[0003] Against this background, it has been proposed to use a wavelength conversion layer containing semiconductor nanoparticles, such as quantum dots, quantum rods, and other inorganic phosphor particles, as a light-emitting material, which convert the wavelength of incident light and emit light in order to increase light utilization efficiency and improve color reproducibility.

[0004] In general, semiconductor nanoparticles such as quantum dots are dispersed in a resin or the like and used, for example, as a wavelength conversion film for wavelength conversion or as a pixel portion of a wavelength conversion type color filter.

[0005] Conventionally, color filter pixel portions in displays such as liquid crystal display devices have been manufactured by photolithography using, for example, a curable resist material containing a pigment and an alkali-soluble resin and / or an acrylic monomer.

[0006] However, when attempting to form wavelength-converting color filter pixel portions by applying the above-mentioned photolithography color filter manufacturing method, there is a drawback in that most of the resist material containing semiconductor nanoparticles is lost during the development process. For this reason, forming wavelength-converting color filter pixel portions by inkjet printing has also been considered (Patent Document 1).

[0007] On the other hand, in order to increase the luminescence efficiency (quantum efficiency) of semiconductor nanoparticles, the combined use of semiconductor nanoparticles and fluorescent dyes in a solvent has been investigated (Non-Patent Document 1). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2019-85537 [Non-patent literature]

[0009] [Non-Patent Document 1] Chem. Phys. Chem., 2010, vol. 11, pp. 3167-3171 Summary of the Invention [Problem to be solved by the invention]

[0010] The inventors have found through their studies that, because semiconductor nanoparticles have low absorbance in the excitation wavelength range, when a wavelength conversion layer produced using a semiconductor nanoparticle-containing composition is used in a display, sufficient luminescence intensity cannot be obtained. Specifically, it has been found that in the pixel portion of a wavelength conversion color filter formed using the semiconductor nanoparticle-containing composition disclosed in Patent Document 1, sufficient luminescence intensity cannot be obtained in desired pixels including red and green. It has been found that the system described in Non-Patent Document 1, in which semiconductor nanoparticles and a fluorescent dye are used in combination in a solvent, has the problem of insufficient emission intensity.

[0011] The present invention aims to provide a semiconductor nanoparticle-containing composition that can efficiently convert the wavelength of excitation light and form a wavelength conversion layer that exhibits sufficient luminescence intensity, a color filter having pixel portions formed by curing the composition, and an image display device having the color filter. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using specific semiconductor nanoparticles, a fluorescent dye, and a (meth)acrylate compound in combination, and have thus completed the present invention. The gist of the present invention is as follows.

[0013] [1] A semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm within a wavelength range of 300 to 780 nm; the fluorescent dye (C) has a substituent that causes it to link to the semiconductor nanoparticles (A), A semiconductor nanoparticle-containing composition, wherein the content of the (meth)acrylate compound (D) in the semiconductor nanoparticle-containing composition is 20% by mass or more. [2] A semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm within a wavelength range of 300 to 780 nm; The semiconductor nanoparticle-containing composition for inkjet printing, wherein the fluorescent dye (C) has a substituent that causes the fluorescent dye to link to the semiconductor nanoparticles (A). [3] The semiconductor nanoparticle-containing composition according to [1] or [2], wherein the substituent that produces the linking action is a sulfanyl group or a salt thereof, an acid group or a salt thereof, an amino group or a salt thereof, a phosphate ester group or a salt thereof, a phosphanetriyl group, or a phosphoryl group. [4] The semiconductor nanoparticle-containing composition according to [3], wherein the acid group or a salt thereof is a carboxy group or a salt thereof, a sulfo group or a salt thereof, or a phosphono group or a salt thereof. [5] The semiconductor nanoparticle-containing composition according to any one of [1] to [4], further comprising a polymerization initiator (E). [6] The semiconductor nanoparticle-containing composition according to any one of [1] to [5], further comprising a ligand (B). [7] The semiconductor nanoparticle-containing composition according to any one of [1] to [6], further comprising light-scattering particles. [8] A color filter having pixel portions formed by curing the semiconductor nanoparticle-containing composition according to any one of [1] to [7]. [9] An image display device having the color filter according to [8]. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a semiconductor nanoparticle-containing composition that can efficiently convert the wavelength of excitation light and form a wavelength conversion layer that exhibits sufficient luminescence intensity. Furthermore, it is possible to provide a color filter having pixel portions obtained by curing the composition of the present invention, and an image display device having the color filter of the present invention. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a schematic cross-sectional view of a color filter of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below. The following description is an example of an embodiment of the present invention, and the present invention is not limited to these unless it exceeds the gist of the present invention. In the present invention, "(meth)acrylic" means "acrylic and / or methacrylic". "Total solids" refers to all components in the semiconductor nanoparticle-containing composition other than the solvent, and when the semiconductor nanoparticle-containing composition does not contain a solvent, it refers to all components of the semiconductor nanoparticle-containing composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solids. In the present invention, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. "A and / or B" means one or both of A and B, and means A, B, or A and B. In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography).

[0017] The semiconductor nanoparticle-containing composition of the present invention can be widely used for producing wavelength-converting layers, and wavelength-converting layers using the semiconductor nanoparticle-containing composition of the present invention are suitable for use in displays. When the wavelength-converting layer using the semiconductor nanoparticle-containing composition of the present invention is a wavelength-converting sheet, the wavelength-converting layer may be contained in a film, may be applied to the surface of a film by a known method, or may be present between two films. The semiconductor nanoparticle-containing composition of the present invention can be used as an ink for use in known and conventional methods for producing color filters, but is preferably prepared and used in a manner suitable for an inkjet system, since pixel portions (wavelength conversion layers) can be formed in the required amounts at the required locations without wasting relatively expensive materials such as semiconductor nanoparticles. In other words, the semiconductor nanoparticle-containing composition of the present invention is suitable for use in forming pixel portions by an inkjet system.

[0018] [1] Semiconductor nanoparticle-containing composition The semiconductor nanoparticle-containing composition of the present invention is a semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), wherein the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm within a wavelength range of 300 to 780 nm, the fluorescent dye (C) has a substituent that causes linking to the semiconductor nanoparticles (A), and the content of the (meth)acrylate compound (D) in the semiconductor nanoparticle-containing composition is 20 mass% or more.

[0019] [1-1] Semiconductor nanoparticles (A) The semiconductor nanoparticle-containing composition of the present invention contains semiconductor nanoparticles (A) (hereinafter, sometimes referred to as "semiconductor nanoparticles (A)") having a maximum emission wavelength in the wavelength range of 300 to 780 nm (hereinafter, unless otherwise specified, "maximum emission wavelength" means the maximum emission wavelength in the wavelength range of 300 to 780 nm) in the range of 500 to 670 nm. Semiconductor nanoparticles are nano-sized particles that absorb excitation light and emit fluorescence or phosphorescence, and are, for example, particles whose maximum particle size as measured by a transmission electron microscope or a scanning electron microscope is 100 nm or less.

[0020] For example, semiconductor nanoparticles can absorb light of a predetermined wavelength and emit light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength. The maximum emission wavelength of the semiconductor nanoparticles (A) is within the range of 500 to 670 nm. The semiconductor nanoparticles (A) may be red-light-emitting semiconductor nanoparticles (red semiconductor nanoparticles) that emit red light, or may be green-light-emitting semiconductor nanoparticles (green semiconductor nanoparticles) that emit green light. The semiconductor nanoparticles (A) are preferably red semiconductor nanoparticles and / or green semiconductor nanoparticles. The light absorbed by the semiconductor nanoparticles is not particularly limited, but may be, for example, light with a wavelength in the range of 400 to 500 nm (blue light) and / or light with a wavelength in the range of 200 to 400 nm (ultraviolet light). In general, semiconductor nanoparticles have a wide absorption band in the wavelength region shorter than the maximum emission wavelength. For example, when the maximum emission wavelength is 530 nm, the absorption band is wide in the wavelength region of 300 to 530 nm, with a base near 530 nm, and when the maximum emission wavelength is 630 nm, the absorption band is wide in the wavelength region of 300 to 630 nm, with a base near 630 nm. The maximum emission wavelength of the semiconductor nanoparticles (A) can be confirmed, for example, in a fluorescence spectrum or phosphorescence spectrum measured using a spectrofluorometer, and the measurement is preferably performed under conditions of an excitation wavelength of 450 nm and an absorptance of 20 to 50%.

[0021] When the semiconductor nanoparticles (A) contain red semiconductor nanoparticles, the maximum emission wavelength is preferably 605 nm or more, more preferably 610 nm or more, even more preferably 615 nm or more, even more preferably 620 nm or more, particularly preferably 625 nm or more, preferably 665 nm or less, more preferably 655 nm or less, even more preferably 645 nm or less, even more preferably 640 nm or less, particularly preferably 635 nm or less, and most preferably 630 nm or less. By setting the wavelength above the lower limit, the red color gamut tends to expand, and a richer color can be expressed as a display. By setting the wavelength below the upper limit, a brighter red color tends to be expressed in terms of luminosity. The above upper and lower limits can be combined arbitrarily. For example, the maximum emission wavelength of the semiconductor nanoparticles (A) is preferably 605 to 665 nm, more preferably 605 to 655 nm, even more preferably 610 to 645 nm, even more preferably 615 to 640 nm, particularly preferably 620 to 635 nm, and particularly preferably 625 to 630 nm.

[0022] When the semiconductor nanoparticles (A) contain green semiconductor nanoparticles, the maximum emission wavelength is preferably 500 nm or more, more preferably 505 nm or more, even more preferably 510 nm or more, even more preferably 515 nm or more, particularly preferably 520 nm or more, most preferably 525 nm or more, preferably 560 nm or less, more preferably 550 nm or less, even more preferably 545 nm or less, even more preferably 540 nm or less, particularly preferably 535 nm or less, and most preferably 530 nm or less. By setting the wavelength above the lower limit, the green color gamut can be expanded, and a brighter green tends to be expressed in terms of luminosity. By setting the wavelength below the upper limit, the green color gamut can be expanded, and a richer color can be expressed as a display. The above upper and lower limits can be combined arbitrarily. For example, when the semiconductor nanoparticles (A) contain green semiconductor nanoparticles, the maximum emission wavelength is preferably 500 to 560 nm, more preferably 505 to 550 nm, even more preferably 510 to 545 nm, even more preferably 515 to 540 nm, particularly preferably 520 to 535 nm, and particularly preferably 525 to 530 nm.

[0023] According to the solution of the Schrödinger wave equation of the well potential model, the maximum emission wavelength (emission color) of light emitted by semiconductor nanoparticles depends on the size (e.g., particle diameter) of the semiconductor nanoparticles, but also on the energy gap of the semiconductor nanoparticles. Therefore, the emission color can be selected by changing the constituent material and size of the semiconductor nanoparticles used.

[0024] The semiconductor nanoparticles (A) may have various shapes, such as spheres, cubes, rods, wires, disks, and multipods, with one dimension being 30 nm or less. For example, CdSe nanorods with a length of 20 nm and a diameter of 4 nm may be used. Semiconductor nanoparticles may also be used in combination with particles of different shapes. A combination of spherical and rod-shaped semiconductor nanoparticles may be used. Spherical semiconductor nanoparticles are preferred from the viewpoints of ease of control of the emission spectrum, reduction of production costs, and improvement of mass productivity while ensuring reliability.

[0025] The semiconductor nanoparticles (A) may consist only of a core containing a first semiconductor material, or may have a core containing the first semiconductor material and a shell that covers at least a portion of the core and contains a second semiconductor material different from the first semiconductor material. In other words, the structure of the semiconductor nanoparticles (A) may be a structure consisting of only a core (core structure), or a structure consisting of a core portion and a shell portion (core / shell structure).

[0026] In addition to the shell (first shell) containing the second semiconductor material, the semiconductor nanoparticles (A) may further have a shell (second shell) that covers at least a portion of the core or the first shell and contains a third semiconductor material different from the first and second semiconductor materials. That is, the structure of the semiconductor nanoparticles (A) may be a structure consisting of a core portion, a first shell portion, and a second shell portion (core / shell / shell structure). Each of the core and the shell may be a mixed crystal containing two or more semiconductor materials (e.g., CdSe+CdS, CuInSe+ZnS, InP+ZnSeS+ZnS, etc.).

[0027] The type of semiconductor material constituting the semiconductor nanoparticles (A) is not particularly limited, but it is preferable that the semiconductor nanoparticles (A) contain at least one semiconductor selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors, and I-II-IV-VI semiconductors, because they have high quantum efficiency and are relatively easy to produce.

[0028] Examples of semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; Examples include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe2, AgInGaS2, CuGaSe2, CuInS2, CuGaS2, CuInSe2, AgInS2, AgGaSe2, AgGaS2, C, and Cu2ZnSnS4.

[0029] From the viewpoints of easily controlling the emission spectrum, ensuring reliability, reducing production costs, and improving mass productivity, it is preferable for the semiconductor laser to contain at least one element selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS2, AgInSe2, AgInGaS2, AgInTe2, AgGaS2, AgGaSe2, AgGaTe2, CuInS2, CuInSe2, CuInTe2, CuGaS2, CuGaSe2, CuGaTe2, Si, C, Ge, and Cu2ZnSnS4.

[0030] Examples of red-emitting semiconductor nanoparticles include CdSe nanoparticles; nanoparticles with a core / shell structure in which the shell portion is CdS and the core portion is CdSe; nanoparticles with a core / shell structure in which the shell portion is CdS and the core portion is ZnSe; nanoparticles of a mixed crystal of CdSe and ZnS; InP nanoparticles; nanoparticles with a core / shell structure in which the shell portion is ZnS and the core portion is InP; nanoparticles of a mixed crystal of CdSe and CdS; nanoparticles of a mixed crystal of ZnSe and CdS; nanoparticles with a core / shell / shell structure in which the first shell portion is ZnSe, the second shell portion is ZnS, and the core portion is InP; and nanoparticles with a core / shell / shell structure in which the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the core portion is InP.

[0031] Examples of green-emitting semiconductor nanoparticles include CdSe nanoparticles; nanoparticles of a mixed crystal of CdSe and ZnS; nanoparticles with a core / shell structure in which the shell is ZnS and the core is InP; nanoparticles with a core / shell structure in which the shell is a mixed crystal of ZnS and ZnSe and the core is InP; nanoparticles with a core / shell / shell structure in which the first shell is ZnSe, the second shell is ZnS, and the core is InP; and nanoparticles with a core / shell / shell structure in which the first shell is a mixed crystal of ZnS and ZnSe, the second shell is ZnS, and the core is InP.

[0032] By changing the average particle diameter of semiconductor nanoparticles with the same chemical composition, the color of light to be emitted can be changed to either red or green. It is preferable to use semiconductor nanoparticles that have as little adverse effect on the human body as possible. When semiconductor nanoparticles containing cadmium, selenium, etc. are used as the semiconductor nanoparticles (A), it is preferable to select semiconductor nanoparticles that contain as little of the above elements (cadmium, selenium, etc.) as possible and use them alone, or to use them in combination with other semiconductor nanoparticles so that the content of the above elements is minimized.

[0033] The shape of the semiconductor nanoparticles (A) is not particularly limited and may be any geometric shape or any irregular shape. The shape of the semiconductor nanoparticles may be, for example, spherical, ellipsoidal, pyramidal, disc-like, branched, net-like, or rod-like. It is preferable to use semiconductor nanoparticles with little directionality in terms of particle shape (for example, spherical or tetrahedral particles) in order to further improve the uniformity and fluidity of the semiconductor nanoparticle-containing composition.

[0034] The average particle diameter (volume average diameter) of the semiconductor nanoparticles (A) may be 1 nm or more, 1.5 nm or more, or even 2 nm or more, from the viewpoint of easily obtaining light emission of the desired wavelength and from the viewpoint of excellent dispersibility and storage stability. From the viewpoint of easily obtaining the desired emission wavelength, it may be 40 nm or less, 30 nm or less, or even 20 nm or less. The average particle diameter (volume average diameter) of the semiconductor nanoparticles is obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter. The above upper and lower limits can be combined arbitrarily. For example, the average particle diameter (volume average diameter) of the semiconductor nanoparticles (A) is preferably 1 to 40 nm, more preferably 1.5 to 30 nm, and even more preferably 2 to 20 nm.

[0035] The semiconductor nanoparticles (A) may be particles dispersed in a colloidal form in a solvent, a polymerizable compound, etc. The surfaces of the semiconductor nanoparticles dispersed in the solvent are preferably passivated with a ligand (B) described below. Examples of the solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or mixtures thereof.

[0036] The method for producing the semiconductor nanoparticles (A) is not particularly limited, but they can be produced by, for example, the methods described in JP 2015-529698 A and JP 2018-109141 A.

[0037] Commercially available semiconductor nanoparticles (A) can also be used, such as indium phosphide / zinc sulfide, D-dots, and CuInS / ZnS from NN-Labs, and InP / ZnS from Aldrich.

[0038] From the viewpoint of excellent effect in improving external quantum efficiency, the content of semiconductor nanoparticles (A) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 4% by mass or more, based on the total solid content of the semiconductor nanoparticle-containing composition. From the viewpoint of coatability, particularly excellent ejection stability from an inkjet head, the content is preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the content of semiconductor nanoparticles (A) is preferably 1 to 60% by mass, more preferably 2 to 60% by mass, even more preferably 3 to 40% by mass, and particularly preferably 4 to 20% by mass, based on the total solid content of the semiconductor nanoparticle-containing composition.

[0039] The semiconductor nanoparticle-containing composition may contain two or more types of semiconductor nanoparticles as the semiconductor nanoparticles (A). It may contain both red semiconductor nanoparticles and green semiconductor nanoparticles, but it is preferable that it contains only one of red semiconductor nanoparticles and green semiconductor nanoparticles. When the semiconductor nanoparticles (A) contain red semiconductor nanoparticles, the content of green semiconductor nanoparticles in the semiconductor nanoparticles is preferably 10% by mass or less, more preferably 0% by mass. When the semiconductor nanoparticles (A) contain green-emitting semiconductor nanoparticles, the content of red-emitting semiconductor nanoparticles in the semiconductor nanoparticles is preferably 10% by mass or less, more preferably 0% by mass.

[0040] [1-2] Ligand (B) The semiconductor nanoparticle-containing composition of the present invention may contain a ligand (B). The ligand (B) is a compound that coats at least a portion of the surface of the semiconductor nanoparticle (A). The ligand (B) coats at least a portion of the surface of the semiconductor nanoparticle (A) by adsorption or coordinate bonding to the surface of the semiconductor nanoparticle (A).

[0041] When used as an ink, semiconductor nanoparticles are preferably treated with a compound having a functional group (hereinafter simply referred to as an "affinity group") for ensuring affinity with solvents and resins, and a functional group (hereinafter simply referred to as an "adsorption group") for ensuring adsorption to the semiconductor nanoparticles, and the semiconductor nanoparticle-containing composition of the present invention preferably contains a ligand (B).

[0042] The ligand (B) is not particularly limited, but preferably has an affinity group from the viewpoint of affinity with solvents, (meth)acrylate compounds, resins, etc. The affinity group is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched, and preferably has 4 or more carbon atoms, more preferably 8 or more, and even more preferably 10 or more. It is also preferably 300 or less, more preferably 40 or less, and even more preferably 30 or less. A group having 4 or more carbon atoms tends to ensure affinity with solvents, (meth)acrylate compounds, and resins, and improve the dispersibility of semiconductor nanoparticles. A group having 300 or less carbon atoms tends to reduce the viscosity of the semiconductor nanoparticle-containing composition, and improve the luminescence intensity and strength of the cured film. The above upper and lower limits can be combined arbitrarily. For example, the affinity group preferably has 8 to 300 carbon atoms, more preferably 8 to 40, and even more preferably 10 to 30. The aliphatic hydrocarbon group may have a polyalkylene glycol chain such as a polyethylene glycol chain, etc. The aliphatic hydrocarbon group may or may not have an unsaturated bond.

[0043] The adsorption group of the ligand (B) may be, for example, a hydroxy group, a carboxy group, an amino group, a sulfanyl group, a sulfo group, a phosphonooxy group, a phosphono group, a phosphanetriyl group, a phosphoryl group, or an alkoxysilyl group. From the viewpoint of the bonding strength with the semiconductor nanoparticles, the sulfanyl group, the phosphine oxide group, or the carboxy group is preferred, and the carboxy group is particularly preferred.

[0044] As the ligand (B), a compound having an adsorptive group at the end can be used, which can contain an aromatic ring or an ether group, and may have a plurality of adsorptive groups in the molecule. Examples of the ligand (B) include benzoic acid, biphenylcarboxylic acid, butylbenzoic acid, hexylbenzoic acid, cyclohexylbenzoic acid, naphthalenecarboxylic acid, hexanoic acid, heptanoic acid, octanoic acid, ethylhexanoic acid, hexenoic acid, octenoic acid, citronellic acid, suberic acid, ethylene glycol bis(4-carboxyphenyl) ether, and (2-butoxyethoxy)acetic acid. From the viewpoint of affinity with solvents, (meth)acrylate compounds, and resins, the ligand (B) is preferably a compound having an adsorptive group and an aliphatic hydrocarbon group having 8 to 300 carbon atoms, or a compound having an adsorptive group and a polyalkylene glycol chain such as a polyethylene glycol chain. Examples of the ligand (B) include nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, tricosanoic acid, lignoceric acid, oleic acid, eicosadienoic acid, linolenic acid, sebacic acid, (2-octyloxy)acetic acid, [2-(2-methoxyethoxy)ethoxy]acetic acid, and compounds represented by the following general formula (bI):

[0045] [ka]

[0046] (In formula (bI), n represents an integer of 0 to 100.)

[0047] The semiconductor nanoparticle-containing composition of the present invention preferably contains a ligand (B). The ligand (B) may contain one type alone or two or more types, and may further contain a ligand other than the ligand (B) (hereinafter, sometimes referred to as "ligand (B1)"). Examples of the ligand (B1) include organic substances such as organic amines, sulfur-containing organic substances, and phosphorus-containing organic substances.

[0048] The molecular weight of the affinity group of the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is not particularly limited. From the viewpoint of ensuring affinity with solvents, (meth)acrylate compounds, and resins and improving the dispersibility of the semiconductor nanoparticles, it is preferably 50 g / mol or more, more preferably 100 g / mol or more, and even more preferably 200 g / mol or more. From the viewpoint of reducing the viscosity of the semiconductor nanoparticle-containing composition and improving the luminescence intensity and strength of the cured film, it is preferably 10,000 g / mol or less, more preferably 5,000 g / mol or less, and even more preferably 1,000 g / mol or less. The above upper and lower limits can be arbitrarily combined. For example, the molecular weight of the affinity group of the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is preferably 50 to 10,000 g / mol, more preferably 100 to 5,000 g / mol, and even more preferably 200 to 1,000 g / mol.

[0049] When the semiconductor nanoparticle-containing composition of the present invention contains a ligand (B), the content of the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is not particularly limited. From the viewpoint of ensuring affinity with solvents, (meth)acrylate compounds, and resins and improving the dispersibility of the semiconductor nanoparticles, the content of the ligand (B) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more, based on the total solid content of the semiconductor nanoparticle-containing composition. From the viewpoint of improving the luminescence intensity and film strength of the semiconductor nanoparticle-containing composition and reducing viscosity, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The above upper and lower limits can be combined as desired. For example, when the semiconductor nanoparticle-containing composition of the present invention contains a ligand (B), the content of the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is preferably 0.005 to 30 mass%, more preferably 0.01 to 30 mass%, even more preferably 0.05 to 30 mass%, even more preferably 0.1 to 20 mass%, and particularly preferably 0.3 to 10 mass%.

[0050] When the semiconductor nanoparticle-containing composition of the present invention contains a ligand (B), the content ratio of the semiconductor nanoparticles (A) to the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is not particularly limited. From the viewpoint of ensuring affinity with solvents, (meth)acrylate compounds, and resins and improving the dispersibility of the semiconductor nanoparticles, the content of the ligand (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more per 100 parts by mass of the semiconductor nanoparticles (A). From the viewpoint of improving the luminescence intensity and film strength of the semiconductor nanoparticle-containing composition and reducing the viscosity, the content is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the semiconductor nanoparticles (A) to the ligand (B) in the semiconductor nanoparticle-containing composition of the present invention is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 100 parts by mass of the ligand (B) per 100 parts by mass of the semiconductor nanoparticles (A).

[0051] [1-3] Fluorescent dye (C) The semiconductor nanoparticle-containing composition of the present invention contains a fluorescent dye (C), and the fluorescent dye (C) has a substituent that causes the dye to link to the semiconductor nanoparticles (A). By using a fluorescent dye (C) having a substituent that causes linking to the semiconductor nanoparticles (A) in combination with the semiconductor nanoparticles (A), it is possible to improve the luminescence efficiency of the semiconductor nanoparticles (A).

[0052] To further improve the luminescence efficiency of the semiconductor nanoparticles (A), it is preferable that the emission spectrum of the fluorescent dye (C) overlaps closely with the absorption spectrum of the semiconductor nanoparticles (A), which have a maximum emission wavelength in the range of 500 to 670 nm. This is thought to be because the large overlap between the emission spectrum of the fluorescent dye (C) and the absorption spectrum of the semiconductor nanoparticles (A) allows the excited energy of the fluorescent dye (C) to be transferred to the semiconductor nanoparticles (A) by Förster energy transfer, thereby increasing the luminescence intensity of the semiconductor nanoparticles (A). In order to further improve the luminous efficiency of the semiconductor nanoparticles (A), the fluorescent dye (C) is preferably a fluorescent dye having an emission spectrum that overlaps largely with the absorption spectrum of the semiconductor nanoparticles (A). For example, fluorescent dyes having a naphthalimide skeleton, a coumarin skeleton, a perylene skeleton, a pyrene skeleton, an anthracene skeleton, a dipyrromethene skeleton, a benzophosphole skeleton, a benzothiadiazole skeleton, a xanthene skeleton, an iminocoumarin skeleton, or a dithienosilole skeleton, or fluorescent dyes having a structure represented by the following general formula (c-IV), (cV), or formula (c-VI), are preferred, with fluorescent dyes having a naphthalimide skeleton, a coumarin skeleton, a perylene skeleton, a fluorescent dye having a structure represented by formula (c-IV), a fluorescent dye having a structure represented by formula (cV), or a fluorescent dye having a structure represented by formula (c-VI) being particularly preferred.

[0053] (Fluorescent dyes with naphthalimide skeleton) The fluorescent dye having a naphthalimide skeleton is preferably a fluorescent dye represented by the following general formula (cI) (hereinafter also referred to as "fluorescent dye (C1)"), from the viewpoints of high solubility in various solvents and semiconductor nanoparticle-containing compositions, high gram extinction coefficient, resistance to concentration quenching, and high fluorescence quantum yield.

[0054] [ka]

[0055] In formula (cI), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 each independently represents a hydrogen atom or an arbitrary substituent, and X is NR 7 R 8 , S.R. 9 , OR 10 It represents one of the following structures: R 7 , R 8 , R 9 , R 10 each independently represents a hydrogen atom or an arbitrary substituent. R 4 and X may be linked to form a ring, and X is NR 7 R 8 If R 7 , R 8 may be linked to form a ring.

[0056] The symbols in formula (cI) are explained below.

[0057] (R 1 ) R in formula (cI) 1 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an alkyl group which may have a substituent and an aryl group which may have a substituent.

[0058] R 1Examples of the alkyl group in include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and a combination thereof, and from the viewpoint of suppressing the formation of aggregates due to steric hindrance, a branched alkyl group is preferred. Some -CH2- in the alkyl group may be substituted with -O-. R 1 The number of carbon atoms in the alkyl group in R is not particularly limited. 1 The number of carbon atoms in the alkyl group in the formula (I) is usually 1 or more, preferably 3 or more, and preferably 20 or less, more preferably 16 or less. By making it equal to or greater than the lower limit, the solubility in the semiconductor nanoparticle-containing composition tends to improve. By making it equal to or less than the upper limit, the excitation light absorption efficiency per mass tends to improve. In addition, when one or more -CH2- in the alkyl group is substituted with -O-, it is preferable that the number of carbon atoms in the alkyl group before substitution is within the above range. The above upper and lower limits can be combined arbitrarily. For example, R 1 The alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 3 to 16 carbon atoms.

[0059] Examples of the substituent that the alkyl group may have include a hydroxy group, a carboxy group, an amino group, a sulfanyl group, and a phosphono group. From the viewpoint of approaching the semiconductor nanoparticles through interaction, a sulfanyl group is preferred.

[0060] R 1 The aryl group in the formula (I) includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited. 1 The number of carbon atoms in the aryl group is preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 12 or less. By making it equal to or greater than the lower limit, the solubility in the semiconductor nanoparticle-containing composition tends to be improved. By making it equal to or less than the upper limit, the excitation light absorption efficiency per mass tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aryl group is preferably 3 to 20, more preferably 6 to 12.

[0061] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, all of which have one free valence. From the viewpoint of high solubility in semiconductor nanoparticle-containing compositions, benzene rings having one free valence and naphthalene rings having one free valence are preferred, and benzene rings having one free valence are more preferred.

[0062] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of aromatic heterocycles include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furopyrrole rings, furofuran rings, thienofuran rings, benzoxazole rings, benzothiazole rings, benzisoxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinnoline rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have one free valence.

[0063] Examples of the substituent that the aryl group may have include alkyl groups. From the viewpoint of solubility in the semiconductor nanoparticle-containing composition, branched alkyl groups such as t-butyl and 2-ethylhexyl groups are preferred.

[0064] R in formula (cI) 1From the viewpoints of improving the solubility in the semiconductor nanoparticle-containing composition and improving the durability of the fluorescent dye (C1), a methyl group, a 2-ethylhexyl group, and a 2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl group are more preferred, and a 2-ethylhexyl group, an o-tolyl group, and a 2-[2-(2-methoxyethoxy)ethoxy]ethoxycarbonyl group are particularly preferred.

[0065] (R 2 , R 3 , R 4 , R 5 , R 6 ) R in formula (cI) 2 , R 3 , R 4 , R 5 , R 6 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples include an alkyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a nitro group, a halogen atom, a cyano group, a hydroxyl group, an amino group, a carboxy group, and a sulfo group.

[0066] R 2 , R 3 , R 4 , R 5 , R 6 Examples of the alkyl group in include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and a combination thereof, and from the viewpoint of suppressing the formation of aggregates due to steric hindrance, a branched alkyl group is preferred. Some -CH2- in the alkyl group may be substituted with -O-. R 2 , R 3 , R 4 , R 5 , R 6 The number of carbon atoms in the alkyl group in R is not particularly limited. 2 , R 3 , R 4 , R 5 , R 6The number of carbon atoms in the alkyl group in is usually 1 or more, preferably 3 or more, preferably 20 or less, more preferably 16 or less. By making it equal to or greater than the lower limit, quantum efficiency tends to be improved by suppressing aggregation. By making it equal to or less than the upper limit, excitation light absorption efficiency per mass tends to be improved. When one or more -CH2- in the alkyl group is substituted with -O-, it is preferable that the number of carbon atoms in the alkyl group before substitution is within the above range. The above upper and lower limits can be combined arbitrarily. For example, R 2 , R 3 , R 4 , R 5 , R 6 The alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 3 to 16 carbon atoms.

[0067] R 2 , R 3 , R 4 , R 5 , R 6 The optionally substituted alkylcarbonyl group in the formula (I) includes a group in which a carbonyl group is bonded to a bond of an alkyl group.

[0068] R 2 , R 3 , R 4 , R 5 , R 6 The alkoxy group in the formula (I) includes a group in which an oxygen atom is bonded to a bond of an alkyl group. Examples of the alkoxy group include a methoxy group and a 2-propyloxy group. From the viewpoint of suppressing the formation of aggregates due to steric hindrance, a branched alkoxy group, such as a 2-propyloxy group, is preferred.

[0069] R 2 , R 3 , R 4 , R 5 , R 6 The optionally substituted alkoxycarbonyl group in the formula (I) includes a group in which an oxycarbonyl group is bonded to a bond of an alkyl group.

[0070] R 2 , R3 , R 4 , R 5 , R 6 The aryl group in the formula (I) includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 12 or less. By making the number equal to or greater than the lower limit, the solubility in the semiconductor nanoparticle-containing composition tends to be improved. By making the number equal to or less than the upper limit, the excitation light absorption efficiency per mass tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aryl group is preferably 3 to 20, more preferably 6 to 12.

[0071] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, all of which have one free valence. From the viewpoint of high solubility in semiconductor nanoparticle-containing compositions, a benzene ring having one free valence and a naphthalene ring having one free valence are preferred, and a benzene ring having one free valence is more preferred.

[0072] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of aromatic heterocycles include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furopyrrole rings, furofuran rings, thienofuran rings, benzoxazole rings, benzothiazole rings, benzisoxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinnoline rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have one free valence. From the viewpoint of high solubility in the semiconductor nanoparticle-containing composition and enhanced interaction between the fluorescent dye (C1) and the semiconductor nanoparticles (A), a pyridine ring, a furan ring, or a thiophene ring, each having one free valence, is preferred.

[0073] R 2 , R 3 , R 4 , R 5 , R 6 The optionally substituted aryloxy group in the formula (I) includes a group in which an oxygen atom is bonded to a bond of an aryl group, such as a phenoxy group or a 2-thienyloxy group.

[0074] R 2 , R 3 , R 4 , R 5 , R 6 In the above, the optionally substituted amino group includes an amino group represented by -NH2, as well as amino groups having the above alkyl groups or aryl groups as substituents, such as a dimethylamino group, a diethylamino group, a (2-ethylhexyl)amino group, and a phenylamino group.

[0075] R 2 , R 3 , R 4 , R 5 , R 6Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of improving the durability of the fluorescent dye (C1), a fluorine atom or a chlorine atom is preferred.

[0076] R 2 , R 3 , R 4 , R 5 , R 6 From the viewpoint of solubility in the semiconductor nanoparticle-containing composition, the alkyl group is preferably a 2-propyl group, a t-butyl group, or an o-tolyl group, and from the viewpoint of excitation light absorption efficiency per mass and stability of the fluorescent dye, a hydrogen atom is desirable.

[0077] (X) X in formula (cI) is NR 7 R 8 , S.R. 9 , OR 10 It represents one of the following structures: For example, when using 450 nm light as excitation light, NR 7 R 8 is preferred.

[0078] (R 7 , R 8 ) R 7 , R 8 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an alkyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryl group which may have a substituent, an arylcarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a hydroxyl group. For example, from the viewpoint of ease of synthesis, an alkyl group which may have a substituent is preferred. X is NR 7 R 8 If R 7 , R 8 may be linked to form a ring.

[0079] (R 9 , R 10 ) R 9 , R 10 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples include an optionally substituted alkyl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted arylcarbonyl group, an optionally substituted aryloxycarbonyl group, and an optionally substituted alkylsulfonyl group.

[0080] R in formula (cI) 4 and X may be linked to form a ring. Examples of formula (cI) when a ring is formed in this way are shown below.

[0081] [ka]

[0082] (Fluorescent dyes with a coumarin skeleton) As a fluorescent dye having a coumarin skeleton, a fluorescent dye represented by formula (c-II) (hereinafter also referred to as "fluorescent dye (C2)") is preferred, from the viewpoints of high solubility in various solvents and semiconductor nanoparticle-containing compositions, high gram extinction coefficient, resistance to concentration quenching, and high fluorescence quantum yield.

[0083] [ka]

[0084] In formula (c-II), R 1 , R 2 , R 3 , R 4 , R 6 each independently represents a hydrogen atom or an arbitrary substituent. R 5 is a hydrogen atom, N(R 7 )2, OR7 Represents R 5 is N(R 7 )2, then R 7 They may be linked together to form a ring. R 7 represents a hydrogen atom or an arbitrary substituent. R 4 , R 5 and R 6 Two or more selected from the group consisting of may be linked to form a ring.

[0085] The symbols in formula (c-II) are explained below.

[0086] (R 1 , R 2 , R 3 , R 4 , R 6 ) R 1 , R 2 , R 3 , R 4 , R 6 each independently represents a hydrogen atom or an arbitrary substituent.

[0087] R 1 , R 2 , R 3 , R 4 , R 6 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples include an alkyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a cyano group, a nitro group, a halogen atom, a hydroxyl group, an amino group, and a carboxy group.

[0088] R 2 , R 3 , R 4 , R 6Among these, from the viewpoint of the absorption efficiency of the excitation light, a methyl group, a cyano group, a trifluoromethyl group, a nitro group, an amino group, and a carboxy group are preferred, and a cyano group and a trifluoromethyl group are more preferred.

[0089] R 1 From the viewpoint that the fluorescent dye (C2) has a structure that exhibits a strong emission spectrum, the group is preferably a group represented by the following general formula (c-II-1).

[0090] [ka]

[0091] In formula (c-II-1), X represents an oxygen atom, a sulfur atom, or NR 9 Represents. R 8 represents a hydrogen atom or an arbitrary substituent. R 9 represents a hydrogen atom or an alkyl group. R 8 NR 9 If R 9 and R 8 may be linked to form a ring. * represents a bond.

[0092] (X) In formula (c-II-1), X represents an oxygen atom, a sulfur atom, or NR 9 The group represented by formula (c-II-1) tends to have a higher fluorescence intensity when it attracts more electrons from the coumarin skeleton, and therefore, from the viewpoint of using a group containing an atom with high electronegativity, an oxygen atom or NR 9 is preferred.

[0093] R 9 represents a hydrogen atom or an alkyl group. R 9Examples of the alkyl group in (C2) include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group formed by combining these. A cyclic alkyl group is preferred because it increases the durability of the fluorescent dye (C2). Some of the -CH2- in the alkyl group may be substituted with -O-.

[0094] (R 8 ) In formula (c-II-1), R 8 represents a hydrogen atom or an arbitrary substituent. R 8 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, a sulfanyl group, an optionally substituted alkylsulfanyl group, an optionally substituted arylsulfanyl group, a hydroxyl group, and an amino group.

[0095] From the viewpoint of the absorption efficiency of the excitation light, R 8 is preferably a methyl group.

[0096] X is NR 9 If R 9 and R 8 may be linked to form a ring. For example, R 8 and any substituents where R 9 can be linked to a hydrogen atom to form a ring, in which case R 9 becomes a single bond. R 9 and R 8 When R are linked to form a ring, the ring may be an aliphatic ring or an aromatic ring. 9 and R 8 When R are linked to form a ring, the ring is preferably an aromatic ring. 9 and R 8 Examples of rings formed by linking are shown below.

[0097] [ka]

[0098] (R 5 ) In formula (c-II), R 5 is a hydrogen atom, N(R 7 )2, OR 7 Represents R 5 is N(R 7 )2, then R 7 They may be linked together to form a ring. R 5 is N(R 7 )2 is preferred.

[0099] R 7 represents a hydrogen atom or an arbitrary substituent. R 7 Examples of the optional substituent in include an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an optionally substituted alkylsulfonyl group, and an optionally substituted arylsulfonyl group.

[0100] R 4 , R 5 and R 6 Two or more selected from the group consisting of may be linked to form a ring. Examples of formula (c-II) when a ring is formed are shown below.

[0101] [ka]

[0102] Among the fluorescent dyes (C2), fluorescent dyes represented by the following general formula (c-II-2) are preferred from the viewpoint of having high solubility in the semiconductor nanoparticle-containing composition.

[0103] [ka]

[0104] In formula (c-II-2), R 1 ~R 3 has the same meaning as formula (c-II). R 10 , R 11 each independently represents an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 4.

[0105] (R 10 , R 11 ) In formula (c-II-2), R 10 , R 11 each independently represents an alkyl group having 1 to 4 carbon atoms. R 10 , R 11 The number of carbon atoms in the alkyl group is not particularly limited as long as it is 1 to 4, but is preferably 1 to 3, and more preferably 1 or 2. By making the carbon number equal to or less than the upper limit, the absorption efficiency of excitation light relative to the mass of the fluorescent dye present in the semiconductor nanoparticle-containing composition tends to be improved.

[0106] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a tertiary butyl group. In terms of high absorption efficiency of excitation light, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0107] (m, n) In formula (c-II-2), m and n each independently represent an integer of 0 to 4. From the viewpoints of high solubility in the semiconductor nanoparticle-containing composition and high excitation light absorption efficiency relative to the mass of the fluorescent dye present in the semiconductor nanoparticle-containing composition, m and n are preferably integers of 2 or less.

[0108] (Fluorescent dyes with perylene skeleton) As the fluorescent dye having a perylene skeleton, from the viewpoint of increasing the luminescence intensity of the semiconductor nanoparticles due to the interaction between the fluorescent dye and the semiconductor nanoparticles, a fluorescent dye represented by the following general formula (c-III) (hereinafter also referred to as "fluorescent dye (C3)") is preferred.

[0109] [ka]

[0110] In formula (c-III), R 11 , R 21 , R 31 , R 41 Each independently represents a hydrogen atom or an arbitrary substituent. 11 , R 21 , R 31 , R 41 At least one of the above is a group represented by the following general formula (c-III-1). R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , R 43 each independently represents a hydrogen atom or an arbitrary substituent.

[0111] [ka]

[0112] In formula (c-III-1), R 5 represents a hydrogen atom or an arbitrary substituent. * represents a bond.

[0113] The symbols in formula (c-III) will be explained below.

[0114] (R 11 , R 21 , R 31 , R 41 ) R 11 , R 21 , R 31 , R 41Each independently represents a hydrogen atom or an arbitrary substituent. 11 , R 21 , R 31 , R 41 At least one of the groups is a group represented by formula (c-III-1).

[0115] [ka]

[0116] In formula (c-III-1), R 5 represents a hydrogen atom or an arbitrary substituent. * represents a bond.

[0117] R 5 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include hydrocarbon groups which may have a substituent. Some of the -CH2- in the hydrocarbon group may be substituted with -O-, and some of the carbon atoms in the hydrocarbon group may be substituted with heteroatoms. Examples of hydrocarbon groups include alkyl groups which may have a substituent and aryl groups which may have a substituent.

[0118] R 5 is R 11 , R 21 , R 31 , R 41 In this case, R 5 Examples of the alkyl group include a carbonyl group (-CO-), a methylene group (-CH2-), an alkylidene methylene group (-C(=C(R 51 )2)-(where R 51 Each independently represents a hydrogen atom or a hydrocarbon group having 2 to 6 carbon atoms. 5 is preferably a carbonyl group (—CO—).

[0119] From the viewpoint of improving the conversion efficiency of pump light, R 5is preferably a 2-ethylhexyl group or a (2-(2-sulfanylethoxy)ethoxy)ethyl group, and from the viewpoint of solubility in the semiconductor nanoparticle-containing composition, a (2-(2-methoxyethoxy)ethoxy)ethyl group is preferred.

[0120] R 11 , R 21 , R 31 , R 41 At least one of the groups is a group represented by formula (c-III-1), more preferably two or more, even more preferably three or more, and particularly preferably all of them. By making the number of groups equal to or greater than the lower limit, the absorption efficiency of the excitation light tends to be improved.

[0121] R 11 , R 21 , R 31 , R 41 The optional substituent in R is not particularly limited as long as it is a substitutable monovalent group other than the group represented by formula (c-III-1), and examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an amide group which may have a substituent, a cyano group, and a halogen atom. 11 and R 21 may be linked to form a ring, and R 31 and R 41 may be linked to form a ring.

[0122] Among the optional substituents, from the viewpoint of improving the conversion efficiency of excitation light, a 2-ethylhexyl group and a (2-(2-sulfanylethoxy)ethoxy)ethyl group are preferred, and from the viewpoint of solubility in a semiconductor nanoparticle-containing composition, a (2-(2-methoxyethoxy)ethoxy)ethyl group is preferred.

[0123] R 11 and R 21 may be linked to form a ring, and R 31 and R 41 may be linked to form a ring. When R forms a ring, 11and R 21 a group linked by R 31 and R 41 Examples of the group to which - is linked include -CO-(NR 6 )-CO-(R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), an ethylene group (-CH2-CH2-), a trimethylene group (-CH2-CH2-CH2-), and a phenylene group are preferred. From the viewpoint of the absorption efficiency of the excitation light and ease of synthesis, -CO-(NR 6 )-CO- is preferred.

[0124] (R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , R 43 ) In formula (c-III), R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , R 43 each independently represents a hydrogen atom or an arbitrary substituent.

[0125] R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , R 43 The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylcarbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylcarbonyl group, an optionally substituted aryloxycarbonyl group, a cyano group, and a halogen atom.

[0126] A hydrogen atom, or from the viewpoint of solubility in the semiconductor nanoparticle-containing composition, a 2-ethylhexyl group or a (2-(2-methoxyethoxy)ethoxy)ethyl group is preferred, and from the viewpoint of ease of synthesis, a hydrogen atom is preferred.

[0127] From the viewpoint of increasing the luminescence intensity of the semiconductor nanoparticles, the fluorescent dye (C) is preferably a fluorescent dye having a partial structure represented by general formula (c-IV) (hereinafter also referred to as "fluorescent dye (C4)"). [ka]

[0128] In formula (c-IV), X represents an O atom or a S atom. Z is CR 2 or represents a N atom. R 1 , R 2 each independently represents a hydrogen atom or an arbitrary substituent. * represents a bond.

[0129] The symbols in formula (c-IV) will be explained below.

[0130] (X) X represents an O atom or a S atom. Among these, O atoms are preferred from the viewpoint of increasing the emission intensity, and S atoms are preferred from the viewpoint of light resistance.

[0131] (Z) Z is CR 2 or represents a N atom. From the viewpoint of ease of synthesis, Z is CR 2 is preferred.

[0132] (R 1 , R 2 ) R 1 , R 2 each independently represents a hydrogen atom or an arbitrary substituent. The optional substituent is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, a sulfanyl group, an optionally substituted dialkylphosphino group, an optionally substituted alkylsulfanyl group, a hydroxyl group, a carboxy group, an amino group, a nitro group, a cyano group, and a halogen atom. 2 In the case of R 1 and R 2 may be linked to form a ring.

[0133] From the viewpoint of absorption wavelength and solubility in the composition, R 1 , R 2 are each independently preferably a hydrogen atom, a 2-ethylhexyl group, a phenyl group, or a 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy group, and more preferably a hydrogen atom.

[0134] Z is CR 2 In the case of R 1 and R 2 may be linked to form a ring, and specific examples of such a ring include the following:

[0135] [ka]

[0136] Among the fluorescent dyes (C4), the fluorescent dye represented by the following general formula (c-IV-1) is preferred from the viewpoint of increasing the emission intensity.

[0137] [ka]

[0138] In formula (c-IV-1), X represents an O atom or a S atom. Z is CR 2 or represents a N atom. R1 , R 2 each independently represents a hydrogen atom or an arbitrary substituent. a 1 , a 2 are each independently a group represented by the following general formula (c-IV-2):

[0139] [ka]

[0140] In formula (c-IV-2), b 11 represents an arylene group which may have a substituent, a —CH═CH— group which may have a substituent, a —C≡C— group, a —CH═N— group which may have a substituent, a —N═CH— group which may have a substituent, a —CO— group, or a —N═N— group. b 12 is a single bond, or b 11 represents a divalent group other than Each x independently represents an integer of 0 to 3. When x is an integer of 2 or more, a plurality of b 11 may be the same or different. Each y independently represents an integer of 1 to 3. When y is an integer of 2 or more, a plurality of b 12 may be the same or different. R 11 represents a hydrogen atom or an arbitrary substituent. *Represents a bond.

[0141] In the case of the fluorescent dye represented by formula (c-IV-1), the fluorescent dyes are less likely to form aggregates, and a decrease in fluorescence intensity (concentration quenching) tends to be less likely to occur.

[0142] X, Z, and R in formula (c-IV-1) 1 and R 2 As the groups, X, Z, and R in formula (c-IV) 1 and R 2 A hydrogen atom or any of the substituents listed as above can be preferably employed.

[0143] (a 1and a 2 ) In the formula (c-IV-1), a 1 and a 2 are each independently a group represented by the following general formula (c-IV-2): a 1 and a 2 may be the same group or different groups, but from the viewpoint of ease of synthesis, they are preferably the same group.

[0144] [ka]

[0145] In formula (c-IV-2), b 11 represents an arylene group which may have a substituent, a —CH═CH— group which may have a substituent, a —C≡C— group, a —CH═N— group which may have a substituent, a —N═CH— group which may have a substituent, a —CO— group, or a —N═N— group. b 12 is a single bond, or b 11 represents a divalent group other than Each x independently represents an integer of 0 to 3. When x is an integer of 2 or more, a plurality of b 11 may be the same or different. Each y independently represents an integer of 1 to 3. When y is an integer of 2 or more, a plurality of b 12 may be the same or different. R 11 represents a hydrogen atom or an arbitrary substituent. *Represents a bond.

[0146] (b 11 ) In formula (c-IV-2), b 11 represents an arylene group which may have a substituent, a —CH═CH— group which may have a substituent, a —C≡C— group, a —CH═N— group which may have a substituent, a —N═CH— group which may have a substituent, —CO—, or a —N═N— group.

[0147] b 11When is an arylene group which may have a substituent, the bound arylene group is twisted from the diazole plane due to steric hindrance, which inhibits stacking of the fluorescent dyes and tends to reduce the occurrence of concentration quenching, which is preferable.

[0148] Examples of the substituent that the arylene group may have include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, a sulfanyl group, a dialkylphosphino group, an alkylsulfanyl group, a hydroxyl group, a carboxy group, an amino group, a nitro group, a cyano group, and a halogen atom. The substituent of the arylene group is preferably an amino group or a sulfanyl group from the viewpoint of energy transfer efficiency to the semiconductor nanoparticles. From the viewpoint of solubility, the substituent of the arylene group is preferably a hydrogen atom, an alkyl group, or an alkoxy group, and more preferably a hydrogen atom, a t-butyl group, or a 2-propyloxy group.

[0149] Examples of the substituent in the optionally substituted -CH=CH- group, the optionally substituted -CH=N- group, or the optionally substituted -N=CH- group include an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylsulfanyl group, an amino group, a cyano group, a sulfanyl group, and a halogen atom. From the viewpoint of energy transfer efficiency to the semiconductor nanoparticles, the substituent in the optionally substituted -CH=CH- group, the optionally substituted -CH=N- group, or the optionally substituted -N=CH- group is preferably an amino group or a sulfanyl group. From the viewpoint of solubility, the substituent in the optionally substituted -CH=CH- group, the optionally substituted -CH=N- group, or the optionally substituted -N=CH- group is preferably a hydrogen atom, an alkyl group, or an alkoxy group, and particularly preferably a hydrogen atom, a t-butyl group, or a 2-propyloxy group.

[0150] b 11is an arylene group which may have a substituent, the planarity of the molecular structure is reduced due to steric hindrance between the lone electron pair on the N atom of the diazole moiety and the hydrogen atom of the arylene group, or ... diazole moiety and the hydrogen atom of the arylene group, thereby suppressing the formation of aggregates between the fluorescent dyes due to π-π stacking or the like, and thus tending to suppress concentration quenching due to the formation of aggregates, which is preferable.

[0151] b 11 However, in the case of a -CH=CH- group which may have a substituent, a -C≡C- group, a -CH=N- group which may have a substituent, a -N=CH- group which may have a substituent, a -CO- group, or a -N=N- group, the fluorescent dye itself only has a π-conjugation of the diazole moiety, and therefore the molecular planarity is small, and concentration quenching due to aggregate formation is thought to tend to be small, and therefore these are preferred.

[0152] In terms of absorption wavelength, b 11 is preferably a divalent benzene ring group, a -CH=CH- group.

[0153] (b 12 ) In formula (c-IV-2), b 12 is a single bond, or b 11 represents a divalent group other than b 11 The divalent group other than the above is not particularly limited. 11 Examples of the divalent group other than the above include an alkylene group which may have a substituent, an alkyleneoxy group which may have a substituent, and an alkyleneamino group which may have a substituent.

[0154] b 12 From the viewpoint of solubility in the composition, a 2-ethylhexanediyl group or an -O-CH2-CH2-O-CH2-CH2-O-CH2-CH2- group is preferred, and from the viewpoint of improving absorbance to excitation light, a single bond or a methylene group is preferred.

[0155] (x) In formula (c-IV-2), each x independently represents an integer of 0 to 3. In view of the absorption wavelength, x is preferably 1 or 2, and more preferably 1.

[0156] a 1 x and a inside 2 Preferably, one or both of the x's in a is an integer of 1 to 3, and 1 x and a inside 2 It is more preferable that both x's in a are 1. 1 x and a inside 2 When one or both of the x's in the formula (1) are integers of 1 or more, the absorption efficiency of the excitation light tends to be improved. If x is an integer greater than or equal to 2, multiple b 11 may be the same or different.

[0157] (y) In formula (c-IV-2), each y independently represents an integer of 1 to 3. From the viewpoints of solubility in the composition and absorbance to excitation light, y is preferably 1 or 2, and particularly 1 is more preferable. If y is an integer greater than or equal to 2, multiple b 12 may be the same or different.

[0158] (R 11 ) In formula (c-IV-2), R 11 represents a hydrogen atom or an arbitrary substituent. The optional substituent is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an optionally substituted aryl group, an optionally substituted aryloxy group, a hydroxyl group, a carboxy group, a formyl group, a sulfo group, an optionally substituted amino group, a sulfanyl group, an optionally substituted alkylsulfanyl group, an optionally substituted dialkylphosphino group, a nitro group, a cyano group, an optionally substituted trialkylsilyl group, an optionally substituted dialkylboryl group, and a halogen atom.

[0159] From the viewpoint of energy transfer efficiency to semiconductor nanoparticles, R 11is preferably a carboxy group, an amino group, a sulfanyl group, or a pyridine ring having one free valence, and from the viewpoint of solubility, a hydrogen atom or a trialkylsilyl group is preferred.

[0160] From the viewpoint of increasing the luminescence intensity of the semiconductor nanoparticles, a fluorescent dye having a partial structure represented by general formula (cV) (hereinafter also referred to as "fluorescent dye (C5)") is also preferred as the fluorescent dye (C).

[0161] [ka]

[0162] In formula (cV), Ar 1 , Ar 2 , Ar 3 each independently represents an aryl group which may have a substituent. R 1 , R 2 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0163] The symbols in formula (cV) will be explained below.

[0164] (Ar 1 , Ar 2 , Ar 3 ) Ar 1 , Ar 2 , Ar 3 each independently represents an aryl group which may have a substituent. The aryl group includes, for example, Ar 1 , Ar 2 Examples of Ar include divalent aromatic hydrocarbon ring groups (aromatic hydrocarbon rings with two free valences) and divalent aromatic heterocyclic groups (aromatic heterocyclic rings with two free valences). 3 Examples of the aromatic heterocyclic group include a monovalent aromatic hydrocarbon ring group (an aromatic hydrocarbon ring having one free valence) and a monovalent aromatic heterocyclic group (an aromatic heterocyclic ring having one free valence).

[0165] From the viewpoint of increasing the emission intensity, Ar 1 is preferably a benzene ring having two free valences or a naphthalene ring having two free valences. From the viewpoint of increasing the emission intensity, Ar 2 is preferably a group represented by any one of the following general formulas (cV-1), (cV-2), and (cV-3). 3 is preferably a benzene ring having one free valence.

[0166] [ka]

[0167] In formulas (cV-1), (cV-2), (cV-3), R 3 , R 4 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0168] (R 3 and R 4 ) In formulas (cV-1), (cV-2), (cV-3), R 3 , R 4 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0169] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group formed by combining these. 3 , R 4 From the viewpoint of solubility, a branched alkyl group is preferred.

[0170] The aryl group includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less. By making the number of carbon atoms equal to or greater than the lower limit, the efficiency of energy transfer to the semiconductor nanoparticles tends to improve, and by making the number of carbon atoms equal to or less than the upper limit, the solubility tends to improve. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 6 to 10.

[0171] (R 1 , R 2 ) In formula (cV), R 1 , R 2 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.

[0172] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group formed by combining these. From the viewpoint of improving light resistance by steric hindrance, R 1 , R 2 is preferably a branched alkyl group or a cyclic alkyl group.

[0173] The aryl group includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less. By making the number of carbon atoms equal to or greater than the lower limit, light resistance tends to be improved due to steric hindrance, and by making the number of carbon atoms equal to or less than the upper limit, solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 6 to 10.

[0174] From the viewpoint of increasing the luminescence intensity of the semiconductor nanoparticles, the fluorescent dye (C) is preferably a fluorescent dye having a partial structure represented by general formula (c-VI) (hereinafter also referred to as "fluorescent dye (C6)").

[0175] [ka]

[0176] In formula (c-VI), X represents C-* or N. * represents a bond. R 1 , R 2 each independently represents a fluorine atom or a cyano group.

[0177] The symbols in formula (c-VI) are explained below.

[0178] (R 1 , R 2 ) R 1 , R 2 each independently represents a fluorine atom or a cyano group. R 1 , R 2 As the atom, a fluorine atom is preferred from the viewpoint of improving the durability of the fluorescent dye (C6).

[0179] (X) X represents C-* or N, and * represents a bond. From the viewpoint of improving the durability of the fluorescent dye and the stability of the absorption spectrum of the fluorescent dye (C6) against pH, X is preferably C-*, and CR 9 is more preferable. 9 represents a hydrogen atom or an arbitrary substituent. When blue excitation light is used, X is preferably C-*, and CR 9 is more preferred.

[0180] (R 9 ) R 9The optional substituent in is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include an optionally substituted alkyl group, an optionally substituted alkylcarbonyl group, an optionally substituted alkylcarbonyloxy group, an optionally substituted alkylcarbonylamino group, an optionally substituted alkylsulfonyl group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted arylcarbonyl group, an optionally substituted arylcarbonyloxy group, an optionally substituted arylcarbonylamino group, an optionally substituted arylsulfonyl group, an optionally substituted aryloxy group, an optionally substituted aryloxycarbonyl group, an optionally substituted amino group, an optionally substituted carbamoyl group, an optionally substituted sulfanyl group, an optionally substituted sulfonyl group, an optionally substituted silyl group, an optionally substituted boryl group, an optionally substituted phosphinoyl group, a carboxy group, a formyl group, a sulfo group, a cyano group, a nitro group, a halogen atom, and a hydroxyl group.

[0181] When blue light is used as the excitation light, R 9 is preferably an alkoxy group or an amino group (particularly an alkylamino group). From the viewpoint of improving the solubility in the semiconductor nanoparticle-containing composition and improving the durability of the fluorescent dye (C6), 9 is preferably an alkyl group, an aryl group, an alkoxy group, or an amino group, more preferably a methyl group, a 2-ethylhexyl group, a phenyl group, a 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy group, a phenoxy group, or a 2-ethylhexylamino group, and particularly preferably a methyl group, a phenyl group, or a 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy group.

[0182] The fluorescent dye (C6) is not particularly limited as long as it is represented by formula (c-VI). From the viewpoints of high solubility in various solvents and semiconductor nanoparticle-containing compositions, high gram extinction coefficient, resistance to concentration quenching, and high fluorescence quantum yield, it is preferably a fluorescent dye represented by the following general formula (c-VI-1):

[0183] [ka]

[0184] In formula (c-VI-1), X is CR 9 Or represents N. R 3 ~R 9 each independently represents a hydrogen atom or an arbitrary substituent. R 4 and R 3 or R 5 may be linked to form a ring. R 7 and R 6 or R 8 may be linked to form a ring. R 1 , R 2 each independently represents a fluorine atom or a cyano group.

[0185] The symbols in formula (c-VI-1) are explained below.

[0186] (R 1 , R 2 ) R 1 , R 2 each independently represents a fluorine atom or a cyano group. R 1 , R 2 is preferably a fluorine atom from the viewpoint of improving the durability of the fluorescent dye.

[0187] (X, R 9 ) X is CR 9 or N, and from the viewpoint of improving the durability of the fluorescent dye, CR 9 is preferred. 9represents a hydrogen atom or an arbitrary substituent, R 9 The optional substituents in the formula (c-VI) include the substituents described in the formula (c-VI), and preferred substituents are also the same as those described in the formula (c-VI).

[0188] (R 3 ~R 8 ) R 3 ~R 8 each independently represents a hydrogen atom or an arbitrary substituent, R 3 ~R 8 In formula (c-VI), R 9 Examples of the optional substituents in the above formula include the substituents described above as optional substituents in the above formula.

[0189] R 3 ~R 8 From the viewpoints of improving the solubility in the semiconductor nanoparticle-containing composition and improving the durability of the fluorescent dye, the alkyl group, aryl group, alkoxycarbonyl group, and aryloxycarbonyl group are preferred, with a methyl group, 2-ethylhexyl group, phenyl group, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxycarbonyl group, and phenoxycarbonyl group being more preferred, and a methyl group, 2-ethylhexyl group, and 2-[2-(2-hydroxyethoxy)ethoxy]ethoxycarbonyl group being particularly preferred.

[0190] R 4 and R 3 or R 5 may be linked to form a ring, and R 7 and R 6 or R 8 may be linked to form a ring. An example of formula (c-VI-1) when a ring is formed is shown below.

[0191] [ka]

[0192] Among the fluorescent dyes represented by formula (c-VI-1), from the viewpoint of improving the durability of the fluorescent dye, 1 and R 2 is a fluorine atom, and X is CR 9 and R 9 is preferably a hydrogen atom or an arbitrary substituent.

[0193] From the viewpoint of improving the solubility in the semiconductor nanoparticle-containing composition and improving the durability of the fluorescent dye, a preferred structure of the fluorescent dye (C6) is 1 , R 2 is a fluorine atom, and X is CR 9 and R 9 is an alkyl group, an aryl group, an alkoxy group, or an amino group, and R 3 ~R 8 is preferably an alkyl group, an aryl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. When blue excitation light is used, from the viewpoint of improving absorption efficiency, a preferred structure of the fluorescent dye (C6) is a structure represented by the formula (c-VI-1), in which X is CR 9 and R 9 is preferably an alkoxy group or an amino group (particularly an alkylamino group).

[0194] The fluorescent dye (C) has a substituent that acts to link to the semiconductor nanoparticle (A). When the fluorescent dye (C) has a substituent that causes it to link to the semiconductor nanoparticle (A), the fluorescent dye (C) becomes more easily adsorbed to the semiconductor nanoparticle (A), and when a wavelength conversion layer is formed, the excitation energy of the fluorescent dye (C) adsorbed on the surface of the semiconductor nanoparticle (A) is transferred to the semiconductor nanoparticle (A) by Förster energy transfer, making it possible to improve the luminescence efficiency of the semiconductor nanoparticle (A). From the viewpoint of making it easier to link to the semiconductor nanoparticles (A), it is preferable that the fluorescent dye (C) has a substituent at the end of its structure that causes it to link to the semiconductor nanoparticles (A).

[0195] Examples of the substituent in the fluorescent dye (C) that acts to link to the semiconductor nanoparticle (A) include a sulfanyl group or a salt thereof, an acid group or a salt thereof, an amino group or a salt thereof, a phosphate ester group or a salt thereof, a phosphanetriyl group, and a phosphoryl group. The amino group is a substituent represented by -NH.

[0196] The acid group or a salt thereof is preferably a carboxy group or a salt thereof, a sulfo group or a salt thereof, or a phosphono group or a salt thereof, from the viewpoint of the bonding strength to the surface of the semiconductor nanoparticle (A).

[0197] The substituent in the fluorescent dye (C) that acts to link to the semiconductor nanoparticle (A) is preferably a sulfanyl group or a salt thereof, an amino group or a salt thereof, a carboxy group or a salt thereof, or a phosphono group or a salt thereof, from the viewpoint of its strong linking effect, more preferably a sulfanyl group, an amino group, or a phosphono group, and particularly preferably a sulfanyl group.

[0198] The substituent that exerts the action of linking to the semiconductor nanoparticles (A) may be bonded to the skeleton or structure of the fluorescent dye (C), and the position thereof is not particularly limited.

[0199] Having a substituent that has the ability to link to the semiconductor nanoparticle (A) means that the fluorescent dye (C) is bonded to the skeleton or structure thereof by a chemical bond such as a covalent bond, an ionic bond, or a coordinate bond (including the bond between a metal element and a ligand that forms a metal complex).

[0200] Whether or not a linking action occurs can be determined, for example, by the following evaluation criteria. A fluorescent dye is added to a butyl acetate solution of semiconductor nanoparticles with ligands containing polyethylene glycol chains, and then the solution is left to stand at room temperature for 2 hours. Normal heptane is then added to precipitate the semiconductor nanoparticles. The precipitate and supernatant are then separated using a centrifuge, and the supernatant is dried to determine the amount of fluorescent dye contained in the residue. 1 Quantitative analysis is performed using H-NMR. At this time, the amount of fluorescent dye contained in the supernatant is 50 mass% or less, it can be determined that the fluorescent dye has been linked to the semiconductor nanoparticles. (To prevent the fluorescent dye not linked to the semiconductor nanoparticles from precipitating when normal heptane is added, it is necessary to confirm in advance that the fluorescent dye to be added dissolves in a mixed solution of butyl acetate and normal heptane.)

[0201] Specific examples of the fluorescent dye (C), particularly, specific examples of a fluorescent dye having a naphthalimide skeleton, a fluorescent dye having a coumarin skeleton, a fluorescent dye having a perylene skeleton, a fluorescent dye having a structure represented by formula (c-IV), a fluorescent dye having a structure represented by formula (cV), and a fluorescent dye having a structure represented by formula (c-VI), are given below.

[0202] [ka]

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] The method for producing the fluorescent dye (C) is not particularly limited, but it can be produced by the methods described in, for example, JP 2003-104976 A, JP 2011-231245 A, WO 2015 / 111647 A, JP 2015-006173 A, Chem. Eur. J., 13, 1746-1753, 2007, and Chem. Rev., 107, pp. 4891-4932, 2007.

[0212] The method for introducing a substituent into the fluorescent dye (C) that has the ability to link to semiconductor nanoparticles is not particularly limited, but examples thereof include the methods described in Chem. Phys. Chem., 11, 3167-3171, 2010; J. Am. Chem. Soc., 127, 3870-3878, 2005; and JP 2017-186564 A.

[0213] The maximum emission wavelength of the fluorescence emitted by the fluorescent dye (C) is not particularly limited, but is preferably 450 nm or longer, more preferably 455 nm or longer, even more preferably 460 nm or longer, and particularly preferably 465 nm or longer. It is also preferably 640 nm or shorter, more preferably 635 nm or shorter, even more preferably 630 nm or shorter, and particularly preferably 625 nm or shorter. The above upper and lower limits can be combined arbitrarily. For example, the maximum emission wavelength of the fluorescence emitted by the fluorescent dye (C) is preferably 450 to 640 nm, more preferably 455 to 635 nm, even more preferably 460 to 630 nm, and particularly preferably 465 to 625 nm. By setting the absorption wavelength at or above the lower limit, when blue light is used as an excitation light source, the semiconductor nanoparticles that could not be sufficiently absorbed and excited can be excited, which tends to lead to an increase in the emission intensity of the semiconductor nanoparticles. Furthermore, by setting the absorption wavelength at or below the upper limit, the emission spectrum of the semiconductor nanoparticles and the emission spectrum of the fluorescent dye (C) can be separated, which increases the energy transferred from the fluorescent dye (C) to the semiconductor nanoparticles. Furthermore, when used in a display, it tends to be easier to absorb emission in unnecessary wavelength regions from the fluorescent dye (C) using a color filter provided separately from the pixel portion. For example, it is preferable that the maximum emission wavelength of the fluorescence emitted by the fluorescent dye (C) is around 460 to 630 nm, as this tends to increase the emission intensity of both the green-emitting semiconductor nanoparticles and the red-emitting semiconductor nanoparticles. The method for measuring the maximum emission wavelength is not particularly limited. For example, the maximum emission wavelength may be read from an emission spectrum measured with a spectrofluorometer using a solution of the fluorescent dye (C) or a film containing the fluorescent dye (C) and light with a wavelength of 445 nm as an excitation light source.

[0214] The semiconductor nanoparticle-containing composition of the present invention may contain one or more fluorescent dyes (C) and may further contain a dye other than the fluorescent dye (C).

[0215] The content of the fluorescent dye (C) in the semiconductor nanoparticle-containing composition of the present invention is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total solid content of the semiconductor nanoparticle-containing composition. By setting the content at or above the lower limit, the fluorescent dye (C) sufficiently absorbs the irradiated light, increasing the amount of energy transfer from the fluorescent dye (C) to the semiconductor nanoparticles (A), and tending to increase the luminescence intensity of the semiconductor nanoparticles (A). Furthermore, by setting the content at or below the upper limit, concentration quenching of the fluorescent dye (C) is suppressed, and energy transfer from the fluorescent dye (C) to the semiconductor nanoparticles (A) is efficient, increasing the luminescence intensity of the semiconductor nanoparticles (A). Furthermore, by including components other than the semiconductor nanoparticles (A) and the fluorescent dye (C), a wavelength conversion layer with sufficient hardness tends to be obtained. The above upper and lower limits can be arbitrarily combined. For example, the content is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, further preferably 0.05 to 10%, and particularly preferably 0.1 to 5% by mass.

[0216] [1-4] (Meth)acrylate compound (D) The semiconductor nanoparticle-containing composition of the present invention contains a (meth)acrylate compound (D). By containing the (meth)acrylate compound (D), when a wavelength conversion layer, particularly a color filter pixel portion, is used in which the semiconductor nanoparticle-containing composition of the present invention is used, the color filter pixel portion tends to be cured.

[0217] The (meth)acrylate compound (D) may be a monofunctional (meth)acrylate having one (meth)acryloyl group, or may be a polyfunctional (meth)acrylate having a plurality of (meth)acryloyl groups.

[0218] As the monofunctional (meth)acrylate, a monofunctional (meth)acrylate having a molecular weight of 150 g / mol to 350 g / mol is preferred from the viewpoints of excellent fluidity when the semiconductor nanoparticle-containing composition is made into an ink and excellent ejection stability.

[0219] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. Examples of the acrylates include methyl acrylate, ... From the viewpoints of dispersibility of semiconductor nanoparticles, inkjet ejection stability, and strength of the cured film, ethoxyethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and benzyl (meth)acrylate are preferred.

[0220] The polyfunctional (meth)acrylate may be, for example, a bifunctional (meth)acrylate, a trifunctional (meth)acrylate, a tetrafunctional (meth)acrylate, a pentafunctional (meth)acrylate, or a hexafunctional (meth)acrylate. The polyfunctional (meth)acrylate may be, for example, a di(meth)acrylate in which two hydroxyl groups of a diol compound are substituted with (meth)acryloyloxy groups, or a di- or tri(meth)acrylate in which two or three hydroxyl groups of a triol compound are substituted with (meth)acryloyloxy groups. From the viewpoints of excellent fluidity and excellent ejection stability when the semiconductor nanoparticle-containing composition is made into an ink, bifunctional (meth)acrylates are preferred.

[0221] From the viewpoint of achieving excellent fluidity and ejection stability when the semiconductor nanoparticle-containing composition is made into an ink, the polyfunctional (meth)acrylate preferably has a molecular weight of 150 g / mol or more, preferably 700 g / mol or less, and more preferably 350 g / mol or less. The above upper and lower limits can be combined arbitrarily. For example, the polyfunctional (meth)acrylate preferably has a molecular weight of 150 to 700 g / mol, more preferably 150 to 350 g / mol.

[0222] Examples of bifunctional (meth)acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropanediol di(meth)acrylate, ... Cyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, and two tris(2-hydroxyethyl)isocyanurates. di(meth)acrylates in which the hydroxyl groups of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol have been substituted with (meth)acryloyloxy groups; di(meth)acrylates in which the two hydroxyl groups of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A have been substituted with (meth)acryloyloxy groups; di(meth)acrylates in which the two hydroxyl groups of a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane have been substituted with (meth)acryloyloxy groups; and di(meth)acrylates in which the two hydroxyl groups of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A have been substituted with (meth)acryloyloxy groups.From the viewpoint of excellent dispersibility of semiconductor nanoparticles, inkjet ejection stability, and strength of the cured film, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate are preferred as the bifunctional (meth)acrylate.

[0223] Examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, glycerin triacrylate, pentaerythritol tri(meth)acrylate, and tri(meth)acrylates in which the three hydroxyl groups of a triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane are substituted with (meth)acryloyloxy groups.

[0224] An example of the tetrafunctional (meth)acrylate is pentaerythritol tetra(meth)acrylate.

[0225] An example of the pentafunctional (meth)acrylate is dipentaerythritol penta(meth)acrylate.

[0226] An example of a hexafunctional (meth)acrylate is dipentaerythritol hexa(meth)acrylate.

[0227] The polyfunctional (meth)acrylate may be, for example, a poly(meth)acrylate in which a plurality of hydroxyl groups of dipentaerythritol in dipentaerythritol hexa(meth)acrylate are substituted with (meth)acryloyloxy groups.

[0228] The (meth)acrylate compound (D) may be a (meth)acrylate having a phosphoric acid group, for example, an ethylene oxide-modified (meth)acrylate phosphate or an ethylene oxide-modified alkyl (meth)acrylate phosphate.

[0229] In the semiconductor nanoparticle-containing composition, when the curable component is composed solely of a (meth)acrylate compound (D) or mainly of a (meth)acrylate compound (D), it is preferable to use a polyfunctional (meth)acrylate as the (meth)acrylate compound (D) from the viewpoint of further improving the durability (strength, heat resistance, etc.) of the cured product. In this case, the content ratio of the polyfunctional (meth)acrylate relative to the total (meth)acrylate compounds (D) is preferably 10% by mass or more, more preferably 20% by mass or more. The upper limit is not particularly limited, but is usually 100% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the polyfunctional (meth)acrylate relative to the total (meth)acrylate compounds (D) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass. From the viewpoints of achieving excellent fluidity when made into an ink, achieving excellent ejection stability, and suppressing a decrease in smoothness due to cure shrinkage during color filter production, it is also preferable to use a combination of a monofunctional (meth)acrylate and a polyfunctional (meth)acrylate as the (meth)acrylate compound (D). In this case, the content of the polyfunctional (meth)acrylate relative to the total (meth)acrylate compound (D) is preferably 90% by mass or less, more preferably 80% by mass or less. The lower limit is not particularly limited, but is usually 0% by mass or more, and preferably 0.1% by mass or more. The above upper and lower limits can be arbitrarily combined. For example, 0 to 90% by mass is preferred, and 0.1 to 80% by mass is more preferred. When two or more types of (meth)acrylates are mixed to form the (meth)acrylate compound (D) component in this manner, the average molecular weight of the mixed (meth)acrylate compound (D) is preferably 150 g / mol or more and 350 g / mol or less, from the viewpoints of excellent fluidity when the semiconductor nanoparticle-containing composition is made into an ink and excellent ejection stability. When a plurality of (meth)acrylates are mixed to form the (meth)acrylate compound (D), the average molecular weight of the mixed (meth)acrylate compound (D) is calculated using the following formula. Average molecular weight of (meth)acrylate compound (D)=Σ[(molecular weight of each (meth)acrylate)×(blending ratio of each (meth)acrylate (mass%)) / 100]

[0230] The content of the (meth)acrylate compound (D) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more, of the total solids content of the semiconductor nanoparticle-containing composition, from the viewpoints of, for example, easily achieving an appropriate viscosity in the coating process as an ink for a wavelength conversion layer, particularly easily achieving an appropriate viscosity as an ink for an inkjet system, improving the curability of the semiconductor nanoparticle-containing composition, increasing the luminescence intensity of the semiconductor nanoparticles (A), and improving the solvent resistance and abrasion resistance of the pixel portion (cured product of the semiconductor nanoparticle-containing composition). From the viewpoint of obtaining better optical properties, the content is preferably 90% by mass or less, more preferably 80% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 20 to 90% by mass is preferred, 40 to 90% by mass is more preferred, 50 to 90% by mass is even more preferred, 60 to 90% by mass is even more preferred, and 70 to 80% by mass is particularly preferred.

[0231] [1-5] Polymerization initiator (E) The semiconductor nanoparticle-containing composition of the present invention may contain a polymerization initiator (E). By containing the polymerization initiator (E), the (meth)acrylate compound (D) tends to be easily polymerized. Examples of the polymerization initiator include a photoradical polymerization initiator (E1), a photocationic polymerization initiator (E2), and a thermal polymerization initiator (E3).

[0232] [1-5-1] Photoradical polymerization initiator (E1) As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitable.

[0233] Examples of molecular cleavage-type photoradical polymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide. Other molecular cleavage-type photoradical polymerization initiators may also be used in combination, such as 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0234] Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. A molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

[0235] Commercially available products can also be used as the photoradical polymerization initiator. Examples of commercially available products include acylphosphine oxide compounds such as "Omnirad (registered trademark; the same applies hereinafter) TPO-H," "Omnirad TPO-L," and "Omnirad 819," all manufactured by IGM Resin; alkylphenone compounds such as "Omnirad 651," "Omnirad 184," "Omnirad 1173," "Omnirad 2959," "Omnirad 127," "Omnirad 907," "Omnirad 369," "Omnirad 369E," and "Omnirad 379EG"; and intramolecular hydrogen abstraction compounds such as "Omnirad MBF" and "Omnirad 754," all manufactured by BASF Japan Ltd.; and "Irgacure (registered trademark; the same applies hereinafter) OXE01," "Irgacure OXE02," "Irgacure OXE03," and "Irgacure Examples of suitable oxime ester compounds include "OXE04" manufactured by Changzhou Strong Electronic New Materials Co., Ltd., "TR-PBG-304" and "TR-PBG-305" manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and "NCI-831" and "NCI-930" manufactured by ADEKA Corporation.

[0236] In addition to these, the oxime ester compounds include, for example, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Laid-Open No. 2000-80068, compounds described in International Publication No. 2012 / 45736, compounds described in International Publication No. 2015 / 36910, compounds described in Japanese Patent Application Laid-Open No. 2006-36750, compounds described in Japanese Patent Application Laid-Open No. 2008-179611, compounds described in International Publication No. 2009 / 131189, compounds described in Japanese Patent Application Laid-Open No. 2012-526185, compounds described in Japanese Patent Application Laid-Open No. 2012-519191, compounds described in International Publication No. 2006 / 18973, compounds described in International Publication No. 2008 / 78678, and compounds described in Japanese Patent Application Laid-Open No. 2011-132215. From the viewpoint of sensitivity, preferred oxime ester compounds are N-acetoxy-N-{4-acetoxyimino-4-[9-ethyl-6-(o-toluoyl)-9H-carbazol-3-yl]butan-2-yl}acetamide, N-acetoxy-N-{3-(acetoxyimino)-3-[9-ethyl-6-(1-naphthoyl)-9H-carbazol-3-yl]-1-methylpropyl}acetamide, and methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate.

[0237] When the semiconductor nanoparticle-containing composition of the present invention contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the (meth)acrylate compound (D), from the viewpoint of the curability of the semiconductor nanoparticle-containing composition. From the viewpoint of the stability over time of the pixel portion (the cured product of the semiconductor nanoparticle-containing composition), the content 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, per 100 parts by mass of the (meth)acrylate compound (D). The above upper and lower limits can be arbitrarily combined. For example, the content of the photoradical polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 100 parts by mass of the (meth)acrylate compound (D).

[0238] [1-5-2] Thermal polymerization initiator (E3) Examples of the thermal polymerization initiator used to cure the (meth)acrylate compound (D) include 2,2'-azobis(isobutyronitrile), di-tert-butyl peroxide, cumene hydroperoxide, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride.

[0239] When the semiconductor nanoparticle-containing composition of the present invention contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the (meth)acrylate compound (D), from the viewpoint of the curability of the semiconductor nanoparticle-containing composition. From the viewpoint of the stability over time of the pixel portion (the cured product of the semiconductor nanoparticle-containing composition), the content 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, per 100 parts by mass of the (meth)acrylate compound (D). The above upper and lower limits can be arbitrarily combined. For example, the content of the thermal polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 100 parts by mass of the (meth)acrylate compound (D).

[0240] [1-6]Light scattering particles The semiconductor nanoparticle-containing composition of the present invention may contain light-scattering particles. The light-scattering particles are, for example, optically inactive inorganic fine particles that can scatter light from a light source irradiating the pixel portions of the color filter, as well as light emitted by semiconductor nanoparticles or fluorescent dyes.

[0241] Examples of materials that constitute the light-scattering particles include: simple metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; metal oxides such as silica, barium sulfate, barium carbonate, calcium carbonate, talc, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, and zinc oxide; metal carbonates such as magnesium carbonate, barium carbonate, bismuth subcarbonate, and calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, and strontium titanate; and metal salts such as bismuth subnitrate. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the light-scattering particles preferably contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and barium titanate, and more preferably contain at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium titanate.

[0242] The shape of the light-scattering particles may be, for example, spherical, filamentous, or irregular. As the light-scattering particles, it is preferable to use particles with little directionality in particle shape (for example, spherical, tetrahedral, or other particles) because this can further improve the uniformity, fluidity, and light-scattering property of the semiconductor nanoparticle-containing composition and can provide excellent discharge stability.

[0243] The average particle size (volume average diameter) of the light-scattering particles in the semiconductor nanoparticle-containing composition is preferably 0.05 μm or more, more preferably 0.07 μm or more, and even more preferably 0.1 μm or more, from the viewpoint of excellent discharge stability and an excellent effect of improving external quantum efficiency. Furthermore, the average particle size (volume average diameter) of the light-scattering particles in the semiconductor nanoparticle-containing composition is preferably 1.0 μm or less, more preferably 0.5 μm or less, even more preferably 0.3 μm or less, and even more preferably 0.2 μm or less, from the viewpoint of excellent discharge stability. The above upper and lower limits can be arbitrarily combined. For example, the average particle size (volume average diameter) of the light-scattering particles in the semiconductor nanoparticle-containing composition is preferably 0.05 to 1.0 μm, more preferably 0.05 to 0.5 μm, even more preferably 0.07 to 0.3 μm, and particularly preferably 0.1 to 0.2 μm. The average particle diameter (volume average diameter) of the light-scattering particles in the semiconductor nanoparticle-containing composition or the light-scattering particles in the light-scattering particle dispersion is measured using a dynamic light-scattering Nanotrac particle size distribution analyzer and calculated from the volume average diameter. When the particle diameter of the light-scattering particles is measured in the form of a powder, the average particle diameter (volume average diameter) of the light-scattering particles is measured using, for example, a transmission electron microscope or a scanning electron microscope and calculated from the volume average diameter.

[0244] When the semiconductor nanoparticle-containing composition of the present invention contains light-scattering particles, the content of the light-scattering particles is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and most preferably 12% by mass or more, based on the total solid content of the semiconductor nanoparticle-containing composition, from the viewpoint of excellent discharge stability and excellent external quantum efficiency improvement effects. The content of the light-scattering particles is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, particularly preferably 25% by mass or less, and most preferably 20% by mass or less, based on the total solid content of the semiconductor nanoparticle-containing composition, from the viewpoint of excellent discharge stability and excellent external quantum efficiency improvement effects. The above upper and lower limits can be arbitrarily combined. For example, the content of the light-scattering particles is preferably 0.1 to 60 mass %, more preferably 1 to 50 mass %, even more preferably 5 to 40 mass %, even more preferably 7 to 30 mass %, particularly preferably 10 to 25 mass %, and particularly preferably 12 to 20 mass %, based on the total solid content of the semiconductor nanoparticle-containing composition.

[0245] When the semiconductor nanoparticle-containing composition of the present invention contains light-scattering particles, the mass ratio of the content of the light-scattering particles to the content of the semiconductor nanoparticles (A) (light-scattering particles / semiconductor nanoparticles (A)) may be 0.1 or more, 0.2 or more, or even 0.5 or more, from the viewpoint of an excellent effect of improving external quantum efficiency. From the viewpoint of an excellent effect of improving external quantum efficiency and suitability for known coating methods, particularly excellent continuous dischargeability (discharge stability) during inkjet printing, the mass ratio may be 5.0 or less, 2.0 or less, or 1.5 or less. The improvement in external quantum efficiency by light-scattering particles is believed to be due to the following mechanism. In other words, in the absence of light-scattering particles, backlight simply passes through the pixel area in a substantially straight line, and is thought to have little opportunity to be absorbed by the semiconductor nanoparticles (A). On the other hand, when light-scattering particles are present in the same pixel area as the semiconductor nanoparticles (A), the backlight is scattered in all directions within the pixel area and can be received by the semiconductor nanoparticles (A). Therefore, even when the same backlight is used, the amount of light absorbed in the pixel area is thought to increase. As a result, it is believed that this mechanism makes it possible to prevent light leakage (light from the light source leaking out of the pixel section without being absorbed by the semiconductor nanoparticles), thereby improving the external quantum efficiency. The above upper and lower limits can be combined arbitrarily. For example, the mass ratio of the content of the light-scattering particles to the content of the semiconductor nanoparticles (A) (light-scattering particles / semiconductor nanoparticles (A)) is preferably 0.1 to 5.0, more preferably 0.2 to 2.0, and even more preferably 0.5 to 1.5.

[0246] [1-7] Other ingredients The semiconductor nanoparticle-containing composition of the present invention may further contain components other than the semiconductor nanoparticles (A), the ligand (B), the fluorescent dye (C), the (meth)acrylate compound (D), the polymerization initiator (E), and the light-scattering particles, such as a polymer dispersant, a sensitizer, and a solvent.

[0247] [Polymer dispersant] In the present invention, the polymer dispersant is a polymer compound having a weight-average molecular weight of 750 or more and having functional groups capable of adsorbing to light-scattering particles, and has the function of dispersing the light-scattering particles. The polymer dispersant adsorbs to the light-scattering particles via the functional groups capable of adsorbing to the light-scattering particles, and disperses the light-scattering particles in the semiconductor nanoparticle-containing composition due to electrostatic and / or steric repulsion between the polymer dispersants. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may also be bonded to the surface of the semiconductor nanoparticles and adsorbed to the semiconductor nanoparticles, or may be free in the semiconductor nanoparticle-containing composition.

[0248] Examples of functional groups capable of adsorbing light-scattering particles include acidic functional groups, basic functional groups, and nonionic functional groups. The acidic functional groups have a dissociable proton and may be neutralized with a base such as an amine or hydroxide ion, while the basic functional groups may be neutralized with an acid such as an organic acid or an inorganic acid.

[0249] Examples of acidic functional groups include a carboxy group (-COOH), a sulfo group (-SO3H), a sulfate group (-OSO3H), a phosphono group (-PO(OH)2), a phosphonooxy group (-OPO(OH)2), a hydroxyphosphoryl group (-PO(OH)-), and a sulfanyl group (-SH).

[0250] Examples of basic functional groups include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.

[0251] Examples of nonionic functional groups include a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO2-), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group.

[0252] From the viewpoints of dispersion stability of the light-scattering particles, the likelihood of the side effect of settling of the semiconductor nanoparticles, ease of synthesis of the polymer dispersant, and stability of the functional groups, a carboxy group, a sulfo group, a phosphonic acid group, and a phosphate group are preferably used as the acidic functional group, and an amino group is preferably used as the basic functional group, more preferably a carboxy group, a phosphonic acid group, and an amino group, and most preferably an amino group.

[0253] When the polymer dispersant has an acidic functional group, the acid value of the polymer dispersant is preferably 1 to 150 mgKOH / g. When the acid value is equal to or greater than the lower limit, sufficient dispersibility of the light-scattering particles is easily obtained, and when the acid value is equal to or less than the upper limit, the storage stability of the pixel portion (cured product of the semiconductor nanoparticle-containing composition) is less likely to decrease.

[0254] When the polymer dispersant has a basic functional group, the amine value of the polymer dispersant is preferably 1 to 200 mgKOH / g. When the amine value is equal to or greater than the lower limit, sufficient dispersibility of the light-scattering particles is easily obtained, and when the amine value is equal to or less than the upper limit, the storage stability of the pixel portion (cured product of the semiconductor nanoparticle-containing composition) is less likely to decrease.

[0255] The polymeric dispersant may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of multiple types of monomers. The polymeric dispersant may be any of a random copolymer, a block copolymer, or a graft copolymer. When the polymeric dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. The polymeric dispersant may be, for example, an acrylic resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyether, a phenolic resin, a silicone resin, a polyurea resin, an amino resin, a polyamine such as polyethyleneimine and polyallylamine, an epoxy resin, or a polyimide.

[0256] Commercially available polymer dispersants can also be used, such as the Ajisper PB series manufactured by Ajinomoto Fine-Techno Co., Ltd., the DISPERBYK series and BYK series manufactured by BYK-Chemie, and the Efka series manufactured by BASF.

[0257] For example, "DISPERBYK (registered trademark, the same applies hereinafter)-130", "DISPERBYK-161", "DISPERBYK-162", "DISPERBYK-163", "DISPERBYK-164", "DISPERBYK-166", "DISPERBYK-167", "DISPERBYK-168", "DISPERBYK-170", "DISPERBYK-171", "DISPERBYK-174", "DISPERBYK-180", "DISPERBYK-182", "DISPERBYK-183", "DISPERBYK-184", "DISPERBYK-185", "DISPERBYK-2000", "DISPERBYK-2001", "DISPERBYK-2008", "DISPERBYK-2009", "DISPERBYK-2020", "DISPERBYK-2022" 2", "DISPERBYK-2025", "DISPERBYK-2050", "DISPERBYK-2070", "DISPERBYK-2096", "DISPERBYK-2150", "DISPERBYK-2155", "DISPERBYK-2163", "DISPERBYK-2164", "BYK-LPN21116" and "BYK-LPN6919"; "EFKA (registered trademark)" manufactured by BASF; Dear Customers, )4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA4320, EFKA4330, EFKA4340, EFKA4560, EFKA4585, EFKA5207, EFKA1501, EFKA1502, EFKA1503 and EFKA PX-4701; Solsperse (registered trademark) manufactured by Lubrizol Corporation. The same applies hereinafter.)3000", "Solsperse 9000", "Solsperse 13240", "Solsperse 13650", "Solsperse 13940", "Solsperse 11200", "Solsperse 13940", "Solsperse 16000", "Solsperse 17000", "Solsperse 18000", "Solsperse 20000", "Solsperse 21000", "Solsperse 24000", "Solsperse 26000", "Solsperse 27000", "Solsperse 28000", "Solsperse 32000", "Solsperse 32500", "Solsperse 32550", "Solsperse 32600", Solsperse 33000, Solsperse 34750, Solsperse 35100, Solsperse 35200, Solsperse 36000, Solsperse 37500, Solsperse 38500, Solsperse 39000, Solsperse 41000, Solsperse 54000, Solsperse 71000, and Solsperse 76500; Ajinomoto Fine-Techno Co., Inc.'s Ajisper (registered trademark; the same applies hereinafter) PB821, Ajisper PB822, Ajisper PB881, PN411, and PA111; Evonik's TEGO (registered trademark; the same applies hereinafter). Dispers650, TEGO Dispers660C, TEGO Dispers662C, TEGO Dispers670, TEGO Dispers685, TEGO Dispers700, TEGO Dispers710, and TEGO Dispers760W; and Disparlon (registered trademark; the same applies hereinafter) DA-703-50, DA-705, and DA-725 manufactured by Kusumoto Chemicals Co., Ltd. can be used.

[0258] In addition to the above-mentioned commercially available polymeric dispersants, polymeric dispersants synthesized by copolymerizing, for example, a cationic monomer containing a basic group and / or an anionic monomer having an acidic group with a monomer having a hydrophobic group, and, if necessary, other monomers (such as a nonionic monomer or a monomer having a hydrophilic group) can be used. Details of the cationic monomer, anionic monomer, monomer having a hydrophobic group, and other monomers can be found, for example, in paragraphs

[0034] to

[0036] of JP 2004-250502 A.

[0259] Suitable examples of polymer dispersants include compounds obtained by reacting polyalkyleneimines with polyester compounds, as described in Japanese Patent Application Laid-Open Nos. 54-37082 and 61-174939; compounds in which amino groups on the side chains of polyallylamine are modified with polyesters, as described in Japanese Patent Application Laid-Open No. 9-169821; graft polymers having polyester macromonomers as copolymerization components, as described in Japanese Patent Application Laid-Open No. 9-171253; and polyester polyol-added polyurethanes, as described in Japanese Patent Application Laid-Open No. 60-166318.

[0260] The weight-average molecular weight of the polymer dispersant is preferably 750 or more, more preferably 1000 or more, even more preferably 2000 or more, and particularly preferably 3000 or more, from the viewpoints of being able to disperse light-scattering particles well and further improving the effect of improving external quantum efficiency. From the viewpoints of being able to disperse light-scattering particles well, further improving the effect of improving external quantum efficiency, and also of achieving a viscosity suitable for known coating methods, particularly a viscosity suitable for inkjet printing that allows for stable ejection, the weight-average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The above upper and lower limits can be arbitrarily combined. For example, the weight-average molecular weight of the polymer dispersant is preferably 750 to 100,000, more preferably 1,000 to 100,000, even more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000.

[0261] When the semiconductor nanoparticle-containing composition of the present invention contains a polymer dispersant, the content of the polymer dispersant is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the light-scattering particles, from the viewpoint of the dispersibility of the light-scattering particles. Furthermore, from the viewpoint of the humidity and heat stability of the pixel portion (the cured product of the semiconductor nanoparticle-containing composition), the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the light-scattering particles. The above upper and lower limits can be arbitrarily combined. For example, the content of the polymer dispersant is preferably 0.5 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 5 to 10 parts by mass, per 100 parts by mass of the light-scattering particles.

[0262] [Sensitizer] A sensitizer is a component that can absorb light of a longer wavelength than that absorbed by a photopolymerization initiator and transfer the absorbed energy to the photopolymerization initiator, thereby initiating a polymerization reaction. By including a sensitizer, for example, it tends to be possible to use h-rays, which are relatively unabsorbed by semiconductor nanoparticles, as the wavelength for curing. The sensitizer may be an amine that does not undergo an addition reaction with the (meth)acrylate compound (D). Examples of the sensitizer include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, and 4,4'-bis(diethylamino)benzophenone.

[0263] [solvent] The semiconductor nanoparticle-containing composition of the present invention may contain a solvent from the viewpoint of coating properties and handling properties. Examples of the solvent include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, 1,4-butanediol diacetate, and glyceryl triacetate.

[0264] The boiling point of the solvent is preferably 50°C or higher from the viewpoint of suitability for known coating methods, and is preferably 180°C or higher from the viewpoint of continuous ejection stability of inkjet inks. When forming pixel portions, the solvent must be removed from the semiconductor nanoparticle-containing composition before curing the semiconductor nanoparticle-containing composition. Therefore, from the viewpoint of ease of solvent removal, the boiling point of the solvent is preferably 300°C or lower. The above upper and lower limits can be arbitrarily combined. For example, the boiling point of the solvent is preferably 50 to 300°C, more preferably 180 to 300°C.

[0265] When the semiconductor nanoparticle-containing composition of the present invention contains a solvent, its content is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 1% by mass or more, particularly preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Also, 90% by mass or less is preferred, more preferably 80% by mass or less, and even more preferably 70% by mass or less. By setting the content at or above the lower limit, the viscosity of the composition is reduced, tending to facilitate suitability for known coating methods, particularly inkjet ejection. By setting the content at or below the upper limit, tending to facilitate suitability for known coating methods, particularly the film thickness after ejection and solvent removal, tends to increase, and a film containing more semiconductor nanoparticles can be formed, resulting in pixel portions with high luminescence intensity. The above upper and lower limits can be combined arbitrarily. For example, the content of the solvent in the semiconductor nanoparticle-containing composition is preferably 0.001 to 90 mass%, more preferably 0.01 to 90 mass%, even more preferably 0.1 to 90 mass%, even more preferably 1 to 90 mass%, particularly preferably 10 to 90 mass%, more particularly preferably 20 to 80 mass%, and particularly preferably 30 to 70 mass%.

[0266] In the semiconductor nanoparticle-containing composition of the present invention, the use of a (meth)acrylate compound that functions as a dispersion medium also makes it possible to disperse light-scattering particles and semiconductor nanoparticles without using a solvent, which has the advantage of eliminating the need for a step of removing the solvent by drying when forming pixel portions.

[0267] [2] Physical properties of semiconductor nanoparticle-containing compositions The viscosity of the semiconductor nanoparticle-containing composition of the present invention at 40°C is not particularly limited. However, from the viewpoint of suitability for known coating methods, particularly ejection stability during inkjet printing, the viscosity is preferably 2 mPa·s or more, more preferably 5 mPa·s or more, and even more preferably 7 mPa·s or more, and is preferably 20 mPa·s or less, more preferably 15 mPa·s or less, and even more preferably 12 mPa·s or less. The viscosity of the semiconductor nanoparticle-containing composition is measured using an E-type viscometer. The above upper and lower limits can be combined arbitrarily. For example, the viscosity of the semiconductor nanoparticle-containing composition of the present invention at 40°C is preferably 2 to 20 mPa·s, more preferably 5 to 15 mPa·s, and even more preferably 7 to 12 mPa·s.

[0268] The viscosity of the semiconductor nanoparticle-containing composition of the present invention at 23°C is not particularly limited. However, from the viewpoint of suitability for known coating methods, particularly ejection stability during inkjet printing, the viscosity is preferably 5 mPa·s or more, more preferably 10 mPa·s or more, and even more preferably 15 mPa·s or more. It is also preferably 40 mPa·s or less, more preferably 35 mPa·s or less, even more preferably 30 mPa·s or less, and particularly preferably 25 mPa·s or less. The above upper and lower limits can be arbitrarily combined. For example, the viscosity of the semiconductor nanoparticle-containing composition of the present invention at 23°C is preferably 5 to 40 mPa·s, more preferably 5 to 35 mPa·s, even more preferably 10 to 30 mPa·s, and particularly preferably 15 to 25 mPa·s.

[0269] The surface tension of the semiconductor nanoparticle-containing composition of the present invention is not particularly limited, but is preferably a surface tension suitable for known coating methods, particularly inkjet printing, and is preferably in the range of 20 to 40 mN / m, more preferably 25 to 35 mN / m. By maintaining the surface tension within this range, the occurrence of deflection of the droplets can be suppressed. Deflection of the droplets refers to the occurrence of a deviation of 30 μm or more from the target position of the semiconductor nanoparticle-containing composition when the composition is ejected from the ink ejection orifice.

[0270] [3] Method for producing a composition containing semiconductor nanoparticles The semiconductor nanoparticle-containing composition can be produced, for example, by a method including a step of mixing semiconductor nanoparticles (A), a (meth)acrylate compound (D), a fluorescent dye (C), and, if necessary, a ligand (B) and a polymerization initiator (E) so that the content of semiconductor nanoparticles (A) is 5 to 50 mass % of the total solid content of the semiconductor nanoparticle-containing composition. For example, the semiconductor nanoparticle-containing composition can be obtained by mixing the components of the semiconductor nanoparticle-containing composition.

[0271] When the semiconductor nanoparticle-containing composition contains light-scattering particles, the semiconductor nanoparticle-containing composition can be produced, for example, by a method including the steps of: preparing a semiconductor nanoparticle dispersion containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), a fluorescent dye (C), and, optionally, a ligand (B); preparing a light-scattering particle dispersion containing light-scattering particles and, optionally, the (meth)acrylate compound (D); and mixing the semiconductor nanoparticle dispersion and the light-scattering particle dispersion. When a polymerization initiator (E) is used in this production method, the polymerization initiator (E) may be incorporated so as to be contained in the mixture obtained by mixing the semiconductor nanoparticle dispersion and the light-scattering particle dispersion. Therefore, the polymerization initiator (E) may be contained in either or both of the semiconductor nanoparticle dispersion and the light-scattering particle dispersion. When the semiconductor nanoparticle dispersion, the light-scattering particle dispersion, and the polymerization initiator (E) are mixed, the polymerization initiator (E) need not be contained in either the semiconductor nanoparticle dispersion or the light-scattering particle dispersion.

[0272] According to this production method, the semiconductor nanoparticles (A) and the light-scattering particles are dispersed in the (meth)acrylate compound (D) before being mixed with each other, and therefore the semiconductor nanoparticles (A) and the light-scattering particles can be sufficiently dispersed, and excellent discharge stability and excellent external quantum efficiency tend to be easily obtained.

[0273] In the step of preparing a semiconductor nanoparticle dispersion, the semiconductor nanoparticle dispersion may be prepared by mixing semiconductor nanoparticles (A), ligands (B), and fluorescent dye (C) with a (meth)acrylate compound (D). The semiconductor nanoparticles (A) may have ligands (B) adsorbed to their surfaces in advance. The mixing process may be carried out using a device such as a paint conditioner, a planetary mixer, a stirrer, an ultrasonic disperser, or a mix rotor. From the viewpoint of improving the dispersibility of the semiconductor nanoparticles (A), ligands (B), and fluorescent dye (C) and obtaining high optical properties, it is preferable to use a stirrer, an ultrasonic disperser, or a mix rotor.

[0274] In the step of preparing a light-scattering particle dispersion, the light-scattering particles may be mixed with a (meth)acrylate compound (D) and dispersed to prepare the light-scattering particle dispersion. The mixing and dispersion may be performed using the same apparatus as in the step of preparing the semiconductor nanoparticle dispersion. From the viewpoints of improving the dispersibility of the light-scattering particles and facilitating the adjustment of the average particle size of the light-scattering particles to a desired range, it is preferable to use a bead mill or a paint conditioner.

[0275] In the step of preparing the light-scattering particle dispersion, a polymer dispersant may be further mixed. That is, the light-scattering particle dispersion may further contain a polymer dispersant. By mixing the light-scattering particles with the polymer dispersant before mixing the semiconductor nanoparticles (A) with the light-scattering particles, the light-scattering particles can be more thoroughly dispersed. Therefore, excellent discharge stability and excellent external quantum efficiency can be more easily obtained.

[0276] In this production method, other components (e.g., sensitizer, solvent) may be further used in addition to the semiconductor nanoparticles (A), ligands (B), fluorescent dye (C), light-scattering particles, (meth)acrylate compound (D), and optionally the polymerization initiator (E), and polymer dispersant. In this case, the other components may be contained in the semiconductor nanoparticle dispersion or the light-scattering particle dispersion. Alternatively, the other components may be mixed with a composition obtained by mixing the semiconductor nanoparticle dispersion and the light-scattering particle dispersion.

[0277] [4] Wavelength conversion layer The wavelength conversion layer of the present invention is a layer obtained by curing the semiconductor nanoparticle-containing composition of the present invention, which contains at least semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), and converts the wavelength of light from an excitation source. The shape of the wavelength conversion layer is not particularly limited, and it may be, for example, a sheet-like shape or any other shape, such as a bar-like shape patterned like the pixel portions of a color filter described below.

[0278] [5] Light conversion layer and color filter The color filter of the present invention has pixel portions formed by curing the semiconductor nanoparticle-containing composition of the present invention. Details of the color filter of the present invention will be described with reference to the drawings. In the following description, the same or corresponding elements will be designated by the same reference numerals, and redundant description will be omitted.

[0279] Fig. 1 is a schematic cross-sectional view of a color filter according to one embodiment. As shown in Fig. 1, the color filter 100 includes a substrate 40 and a light conversion layer 30 provided on the substrate 40. The light conversion layer 30 includes a plurality of pixel units 10 (a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c) and a light-shielding unit 20.

[0280] The light conversion layer 30 has pixel sections 10, which include a first pixel section 10a, a second pixel section 10b, and a third pixel section 10c. The first pixel section 10a, the second pixel section 10b, and the third pixel section 10c are arranged in a grid pattern, repeating in this order. Light-shielding sections 20 are provided between adjacent pixel sections, i.e., between the first pixel section 10a and the second pixel section 10b, between the second pixel section 10b and the third pixel section 10c, and between the third pixel section 10c and the first pixel section 10a. In other words, these adjacent pixel sections are separated by the light-shielding sections 20.

[0281] The first pixel portion 10a and the second pixel portion 10b each contain a cured product of the semiconductor nanoparticle-containing composition of the present invention. The cured product contains semiconductor nanoparticles having ligands adsorbed to at least a portion of their surfaces, fluorescent dye, light-scattering particles, and a curing component. The curing component is a cured product of a (meth)acrylate compound, specifically, a cured product obtained by polymerization of the (meth)acrylate compound. That is, the first pixel portion 10a contains a first curing component 13a, and first semiconductor nanoparticles 11a, first light-scattering particles 12a, and first fluorescent dye 14a, each dispersed in the first curing component 13a. Similarly, the second pixel portion 10b contains a second curing component 13b, and second semiconductor nanoparticles 11b, second light-scattering particles 12b, and second fluorescent dye 14b, each dispersed in the second curing component 13b. In the first pixel portion 10a and the second pixel portion 10b, the first curing component 13a and the second curing component 13b may be the same or different, the first light-scattering particles 12a and the second light-scattering particles 12b may be the same or different, and the first fluorescent dye 14a and the second fluorescent dye 14b may be the same or different.

[0282] The first semiconductor nanoparticles 11a are red-light-emitting semiconductor nanoparticles that absorb light with a wavelength in the range of 420 to 480 nm and emit light with a peak emission wavelength in the range of 605 to 665 nm. That is, the first pixel portion 10a may be rephrased as a red pixel portion for converting blue light to red light. The second semiconductor nanoparticles 11b are green-light-emitting semiconductor nanoparticles that absorb light with a wavelength in the range of 420 to 480 nm and emit light with a peak emission wavelength in the range of 500 to 560 nm. The second pixel portion 10b may be rephrased as a green pixel portion for converting blue light to green light.

[0283] The third pixel unit 10c has a transmittance of 30% or more for light with a wavelength in the range of 420 to 480 nm. When a light source emitting light with a wavelength in the range of 420 to 480 nm is used, the third pixel unit 10c functions as a blue pixel unit. The third pixel unit 10c includes, for example, a cured product of a composition containing the above-mentioned (meth)acrylate compound. The cured product includes a third curing component 13c. The third curing component 13c is a cured product of a (meth)acrylate compound, and is a cured product obtained by polymerization of the (meth)acrylate compound. The third pixel unit 10c includes the third curing component 13c. When the third pixel unit 10c includes the above-mentioned cured product, the composition containing the (meth)acrylate compound may further contain components other than the (meth)acrylate compound among the components contained in the above-mentioned semiconductor nanoparticle-containing composition, as long as the composition has a transmittance of 30% or more for light with a wavelength in the range of 420 to 480 nm. The transmittance of the third pixel portion 10c can be measured by a microspectrometer.

[0284] The thickness of the pixel sections (first pixel section 10a, second pixel section 10b, and third pixel section 10c) is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more. The thickness of the pixel sections (first pixel section 10a, second pixel section 10b, and third pixel section 10c) is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The above upper and lower limits can be combined arbitrarily. For example, the thickness of the pixel sections (first pixel section 10a, second pixel section 10b, and third pixel section 10c) is preferably 1 to 30 μm, more preferably 2 to 20 μm, and even more preferably 3 to 15 μm.

[0285] The light-shielding portion 20 is a so-called black matrix, which is provided to separate adjacent pixel portions to prevent color mixing and to prevent light leakage from the light source. The material constituting the light-shielding portion 20 is not particularly limited, and examples thereof include metals such as chromium, as well as cured resin compositions containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a binder polymer. Examples of binder polymers that can be used include polyimide resins, acrylic resins, epoxy resins, polyacrylamides, polyvinyl alcohols, gelatin, casein, cellulose, and other resins, as well as mixtures of two or more of these resins, photosensitive resins, and O / W emulsion-type resin compositions (e.g., emulsified reactive silicones). The thickness of the light-shielding portion 20 is preferably 0.5 μm to 10 μm.

[0286] The substrate 40 is a transparent substrate with optical transparency, and examples thereof include transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plates, as well as transparent flexible substrates such as transparent resin films and optical resin films. Among these, it is preferable to use a glass substrate made of alkali-free glass, which does not contain any alkali components. Examples include Corning's "7059 Glass," "1737 Glass," "Eagle 200," and "Eagle XG," AGC's "AN100," and Nippon Electric Glass's "OA-10G" and "OA-11." These materials have a low coefficient of thermal expansion and are excellent in dimensional stability and workability during high-temperature heat treatment.

[0287] The color filter 100 having the above-described light conversion layer 30 is suitably used when an excitation light source that emits light with a wavelength in the range of 420 to 480 nm is used.

[0288] The wavelength region of the light emitted by the excitation light source is not limited to the above range. In the light conversion layer of the present invention, it is thought that the excited energy of the fluorescent dye (C) is transferred to the semiconductor nanoparticles (A) by Förster energy transfer, thereby increasing the luminescence intensity of the semiconductor nanoparticles (A). Therefore, any light in a wavelength region that can be absorbed by the fluorescent dye (C) may be used as excitation light.

[0289] The color filter 100 can be produced, for example, by forming a pattern of light-shielding portions 20 on a substrate 40, selectively applying the above-mentioned semiconductor nanoparticle-containing composition to pixel portion formation regions partitioned by the light-shielding portions 20 on the substrate 40 using an inkjet method, and curing the semiconductor nanoparticle-containing composition by irradiating it with active energy rays.

[0290] The light-shielding portion 20 can be formed, for example, by forming a thin metal film such as chromium or a thin film of a resin composition containing light-shielding particles in the boundary region between multiple pixel portions on one surface of the substrate 40, and then patterning the thin film. The metal thin film can be formed by, for example, sputtering or vacuum deposition, and the thin film of a resin composition containing light-shielding particles can be formed by, for example, coating or printing. The patterning method can be, for example, photolithography.

[0291] Examples of inkjet methods include a bubble jet (registered trademark) method using an electrothermal converter as an energy generating element, and a piezo jet method using a piezoelectric element.

[0292] When the semiconductor nanoparticle-containing composition is cured by irradiation with active energy rays (e.g., ultraviolet rays), for example, a mercury lamp, a metal halide lamp, a xenon lamp, or an LED may be used. The wavelength of the irradiated light may be, for example, 200 nm or more and 440 nm or less. The exposure dose may be, for example, 10 to 4000 mJ / cm. 2 is preferred.

[0293] When the semiconductor nanoparticle-containing composition contains a solvent, it is subjected to a drying treatment to volatilize the solvent. Examples of the drying treatment include drying under reduced pressure and drying by heating. In the case of drying by heating, the drying temperature for volatilizing the solvent may be, for example, 50 to 150°C, and the drying time may be, for example, 3 to 30 minutes.

[0294] [6] Image display device The image display device of the present invention has the color filter of the present invention. Examples of image display devices include liquid crystal display devices and image display devices including organic electroluminescent devices. An example of a liquid crystal display device is one that includes a light source having a blue LED and a liquid crystal layer having electrodes that control the blue light emitted from the light source for each pixel. An example of an image display device including an organic electroluminescent device is one in which blue-emitting organic electroluminescent devices are arranged at positions corresponding to the pixel portions of a color filter. [Example]

[0295] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0296] (Meth)acrylate compound D-1: 1,6-hexanediol diacrylate (HDDA) Photopolymerization initiator 1: Omnirad TPO (manufactured by IGM Resins) Antioxidant 1: Irganox 1010 (manufactured by BASF) Antioxidant 2: Triphenyl phosphite (TPP)

[0297] <Ligand structure> The structure of the ligand E-1 used in the examples and comparative examples is shown below. Ligand E-1: A compound having a carboxy group and a polyethylene glycol chain with a molecular weight of about 400.

[0298] <Fluorescent dye structure> The structures of the fluorescent dyes C-1 and C-2 used in the examples and comparative examples are shown below.

[0299] [Table 1]

[0300] The fluorescent dye C-1 was synthesized by the method described below. Compound 1, represented by the following chemical formula, i.e., bromonaphthalic anhydride (1 part by mass) and ethanol (8 parts by mass) were mixed under a nitrogen atmosphere, and 2-ethylhexylamine (0.51 parts by mass, 1.1 equivalents) was added dropwise thereto. The mixture was allowed to react at reflux temperature for 5 hours and then cooled to room temperature over 1 hour. The precipitated solid was collected by filtration and washed with ethanol (3 parts by mass). The solid was dried in a vacuum dryer to obtain compound 2 in 87% yield.

[0301] [ka]

[0302] Next, under a nitrogen atmosphere, compound 2 (1 part by mass) and 2-methoxyethanol (9.6 parts by mass) were mixed, to which 2-(methylamino)ethanol (0.23 parts by mass, 1.2 equivalents) and triethylamine (0.31 parts by mass, 1.2 equivalents) were added, and the mixture was refluxed and stirred for 22 hours. After cooling to room temperature, the mixture was separated into toluene (17.3 parts by mass) and purified water (10 parts by mass), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The resulting viscous mass was purified by silica gel column chromatography to obtain compound 3, represented by the following chemical formula, in a 67% yield.

[0303] [ka]

[0304] Next, under a nitrogen atmosphere, compound 3 (1 part by mass), dichloromethane (13.3 parts by mass), and triethylamine (0.48 parts by mass, 2 equivalents) were mixed and ice-cooled. 4-(dimethylamino)pyridine (0.0014 parts by mass, 0.05 equivalents) was added, followed by paratoluenesulfonyl chloride (0.55 parts by mass, 1.2 equivalents). The mixture was returned to room temperature and stirred for 3 hours, after which it was separated and washed with purified water. The mixture was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The resulting viscous mass was purified by silica gel column chromatography to obtain compound 4, represented by the following chemical formula, in a 75% yield.

[0305] [ka]

[0306] Next, under a nitrogen atmosphere, compound 4 (1 part by mass) and N,N-dimethylformamide (10 parts by mass) were mixed, and S-potassium thioacetate (0.22 parts by mass, 1 equivalent) was added thereto and stirred at room temperature for 15 hours. Dichloromethane (50 parts by mass) was added to the reaction solution, and the mixture was washed twice with purified water (10 parts by mass) and then with brine (10 parts by mass). The mixture was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The resulting viscous mass was purified by silica gel column chromatography to obtain compound 5, represented by the following chemical formula, in an 89% yield.

[0307] [ka]

[0308] Next, under a nitrogen atmosphere, compound 5 (1 part by mass) and N,N-dimethylacetamide (16 parts by mass) were mixed, to which (±)-dithiothreitol (1 part by mass, 3 equivalents) and sodium bicarbonate (0.06 parts by mass, 0.3 equivalents) were added, followed by stirring at room temperature for 7 hours. Toluene (70 parts by mass) was added to the reaction mixture, which was then washed twice with purified water (20 parts by mass). The mixture was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The resulting viscous material was purified by silica gel column chromatography to obtain the desired fluorescent dye C-1 (yellow solid) in a 75% yield.

[0309] [ka]

[0310] "Solvent Yellow 43" was used as the fluorescent dye C-2.

[0311] <Linking of fluorescent dyes to semiconductor nanoparticles> Whether or not a linking action was produced was judged according to the following evaluation criteria. To a semiconductor nanoparticle dispersion containing 11.4 parts by mass of InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: 630 nm (excitation wavelength of 445 nm)), 3.2 parts by mass of ligand E-1, and 22.4 parts by mass of butyl acetate, 74.0 parts by mass of butyl acetate and 0.5 parts by mass of fluorescent dye were added and dissolved, and the mixture was allowed to stand at room temperature for 2 hours. Thereafter, 116.0 parts by mass of normal heptane was added, and the mixture was stirred with a vortex mixer to precipitate the semiconductor nanoparticles. Furthermore, after separating the precipitate and the supernatant using a centrifuge, the supernatant was dried and the amount of fluorescent dye contained in the residue was quantified by 1H-NMR. If the amount of fluorescent dye contained in the supernatant was 50% by mass or less of the amount added, it was determined that the fluorescent dye had bound to the semiconductor nanoparticles. It was confirmed in advance that the fluorescent dye to be added would dissolve in a mixed solution of butyl acetate and normal heptane so that the fluorescent dye not bound to the semiconductor nanoparticles would not precipitate when normal heptane was added.

[0312] <Evaluation results> Fluorescent dye C-1: 88 mass % of the total amount of mixed fluorescent dye C-1 precipitated (coordinated to semiconductor nanoparticles), and 12 mass % was contained in the supernatant (not coordinated to semiconductor nanoparticles). Fluorescent dye C-2: 47 mass % of the total amount of mixed fluorescent dye C-1 precipitated (coordinated to semiconductor nanoparticles), and 53 mass % was contained in the supernatant (not coordinated to semiconductor nanoparticles).

[0313] <Preparation of Light-Scattering Particle Dispersion> A container was filled with 2.52 parts by weight of PT-401M (Ishihara Sangyo Kaisha, Ltd., average particle size 0.07 μm) titanium dioxide, 0.25 parts by weight of DISPERBYK-111 (BYK-Chemie) dispersant, 7.22 parts by weight of tetrahydrofurfuryl acrylate solvent, and 20 parts by weight of zirconia beads with a diameter of 0.3 mm, and the mixture was dispersed for 6 hours using a paint shaker. After dispersion was completed, the beads and dispersion were separated using a filter to prepare a light-scattering particle dispersion. Measurement using a dynamic light-scattering Nanotrac particle size distribution analyzer revealed that the average particle size (volume average diameter) of the light-scattering particles in the light-scattering particle dispersion was 0.11 μm.

[0314] [Example 1] To semiconductor nanoparticle dispersion 1 containing 10 parts by mass of InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: 630 nm (excitation wavelength of 445 nm)), 3.3 parts by mass of ligand E-1, and 12 parts by mass of (meth)acrylate compound D-1, 50 parts by mass of (meth)acrylate compound D-1 and 1 part by mass of fluorescent dye C-1 were added, and then 24 parts by mass of light-scattering particle dispersion was added and mixed using a vortex mixer to obtain target composition 1.

[0315] [Comparative Example 1] To the semiconductor nanoparticle dispersion 1 of Example 1, 51 parts by mass of (meth)acrylate compound D-1 was added, and then 24 parts by mass of the light-scattering particle dispersion was added, followed by mixing with a vortex mixer to obtain the target composition 2.

[0316] Comparative Example 2 After adding 1 part by mass of fluorescent dye C-1 to 75 parts by mass of (meth)acrylate compound D-1, 24 parts by mass of light-scattering particle dispersion was added and mixed using a vortex mixer to obtain the target composition 3.

[0317] Comparative Example 3 The same procedure as in Comparative Example 2 was carried out except that fluorescent dye C-2 was used instead of fluorescent dye C-1, to obtain the target composition 4.

[0318] Comparative Example 4 The same procedure as in Example 1 was carried out except that fluorescent dye C-2 was used instead of fluorescent dye C-1, to obtain the target composition 5.

[0319] Comparative Example 5 To the semiconductor nanoparticle dispersion 1 of Example 1, 50 parts by mass of chloroform (CHCl3) and 1 part by mass of fluorescent dye C-1 were added, and then 24 parts by mass of light-scattering particle dispersion was added and mixed using a vortex mixer to obtain the target composition 6.

[0320] Comparative Example 6 To the semiconductor nanoparticle dispersion 1 of Example 1, 51 parts by mass of chloroform and 24 parts by mass of the light-scattering particle dispersion were added and mixed in a vortex mixer to obtain the target composition 7.

[0321] Comparative Example 7 The same procedure as in Comparative Example 2 was carried out except that chloroform was used instead of the (meth)acrylate compound D-1, to obtain the target composition 8.

[0322] <Measurement of the emission spectrum of the solution> The emission spectra of Example 1 and Comparative Examples 1 to 7 were measured as follows. Each composition was placed in a glass cell (Sun Trading S-0088-4-NW) with a 4 μm gap, and the glass cell was then placed inside an integrating sphere. The sample was irradiated with a 445 nm laser diode (Audio-Technica SU-61C-445-50) as a light source, and the emission spectrum was measured using a spectrometer (SpectraCorp Solid Lambda CCD UV-NIR). The light from the integrating sphere was guided to the spectrometer using an optical fiber. Table 2 shows the relative values ​​of the emission intensity (wavelength 630 nm) for each composition, when Comparative Example 1 is set to 1.00, and the maximum emission wavelength (wavelength range 300-780 nm) for each composition. Table 3 shows the relative values ​​of the emission intensity (wavelength 630 nm) for each composition, when Comparative Example 6 is set to 1.00, and the maximum emission wavelength (wavelength range 300-780 nm) for each composition.

[0323] [Table 2]

[0324] [Table 3]

[0325] [Example 2] To the semiconductor nanoparticle dispersion 1 of Example 1, 48 parts by mass of (meth)acrylate compound D-1, 0.5 parts by mass of photopolymerization initiator 1, 0.75 parts by mass each of antioxidant 1 and antioxidant 2, and 1 part by mass of fluorescent dye C-1 were added, followed by addition of 24 parts by mass of light-scattering particle dispersion and mixing using a vortex mixer to obtain the target composition 9.

[0326] [Comparative Example 8] To the semiconductor nanoparticle dispersion liquid 1 of Example 1, 49 parts by mass of (meth)acrylate compound D-1, 0.5 parts by mass of photopolymerization initiator 1, and 0.75 parts by mass each of antioxidant 1 and antioxidant 2 were added, and then 24 parts by mass of light-scattering particle dispersion liquid was added and mixed using a vortex mixer to obtain the target composition 10.

[0327] Comparative Example 9 To 73 parts by mass of (meth)acrylate compound D-1, 0.5 parts by mass of photopolymerization initiator 1, 0.75 parts by mass each of antioxidant 1 and antioxidant 2, and 1 part by mass of fluorescent dye C-1 were added, followed by 24 parts by mass of a light-scattering particle dispersion and mixing using a vortex mixer to obtain the target composition 11.

[0328] [Comparative Example 10] The same procedure as in Comparative Example 9 was carried out except that fluorescent dye C-2 was used instead of fluorescent dye C-1, to obtain the target composition 12.

[0329] [Comparative Example 11] The same procedure as in Example 2 was carried out except that fluorescent dye C-2 was used instead of fluorescent dye C-1, and the target composition 13 was obtained.

[0330] [Comparative Example 12] To the semiconductor nanoparticle dispersion 1 of Example 1, 48 parts by mass of chloroform, 0.5 parts by mass of photopolymerization initiator 1, 0.75 parts by mass each of antioxidant 1 and antioxidant 2, and 1 part by mass of fluorescent dye C-1 were added, followed by addition of 24 parts by mass of the light-scattering particle dispersion and mixing using a vortex mixer to obtain the target composition 14.

[0331] [Comparative Example 13] To the semiconductor nanoparticle dispersion liquid 1 of Example 1, 49 parts by mass of chloroform, 0.5 parts by mass of photopolymerization initiator 1, and 0.75 parts by mass each of antioxidant 1 and antioxidant 2 were added, and then 24 parts by mass of the light-scattering particle dispersion liquid was added and mixed using a vortex mixer to obtain the target composition 15.

[0332] [Comparative Example 14] To 73 parts by mass of chloroform, 0.5 parts by mass of photopolymerization initiator 1, 0.75 parts by mass each of antioxidant 1 and antioxidant 2, and 1 part by mass of fluorescent dye C-1 were added, followed by adding 24 parts by mass of a light-scattering particle dispersion and mixing using a vortex mixer to obtain the target composition 16.

[0333] <Measurement of the emission spectrum of the cured film> The emission spectra of Example 2 and Comparative Examples 8 to 14 were measured as follows. Each composition was used to form a coating film of approximately 10 μm thickness on a glass substrate using a spin coater, and then irradiated with an LED light irradiation device with a peak wavelength of 405 nm at an irradiation intensity of 4 mJ / cm in a nitrogen glove box. 2 , cumulative light intensity 120mJ / cm 2 By irradiating at 1000 nm, cured films were obtained for Example 2 and Comparative Examples 8 to 11. For Comparative Examples 12 to 14, the compositions did not cure, and cured films could not be obtained. The resulting cured film was placed in an integrating sphere, and the sample was irradiated with light from a 445 nm laser diode (SU-61C-445-50, manufactured by Audio-Technica) as a light source. The emission spectrum was measured using a spectrometer (Solid Lambda CCD UV-NIR, manufactured by SpectraCorp). The light from the integrating sphere was guided to the spectrometer using an optical fiber. Table 4 shows the relative emission intensity (wavelength 630 nm) of each cured film, with Comparative Example 8 set to 1.00, and the maximum emission wavelength (wavelength within the range of 300 to 780 nm) of each cured film.

[0334] [Table 4]

[0335] As can be seen from Tables 2 and 3, the composition (Example 1) containing semiconductor nanoparticles with a maximum emission wavelength in the range of 500 to 670 nm within the range of 300 to 780 nm, a fluorescent dye having a substituent capable of linking to the semiconductor nanoparticles, and a (meth)acrylate compound in a certain amount or more had a higher emission intensity at a wavelength of 630 nm than compositions containing the semiconductor nanoparticles or the fluorescent dye alone (Comparative Examples 1 and 2), compositions using a fluorescent dye without a substituent capable of linking to the semiconductor nanoparticles (Comparative Examples 3 and 4), and compositions containing chloroform as a solvent (Comparative Examples 5 to 7).

[0336] As can be seen from Table 4, the cured film (Example 2) containing semiconductor nanoparticles with a maximum emission wavelength in the range of 500 to 670 nm in the range of 300 to 780 nm, a fluorescent dye having a substituent capable of linking to the semiconductor nanoparticles, and a (meth)acrylate compound in a certain amount or more had a higher emission intensity at a wavelength of 630 nm than cured films containing the semiconductor nanoparticles or the fluorescent dye alone (Comparative Examples 8 and 9) and cured films using a fluorescent dye without a substituent capable of linking to the semiconductor nanoparticles (Comparative Examples 10 and 11). Furthermore, the compositions containing chloroform as a solvent (Comparative Examples 12 to 14) did not cure, and no cured films were obtained.

[0337] The reason for the increased luminescence intensity of the semiconductor nanoparticles in Examples 1 and 2 is that the excited energy of the fluorescent dye C-1 is transferred to the semiconductor nanoparticles by Förster energy transfer. Furthermore, the following three points can be cited as reasons why Förster energy transfer is particularly likely to occur in the fluorescent dye C-1. First, there is a large overlap between the emission spectrum of the fluorescent dye and the absorption spectrum of semiconductor nanoparticles, which have a maximum emission wavelength of 500 to 670 nm. Second, the sulfanyl group of the fluorescent dye is coordinated to the surface of the semiconductor nanoparticle, bringing the fluorescent dye and the semiconductor nanoparticle close to each other. Third, because fluorescent dyes have low solubility in (meth)acrylate compounds, the state in which the fluorescent dye is coordinated to the surface of semiconductor nanoparticles is stable in the presence of (meth)acrylate compounds.

Claims

1. A semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm in a wavelength range of 300 to 780 nm; the fluorescent dye (C) has a substituent that causes the dye to link to the semiconductor nanoparticles (A), the linking substituent contains a sulfanyl group or a salt thereof; The semiconductor nanoparticle-containing composition, wherein the content of the (meth)acrylate compound (D) in the semiconductor nanoparticle-containing composition is 20 mass % or more.

2. A semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a (meth)acrylate compound (D), and a fluorescent dye (C), the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm in a wavelength range of 300 to 780 nm; the fluorescent dye (C) has a substituent that causes the dye to link to the semiconductor nanoparticles (A), The semiconductor nanoparticle-containing composition for ink-jet printing, wherein the substituent that produces a linking effect contains a sulfanyl group or a salt thereof.

3. The semiconductor nanoparticle-containing composition according to claim 1 or 2, further comprising a polymerization initiator (E).

4. The semiconductor nanoparticle-containing composition according to any one of claims 1 to 3, further comprising a ligand (B).

5. The semiconductor nanoparticle-containing composition according to any one of claims 1 to 4, further comprising light-scattering particles.

6. A color filter having pixel portions formed by curing the semiconductor nanoparticle-containing composition according to any one of claims 1 to 5.

7. An image display device comprising the color filter according to claim 6.

Images