WO2022044759A1 - 半導体ナノ粒子含有組成物、カラーフィルタ、及び画像表示装置 - Google Patents

半導体ナノ粒子含有組成物、カラーフィルタ、及び画像表示装置 Download PDF

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WO2022044759A1
WO2022044759A1 PCT/JP2021/029126 JP2021029126W WO2022044759A1 WO 2022044759 A1 WO2022044759 A1 WO 2022044759A1 JP 2021029126 W JP2021029126 W JP 2021029126W WO 2022044759 A1 WO2022044759 A1 WO 2022044759A1
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semiconductor nanoparticles
ring
mass
substituent
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French (fr)
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洸毅 石井
崇志 藤原
政昭 西村
智隆 谷口
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三菱ケミカル株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/877—Arrangements for extracting light from the devices comprising scattering means

Definitions

  • the present invention relates to a semiconductor nanoparticle-containing composition, a color filter, and an image display device.
  • This application claims priority under Japanese Patent Application No. 2020-145534 filed in Japan on August 31, 2020 and Japanese Patent Application No. 2020-218441 filed in Japan on December 28, 2020. Incorporate the content here.
  • Displays such as liquid crystal displays have low power consumption and their applications are expanding year by year as space-saving image display devices, but in recent years, further power saving and improvement of color reproducibility are required.
  • semiconductor nanoparticles such as quantum dots, quantum rods, and other inorganic phosphor particles that emit light by converting the wavelength of incident light in order to improve light utilization efficiency and color reproducibility are used as light emitting materials. It has been proposed to utilize the wavelength conversion layer included in.
  • such 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 wavelength conversion type color filter pixel portion.
  • a color filter pixel portion in a display such as a liquid crystal display device has been manufactured by a photolithography method using, for example, a curable resist material containing a pigment and an alkali-soluble resin and / or an acrylic monomer. rice field.
  • Patent Document 1 When an attempt is made to form a wavelength conversion type color filter pixel portion by applying the method for manufacturing a color filter by the above photolithography method, there is a drawback that most of the resist material containing semiconductor nanoparticles is lost in the developing process. there were. Therefore, it is also considered to form a wavelength conversion type color filter pixel portion by an inkjet method (Patent Document 1).
  • Non-Patent Document 1 a combination of semiconductor nanoparticles having trioctylphosphine oxide as a ligand and a fluorescent dye has been studied.
  • the semiconductor nanoparticles have low absorbance in the excitation wavelength range, sufficient emission intensity can be obtained when a wavelength conversion layer produced by using the semiconductor nanoparticles-containing composition is used for a display. It was found that there was a problem that it could not be done. Specifically, in the pixel portion of the wavelength conversion type color filter formed by using the semiconductor nanoparticles-containing composition disclosed in Patent Document 1, a desired pixel such as red or green has sufficient emission intensity. It was found that there was a problem that it could not be obtained.
  • Non-Patent Document 1 Even if the combination of the semiconductor nanoparticles using trioctylphosphine oxide as a ligand and the fluorescent dye disclosed in Non-Patent Document 1 can be applied to the pixel portion of the wavelength conversion type color filter, the emission intensity is not sufficient. It was found that there was a problem.
  • the present invention relates to a semiconductor nanoparticle-containing composition capable of efficiently converting the wavelength of excitation light to form a wavelength conversion layer exhibiting sufficient emission intensity, and a color filter having a pixel portion obtained by curing the composition. And an image display device having the color filter.
  • the gist of the present invention is as follows.
  • the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm in the wavelength range of 300 to 780 nm, and have a maximum emission wavelength in the range of 500 to 670 nm.
  • the ligand (B) is a semiconductor nanoparticle-containing composition characterized by having a hydroxy group.
  • the fluorescent dye (C) has a carboxy group, a sulfanyl group, a disulfanyl group, a sulfandyl group, a disulfandyl group, a thiocarboxy group, a dithiocarboxy group, a sulfino group, a sulfo group, an amino group and an imino.
  • nitrilo group azanilydin group, carbamoyl group, thiocarbamoyl group, phosphanyl group, oxophosphanyl group, phosphandiyl group, phosphantriyl group, phosphinoyl group, phosphonoyl group, phosphoryl group, phosphono group, hydroxyphosphoryl group and A phosphonooxy group and a pyrrolidine ring, a pyrrol ring, an imidazoline ring, an imidazole ring, a tetrahydrothiophene ring, a thiophene ring, a thiazole ring, a piperidine ring, a pyridine ring, a pyrazine ring, and a thian ring having one free valence.
  • a composition containing semiconductor nanoparticles [5] The semiconductor nanoparticles-containing composition according to any one of [1] to [4], which further contains a polymerizable compound (D). [6] The semiconductor nanoparticle-containing composition according to [5], which comprises the (meth) acrylate compound as the polymerizable compound (D).
  • [7] The semiconductor nanoparticles-containing composition according to any one of [1] to [6], which further contains a polymerization initiator (E).
  • E polymerization initiator
  • [8] The semiconductor nanoparticle-containing composition according to any one of [1] to [7], which further contains light-scattering particles.
  • a color filter having a pixel portion obtained by curing the semiconductor nanoparticles-containing composition according to any one of [1] to [9].
  • An image display device having the color filter according to [10].
  • the present invention it is possible to provide a semiconductor nanoparticle-containing composition capable of efficiently wavelength-converting excitation light and forming a wavelength conversion layer exhibiting sufficient emission intensity. Further, it is possible to provide a color filter having a pixel portion obtained by curing the composition of the present invention and an image display device having the color filter of the present invention.
  • FIG. 1 is a schematic cross-sectional view of the color filter of the present invention.
  • (meth) acrylic shall mean “acrylic and / or methacrylic”.
  • total solid content means all components other than the solvent in the semiconductor nanoparticles-containing composition, and when the semiconductor nanoparticles-containing composition does not contain a solvent, all the components of the semiconductor nanoparticles-containing composition are used. means. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
  • the numerical range represented by using “-” means a range including the numerical values before and after “-” as the lower limit value and the upper limit value.
  • “A and / or B” means one or both of A and B, and means A, B, or A and B.
  • the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the semiconductor nanoparticles-containing composition of the present invention can be widely used for producing a wavelength conversion layer, and the wavelength conversion layer using the semiconductor nanoparticles-containing composition of the present invention is suitable for use in a display.
  • the wavelength conversion layer using the semiconductor nanoparticles-containing composition of the present invention is a wavelength conversion sheet
  • the wavelength conversion layer may be contained in the film and is coated on the film surface by a known method. It may be present between films.
  • the semiconductor nanoparticles-containing composition of the present invention can be applied as an ink used in a known and conventional method for producing a color filter, but it is necessary without wasting materials such as semiconductor nanoparticles, which are relatively expensive.
  • the semiconductor nanoparticle-containing composition of the present invention is suitable for use in forming pixel portions by an inkjet method.
  • the semiconductor nanoparticle-containing composition of the present invention is a semiconductor nanoparticle-containing composition containing semiconductor nanoparticles (A), a ligand (B), and a fluorescent dye (C).
  • the semiconductor nanoparticles (A) have a maximum emission wavelength in the range of 500 to 670 nm in the wavelength range of 300 to 780 nm, and the ligand (B) has a hydroxy group.
  • the semiconductor nanoparticle-containing composition of the present invention may further contain, for example, a polymerizable compound (D), a polymerization initiator (E), light-scattering particles, and the like.
  • semiconductor nanoparticles A
  • the semiconductor nanoparticle-containing composition of the present invention has a maximum emission wavelength in the wavelength range of 300 to 780 nm (hereinafter, “maximum emission wavelength” means the maximum emission wavelength in the wavelength range of 300 to 780 nm unless otherwise specified.
  • the semiconductor nanoparticles are nano-sized particles that absorb excitation light and emit fluorescence or phosphorescence, and are, for example, particles having a maximum particle diameter of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope. ..
  • the semiconductor nanoparticles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength, for example, by absorbing light having a predetermined wavelength.
  • the maximum emission wavelength of the semiconductor nanoparticles (A) exists in the range of 500 to 670 nm.
  • the semiconductor nanoparticles (A) may be red-emitting semiconductor nanoparticles (red semiconductor nanoparticles) that emit red light, or may be green-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, and may be, for example, light having a wavelength in the range of 400 to 500 nm (blue light) and / or light having a wavelength in the range of 200 to 400 nm (ultraviolet light). ..
  • semiconductor nanoparticles have a wide absorption in a region shorter than the maximum emission wavelength.
  • the maximum emission wavelength is 530 nm
  • it has a wide absorption band in the wavelength region of 300 to 530 nm with the vicinity of 530 nm as the hem.
  • the maximum emission wavelength is 630 nm
  • it has a wide absorption band in the wavelength region of 300 to 630 nm with the vicinity of 630 nm as the hem.
  • the maximum emission wavelength of the semiconductor nanoparticles (A) can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using a spectrofluorescence meter, and is measured under the conditions of an excitation wavelength of 450 nm and an absorptance of 20 to 50%. It is preferable to do.
  • the maximum emission wavelength thereof is preferably 605 nm or more, more preferably 610 nm or more, further preferably 615 nm or more, further preferably 620 nm or more, and more preferably 625 nm or more. Particularly preferably, it is preferably 665 nm or less, more preferably 655 nm or less, further preferably 645 nm or less, further preferably 640 nm or less, particularly preferably 635 nm or less, and most preferably 630 nm or less.
  • the red color gamut is expanded, and there is a tendency that richer colors can be expressed as a display.
  • the semiconductor nanoparticles (A) include red light emitting semiconductor nanoparticles
  • the maximum emission wavelength thereof is preferably 605 to 665 nm, more preferably 605 to 655 nm, further preferably 610 to 645 nm, and preferably 615 to 640 nm. Even more preferably, 620 to 635 nm is particularly preferable, and 625 to 630 nm is particularly preferable.
  • the maximum emission wavelength thereof is preferably 500 nm or more, more preferably 505 nm or more, further preferably 510 nm or more, further preferably 515 nm or more, and further preferably 520 nm or more.
  • 525 nm or more is most preferable, 560 nm or less is preferable, 550 nm or less is more preferable, 545 nm or less is further preferable, 540 nm or less is further preferable, 535 nm or less is particularly preferable, and 530 nm or less is most preferable.
  • the green color gamut can be expanded, and there is a tendency that a brighter green can be expressed due to the relationship of luminosity factor.
  • the value to the upper limit or less By setting the value to the upper limit or less, the green color gamut is expanded, and there is a tendency that richer colors can be expressed as a display.
  • the above upper and lower limits can be combined arbitrarily.
  • the semiconductor nanoparticles (A) include green light emitting semiconductor nanoparticles
  • the maximum emission wavelength thereof is preferably 500 to 560 nm, more preferably 505 to 550 nm, further preferably 510 to 545 nm, and 515 to 540 nm. Even more preferably, 520 to 535 nm is particularly preferable, and 525 to 530 nm is particularly preferable.
  • the maximum emission wavelength (emission color) of the light emitted by the semiconductor nanoparticles depends on the size (for example, particle diameter) of the semiconductor nanoparticles, but the semiconductor nanoparticles have. It also depends on the energy gap. Therefore, the emission color can be selected by changing the constituent material and size of the semiconductor nanoparticles used.
  • the semiconductor nanoparticles (A) can have various shapes such as a sphere, a cube, a rod, a wire, a disk, and a multipod having a dimension of 30 nm or less in one dimension.
  • CdSe nanorods having a length of 20 nm and a diameter of 4 nm can be mentioned.
  • Semiconductor nanoparticles can also be used in combination with particles having different shapes.
  • a combination of spherical semiconductor nanoparticles and rod-shaped semiconductor nanoparticles can also be used.
  • Spherical semiconductor nanoparticles are preferable from the viewpoint that the emission spectrum can be easily controlled, reliability can be ensured, production cost can be reduced, and mass productivity can be improved.
  • the semiconductor nanoparticles (A) may be composed of only a core containing the first semiconductor material, and the core containing the first semiconductor material and at least a part of the core are covered with the first semiconductor material. It may have a shell containing a different second semiconductor material. That is, the structure of the semiconductor nanoparticles (A) may be a structure consisting of only a core (core structure), or may be a structure consisting of a core portion and a shell portion (core / shell structure).
  • the semiconductor nanoparticles (A) cover at least a part of the core or the first shell in addition to the shell (first shell) containing the second semiconductor material, and are the first and second semiconductor materials. It may further have a shell (second shell) containing a different third semiconductor material. That is, the structure of the semiconductor nanoparticles (A) may be a structure (core / shell / shell structure) including a core portion, a first shell portion, and a second shell portion. Each of the core and the shell may be a mixed crystal containing two or more kinds of semiconductor materials (for example, CdSe + CdS, CuInSe + ZnS, InP + ZnSeS + ZnS).
  • the type of semiconductor material constituting the semiconductor nanoparticles (A) is not particularly limited, but since it has high quantum efficiency and is relatively easy to manufacture, it is a group II-VI semiconductor, a group III-V semiconductor, or an I-III-. It is preferable to include at least one selected from the group consisting of group VI semiconductors, group IV semiconductors, and group I-II-IV-VI semiconductors.
  • Examples of the semiconductor material include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSedZn.
  • red-emitting semiconductor nanoparticles examples include CdSe nanoparticles; nanoparticles having a core / shell structure in which the shell portion is CdS and the core portion is CdSe; the shell portion is CdS and the core portion is. Nanoparticles with a core / shell structure that is ZnSe; nanoparticles with a mixed crystal of CdSe and ZnS; nanoparticles of InP; nanos with a core / shell structure in which the shell part is ZnS and the core part is InP.
  • Nanoparticles having a core / shell structure in which the shell portion is a mixed crystal of ZnS and ZnSe and the core portion is InP Nanoparticles in a mixed crystal of CdSe and CdS
  • the first shells are ZnS and ZnSe.
  • Examples thereof include nanoparticles having a core / shell / shell structure in which the second shell portion is ZnS and the core portion is InP.
  • Examples of the green light emitting semiconductor nanoparticles include nanoparticles of CdSe; nanoparticles of mixed crystals of CdSe and ZnS; nanoparticles having a core / shell structure in which the shell portion is ZnS and the core portion is InP.
  • Semiconductor nanoparticles have the same chemical composition, but by changing the average particle size of themselves, the color to be emitted can be changed to red or green.
  • the semiconductor nanoparticles it is preferable to use particles having as little adverse effect on the human body and the like.
  • semiconductor nanoparticles containing cadmium, selenium, etc. are used as the semiconductor nanoparticles (A)
  • either the semiconductor nanoparticles containing the above elements (cadmium, selenium, etc.) as little as possible are selected and used alone, or the above elements are used. It is preferable to use it in combination with other semiconductor nanoparticles so as to reduce the amount as much as possible.
  • 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, branch-like, net-like, or rod-like.
  • the semiconductor nanoparticles it is preferable to use particles having less directional particle shape (for example, spherical or regular tetrahedral particles) in that the uniformity and fluidity of the semiconductor nanoparticles-containing composition can be further improved. ..
  • the average particle diameter (volume average diameter) of the semiconductor nanoparticles (A) may be 1 nm or more from the viewpoint of easily obtaining light emission of a desired wavelength and from the viewpoint of excellent dispersibility and storage stability. It may be 5 nm or more, and may be 2 nm or more. From the viewpoint that a desired emission wavelength can be easily obtained, it may be 40 nm or less, 30 nm or less, or 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.
  • 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, still more preferably 2 to 20 nm.
  • the semiconductor nanoparticles (A) particles dispersed in a colloidal form in a solvent, a polymerizable compound, or the like can be used. It is preferable that the surface of the semiconductor nanoparticles dispersed in the solvent is passivated by the ligand (B) described later.
  • the solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or a mixture thereof.
  • the semiconductor nanoparticles (A) a commercially available product can be used.
  • Examples of commercially available semiconductor nanoparticles include indium phosphide / zinc sulfide, D-dot, CuInS / ZnS from NN-Labs, and InP / ZnS from Aldrich.
  • the content ratio of the semiconductor nanoparticles (A) is preferably 1% by mass or more, more preferably 5% by mass or more in the total solid content of the semiconductor nanoparticles-containing composition, from the viewpoint of excellent effect of improving the external quantum efficiency. Mass% or more is further preferable, 20% by mass or more is further preferable, 30% by mass or more is particularly preferable, and 60% by mass or less is preferable, and 50% by mass or less is preferable from the viewpoint of coatability, particularly from the viewpoint of being more excellent in ejection stability from the inkjet head. It is more preferably mass% or less, and further preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the semiconductor nanoparticles (A) is preferably 1 to 60% by mass, more preferably 5 to 60% by mass, further preferably 10 to 60% by mass, still more preferably 20 to 50% by mass, and 30. -40% by mass is particularly preferable.
  • the semiconductor nanoparticles-containing composition may contain, as the semiconductor nanoparticles (A), two or more of red-emitting semiconductor nanoparticles and green-emitting semiconductor nanoparticles, and among these particles. It is preferable to contain only one of the above.
  • the semiconductor nanoparticles (A) contain red-emitting semiconductor nanoparticles
  • the content ratio of the green-emitting semiconductor nanoparticles is preferably 10% by mass or less, more preferably 0% by mass in the semiconductor nanoparticles.
  • the semiconductor nanoparticles (A) contain green light emitting semiconductor nanoparticles
  • the content ratio of the red light emitting semiconductor nanoparticles is preferably 10% by mass or less, more preferably 0% by mass in the semiconductor nanoparticles.
  • Ligand (B) The ligand (B) is a compound that covers at least a part of the surface of the semiconductor nanoparticles (A). The ligand (B) covers at least a part of the surface of the semiconductor nanoparticles (A) by adsorbing or coordinate-bonding to the surface of the semiconductor nanoparticles (A).
  • the semiconductor nanoparticle-containing composition of the present invention contains a ligand (B), and the ligand (B) has a hydroxy group.
  • a ligand B
  • the ligand (B) has a hydroxy group.
  • affinity groups functional groups for ensuring affinity with solvents and resins
  • adsorptivity to semiconductor nanoparticles.
  • the present inventors have found that the ligand (B) having a hydroxy group as an adsorbing group exhibits sufficient emission intensity when a wavelength conversion layer is formed by the semiconductor nanoparticles-containing composition of the present invention.
  • the ligand (B) has a hydroxy group, which has a relatively weak binding force to the semiconductor nanoparticles among the adsorbent groups as compared with the phosphinoxide group and the sulfanyl group, so that the ligand (A) has a ligand on the surface of the semiconductor nanoparticles (A). Since (B) repeats adsorption and desorption, the fluorescent dye (C) is likely to be adsorbed on the semiconductor nanoparticles (A).
  • the exchange between the ligand (B) and the fluorescent dye (C) on the surface of the semiconductor nanoparticles (A) is likely to occur. Therefore, when the wavelength conversion layer is formed, the excitation energy of the fluorescent dye (C) adsorbed on the surface of the semiconductor nanoparticles (A) is transferred to the semiconductor nanoparticles (A) by Felster-type energy transfer, and the semiconductor nanoparticles (A) It is considered that the emission intensity of A) is increased.
  • the hydroxy group examples include an alcoholic hydroxyl group and a phenolic hydroxyl group, and examples of the substituent having a hydroxy group include a hydroxyamino group, a hydroxyimino group, a dihydroxyboryl group, a hydroxyboryl group, and an oxoacid group. .. From the viewpoint of exchange between the ligand (B) and the fluorescent dye (C) on the surface of the semiconductor nanoparticles (A), the ligand (B) preferably has an oxoacid group.
  • Examples of the oxo acid group include a carboxy group, a sulfino group, a sulfo group, a phosphonic acid group, a hydroxyphosphoryl group and a phosphoric acid group, and the carboxy group is particularly preferable.
  • the ligand (B) is not particularly limited as long as it has a hydroxy group. From the viewpoint of affinity with solvents, polymerizable compounds, resins and the like, it is preferable to have an affinity group.
  • an aliphatic hydrocarbon group is preferable.
  • the aliphatic hydrocarbon group may be a linear type or may have a branched structure.
  • the aliphatic hydrocarbon group may have a polyalkylene glycol chain such as a polyethylene glycol chain. Further, the aliphatic hydrocarbon group may have an unsaturated bond or may not have an unsaturated bond.
  • the ligand (B) may have an adsorbing group other than the hydroxy group as long as the gist of the present invention is not impaired, and examples of the adsorbing group other than the hydroxy group include an amino group, a sulfanyl group and a phosphate group. , Phosphonic acid group, phosphin group, phosphinoxide group, alkoxysilyl, etc., but it is preferable not to have a functional group such as sulfanyl group, phosphinoxide group, etc., which has a stronger binding force to semiconductor nanoparticles than a carboxy group.
  • a compound having a hydroxy group at the terminal can be used, an aromatic ring or an ether group can be used, and a plurality of hirodoxy groups may be contained in the molecule.
  • the ligand (B) for example, benzoic acid, biphenylcarboxylic acid, butylbenzoic acid, hexylbenzoic acid, cyclohexylbenzoic acid, naphthalenecarboxylic acid, hexanoic acid, heptanic acid, octanoic acid, ethylhexanoic acid, hexenoic acid, octenoic acid, Examples thereof include citroneric acid, suberic acid, ethylene glycol bis (4-carboxyphenyl) ether and (2-butoxyethoxy) acetic acid.
  • the ligand (B) includes a compound having a carboxy group and an aliphatic hydrocarbon group having 8 or more carbon atoms, and a poly such as a carboxy group and a polyethylene glycol chain from the viewpoint of compatibility with a solvent, a polymerizable compound, a resin and the like.
  • Compounds having an alkylene glycol chain are preferred.
  • Examples of the compound having a carboxy group and an aliphatic hydrocarbon group having 8 or more carbon atoms and the compound having a polyalkylene glycol chain such as a carboxy group and a polyethylene glycol chain include nonanoic acid, decanoic acid, lauric acid and myristic acid.
  • n represents an integer from 0 to 100.
  • the semiconductor nanoparticle-containing composition of the present invention contains a ligand (B), and the ligand (B) may contain one kind alone or two or more kinds.
  • the semiconductor nanoparticle-containing composition of the present invention may further contain a ligand other than the ligand (B) (hereinafter, may be referred to as “ligand (B1)”).
  • ligand (B1) examples include organic substances such as organic amines, sulfur-containing organic substances, and phosphorus-containing organic substances.
  • the content ratio of the ligand (B) in the semiconductor nanoparticles-containing composition of the present invention is not particularly limited, but from the viewpoint of ensuring compatibility with a solvent, a polymerizable compound, and a resin and improving the dispersibility of the semiconductor nanoparticles.
  • 0.005% by mass or more more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, still more preferably 0.1% by mass or more in the total solid content of the semiconductor nanoparticles-containing composition. It is preferably 0.3% by mass or more, particularly preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of improving the emission intensity, improving the film strength and reducing the viscosity of the semiconductor nanoparticles-containing composition.
  • the content ratio of the ligand (B) in the semiconductor nanoparticles-containing composition is preferably 0.005 to 30% by mass, more preferably 0.01 to 30% by mass. It is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.3 to 10% by mass.
  • the content ratio of the semiconductor nanoparticles (A) and the ligand (B) in the semiconductor nanoparticles-containing composition of the present invention is not particularly limited, but the affinity with the solvent, the polymerizable compound, and the resin is ensured, and the semiconductor nanoparticles are dispersed.
  • the ligand (B) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and the semiconductor nano.
  • 300 parts by mass or less is preferable, 200 parts by mass or less is more preferable, and 100 parts by mass or less is further preferable.
  • the content ratio of the semiconductor nanoparticles (A) and the ligand (B) in the semiconductor nanoparticles-containing composition is 100 parts by mass of the semiconductor nanoparticles (A).
  • the ligand (B) is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, still more preferably 10 to 100 parts by mass.
  • Fluorescent dye (C) The semiconductor nanoparticle-containing composition of the present invention contains a fluorescent dye (C). By using the fluorescent dye (C) in combination with the semiconductor nanoparticles (A), it is possible to improve the luminous efficiency of the semiconductor nanoparticles (A).
  • the emission spectrum of the fluorescent dye (C) and the absorption spectrum of the semiconductor nanoparticles (A) having a maximum emission wavelength in the range of 500 to 670 nm are used. It is considered preferable that the overlap is large. Due to the large overlap between the emission spectrum of the fluorescent dye (C) and the absorption spectrum of the semiconductor nanoparticles (A), the excited energy of the fluorescent dye (C) is transferred to the semiconductor nanoparticles (A) by Felster-type energy transfer. It is considered that this is because the semiconductor nanoparticles (A) move and the emission intensity of the semiconductor nanoparticles (A) increases.
  • the fluorescent dye (C) is preferably a fluorescent dye having an emission spectrum having a large overlap with the absorption spectrum of the semiconductor nanoparticles (A).
  • a fluorescent dye having a structure represented by the formula (c-VI) is preferable, and a fluorescent dye having a naphthalimide skeleton, a fluorescent dye having a coumarin skeleton, a fluorescent dye having a perylene skeleton, and a fluorescent dye having a perylene skeleton are represented by the formula (c-IV).
  • a fluorescent dye having a structure represented by the above, a fluorescent dye having a structure represented by the formula (cV), and a fluorescent dye having a structure represented by the formula (c-VI) are particularly preferable.
  • fluorescent dye with naphthalimide skeleton The fluorescent dyes having a naphthalimide skeleton are described below from the viewpoints of high solubility in various solvents and compositions containing semiconductor nanoparticles, high gram absorption coefficient, difficulty in concentration quenching, and high fluorescence quantum yield. It is preferably a fluorescent dye represented by the general formula (c-I) (hereinafter, also referred to as "fluorescent dye (C1)").
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom or an arbitrary substituent
  • X is NR 7 R 8 , SR.
  • R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom or an arbitrary substituent.
  • R 4 and X may be connected to form a ring, and when X is NR 7 R 8 , R 7 and R 8 may be connected to form a ring.
  • R 1 The arbitrary substituent in R1 is not particularly limited as long as it is a substitutable monovalent group, and for example, an alkyl group which may have a substituent and an aryl group which may have a substituent may be used. Can be mentioned. From the viewpoint of improving the solubility in the composition containing semiconductor nanoparticles 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 used. More preferably, 2-ethylhexyl group, o-tolyl group and 2- [2- (2-methoxyethoxy) ethoxy] ethoxycarbonyl group are particularly preferable.
  • R 2 , R 3 , R 4 , R 5 , R 6 The arbitrary substituent in R 2 , R 3 , R 4 , R 5 , R 6 is not particularly limited as long as it is a substitutable monovalent group, and for example, an alkyl group which may have a substituent may be used.
  • An alkylsulfonyl group which may have a substituent, an aminosulfonyl group which may have a substituent, a cyano group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group, an amino group Examples thereof include a carboxy group and a sulfo group.
  • (X) X represents any of the structures of NR 7 R 8 , SR 9 , and OR 10 .
  • NR 7 R 8 is preferable from the viewpoint of absorption wavelength.
  • R 7 and R 8 The arbitrary substituent in R 7 and R 8 is not particularly limited as long as it is a substitutable monovalent group, and for example, it may have an alkyl group or a substituent which may have a substituent. It has a good alkylcarbonyl group, an alkoxycarbonyl group which may have a substituent, an aryl group which may have a substituent, an arylcarbonyl group which may have a substituent, and a substituent. Examples thereof include an aryloxycarbonyl group, an alkylsulfonyl group which may have a substituent, and a hydroxyl group. From the viewpoint of easiness of synthesis, an alkyl group which may have a substituent is preferable. When X is NR 7 R 8 , R 7 and R 8 may be connected to form a ring.
  • R 9 and R 10 The arbitrary substituent in R 9 and R 10 is not particularly limited as long as it is a substitutable monovalent group, and for example, it may have an alkyl group or a substituent which may have a substituent.
  • R4 and X may be connected to form a ring.
  • An example of the formula (c-I) when the ring is formed in this way is shown below.
  • fluorescent dye with coumarin skeleton As the fluorescent dye having a coumarin skeleton, the following general is used from the viewpoints of high solubility in various solvents and compositions containing semiconductor nanoparticles, high gram absorption coefficient, difficulty in concentration quenching, and high fluorescence quantum yield. It is preferably a fluorescent dye represented by the formula (c-II) (hereinafter, also referred to as “fluorescent dye (C2)”).
  • R 1 , R 2 , R 3 , R 4 , and R 6 each independently represent a hydrogen atom or an arbitrary substituent.
  • R 5 represents a hydrogen atom, N (R 7 ) 2 , or OR 7 .
  • R 7 may be connected to each other to form a ring.
  • R 7 represents a hydrogen atom or any substituent. Two or more selected from the group consisting of R 4 , R 5 and R 6 may be connected to form a ring.
  • R 1 , R 2 , R 3 , R 4 , R 6 each independently represent a hydrogen atom or an arbitrary substituent.
  • the arbitrary substituent in R 1 , R 2 , R 3 , R 4 , and R 6 is not particularly limited as long as it is a substitutable monovalent group, and for example, an alkyl group which may have a substituent may be used.
  • a methyl group, a cyano group, a trifluoromethyl group, a nitro group, an amino group and a carboxy group are preferable, and a cyano group and a trifluoro group are preferable from the viewpoint of absorption efficiency of excitation light.
  • Methyl groups are more preferred.
  • R 1 is preferably a group represented by the following general formula (c-II-1) from the viewpoint that the fluorescent dye (C2) has a structure showing a strong emission spectrum.
  • X represents an oxygen atom, a sulfur atom, or NR 9 .
  • R 8 represents a hydrogen atom or any substituent.
  • R 9 represents a hydrogen atom or an alkyl group. When R 8 is NR 9 , R 9 and R 8 may be connected to form a ring. * Represents a bond.
  • X represents an oxygen atom, a sulfur atom, or NR 9 .
  • the group represented by the formula (c-II-1) attracts more electrons from the coumarin skeleton, the fluorescence intensity tends to be higher, so that the group contains an atom having a large electronegativity. From this point of view, an oxygen atom or NR 9 is preferable.
  • R 9 represents a hydrogen atom or an alkyl group.
  • the alkyl group in R 9 include a linear group, a branched chain group, a cyclic group, and a combination thereof, and a cyclic group from the viewpoint of increasing the durability of the dye (B1). Is preferable.
  • Some -CH 2- in the alkyl group may be substituted with -O-.
  • R 8 represents a hydrogen atom or any substituent.
  • the arbitrary substituent in R8 is not particularly limited as long as it is a substitutable monovalent group, for example, an alkyl group which may have a substituent and an alkoxy group which may have a substituent.
  • An aryl group which may have a substituent, an aryloxy group which may have a substituent, a sulfanyl group, an alkylsulfanyl group which may have a substituent, and a substituent may be present. Examples thereof include an arylsulfanyl group, a hydroxyl group and an amino group.
  • R8 is preferably a methyl group.
  • R 9 and R 8 may be connected to form a ring.
  • any substituent R 8 and a hydrogen atom R 9 can be linked to form a ring, in which case R 9 is a single bond.
  • the ring when R 9 and R 8 are connected to form a ring may be an aliphatic ring or an aromatic ring, but is preferably an aromatic ring from the viewpoint of durability of the fluorescent dye (C2).
  • An example of a ring formed by connecting R 9 and R 8 is shown below.
  • R 5 represents a hydrogen atom, N (R 7 ) 2 , or OR 7 .
  • R 7 may be connected to each other to form a ring.
  • N (R 7 ) 2 is preferable from the viewpoint that the electron donating property is high and the fluorescence intensity tends to be high.
  • R 7 represents a hydrogen atom or an arbitrary substituent.
  • Arbitrary substituents in R 7 include, for example, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent. Examples thereof include an arylcarbonyl group which may have a group, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent.
  • R 4 , R 5 and R 6 may be connected to form a ring.
  • An example of the formula (c-II) when the ring is formed in this way is shown below.
  • the fluorescent dye represented by the formula (c-II-2) is preferable from the viewpoint of having high solubility in the composition containing semiconductor nanoparticles.
  • R 1 to R 3 are synonymous with the formula (c-II).
  • R 10 and R 11 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • m and n each independently represent an integer of 0 to 4.
  • R 10 and R 11 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • the number of carbon atoms of the alkyl group in R 10 and R 11 is not particularly limited as long as it is 1 to 4, but it is preferably 3 or less, and more preferably 2 or less. By setting the value to the upper limit or less, the absorption efficiency of the excitation light with respect to the mass of the fluorescent dye present in the semiconductor nanoparticles-containing composition tends to be improved.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an isopropyl group, an isobutyl group and a tertiary butyl group, and a methyl group and an ethyl group are preferable from the viewpoint of high absorption efficiency of excitation light. , Methyl group is more preferred.
  • m and n each independently represent an integer of 0 to 4.
  • m and n may be integers of 2 or less from the viewpoint of high solubility in the semiconductor nanoparticles-containing composition and high absorption efficiency of excitation light with respect to the mass of the fluorescent dye present in the semiconductor nanoparticles-containing composition. preferable.
  • the fluorescent dye having a perylene skeleton is a fluorescent dye represented by the following general formula (c-III) from the viewpoint of increasing the emission intensity of the semiconductor nanoparticles due to the interaction between the dye and the semiconductor nanoparticles (hereinafter, “fluorescence”). Also referred to as “dye (C3)”) is preferable.
  • R 11 , R 21 , R 31 , and R 41 each independently represent a hydrogen atom or any substituent.
  • R 11 , R 21 , R 31 , and R 41 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 represent a hydrogen atom or any substituent.
  • R5 represents a hydrogen atom or any substituent. * Represents a bond.
  • R 11 , R 21 , R 31 , R 41 each independently represent a hydrogen atom or any substituent.
  • R 11 , R 21 , R 31 , and R 41 is a group represented by the formula (c-III-1).
  • R5 represents a hydrogen atom or any substituent. * Represents a bond.
  • the arbitrary substituent in R5 is not particularly limited as long as it is a substitutable monovalent group, and examples thereof include a hydrocarbon group which may have a substituent. Some -CH 2- in the hydrocarbon group may be substituted with -O-, and some carbon atoms in the hydrocarbon group may be substituted with heteroatoms. Examples of the hydrocarbon group include an alkyl group which may have a substituent and an aryl group which may have a substituent.
  • R 5 may be connected to any of R 11 , R 21 , R 31 , and R 41 to form a ring.
  • R5 is preferably a 2 -ethylhexyl group or a (2- (2-sulfanylethoxy) ethoxy) ethyl group, and from the viewpoint of solubility in the semiconductor nanoparticles-containing composition, ( A 2- (2-methoxyethoxy) ethoxy) ethyl group is preferred.
  • R 11 , R 21 , R 31 , and R 41 are groups represented by the formula (c-III-1), but two or more are more preferable, and three or more are more preferable, and all of them are. Especially preferable. By setting the value to the lower limit or higher, the absorption efficiency of the excitation light tends to be improved.
  • the arbitrary substituent in R 11 , R 21 , R 31 , and R 41 is particularly limited as long as it is a substitutable monovalent group other than the group represented by the formula (c-III-1).
  • it may have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, and a substituent.
  • substituents include an arylcarbonyl group, an alkylsulfonyl group which may have a substituent, an amide group which may have a substituent, a cyano group, and a halogen atom.
  • R 11 and R 21 may be connected to form a ring, or R 31 and R 41 may be connected to form a ring.
  • 2-ethylhexyl group and (2- (2-sulfanylethoxy) ethoxy) ethyl group are preferable from the viewpoint of improving the conversion efficiency of excitation light, and from the viewpoint of solubility in the semiconductor nanoparticles-containing composition.
  • (2- (2-Methoxyethoxy) ethoxy) ethyl group is preferred.
  • R 11 and R 21 may be connected to form a ring, or R 31 and R 41 may be connected to form a ring.
  • the group in which R 11 and R 21 are linked and the group in which R 31 and R 41 are linked are -CO- (NR 6 ) -CO- (where R 6 is a hydrogen atom or carbon.
  • R 6 is a hydrogen atom or carbon.
  • R 6 is a hydrogen atom or carbon.
  • the carbonyl group-CO- (NR 6 ) -CO- is preferable.
  • R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , R 43 each independently represent a hydrogen atom or an arbitrary substituent.
  • the arbitrary substituent in R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 , and R 43 is not particularly limited as long as it is a substitutable monovalent group, and is, for example, a substituent.
  • An aryl group which may have a substituent an aryloxy group which may have a substituent, an arylcarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, Examples include a cyano group and a halogen atom.
  • a 2-ethylhexyl group or a (2- (2-methoxyethoxy) ethoxy) ethyl group is preferable from the viewpoint of solubility in a hydrogen atom or a composition containing semiconductor nanoparticles, and a hydrogen atom is preferable from the viewpoint of easiness of synthesis.
  • fluorescent dye (C4) having a partial structure represented by the general formula (c-IV) (hereinafter, also referred to as “fluorescent dye (C4)”) is also preferable.
  • X represents an O atom or an S atom.
  • Z represents CR 2 or N atom.
  • R 1 and R 2 each independently represent a hydrogen atom or an arbitrary substituent. * Represents a bond.
  • (X) X represents an O atom or an S atom.
  • the O atom is preferable from the viewpoint of increasing the emission intensity
  • the S atom is preferable from the viewpoint of light resistance.
  • (Z) Z represents CR 2 or N atom.
  • CR 2 is preferable from the viewpoint of ease of synthesis.
  • R 1 , R 2 each independently represent a hydrogen atom or an arbitrary substituent.
  • the arbitrary substituent is not particularly limited as long as it is a substitutable monovalent group.
  • the optional substituent includes, for example, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent.
  • An aryl group which may have a substituent an aryloxy group which may have a substituent, a sulfanyl group, a dialkylphosphino group which may have a substituent, an alkylsulfanyl group which may have a substituent, Examples thereof include a hydroxyl group, a carboxy group, an amino group, a nitro group, a cyano group and a halogen atom. Further, when Z is CR 2 , R 1 and R 2 may be connected to form a ring.
  • R 1 and R 2 are independently hydrogen atom, 2-ethylhexyl group, phenyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethoxy.
  • a group is preferable, and a hydrogen atom is more preferable.
  • R 1 and R 2 may be connected to form a ring, and when the ring is formed, for example, the following structure can be mentioned.
  • the fluorescent dye represented by the following general formula (c-IV-1) is preferable from the viewpoint of increasing the emission intensity.
  • X represents an O atom or an S atom.
  • Z represents CR 2 or N atom.
  • R 1 and R 2 each independently represent a hydrogen atom or an arbitrary substituent.
  • a 1 and a 2 are independent groups represented by the following general formula (c-IV-2).
  • b 12 represents a single bond or a divalent group other than b 11 .
  • Each x independently represents an integer of 0 to 3. When x is an integer of 2 or more, the plurality of b 11s may be the same or different. y independently represents an integer of 1 to 3. When y is an integer of 2 or more, the plurality of b 12 may be the same or different.
  • R 11 represents a hydrogen atom or any substituent. * Represents a bond.
  • a1 and a2 are independent groups represented by the following general formula (c-IV-2). Although a 1 and a 2 may be the same group or different groups, they are preferably the same group from the viewpoint of easiness of synthesis.
  • b 12 represents a single bond or a divalent group other than b 11 .
  • Each x independently represents an integer of 0 to 3. When x is an integer of 2 or more, the plurality of b 11s may be the same or different. y independently represents an integer of 1 to 3. When y is an integer of 2 or more, the plurality of b 12s may be the same or different.
  • R 11 represents a hydrogen atom or any substituent. * Represents a bond.
  • b 11 is an arylene group which may have a substituent
  • the bonded arylene group tends to be twisted from the diazole plane due to steric hindrance, stacking of fluorescent dyes is hindered, and concentration quenching tends to be less likely to occur. Therefore, as b11 , an arylene group which may have a substituent is preferable.
  • 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 and an amino.
  • substituents of the arylene group an amino group or a sulfanyl group is preferable from the viewpoint of energy transfer efficiency to semiconductor nanoparticles. From the viewpoint of solubility, a hydrogen atom, an alkyl group, or an alkoxy group is preferable, and a hydrogen atom, a t-butyl group, or a 2-propyloxy group is particularly preferable.
  • the 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, a halogen atom and the like.
  • an amino group or a sulfanil group is preferable.
  • a hydrogen atom, an alkyl group, or an alkoxy group is preferable, and a hydrogen atom, a t-butyl group, or a 2-propyloxy group is particularly preferable.
  • the plane of the molecular structure is due to steric hindrance between the isolated electron pair on the N atom of the diazole moiety and the hydrogen atom of the arylene group, or the substituent.
  • the properties are reduced, and the formation of aggregates between fluorescent dyes due to ⁇ - ⁇ stacking or the like is suppressed. This is preferable because it is considered that the concentration quenching due to the formation of aggregates tends to be suppressed.
  • the flatness of the molecule is small because the fluorescent dye itself only has the ⁇ -conjugation of the diazole moiety in the first place. Concentration dimming due to aggregate formation is considered to tend to be small, which is preferable.
  • b 12 represents a single bond or a divalent group other than b 11 .
  • the divalent group other than b 11 is not particularly limited, and for example, it may have an alkylene group which may have a substituent, an alkyleneoxy group which may have a substituent, or a substituent. Good alkyleneamino groups are mentioned.
  • b 12 includes a 2-ethylhexanediyl group and a -O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -group from the viewpoint of solubility in the composition.
  • a single bond or a methylene group is preferable from the viewpoint of improving the absorbance with respect to the excitation light.
  • x independently represents an integer of 0 to 3. From the viewpoint of absorption wavelength, x is preferably 1 or 2, and more preferably 1.
  • One or both of x in a1 and x in a2 are preferably integers of 1 to 3, and both x in a1 and x in a2 are more preferably 1.
  • the absorption efficiency of the excitation light tends to be improved.
  • the plurality of b 11s may be the same or different.
  • y independently represents an integer of 1 to 3. From the viewpoint of solubility in the composition and absorbance to excitation light, y is preferably 1 or 2, and 1 is particularly preferable. When y is an integer of 2 or more, the plurality of b 12s may be the same or different.
  • R 11 represents a hydrogen atom or any substituent.
  • the arbitrary substituent is not particularly limited as long as it is a substitutable monovalent group.
  • an aryl group which may have a substituent an aryloxy group which may have a substituent, a hydroxyl group, a carboxy group, a formyl group, a sulfo group, an amino group which may have a substituent, and sulfanyl.
  • alkylsulfanyl group which may have a substituent dialkylphosphino group which may have a substituent, nitro group, cyano group, trialkylsilyl group which may have a substituent, substituent. Examples thereof include a dialkylboryl group which may have a group and a halogen atom.
  • R 11 is preferably a pyridine ring having a carboxy group, an amino group, a sulfanyl group and one free valence, while from the viewpoint of solubility, a hydrogen atom and a trialkyl.
  • a silyl group is preferred.
  • fluorescent dye (C5) having a partial structure represented by the general formula (cV) (hereinafter, also referred to as “fluorescent dye (C5)”) is also preferable.
  • Ar 1 , Ar 2 , and Ar 3 each independently represent an aryl group that may have a substituent.
  • R 1 and R 2 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • Ar 1 , Ar 2 , Ar 3 each independently represent an aryl group that may have a substituent.
  • aryl groups in Ar 1 and Ar 2 , a divalent aromatic hydrocarbon ring group (aromatic hydrocarbon ring having two free valences) and a divalent aromatic heterocyclic group (two free atoms) Aromatic heterocycles with valence).
  • Ar 3 a monovalent aromatic hydrocarbon ring group (aromatic hydrocarbon ring having one free valence) and a monovalent aromatic heterocyclic group (aromatic heterocycle having one free valence) ).
  • Ar 1 is a benzene ring having two free valences and a naphthalene ring having two free valences.
  • Ar 2 is a group represented by any of the following general formulas (cV-1), (cV-2) and (cV-3). ..
  • Ar 3 is a benzene ring having one free valence.
  • R 3 and R 4 are each independently an alkyl group or a substituent which may have a substituent. Represents an aryl group that may have a group.
  • R 3 and R 4 are each independently an alkyl group or a substituent which may have a substituent. Represents an aryl group that may have a group.
  • alkyl group examples include a linear group, a branched chain group, a cyclic group, and a combination thereof, and a branched chain group is preferable from the viewpoint of solubility.
  • the aryl group examples include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms of the aryl group is not particularly limited, but 4 or more is preferable, 6 or more is more preferable, 12 or less is preferable, and 10 or less is more preferable.
  • the aryl group preferably has 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • R 1 and R 2 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • alkyl group examples include a linear group, a branched chain group, a cyclic group, and a combination thereof. From the viewpoint of improving light resistance due to steric hindrance, for example, a branched chain or an annular one is preferable.
  • the aryl group examples include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms of the aryl group is not particularly limited, but 4 or more is preferable, 6 or more is more preferable, 12 or less is preferable, and 10 or less is more preferable.
  • the aryl group preferably has 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • fluorescent dye (C6) having a partial structure represented by the general formula (c-VI) (hereinafter, also referred to as “fluorescent dye (C6)”) is also preferable.
  • X represents C- * or N. * Represents a bond.
  • R 1 and R 2 independently represent a fluorine atom or a cyano group.
  • R 1 , R 2 independently represent a fluorine atom or a cyano group.
  • R 1 and R 2 fluorine atoms are preferable from the viewpoint of improving the durability of the fluorescent dye (C6).
  • 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) with respect to pH, C- * is preferable, and CR 9 is more preferable.
  • R 9 represents a hydrogen atom or an arbitrary substituent. When blue excitation light is used, C- * is preferable, and CR 9 is more preferable, from the viewpoint of improving absorption efficiency.
  • R 9 The arbitrary substituent in R 9 is not particularly limited as long as it is a substitutable monovalent group.
  • it may have an alkyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkylcarbonyloxy group which may have a substituent, and a substituent.
  • It has an alkylcarbonylamino group, an alkylsulfonyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent.
  • aryloxycarbonyl group which may be present, an amino group which may have a substituent, a carbamoyl group which may have a substituent, a sulfanyl group which may have a substituent, and a substituent.
  • R 9 is preferably an alkoxy group or an amino group (particularly an alkylamino group) from the viewpoint of improving the absorption efficiency of the excitation light.
  • an alkyl group, an aryl group, an alkoxy group and an amino group are preferable, and a methyl group, a 2-ethylhexyl group and a phenyl group are preferable.
  • 2- [2- (2-Hydroxyethoxy) ethoxy] ethoxy group, phenoxy group, 2-ethylhexylamino group are more preferable, methyl group, phenyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethoxy group. Is particularly preferable.
  • the fluorescent dye (C6) is not particularly limited as long as it is represented by the formula (c-VI), but has high solubility in various solvents and semiconductor nanoparticles-containing compositions, has a high gram absorption coefficient, and provides concentration quenching. From the viewpoint that it is difficult to obtain and the quantum yield of fluorescence is high, a fluorescent dye represented by the following general formula (c-VI-1) is preferable.
  • X represents CR 9 or N.
  • R 3 to R 9 independently represent a hydrogen atom or an arbitrary substituent.
  • R 4 and R 3 or R 5 may be connected to form a ring.
  • R 7 and R 6 or R 8 may be connected to form a ring.
  • R 1 and R 2 independently represent a fluorine atom or a cyano group.
  • R 1 and R 2 independently represent a fluorine atom or a cyano group.
  • R 1 and R 2 fluorine atoms are preferable from the viewpoint of improving the durability of the fluorescent dye.
  • X represents CR 9 or N, and CR 9 is preferable from the viewpoint of improving the durability of the fluorescent dye.
  • R 9 represents a hydrogen atom or an arbitrary substituent, examples of the arbitrary substituent in R 9 include the substituents described in the formula (c-VI), and preferred substituents are also described in the formula (c-VI). It is the same as the substituent.
  • R 3 to R 8 independently represent a hydrogen atom or an arbitrary substituent, and the arbitrary substituents in R 3 to R 8 are described as arbitrary substituents in R 9 in the formula (c-VI). Substituents can be mentioned.
  • an alkyl group, an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group are preferable, and a methyl group is preferable from the viewpoint of improving the solubility in the semiconductor nanoparticles-containing composition and improving the durability of the fluorescent dye.
  • 2-Ethylhexyl group, phenyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethoxycarbonyl group and phenoxycarbonyl group are more preferable, and methyl group, 2-ethylhexyl group and 2- [2- (2-hydroxyethoxy) group. ) Ethoxy] ethoxycarbonyl group is particularly preferred.
  • R 4 and R 3 or R 5 may be connected to form a ring, or R 7 and R 6 or R 8 may be connected to form a ring.
  • An example of the general formula (c-VI-1) when the ring is formed in this way is shown below.
  • R 1 and R 2 are fluorine atoms in the formula (c-VI-1) from the viewpoint of improving the durability of the fluorescent dye, and X is used.
  • the preferable structure of the fluorescent dye (C6) is that R 1 and R 2 are fluorine in the formula (c-VI-1). It is an atom, X is C-R 9 , R 9 is an alkyl group, an aryl group, an alkoxy group and an amino group, and R 3 to R 8 are an alkyl group, an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Is preferable.
  • the structure of the fluorescent dye (C6) is such that X is CR 9 and R 9 in the general formula (c-VI-1). Is preferably an alkoxy group or an amino group (particularly an alkylamino group).
  • the fluorescent dye (C) preferably has a substituent that causes an action of linking to the semiconductor nanoparticles (A).
  • the fluorescent dye (C) is easily adsorbed on the semiconductor nanoparticles (A). That is, the exchange between the ligand (B) and the fluorescent dye (C) on the surface of the semiconductor nanoparticles (A) is likely to occur.
  • the excitation energy of the fluorescent dye (C) adsorbed on the surface of the semiconductor nanoparticles (A) is transferred to the semiconductor nanoparticles (A) by Felster-type energy transfer, and the semiconductor nanoparticles.
  • the substituent may be a heterocyclic group, and the heterocycle may be a monocyclic ring or a condensed ring.
  • the heterocyclic group include a pyrrolidine ring, a pyrrol ring, a pyrrolopyrrole ring, a thienopyrrole ring, an imidazolidine ring, an imidazoline ring, a pyrazole ring, a pyrrolopyrazole ring, an imidazole ring, and a pyrrolobymidazole ring having one free valence.
  • Benzoimidazole ring tetrahydrofuran ring, furan ring, tetrahydrothiophene ring, thiophene ring, benzothiophene ring, thienothiophene ring, thienoflan ring, oxazole ring, benzoxazole ring, isooxazole ring, benzoisoxazole ring, thiazole ring, benzothiazole.
  • Ring isothiazole ring, benzoisothiazole ring, oxathiolane ring, thiadiazole ring, piperidine ring, pyridine ring, pyrazine ring, pyridazine ring, piperazine ring, pyrimidine ring, triazine ring, tetrahydropyran ring, dioxane ring, thian ring, Dithian ring, morpholine ring, thiomorpholin ring, indole ring, quinoline ring, isoquinoline ring, quinoxalin ring, quinazoline ring, phenazine ring, phenothiazine ring, phenoxatiin ring, phenanthridine ring, quinuclidine ring, azulene ring, thiirane ring, Examples include the azetidine ring and the thietan ring.
  • the fluorescent dye (C) contains a carboxy group, a sulfanyl group, a disulfanyl group, a sulfandyl group, a disulfandyl group, a thiocarboxy group, a dithiocarboxy group, and a sulfino.
  • sulfo group amino group, imino group, nitrilo group, azanilydin group, carbamoyl group, thiocarbamoyl group, phosphanyl group, oxophosphanyl group, phosphandiyl group, phosphantriyl group, phosphinoyl group, phosphonoyl group, phosphoryl Group, phosphono group, hydroxyphosphoryl group, phosphonooxy group; pyrrolidine ring, pyrrol ring, imidazolidine ring, imidazole ring, tetrahydrothiophene ring, thiophene ring, thiazole ring, piperidine ring, pyridine having one free valence.
  • the fluorescent dye (C) contains a sulfanyl group, a sulfandyl group, a disulfandyl group, a thiocarboxy group, a dithiocarboxy group, an amino group, a nitrilo group and an oxophos from the viewpoint of improving the bond strength to the semiconductor nanoparticles.
  • the left end of the composition formula of each substituent indicates that it binds to the skeleton of the fluorescent dye (C), and-and ⁇ at the right end indicate that it binds to any substituent.
  • those having hydrogen atoms bonded to heteroatoms generally desorb hydrogen atoms and form ionic bonds or covalent bonds with the metals constituting the nanoparticles.
  • Heteroatoms that do not have a hydrogen atom are adsorbed by donating their unshared electron pair to a metal atom.
  • the molecule is more strongly adsorbed and is less likely to be detached.
  • the substituent that causes the action of linking to the semiconductor nanoparticles (A) may be bonded to the skeleton and structure of the fluorescent dye (C), and its position is not particularly limited.
  • the fluorescent dye (C) particularly a fluorescent dye having a naphthalimide skeleton, a fluorescent dye having a coumarin skeleton, a fluorescent dye having a perylene skeleton, and a fluorescent dye having a structure represented by the general formula (c-VI), (c).
  • a fluorescent dye having a structure represented by the general formula (c-VI), (c) Specific examples of the fluorescent dye having the structure shown by —V) and the fluorescent dye having the structure shown by (c-VI) will be given.
  • the method for producing the fluorescent dye (C) is not particularly limited, and for example, Japanese Patent Application Laid-Open No. 2003-104976, Japanese Patent Application Laid-Open No. 2011-231245, International Publication No. 2015/111647, Japanese Patent Application Laid-Open No. 2015- 006173, Chem. Eur. J. , 13,1746-1753, 2007, Chem. Rev. , 107, p. It can be produced by the method described in 4891-4932, 2007.
  • the maximum emission wavelength of the fluorescence emitted by the fluorescent dye (C) is not particularly limited, but is preferably 450 nm or more, more preferably 455 nm or more, further preferably 460 nm or more, particularly preferably 465 nm or more, preferably 640 nm or less, and more preferably 635 nm or less. It is preferable, more preferably 630 nm or less, and particularly preferably 625 nm or less.
  • the emission spectrum of the semiconductor nanoparticles and the emission spectrum of the fluorescent dye (C) can be separated, so that the energy transferred from the fluorescent dye (C) to the semiconductor nanoparticles increases.
  • a color filter provided separately from the pixel portion tends to facilitate absorption of light emitted from the fluorescent dye (C) in an unnecessary wavelength region.
  • the maximum emission wavelength of the fluorescence emitted by the fluorescent dye (C) is in the vicinity of 460 to 630 nm, the emission intensity of both the green-emitting semiconductor nanoparticles and the red-emitting semiconductor nanoparticles tends to be increased. preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 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, further preferably 460 to 630 nm, and particularly preferably 465 to 625 nm.
  • the method for measuring the maximum emission wavelength is not particularly limited, but for example, a spectrofluorometer using light having a wavelength of 445 nm as an excitation light source using a solution of the fluorescent dye (C) or a film containing the fluorescent dye (C). It may be read from the emission spectrum measured in the above.
  • the semiconductor nanoparticle-containing composition of the present invention may contain one kind of fluorescent dye (C) alone, or may contain two or more kinds of fluorescent dyes (C).
  • the fluorescent dye (C) may further contain a dye other than the fluorescent dye (C).
  • the content ratio of the fluorescent dye (C) in the semiconductor nanoparticles-containing composition of the present invention is not particularly limited, but is preferably 0.001% by mass or more, preferably 0.01% by mass, in the total solid content of the semiconductor nanoparticles-containing composition.
  • the above is more preferable, 0.05% by mass or more is further preferable, 0.1% by mass or more is particularly preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is further preferable. % Or less is particularly preferable.
  • the fluorescent dye (C) By setting the value to the lower limit or higher, the fluorescent dye (C) sufficiently absorbs the irradiated light, the amount of energy transfer from the fluorescent dye (C) to the semiconductor nanoparticles (A) is increased, and the semiconductor nanoparticles. There is a tendency to increase the emission intensity of (A). Further, by setting the value to the upper limit or less, the concentration quenching of the fluorescent dye (C) is suppressed, and the energy is efficiently transferred from the fluorescent dye (C) to the semiconductor nanoparticles (A), so that the semiconductor nanoparticles (A) can be subjected to energy transfer. By increasing the emission intensity and containing components other than the semiconductor nanoparticles (A) and the fluorescent dye (C), a wavelength conversion layer having sufficient hardness tends to be obtained.
  • the content ratio of the fluorescent dye (C) in the semiconductor nanoparticles-containing composition of the present invention is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, and 0.05 to 10% by mass. Is more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the semiconductor nanoparticle-containing composition of the present invention may further contain the polymerizable compound (D).
  • the polymerizable compound (D) By containing the polymerizable compound (D), there is a tendency that the wavelength conversion layer, particularly the color filter pixel portion can be cured when the semiconductor nanoparticle-containing composition of the present invention is used for the color filter pixel portion.
  • the polymerizable compound include a photopolymerizable compound (D1) and a thermopolymerizable compound (D2).
  • Photopolymerizable compound (D1) The photopolymerizable compound is a polymerizable component that polymerizes by irradiation with light.
  • the photopolymerizable compound include a photoradical polymerizable compound and a photocationic polymerizable compound, which may be a photopolymerizable monomer or oligomer. These are usually used with photopolymerization initiators. That is, the photoradical polymerizable compound is usually used with a photoradical polymerization initiator, and the photocationic polymerizable compound is usually used with a photocationic polymerization initiator.
  • the semiconductor nanoparticles-containing composition may contain a photopolymerizable component containing a photopolymerizable compound and a photopolymerization initiator, for example, a photoradical containing a photoradical polymerizable compound and a photoradical polymerization initiator. It may contain a polymerizable component, or may contain a photocationic polymerizable component containing a photocationic polymerizable compound and a photocationic polymerization initiator.
  • a photoradical polymerizable compound and a photocationic polymerizable compound may be used in combination, or a compound having photoradical polymerizable property and photocationic polymerizable property may be used, and a photoradical polymerization initiator and a photocationic polymerization initiator may be used. May be used together.
  • One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.
  • Examples of the photoradical polymerizable compound include (meth) acrylate compounds.
  • the (meth) acrylate compound 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.
  • Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl.
  • 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.
  • a di (meth) acrylate in which two hydroxyl groups of a diol compound are substituted with a (meth) acryloyloxy group and a di or tri (meth) in which two or three hydroxyl groups of a triol compound are substituted with a (meth) acryloyloxy group.
  • It may be acrylate.
  • bifunctional (meth) acrylate examples include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, and 3-methyl.
  • Di (meth) in which two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of substituted di (meth) acrylate and neopentyl glycol are substituted with a (meth) acryloyloxy group.
  • Di (meth) acrylate in which two hydroxyl groups of the diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of acrylate and bisphenol A are substituted with a (meth) acryloyloxy group, and 3 mol in 1 mol of trimethylpropane.
  • trifunctional (meth) acrylate for example, trimethylolpropane tri (meth) acrylate, glycerin triacrylate, pentaerythritol tri (meth) acrylate, and 1 mol of trimethylolpropane are added with 3 mol or more of ethylene oxide or propylene oxide.
  • examples thereof include tri (meth) acrylates in which the three hydroxyl groups of the resulting triol are substituted with (meth) acryloyloxy groups.
  • tetrafunctional (meth) acrylate examples include pentaerythritol tetra (meth) acrylate.
  • pentafunctional (meth) acrylate examples include dipentaerythritol penta (meth) acrylate.
  • hexafunctional (meth) acrylate examples include dipentaerythritol hexa (meth) acrylate.
  • the polyfunctional (meth) acrylate may be, for example, a poly (meth) acrylate in which a plurality of hydroxyl groups of dipentaerythritol of dipentaerythritol hexa (meth) acrylate are substituted with a (meth) acryloyloxy group.
  • the (meth) acrylate compound may be a (meth) acrylate having a phosphoric acid group, for example, an ethylene oxide-modified phosphoric acid (meth) acrylate or an ethylene oxide-modified alkyl phosphate (meth) acrylate.
  • Examples of the photocationically polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.
  • epoxy compound examples include aliphatic epoxy compounds such as bisphenol A type epoxy compound, bisphenol F type epoxy compound, phenol novolac type epoxy compound, trimethylolpropane polyglycidyl ether, and neopentyl glycol diglycidyl ether, 1,2-.
  • examples thereof include alicyclic epoxy compounds such as epoxy-4-vinylcyclohexane and 1-methyl-4- (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane.
  • epoxy compound for example, "Celoxide (registered trademark; the same shall apply hereinafter) 2000", “Celoxiside 3000” and “Celoxiside 4000” manufactured by Daicel Corporation can be used.
  • Examples of the cationically polymerizable oxetane compound include 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl.
  • oxetane compound It is also possible to use a commercially available product as an oxetane compound.
  • examples of commercially available oxetane compounds include Aron Oxetane (registered trademark) series manufactured by Toagosei Co., Ltd.
  • vinyl ether compound examples include 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.
  • the photopolymerizable compound As the photopolymerizable compound, the photopolymerizable compound described in paragraphs [0042] to [0049] of Japanese Patent Application Laid-Open No. 2013-182215 can also be used.
  • the photopolymerizable compound as described above contains a polymerizable functional group in one molecule. It is more preferable to use a bifunctional or higher polyfunctional photopolymerizable compound having two or more as an essential component because the durability (strength, heat resistance, etc.) of the cured product can be further enhanced.
  • the content ratio of the photopolymerizable compound is from the viewpoint that an appropriate viscosity can be easily obtained in a process such as coating as an ink for a wavelength conversion layer, particularly from the viewpoint that an appropriate viscosity can be easily obtained as an ink for an inkjet method, and a composition containing semiconductor nanoparticles. From the viewpoint of improving the curability of the semiconductor nanoparticles and improving the solvent resistance and abrasion resistance of the pixel portion (cured product of the semiconductor nanoparticles-containing composition), the solid content of the semiconductor nanoparticles-containing composition is increased.
  • 10% by mass or more is preferable, 15% by mass or more is more preferable, 20% by mass or more is further preferable, and it is suitable as an ink for a wavelength conversion layer from the viewpoint that an appropriate viscosity can be easily obtained in a process such as coating, particularly as an ink for an inkjet method.
  • 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is further preferable, and 60% by mass or less is more. More preferably, 50% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the photopolymerizable compound is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 10 to 70% by mass, based on the total solid content of the semiconductor nanoparticles-containing composition. 15-60% by mass is even more preferable, and 20-50% by mass is particularly preferable.
  • thermopolymerizable compound (D2) The thermopolymerizable compound is a compound (resin) that is crosslinked and cured by heat.
  • the thermosetting compound has a thermosetting group.
  • the thermosetting group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxy group, a methylol group and the like, from the viewpoint of excellent heat resistance and storage stability of the cured product of the semiconductor nanoparticles-containing composition, and
  • An epoxy group is preferable from the viewpoint of excellent adhesion to a light-shielding portion (for example, a black matrix) and a substrate.
  • the thermosetting compound may have one type of thermosetting group or may have two or more types of thermosetting groups.
  • the heat-polymerizable compound may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of types of monomers.
  • the thermopolymerizable compound may be either a random copolymer, a block copolymer or a graft copolymer.
  • thermosetting compound a compound having two or more thermosetting groups in one molecule is used, and is usually used in combination with a curing agent.
  • a catalyst curing catalyst capable of accelerating the thermosetting reaction may be further added.
  • the semiconductor nanoparticle-containing composition may contain a thermosetting compound and a thermosetting component including a curing agent and a curing catalyst used as needed.
  • polymers that are not themselves polymerizable may be further used.
  • an epoxy resin having two or more epoxy groups in one molecule may be used as a compound having two or more thermosetting groups in one molecule.
  • the "epoxy resin” includes both a monomeric epoxy resin and a polymer epoxy resin.
  • the number of epoxy groups contained in one molecule of the polyfunctional epoxy resin is preferably 2 to 50, more preferably 2 to 20.
  • the epoxy group may be any structure as long as it has an oxylan ring structure, and may be, for example, a glycidyl group, an oxyethylene group, or an epoxycyclohexyl group.
  • the epoxy resin include known polyvalent epoxy resins that can be cured by a carboxylic acid. Such epoxy resins are widely disclosed in, for example, "Epoxy Resin Handbook" edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (1987), and these can be used.
  • thermopolymerizable compound having an epoxy group examples include a polymer of a monomer having an oxylan ring structure and a copolymer of a monomer having an oxylan ring structure and another monomer.
  • polyfunctional epoxy resin examples include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, and 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer.
  • thermopolymerizable compound examples thereof include a copolymer, (3-ethyl-3-oxetanyl) methylmethacrylate-glycidylmethacrylate copolymer, and styrene-glycidylmethacrylate.
  • thermopolymerizable compound examples thereof include a copolymer, (3-ethyl-3-oxetanyl) methylmethacrylate-glycidylmethacrylate copolymer, and styrene-glycidylmethacrylate.
  • the thermopolymerizable compound the compounds described in paragraphs [0044] to [0066] of Japanese Patent Application Laid-Open No. 2014-56248 can also be used.
  • polyfunctional epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, and naphthalene type epoxy resin.
  • bisphenol A type epoxy resin such as the product name "Epicoat (registered trademark. The same shall apply hereinafter) 828" (manufactured by Mitsubishi Chemical Co., Ltd.), and bisphenol F such as the product name "YDF-170” (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
  • Type epoxy resin brominated bisphenol A type epoxy resin such as trade name "SR-T5000” (manufactured by Sakamoto Pharmaceutical Co., Ltd.), bisphenol such as trade name "EPICLON (registered trademark. The same shall apply hereinafter) EXA1514" (manufactured by DIC).
  • Cresol novolak type epoxy resin manufactured by DIC
  • dicyclopentadienphenol type epoxy resin such as trade name "EPICLON HP-7200", “HP-7200H” (manufactured by DIC)
  • trade name "Epicoat 1032H60” Mitsubishi
  • Trishydroxyphenylmethane type epoxy resin such as (Chemical Co., Ltd.)
  • trifunctional epoxy resin such as trade name "Adecaglycylol (registered trademark. The same shall apply hereinafter) ED-505" (manufactured by ADEKA), product name "Epicoat 1031S”.
  • Hydrogenated bisphenol A type epoxy resin such as "ST-3000” (manufactured by Nittetsu Chemical & Materials Co., Ltd.), glycidyl ester type epoxy resin such as product name "Epicoat 190P” (manufactured by Mitsubishi Chemical Co., Ltd.), product name “YH-434" ”(Nittetsu Chemical & Materials Co., Ltd.) and other glycidylamine-type epoxy resins, trade name“ YDG-414 ”(Toto Kasei Co., Ltd.) and other glioxal-type epoxy resins, product name“ Eporide GT-401 ”(manufactured by Daicel).
  • ST-3000 manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • glycidyl ester type epoxy resin such as product name "Epicoat 190P” (manufactured by Mitsubishi Chemical Co., Ltd.)
  • ком ⁇ онент )etc. examples thereof include alicyclic polyfunctional epoxy compounds and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC). If necessary, for example, the trade name "Neo Tote S” (manufactured by Nittetsu Chemical & Materials Co., Ltd.) can be mixed as the epoxy reactive diluent.
  • TGIC triglycidyl isocyanate
  • polyfunctional epoxy resin examples include “Findick (registered trademark; the same applies hereinafter) A-247S”, “Findick A-254", “Findick A-253”, and “Findick A-” manufactured by DIC Corporation. 229-30A ",” Finedick A-261 “,” Finedick A-249 “,” Finedick A-266 “,” Finedick A-241 “,” Finedick M-8020 “,” Epicron N-740 “ , “Epoxy N-770”, “Epoxy N-865" (trade name) can be used.
  • thermopolymerizable compound When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermopolymerizable compound, epoxy groups are replenished in the semiconductor nanoparticles-containing composition, the reaction point concentration of the epoxy becomes high, and the crosslink density can be increased. ..
  • polyfunctional epoxy resins it is preferable to use an epoxy resin having four or more epoxy groups in one molecule (polyfunctional epoxy resin having four or more functionalities) from the viewpoint of increasing the crosslink density.
  • polyfunctional epoxy resin having four or more functionalities it is preferable to use an epoxy resin having four or more epoxy groups in one molecule (polyfunctional epoxy resin having four or more functionalities) from the viewpoint of increasing the crosslink density.
  • a thermally polymerizable compound having a weight average molecular weight of 10,000 or less is used in order to improve the ejection stability from the ejection head in the inkjet method, the strength of the pixel portion (cured product of the semiconductor nanoparticles-containing composition) and Since the hardness tends to decrease, it is preferable to add a tetrafunctional or higher functional epoxy resin to the semiconductor nanoparticles-containing composition from the viewpoint of sufficiently increasing the crosslink density.
  • the weight average molecular weight of the thermopolymerizable compound is from the viewpoint that an appropriate viscosity can be easily obtained in a process such as coating as an ink for a wavelength conversion layer, particularly from the viewpoint that an appropriate viscosity can be easily obtained as an ink for an inkjet method, and a composition containing semiconductor nanoparticles.
  • a composition containing semiconductor nanoparticles From the viewpoint of improving the curability of the product and improving the solvent resistance and abrasion resistance of the pixel portion (cured product of the composition containing semiconductor nanoparticles), 750 or more is preferable, 1000 or more is more preferable, and 2000. The above is more preferable.
  • the weight average molecular weight of the heat-polymerizable compound is preferably 750 to 500,000, more preferably 1,000 to 300,000, and even more preferably 2000 to 200,000. However, this does not apply to the molecular weight after cross-linking.
  • the content ratio of the thermopolymerizable compound is from the viewpoint that an appropriate viscosity can be easily obtained in a process such as coating as an ink for a wavelength conversion layer, particularly from the viewpoint that an appropriate viscosity can be easily obtained as an ink for an inkjet method, and a composition containing semiconductor nanoparticles.
  • a composition containing semiconductor nanoparticles From the viewpoint of improving the curability of the semiconductor nanoparticles and improving the solvent resistance and abrasion resistance of the pixel portion (cured product of the semiconductor nanoparticles-containing composition), 10 in the total solid content of the semiconductor nanoparticles-containing composition.
  • mass or more is preferable, 15% by mass or more is more preferable, and 20% by mass or more is further preferable.
  • the viscosity of the ink for the inkjet method does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function
  • 90% by mass or less is preferable in the total solid content of the semiconductor nanoparticles-containing composition.
  • 80% by mass or less is more preferable, 70% by mass or less is further preferable, 60% by mass or less is further preferable, and 50% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the thermopolymerizable compound is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 10 to 70% by mass, based on the total solid content of the semiconductor nanoparticles-containing composition. 15-60% by mass is even more preferable, and 20-50% by mass is particularly preferable.
  • the semiconductor nanoparticle-containing composition of the present invention may further contain a polymerization initiator (E).
  • a polymerization initiator By containing the polymerization initiator (E), the polymerizable compound (D) tends to be easily polymerized.
  • the polymerization initiator include a photoradical polymerization initiator (E1), a photocationic polymerization initiator (E2), and a thermal polymerization initiator (E3).
  • Photoradical Polymerization Initiator As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitable.
  • Examples of the molecular cleavage type photoradical polymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-benzyl-2-dimethyl.
  • Amino-1- (4-morpholinophenyl) -butane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl) Ethoxyphenylphosphine oxide can be mentioned.
  • Examples of other molecular cleavage type photoradical polymerization initiators include 1-hydroxycyclohexylphenylketone, benzoinethyl ether, benzyldimethylketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-. (4-Isopropylphenyl) -2-hydroxy-2-methylpropane-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one may be used in combination.
  • Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenylsulfide.
  • a molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.
  • a commercially available product can also be used as a photoradical polymerization initiator.
  • Examples of commercially available products include acylphosphine oxide compounds such as "Omnirad (registered trademark. The same shall apply hereinafter) TPO-H", “Omnirad TPO-L”, and “Omnirad 819" manufactured by IGM resin, "Omnirad 651".
  • the oxime ester compounds are described in, for example, the compounds described in JP-A-2004-534797 of Japan, the compounds described in JP-A-2000-80068 of Japan, and International Publication No. 2012/45736.
  • the content ratio of the photoradical polymerization initiator is preferably 0.1 part by mass or more, and 0.5 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound. More preferably, 1 part by mass or more is further preferable. Further, from the viewpoint of stability over time of the pixel portion (cured product of the semiconductor nanoparticles-containing composition), 40 parts by mass or less is preferable, 30 parts by mass or less is more preferable, and 20 parts by mass is more preferable with respect to 100 parts by mass of the photopolymerizable compound. More preferably, it is by mass or less. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the photoradical polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. Especially preferable.
  • Photocationic polymerization initiator examples include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate and P-nonylphenyliodonium hexafluoroantimonate. Polyaryliodonium salts such as Nate can be mentioned.
  • a commercially available product can also be used as the photocationic polymerization initiator.
  • Commercially available products include, for example, sulfonium salt-based photocations such as "CPI-100P” manufactured by Sun Appro, "Omnicat (registered trademark; the same applies hereinafter) 270" manufactured by IGM resin, and “Irgacure 290” manufactured by BASF Japan.
  • Examples of the polymerization initiator include iodonium salt-based photocationic polymerization initiators such as "Omnicat 250" manufactured by IGM resin.
  • the content ratio of the photocationic polymerization initiator is preferably 0.1 part by mass or more, and 0.5 part by mass or more with respect to 100 parts by mass of the photopolymerizable compound. More preferably, 1 part by mass or more is further preferable.
  • the content ratio of the photopolymerization initiator is preferably 40 parts by mass or less, preferably 30 parts by mass, based on 100 parts by mass of the photopolymerizable compound, from the viewpoint of the stability over time of the pixel portion (cured product of the semiconductor nanoparticles-containing composition). More preferably, it is more preferably 20 parts by mass or less, and further preferably 20 parts by mass or less.
  • the content ratio of the photocationic polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. Especially preferable.
  • thermal Polymerization Initiator examples include 4-methylhexahydrophthalic anhydride, triethylenetetramine, diaminodiphenylmethane, phenol novolac resin, tris (dimethylaminomethyl) phenol, and N. , N-Dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1,1-dimethylurea.
  • the content ratio of the heat polymerization initiator is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the heat-polymerizable compound. It is preferable, and more preferably 1 part by mass or more. From the viewpoint of stability over time of the pixel portion (cured product of the semiconductor nanoparticles-containing composition), 40 parts by mass or less is preferable, 30 parts by mass or less is more preferable, and 20 parts by mass is more preferable with respect to 100 parts by mass of the heat-polymerizable compound. The following is more preferable. The above upper and lower limits can be combined arbitrarily.
  • the content ratio of the heat polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass with respect to 100 parts by mass of the heat-polymerizable compound. preferable.
  • the semiconductor nanoparticle-containing composition of the present invention may further contain light-scattering particles.
  • the light-scattering particles are, for example, optically inert inorganic particles.
  • the light-scattering particles can scatter the light from the light source irradiated to the color filter pixel portion and the light emitted by the semiconductor nanoparticles or the dye.
  • Materials constituting the light-scattering particles include, for example, simple metal such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum and gold; silica, barium sulfate, barium carbonate, calcium carbonate, etc.
  • Metal oxides such as talc, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide; magnesium carbonate, barium carbonate, Secondary bismuth carbonate, metal carbonates such as calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, bismuth hyponitrate Metal salts such as.
  • the light-scattering particles are selected from the group consisting of titanium oxide, alumina, zinc oxide, zinc oxide, calcium carbonate, barium sulfate and barium titanate from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency. It is preferable to contain at least one kind, and it is more preferable to contain at least one kind selected from the group consisting of titanium oxide, zinc oxide, zinc oxide and barium titanate.
  • the shape of the light-scattering particles may be, for example, spherical, filamentous, or indefinite.
  • using particles having less directional particle shape for example, spherical particles, regular tetrahedral particles, etc.
  • it is preferable in that it can be further enhanced and excellent ejection stability can be obtained.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the semiconductor nanoparticles-containing composition is preferably 0.05 ⁇ m or more, preferably 0, from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency. .2 ⁇ m or more is more preferable, and 0.3 ⁇ m or more is further preferable.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the semiconductor nanoparticles-containing composition is preferably 1.0 ⁇ m or less, more preferably 0.6 ⁇ m or less, and more preferably 0.4 ⁇ m from the viewpoint of excellent ejection stability. The following is more preferable. The above upper and lower limits can be combined arbitrarily.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the semiconductor nanoparticles-containing composition is preferably 0.05 to 1.0 ⁇ m, more preferably 0.2 to 0.6 ⁇ m, and 0.3. It is more preferably ⁇ 0.4 ⁇ m.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the semiconductor nanoparticles-containing composition is obtained by measuring with a dynamic light-scattering nanotrack particle size distribution meter and calculating the volume average diameter.
  • the average particle diameter (volume average diameter) of the light-scattering particles used can be obtained by, for example, measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
  • the content ratio of the light-scattering particles is preferably 0.1% by mass or more, more preferably 1% by mass or more in the total solid content of the semiconductor nanoparticles-containing composition from the viewpoint of being more excellent in the effect of improving the external quantum efficiency. 5% by mass or more is further preferable, 7% by mass or more is further preferable, 10% by mass or more is particularly preferable, and 12% by mass or more is most preferable. Further, from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency, the total solid content of the semiconductor nanoparticles-containing composition is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass.
  • the following is further preferable, more preferably 30% by mass or less, particularly preferably 25% by mass or less, and most preferably 20% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the content ratio of the light-scattering particles is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass, and further preferably 5 to 40% by mass in the total solid content of the semiconductor nanoparticles-containing composition. It is preferable, 7 to 30% by mass is more preferable, 10 to 25% by mass is particularly preferable, and 12 to 20% by mass is particularly preferable.
  • the mass ratio of the content ratio of the light-scattering particles to the content ratio of the semiconductor nanoparticles may be 0.1 or more from the viewpoint of excellent effect of improving the external quantum efficiency, and may be 0. It may be .2 or more, or 0.5 or more. It may be 5.0 or less, and may be 2.0 or less, from the viewpoint of being excellent in the effect of improving the external quantum efficiency and being suitable for a known coating method, particularly excellent in continuous ejection property (ejection stability) during inkjet printing. It may be 1.5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the mass ratio of the content ratio of the light-scattering particles to the content ratio of the semiconductor nanoparticles is preferably 0.1 to 5.0, more preferably 0.2 to 2.0. It is preferable, and 0.5 to 1.5 is more preferable.
  • the improvement of external quantum efficiency by light-scattering particles is considered to be due to the following mechanism. That is, in the absence of light-scattering particles, the backlight light only travels almost straight through the pixel portion and is considered to have little chance of being absorbed by the semiconductor nanoparticles.
  • the backlight light is scattered in all directions in the pixel portion, and the semiconductor nanoparticles can receive the same back light. Even if a light is used, it is considered that the amount of light absorption in the pixel portion increases. As a result, it is possible to prevent leaked light (light that leaks from the pixel portion without being absorbed by the semiconductor nanoparticles from the light source) by such a mechanism, and it is possible to improve the external quantum efficiency. Conceivable.
  • the semiconductor nanoparticles-containing composition of the present invention contains semiconductor nanoparticles (A), a ligand (B), a fluorescent dye (C), a polymerizable compound (D), and a polymerization initiator (E).
  • semiconductor nanoparticles A
  • B a ligand
  • C fluorescent dye
  • D polymerizable compound
  • E polymerization initiator
  • other components other than the light-scattering particles may be further contained. Examples of other components include polymer dispersants, sensitizers, solvents and the like.
  • the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an adsorptive ability to light-scattering particles, and has a function of dispersing light-scattering particles.
  • the polymer dispersant is adsorbed on the light-scattering particles via a functional group having an adsorption ability for the light-scattering particles, and the light-scattering particles are generated by electrostatic repulsion and / or steric repulsion between the polymer dispersants. Disperse in a composition containing semiconductor nanoparticles.
  • the polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may be bonded to the surface of the semiconductor nanoparticles and adsorbed to the semiconductor nanoparticles. It may be free in the composition containing semiconductor nanoparticles.
  • Examples of the functional group having an adsorptive ability to light-scattering particles include an acidic functional group, a basic functional group and a nonionic functional group.
  • the acidic functional group has a dissociative proton and may be neutralized by a base such as an amine or a hydroxide ion, and the basic functional group is neutralized by an acid such as an organic acid or an inorganic acid. May be.
  • Examples of the acidic functional group include a carboxy group (-COOH), a sulfo group (-SO 3 H), a sulfate group (-OSO 3 H), a phosphorno group (-PO (OH) 2 ), and a phosphoroxy group (-OPO (OH)). 2 ), hydroxyphosphoryl group (-PO (OH)-), sulfanyl group (-SH) and the like.
  • Examples of the basic functional group include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.
  • nonionic functional group examples 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 and an amide.
  • Examples thereof include a 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.
  • an acidic functional group from the viewpoint of dispersion stability of light-scattering particles, from the viewpoint of less likely to cause the side effect of sedimentation of semiconductor nanoparticles, from the viewpoint of ease of synthesis of a polymer dispersant, and from the viewpoint of functional group stability.
  • a carboxy group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used, and an amino group is preferably used as the basic functional group.
  • a carboxy group, a phosphonic acid group and an amino group are more preferably used, and most preferably an amino group is used.
  • a polymer dispersant having an acidic functional group has an acid value.
  • the acid value of the polymer dispersant having an acidic functional group is preferably 1 to 150 mgKOH / g.
  • the acid value is at least the above lower limit value, sufficient dispersibility of the light scattering particles can be easily obtained, and when the acid value is at least the above upper limit value, the pixel portion (cured product of the semiconductor nanoparticles-containing composition) Storage stability does not easily decrease.
  • the polymer dispersant having a basic functional group has an amine value.
  • the amine value of the polymer dispersant having a basic functional group is preferably 1 to 200 mgKOH / g.
  • the amine value is at least the above lower limit value, sufficient dispersibility of the light scattering particles can be easily obtained, and when the amine value is at least the above upper limit value, the pixel portion (cured product of the semiconductor nanoparticles-containing composition) Storage stability does not easily decrease.
  • the polymer dispersant may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of types of monomers.
  • the polymer dispersant may be either a random copolymer, a block copolymer or a graft copolymer.
  • the polymer dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer.
  • the polymer dispersant may be, for example, acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, polyamine such as polyethyleneimine and polyallylamine, epoxy resin, polyimide and the like. It may be there.
  • polymer dispersant Commercially available products can be used as the polymer dispersant, and the commercially available products include Ajinomoto Fine-Techno's Azispar PB series, Big Chemie's DISPERBYK series, BYK-series, and BASF's Efka series. Can be used.
  • DISPERBYK registered trademark. The same shall apply hereinafter
  • DISPERBYK-161 DISPERBYK-162
  • DISPERBYK-163 DISPERBYK-164
  • DISPERBYK-164" manufactured by Big Chemie.
  • PB821 “ Ajispar PB822 ”,“ Ajisper PB881 ”,“ PN411 ”and“ PA111 ”; Evonik's“ TEGO (registered trademark. "TEGO Dispers 670”, “TEGO Dispers 685", “TEGO Dispers 700”, “TEGO Dispers 710” and “TEGO Dispers 760W”; And “DA-725" can be used.
  • polymer dispersant examples include, for example, a cationic monomer containing a basic group and / or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and if necessary, other than the commercially available products as described above. Can be used by copolymerizing with the above-mentioned monomer (nonionic monomer, monomer having a hydrophilic group, etc.).
  • a cationic monomer containing a basic group and / or an anionic monomer having an acidic group a monomer having a hydrophobic group, and if necessary, other than the commercially available products as described above.
  • the cationic monomer, the anionic monomer, the monomer having a hydrophobic group and other monomers for example, the monomers described in paragraphs [0034] to [0036] of Japanese Patent Application Laid-Open No. 2004-250502 can be mentioned. can.
  • polymer dispersant examples include a compound obtained by reacting a polyester compound with a polyalkyleneimine described in Japanese Patent Application Laid-Open No. 54-37082 and Japanese Patent Application Laid-Open No. 61-174939, and Japanese Patent Application Laid-Open No. 9 -A compound in which the amino group of the side chain of polyallylamine described in JP-A-169821 is modified with polyester, a graft polymer containing a polyester-type macromonomer described in JP-A-9-171253, Japan as a copolymerization component, Japan.
  • polyester polyol-added polyurethane described in JP-A-60-166318 examples include the polyester polyol-added polyurethane described in JP-A-60-166318.
  • the weight average molecular weight of the polymer dispersant is preferably 750 or more, more preferably 1000 or more, from the viewpoint of being able to satisfactorily disperse light-scattering particles and further improving the effect of improving external quantum efficiency. 2000 or more is more preferable, and 3000 or more is particularly preferable. Light-scattering particles can be dispersed well, the effect of improving external quantum efficiency can be further improved, and the viscosity suitable for known coating methods, especially the viscosity of ink for inkjet method, can be ejected for stable ejection. From the viewpoint of obtaining a suitable viscosity, 100,000 or less is preferable, 50,000 or less is more preferable, and 30,000 or less is further preferable.
  • the weight average molecular weight of the polymer dispersant is preferably 750 to 100,000, more preferably 1,000 to 100,000, still more preferably 2000 to 50,000, and even more preferably 3000 to 30,000.
  • the content ratio of the polymer dispersant is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and 5 parts by mass with respect to 100 parts by mass of the light-scattering particles. More than a portion is more preferable. From the viewpoint of moist heat stability of the pixel portion (cured product of the semiconductor nanoparticles-containing composition), 50 parts by mass or less is preferable, 30 parts by mass or less is more preferable, and 10 parts by mass is more preferable with respect to 100 parts by mass of the light scattering particles. The following is more preferable. The above upper and lower limits can be combined arbitrarily.
  • the content ratio 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 with respect to 100 parts by mass of the light scattering particles.
  • the sensitizer means a component capable of initiating a polymerization reaction by absorbing light having a wavelength longer than that absorbed by the photopolymerization initiator and transferring the absorbed energy to the photopolymerization initiator.
  • a sensitizer By containing a sensitizer, there is a tendency that h-rays and the like, which are relatively not absorbed by semiconductor nanoparticles, can be used as a wavelength at the time of curing.
  • amines that do not cause an addition reaction with the photopolymerizable compound can be used as the sensitizer.
  • sensitizer examples include trimethylamine, methyldimethylamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, 4, Examples thereof include 4'-bis (diethylamino) benzophenone.
  • the semiconductor nanoparticle-containing composition of the present invention may contain a solvent from the viewpoint of coatability and handleability.
  • 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, and diethyl succinate.
  • the boiling point of the solvent is preferably 50 ° C. or higher from the viewpoint of suitability for a known coating method, and particularly preferably 180 ° C. or higher from the viewpoint of continuous ejection stability of ink for an inkjet method. Since it is necessary to remove the solvent from the semiconductor nanoparticles-containing composition before curing the semiconductor nanoparticles-containing composition at the time of forming the pixel portion, the boiling point of the solvent is preferably 300 ° C. or lower from the viewpoint of easy removal of the solvent.
  • the content ratio thereof is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass in the semiconductor nanoparticles-containing composition.
  • the above is more preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is further preferable.
  • the suitability for a known coating method, particularly the thickness of the film after discharging and removing the solvent becomes thicker, and a film containing more semiconductor nanoparticles can be formed, so that the emission intensity becomes higher. There is a tendency to obtain a large pixel portion.
  • the above upper and lower limits can be combined arbitrarily.
  • the semiconductor nanoparticles-containing composition of the present invention contains a solvent, the content ratio thereof is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass.
  • the semiconductor nanoparticles-containing composition of the present invention it is also possible to disperse light-scattering particles and semiconductor nanoparticles without a solvent by using a polymerizable compound that functions as a dispersion medium. In this case, there is an advantage that the step of removing the solvent by drying when forming the pixel portion becomes unnecessary.
  • the viscosity of the semiconductor nanoparticle-containing composition of the present invention at 40 ° C. is not particularly limited, but for example, suitability for a known coating method, particularly ejection stability during inkjet printing. From the viewpoint, 2 mPa ⁇ s or more is preferable, 5 mPa ⁇ s or more is more preferable, 7 mPa ⁇ s or more is further preferable, 20 mPa ⁇ s or less is preferable, 15 mPa ⁇ s or less is more preferable, and 12 mPa ⁇ s or less is further preferable. ..
  • the viscosity of the semiconductor nanoparticles-containing composition is measured by an E-type viscometer.
  • the above upper and lower limits can be combined arbitrarily.
  • 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.
  • the viscosity of the semiconductor nanoparticle-containing composition of the present invention at 23 ° C. is not particularly limited, but for example, from the viewpoint of suitability for a known coating method, particularly ejection stability during inkjet printing, 5 mPa ⁇ s or more is preferable, and 10 mPa. -S or more is more preferable, 15 mPa ⁇ s or more is further preferable, 40 mPa ⁇ s or less is preferable, 35 mPa ⁇ s or less is more preferable, 30 mPa ⁇ s or less is further preferable, and 25 mPa ⁇ s or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 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, further preferably 10 to 30 mPa ⁇ s, and 15 to 25 mPa ⁇ s. Especially preferable.
  • 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 a known coating method, particularly suitable for an inkjet method, preferably 20 to 40 mN / m, and 25 to 25. 35 mN / m is more preferable.
  • the flight bending means that when the semiconductor nanoparticles-containing composition is ejected from the ink ejection holes, the landing position of the semiconductor nanoparticles-containing composition deviates from the target position by 30 ⁇ m or more.
  • the semiconductor nanoparticles-containing composition includes, for example, semiconductor nanoparticles (A), a ligand (B) and a fluorescent dye (C), and a polymerizable compound (D), if necessary. ) And the polymerization initiator (E) by a method including a step of mixing the semiconductor nanoparticles (A) so that the content of the semiconductor nanoparticles (A) is 5 to 50% by mass in the total solid content of the semiconductor nanoparticles-containing composition.
  • a semiconductor nanoparticle-containing composition can be obtained by mixing the constituents of the semiconductor nanoparticle-containing composition.
  • the method for producing the semiconductor nanoparticles-containing composition includes, for example, semiconductor nanoparticles (A), a ligand (B), and a fluorescent dye (C), if necessary.
  • a step of mixing the semiconductor nanoparticle dispersion and the light-scattering particle dispersion is if necessary.
  • the polymerization initiator (E) When the polymerization initiator (E) is used in this production method, the polymerization initiator (E) is blended so as to be contained in a mixture obtained by mixing a semiconductor nanoparticle dispersion and a light-scattering particle dispersion. Just do it. Therefore, the polymerization initiator (E) may be contained in one or both of the semiconductor nanoparticles dispersion and the light-scattering particle dispersion, and the semiconductor nanoparticles dispersion, the light-scattering particle dispersion, and the polymerization initiator ( When mixed with E), the polymerization initiator (E) may not be contained in either the semiconductor nanoparticle dispersion or the light-scattering particle dispersion.
  • the semiconductor nanoparticles (A) and the light-scattering particles are dispersed in the polymerizable compound (D) before being mixed with each other, so that the semiconductor nanoparticles are dispersed.
  • (A) and light-scattering particles can be sufficiently dispersed, and excellent ejection stability and excellent external quantum efficiency tend to be easily obtained.
  • the semiconductor nanoparticles dispersion is prepared by mixing the semiconductor nanoparticles (A), the ligand (B) and the fluorescent dye (C) with the polymerizable compound (D). You may.
  • the semiconductor nanoparticles (A) may have the ligand (B) adsorbed on its surface in advance.
  • the mixing process may be performed using an apparatus such as a paint conditioner, a planetary stirrer, a stirrer, an ultrasonic disperser, and a mix rotor.
  • a stirrer an ultrasonic disperser, or a mix rotor from the viewpoint that the dispersibility of the semiconductor nanoparticles (A), the ligand (B) and the fluorescent dye (C) is good and high optical characteristics can be obtained.
  • the light-scattering particle dispersion may be prepared by mixing the light-scattering particles and the polymerizable compound (D) and performing a dispersion treatment.
  • the mixing and dispersion treatment may be performed using the same apparatus as in the step of preparing the semiconductor nanoparticle dispersion. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light-scattering particles is good and the average particle size of the light-scattering particles can be easily adjusted to a desired range.
  • the polymer dispersant may be further mixed. That is, the light-scattering particle dispersion may further contain a polymer dispersant.
  • semiconductor nanoparticles A), ligand (B), fluorescent dye (C), light scattering particles, and optionally a polymerizable compound (D), a polymerization initiator (E), and a polymerization initiator (E), and Other components other than the polymer dispersant (for example, sensitizer, solvent, etc.) may be further used.
  • the other components may be contained in the semiconductor nanoparticle dispersion or may be contained in the light-scattering particle dispersion.
  • Other components may be mixed in a composition obtained by mixing a semiconductor nanoparticle dispersion and a light scattering particle dispersion.
  • the wavelength conversion layer of the present invention is a layer obtained by curing the semiconductor nanoparticles-containing composition of the present invention, and is at least a semiconductor nanoparticles (A), a ligand (B), and a fluorescent dye ( A layer containing C) and converting the wavelength of light from an excitation source.
  • the form of the wavelength conversion layer is not particularly limited, and may be, for example, a sheet shape or an arbitrary shape such as a patterned bar shape like the pixel portion of a color filter described later.
  • the color filter of the present invention has a pixel portion obtained by curing the semiconductor nanoparticles-containing composition of the present invention.
  • the details of the color filter of the present invention will be described with reference to the drawings. In the following description, the same reference numerals will be used for the same or equivalent elements, and duplicate description will be omitted.
  • FIG. 1 is a schematic cross-sectional view of the color filter of one embodiment.
  • the color filter 100 includes a base material 40 and a light conversion layer 30 provided on the base material 40.
  • the optical conversion layer 30 includes a plurality of pixel units 10 (first pixel unit 10a, second pixel unit 10b, and third pixel unit 10c) and a light-shielding unit 20.
  • the optical conversion layer 30 has a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c as the pixel unit 10.
  • the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c are arranged in a grid pattern so as to repeat in this order.
  • the light-shielding portion 20 is located between adjacent pixel portions, that is, between the first pixel portion 10a and the second pixel portion 10b, between the second pixel portion 10b and the third pixel portion 10c, and the third. It is provided between the pixel portion 10c of the above and the first pixel portion 10a. In other words, these adjacent pixel portions are separated from each other by the light-shielding portion 20.
  • the first pixel portion 10a and the second pixel portion 10b each include a cured product of the semiconductor nanoparticles-containing composition of the present invention described above.
  • the cured product contains semiconductor nanoparticles and fluorescent dyes in which a ligand is adsorbed on at least a part of the surface thereof, light-scattering particles, and a cured component.
  • the curing component is a cured product of the polymerizable compound, and is a cured product obtained by polymerizing the polymerizable compound. That is, in the first pixel portion 10a, the first curing component 13a, the first semiconductor nanoparticles 11a dispersed in the first curing component 13a, the first light scattering particles 12a, and the first Includes the fluorescent dye 14a of.
  • the second curing component 13b in the second pixel portion 10b, the second curing component 13b, the second semiconductor nanoparticles 11b and the second light scattering particles 12b dispersed in the second curing component 13b, respectively, and the second Includes 2 fluorescent dyes 14b.
  • the first curing component 13a and the second curing component 13b may be the same or different, and may be the same as or different from the first light scattering particles 12a.
  • 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.
  • the first semiconductor nanoparticles 11a are red light emitting semiconductor nanoparticles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel portion 10a may be paraphrased as a red pixel portion for converting blue light into red light.
  • the second semiconductor nanoparticles 11b are green light emitting semiconductor nanoparticles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 10b may be paraphrased as a green pixel portion for converting blue light into green light.
  • the third pixel portion 10c has a transmittance of 30% or more with respect to light having a wavelength in the range of 420 to 480 nm. Therefore, the third pixel unit 10c functions as a blue pixel unit when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the third pixel portion 10c contains, for example, a cured product of the composition containing the above-mentioned polymerizable compound.
  • the cured product contains a third cured component 13c.
  • the third curing component 13c is a cured product obtained by polymerizing the polymerizable compound. That is, the third pixel portion 10c contains the third curing component 13c.
  • the composition containing the polymerizable compound has the above-mentioned semiconductor nano as long as the transmittance for light having a wavelength in the range of 420 to 480 nm is 30% or more.
  • the components contained in the particle-containing composition components other than the polymerizable compound may be further contained.
  • the transmittance of the third pixel portion 10c can be measured by a microspectroscopy device.
  • the thickness of the pixel portion is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more, for example. preferable.
  • the thickness of the pixel portion (first pixel portion 10a, second pixel portion 10b, and third pixel portion 10c) is, for example, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the thickness of the pixel portion is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, still more preferably 3 to 15 ⁇ m. ..
  • the light-shielding portion 20 is a so-called black matrix provided for the purpose of separating adjacent pixel portions to prevent color mixing and for the purpose of preventing light leakage from a light source.
  • the material constituting the light-shielding portion 20 is not particularly limited, and the curing of the resin composition containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the binder polymer in addition to a metal such as chromium. Objects and the like can be used.
  • the binder polymer used here includes one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, photosensitive resin, and O / W.
  • An emulsion-type resin composition for example, an emulsion of reactive silicone or the like can be used.
  • the thickness of the light-shielding portion 20 is preferably, for example, 0.5 ⁇ m to 10 ⁇ m.
  • the base material 40 is a transparent base material having light transmission, and is, for example, a transparent glass substrate such as quartz glass, Pylex (registered trademark) glass, a synthetic quartz plate, a transparent resin film, an optical resin film, or the like.
  • a flexible substrate can be used.
  • a glass substrate made of non-alkali glass that does not contain an alkaline component in the glass.
  • the color filter 100 provided with the above optical conversion layer 30 is preferably used when an excitation light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the wavelength range of light emitted by the excitation light source is not limited to the above range.
  • the excited energy of the fluorescent dye (C) is transferred to the semiconductor nanoparticles (A) by Felster-type energy transfer, and the emission intensity of the semiconductor nanoparticles (A) is increased. Any light in the wavelength range that can be absorbed by the fluorescent dye (C) may be used as excitation light.
  • the above-mentioned semiconductor nanoparticles-containing composition is formed in the pixel portion-forming region partitioned by the light-shielding portion 20 on the base material 40. It can be produced by a method of selectively adhering by an inkjet method and curing a semiconductor nanoparticle-containing composition by irradiation with active energy rays.
  • a resin composition containing a metal thin film such as chromium or light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material 40 for example, a resin composition containing a metal thin film such as chromium or light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material 40.
  • a method of forming a thin film and patterning the thin film include a method of forming a thin film and patterning the thin film.
  • the metal thin film can be formed by, for example, a sputtering method or a vacuum vapor deposition method, and the thin film of the resin composition containing the light-shielding particles can be formed by, for example, coating or printing.
  • the method for patterning include a photolithography method.
  • Examples of the inkjet method include a bubble jet (registered trademark) method using an electric heat converter as an energy generating element and a piezojet method using a piezoelectric element.
  • the semiconductor nanoparticles-containing composition is cured by irradiation with active energy rays (for example, ultraviolet rays), for example, a mercury lamp, a metal halide lamp, a xenon lamp, or an LED may be used.
  • active energy rays for example, ultraviolet rays
  • the wavelength of the light to be irradiated may be, for example, 200 nm or more, or 440 nm or less.
  • the exposure amount is preferably, for example, 10 to 4000 mJ / cm 2 .
  • a drying treatment is performed to volatilize the solvent.
  • the drying treatment include vacuum drying and heat drying.
  • the drying temperature for volatilizing the solvent may be, for example, 50 to 150 ° C.
  • the drying time may be, for example, 3 to 30 minutes.
  • the image display device of the present invention has the color filter of the present invention.
  • the image display device include a liquid crystal display device and an image display device including an organic electroluminescent element.
  • the liquid crystal display device include a device including a light source provided with a blue LED and a liquid crystal layer provided with an electrode for controlling blue light emitted from the light source for each pixel portion.
  • the image display device including the organic electroluminescent element include a device in which an organic electroluminescent element that emits blue light is arranged at a position corresponding to each pixel portion of the color filter.
  • titanium oxide PT-401M (manufactured by Ishihara Sangyo Co., Ltd.) 3.20 parts by mass, acrylic block dispersant (amine value 29 mgKOH / g, propylene glycol monomethyl ether acetate solution having a solid content concentration of 40% by mass) 0.76 parts by mass
  • acrylic block dispersant amine value 29 mgKOH / g, propylene glycol monomethyl ether acetate solution having a solid content concentration of 40% by mass
  • As a solvent 6.04 parts by mass of toluene and 20 parts by mass of zirconia beads having a diameter of 0.3 mm were filled in a container and dispersed in a paint shaker for 6 hours. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a light-scattering particle dispersion 2.
  • B-1 Compound having a carboxy group and a polyethylene glycol chain having a molecular weight of about 400
  • B-2 Compound having a sulfanyl group and a polyethylene glycol chain having a molecular weight of about 400
  • B-3 Oleic acid
  • B-4 [2- (2- (2- (2-) Methoxyethoxy) ethoxy] acetate
  • B-5 oleylamine
  • the fluorescent dye C-1 was synthesized by the method described below. Under a nitrogen atmosphere, compound 1 represented by the following chemical formula, that is, bromonaphthalic anhydride (1 part by mass) and ethanol (8 parts by mass) are mixed, and 2-ethylhexylamine (0.51 part by mass, 1.1 equivalent) is mixed therein. ) was dropped. This was reacted at reflux temperature for 5 hours and 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 under reduced pressure to give compound 2 in 87% yield.
  • compound 1 represented by the following chemical formula, that is, bromonaphthalic anhydride (1 part by mass) and ethanol (8 parts by mass) are mixed, and 2-ethylhexylamine (0.51 part by mass, 1.1 equivalent) is mixed therein. ) was dropped. This was reacted at reflux temperature for 5 hours and cooled to room temperature over 1 hour. The precipitated solid was collected by filtration and washed with ethanol
  • the fluorescent dye C-3 was synthesized by the method described in Japanese Patent No. 5691235.
  • C-Nafox-TEG manufactured by Tokyo Chemical Industry Co., Ltd. was used as the fluorescent dye C-4.
  • the fluorescent dye C-5 was synthesized by the method described below.
  • the raw material is acid anhydride 1 (9.87 g, 25.2 mmol) represented by the following chemical formula, 1,8-diazabicyclo [5.4.0] -7-undecene (15.2 ml, 100 mmol), 2-ethyl.
  • a mixture of -1-hexanol (21 ml, 134 mmol), 2-ethylhexyl bromide (14 ml, 81.2 mmol) and N, N-dimethylformamide (200 ml) was stirred at 70 ° C. for 10 hours. After cooling to room temperature, it was poured into ice water, extracted with toluene, and concentrated under reduced pressure. Purification by silica gel column chromatography gave 15.3 g of the target fluorescent dye C-5.
  • Fluorescent dye C-7 was purchased from Sigma-Aldrich and used.
  • Example 1 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: 630 nm (wavelength 445 nm excited) by 10 parts by mass, ligand B-1 by 1.5 parts by mass, and isobornyl acrylate by 11. 52 parts by mass of isobornyl acrylate, 1 part by mass of fluorescent dye C-1, and 24 parts by mass of light-scattering particle dispersion 1 are added to the semiconductor nanoparticle dispersion liquid 1 containing 5 parts by mass, and mixed by a vortex mixer. And the composition 1 was obtained.
  • Example 2 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: 10 parts by mass (excitation at wavelength 445 nm)), 1.5 parts by mass of ligand B-1, and 1,6-hexanediol di. 52 parts by mass of 1,6-hexanediol diacrylate, 1 part by mass of fluorescent dye C-2, and 24 parts by mass of light-scattering particle dispersion 3 in a semiconductor nanoparticle dispersion 2 containing 11.5 parts by mass of acrylate. In addition, the mixture was mixed with a vortex mixer to obtain composition 2.
  • Example 3 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: semiconductor containing 20 parts by mass of 630 nm (wavelength 445 nm excitation), 3.5 parts by mass of ligand B-3, and 55 parts by mass of toluene.
  • To the nanoparticle dispersion liquid 3 2 parts by mass of the fluorescent dye C-3 and 19 parts by mass of the light-scattering particle dispersion liquid 2 were added and mixed with a vortex mixer to obtain a composition 3.
  • Example 4 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: 630 nm (wavelength 445 nm excited) by 20 parts by mass, ligand B-4 by 6.7 parts by mass, and 1,6-hexanediol di. 21 parts by mass of 1,6-hexanediol diacrylate and 2 parts by mass of fluorescent dye C-4 (C-Nafox-TEG (manufactured by Tokyo Kasei Kogyo Co., Ltd.)) in a semiconductor nanoparticle dispersion 4 containing 27 parts by mass of an acrylate solution. After adding the parts, the mixture was heated and mixed at 95 ° C. for 1 hour with a hot stirrer. Then, 24 parts by mass of the light-scattering particle dispersion 3 was added and mixed with a vortex mixer to obtain a composition 4.
  • Example 5 The same procedure as in Example 3 was carried out except that the fluorescent dye C-5 was used instead of the fluorescent dye C-3, to obtain the composition 5.
  • Example 6 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: semiconductor containing 20 parts by mass of 535 nm (wavelength 445 nm excitation), 6.3 parts by mass of ligand B-3, and 61 parts by mass of toluene. 0.2 parts by mass of fluorescent dye C-6 (Coumarin 521T (manufactured by Tokyo Kasei Kogyo Co., Ltd.)) and 19 parts by mass of light-scattering particle dispersion 2 were added to the nanoparticle dispersion liquid 5 and mixed with a vortex mixer. Composition 6 was obtained.
  • Example 7 InP / ZnSeS / ZnS semiconductor nanoparticles (maximum emission wavelength in the wavelength range of 300 to 780 nm: semiconductor containing 20 parts by mass of 630 nm (wavelength 445 nm excitation), 3.5 parts by mass of ligand B-3, and 55 parts by mass of toluene. Add 0.4 parts by mass of fluorescent dye C-6 (Coumarin 521T (manufactured by Tokyo Kasei Kogyo Co., Ltd.)) and 19 parts by mass of light-scattering particle dispersion 2 to the nanoparticle dispersion 3 and mix them with a vortex mixer to compose the composition. I got a thing 7.
  • fluorescent dye C-6 Coumarin 521T (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
  • 19 parts by mass of light-scattering particle dispersion 2 to the nanoparticle dispersion 3 and mix them with a vortex mixer to compose the composition. I got a thing 7.
  • Example 8 The same procedure as in Example 3 was carried out except that the fluorescent dye C-7 was used instead of the fluorescent dye C-3, to obtain the composition 8.
  • Example 1 The same procedure as in Example 1 was carried out except that the ligand B-2 was used instead of the ligand B-1, and the composition 9 was obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that the fluorescent dye C-1 was not added and isobornyl acrylate was added instead by the mass thereof to obtain the composition 10.
  • Comparative Example 3 The same procedure as in Comparative Example 1 was carried out except that the fluorescent dye C-1 was not added and isobornyl acrylate was added instead by the mass thereof to obtain the composition 11.
  • Example 4 The same procedure as in Example 1 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and isobornyl acrylate was added instead by the mass thereof to obtain the composition 12.
  • Example 8 The same procedure as in Example 2 was carried out except that the InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and 1,6-hexanediol diacrylate was added instead by the mass thereof to obtain the composition 16. ..
  • Example 9 The same procedure as in Example 3 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and toluene was added instead by the mass thereof to obtain the composition 17.
  • Example 10 The same procedure as in Example 4 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and 1,6-hexanediol diacrylate was added instead by the mass thereof to obtain the composition 18. ..
  • Example 11 The same procedure as in Example 5 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and toluene was added instead by the mass thereof, to obtain the composition 19.
  • Example 12 The same procedure as in Example 6 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and toluene was added instead by the mass thereof, to obtain the composition 20.
  • Example 13 The same procedure as in Example 7 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and toluene was added instead by the mass thereof, to obtain the composition 21.
  • Example 14 The same procedure as in Example 8 was carried out except that InP / ZnSeS / ZnS semiconductor nanoparticles and the ligand were not added and toluene was added instead by the mass thereof, to obtain the composition 22.
  • the emission spectrum measurement was carried out as follows. After each composition was placed in a glass cell having a gap of 4 ⁇ m (S-0088-4-NW manufactured by Sun Trading Co., Ltd.), the glass cell was placed in an integrating sphere, and a laser diode having a wavelength of 445 nm (Audio Technica) was placed. The sample was irradiated with a light source (SU-61C-445-50) manufactured by Spectracorp, and the emission spectrum was measured using a spectroscopic measuring device (Solid Lambda CCD UV-NIR manufactured by Spectracorp). The light in the integrating sphere was guided to the spectroscopic measuring device using an optical fiber.
  • Tables 2 and 3 show the relative values of the emission intensity (wavelength 630 nm) of each composition when Comparative Example 2 or Comparative Example 5 is 1.00, and the maximum emission wavelength (wavelength 300 to 780 nm) of each composition. The result of (within range) is shown.
  • Table 4 shows the relative values of the emission intensity (wavelength 535 nm) of each composition when Comparative Example 7 is 1.00, and the results of the maximum emission wavelength (wavelength 300 to 780 nm) of each composition.
  • compositions in which semiconductor nanoparticles having a maximum emission wavelength in the range of 300 nm to 780 nm in the range of 500 to 670 nm, a ligand having a carboxy group, and a fluorescent dye are used in combination (Examples 1 to 8).
  • the emission intensity at a wavelength of 630 nm or a wavelength of 535 nm was improved, respectively.
  • the composition containing a ligand having a carboxy group is a composition containing a ligand having a sulfanil group (Comparative Example 1), a composition containing a ligand having a sulfanil group, and a composition containing a ligand having an amino group. Compared with the thing (Comparative Example 15), it showed a larger emission intensity.
  • the fluorescent dye (C-) is the reason why the emission intensity of the semiconductor nanoparticles is increased despite the presence of the fluorescent dye having absorption at a wavelength of 445 nm.
  • the excited energy of 1 to C-7) is transferred to the semiconductor nanoparticles by Felster-type energy transfer.
  • the reasons for the Felster-type energy transfer are as follows. In particular, in Example 1, the following (2) and (3) can be cited as reasons why Förster-type energy transfer occurs more prominently.
  • the excited energy of the fluorescent dye is transferred to the semiconductor nanoparticles, and the semiconductor It is considered that the emission intensity of the nanoparticles increased.
  • the sulfanyl group of the fluorescent dye used coordinates on the surface of the semiconductor nanoparticles, in other words, the sulfanyl group acts to bind to the semiconductor nanoparticles, and the distance between the fluorescent dye and the semiconductor nanoparticles is shortened. Therefore, it is considered that the efficiency of Förster-type energy transfer has further increased.
  • the adsorptive group of the ligand is a carboxy group whose interaction with the surface of the semiconductor nanoparticles is weaker than that of the sulfanyl group, the coordination (ligand exchange) of the fluorescent dye to the surface of the semiconductor nanoparticles is more efficient. It can be mentioned that it was done in.

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