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WO2022107598A1 - Composition d'encre, couche de conversion de lumière et filtre coloré - Google Patents

Composition d'encre, couche de conversion de lumière et filtre coloré Download PDF

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Publication number
WO2022107598A1
WO2022107598A1 PCT/JP2021/040510 JP2021040510W WO2022107598A1 WO 2022107598 A1 WO2022107598 A1 WO 2022107598A1 JP 2021040510 W JP2021040510 W JP 2021040510W WO 2022107598 A1 WO2022107598 A1 WO 2022107598A1
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WIPO (PCT)
Prior art keywords
group
ink composition
mass
particles
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/040510
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English (en)
Japanese (ja)
Inventor
浩一 延藤
栄志 乙木
麻里子 利光
智樹 古矢
博友 佐々木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2022563685A priority Critical patent/JP7311055B2/ja
Priority to KR1020237014370A priority patent/KR20230107797A/ko
Priority to CN202180067395.5A priority patent/CN116323827A/zh
Publication of WO2022107598A1 publication Critical patent/WO2022107598A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • H10K50/00—Organic light-emitting devices
    • 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

Definitions

  • the present invention relates to an ink composition, a light conversion layer and a light emitting element.
  • Patent Document 1 discloses an ink composition containing semiconductor fine particles having a core / shell structure, and describes that a surface tension adjusting agent is used to set a surface tension suitable for an inkjet method.
  • the excitation light leaks out in the optical conversion layer without being converted into light
  • the excitation light and the light after optical conversion that is, light having different wavelengths
  • the excitation light and the light after optical conversion are mixed to narrow the color range of the display.
  • the light scattering particles it is preferable to add light scattering particles to the ink composition.
  • Semiconductor nanocrystals having a perovskite-type crystal structure are not only relatively easy to control the particle size, but also the emission wavelength can be arbitrarily changed depending on the type of halogen element, and the half-value width of the peak width of the emission spectrum is small. There is also an advantage.
  • the concentration of luminescent particles or light scattering particles containing core / shell type or perovskite type semiconductor nanocrystals in the ink composition is increased in order to obtain high light emission characteristics in the light conversion layer, the ink viscosity may increase. , The dispersibility of the luminescent particles was lowered.
  • problems in the inkjet process such as ink clogging in the nozzle portion of the inkjet head and damage to the head member occur, and variations in optical characteristics are likely to occur in the optical conversion layer.
  • a silicone-based surface tension adjuster is also used to solve these problems, but in reality, not only the problems in the inkjet process cannot be solved, but also the surface of the optical conversion layer is coated. There was a disadvantage that the surface tension adjuster exudes and the optical characteristics deteriorate.
  • the problem to be solved by the present invention is to use an ink composition having high compatibility with an inkjet process and capable of forming a coating film having excellent optical properties and reproducibility thereof, and the ink composition.
  • the present invention is to provide a cured product, an optical conversion layer, and a color filter.
  • the present inventors have made reactivity in an ink composition containing luminescent nanocrystal particles, light-scattering particles, a photopolymerizable compound, and a photopolymerization initiator. It has been found that further use of the silicone compound provides excellent optical properties and their reproducibility and high compatibility with the inkjet process.
  • the ink composition of the present invention is characterized by containing nanoparticles containing luminescent nanocrystals, light scattering particles, a photopolymerizable compound, a photopolymerization initiator, and a reactive silicone compound. And.
  • the optical conversion layer of the present invention includes a pixel portion, and the pixel portion contains a cured product of the above-mentioned ink composition.
  • the color filter of the present invention is characterized by including the above-mentioned optical conversion layer.
  • an ink composition having high compatibility with an inkjet process and capable of forming a coating film having excellent optical properties and reproducibility thereof, an optical conversion layer using the ink composition, and an optical conversion layer. can be provided.
  • FIG. 1 is a cross-sectional view showing an embodiment of a method for producing nanoparticles containing luminescent nanocrystals of the present invention.
  • a production example when hollow silica particles are used as hollow particles is shown.
  • the description of the pores 912b is omitted in the hollow particles 912 after the nanocrystal raw material is added in the lower stage.
  • 2 and 3 are cross-sectional views showing other structural examples of nanoparticles.
  • the ink composition comprising the luminescent nanocrystals of the embodiment of the present invention comprises a photopolymerizable compound, a photoscatterable particle, a photopolymerizable compound, a photopolymerization initiator, and the like. Contains a reactive silicone compound.
  • the ink composition containing the luminescent nanocrystals of one embodiment can be suitably used for an application of forming an optical conversion layer of a luminescent display element using an organic EL by an inkjet method.
  • the ink composition does not wastefully consume materials such as nanoparticles containing luminescent nanocrystals and photopolymerizable compounds, which are relatively expensive, and the pixel portion (light) can be obtained by simply using a necessary amount in a necessary place.
  • the surface tension of the ink composition does not decrease, and the ink may not be normally ejected from the nozzle portion of the inkjet head.
  • the ink composition of the present invention contains the reactive silicone compound, so that it is less likely to cause an ink ejection abnormality and has excellent ejection stability. Further, according to the optical conversion layer obtained by the ink composition of the present invention, excellent external quantum efficiency can be obtained.
  • the nanoparticles-containing ink composition containing the luminescent nanocrystals of the present embodiment and its constituent components will be described by taking as an example an inkjet ink composition for forming a color filter pixel portion constituting an optical conversion layer.
  • the constituent components include nanoparticles containing luminescent nanocrystals, light scattering particles, photopolymerizable compounds, photopolymerization initiators and reactive silicone compounds, as well as antioxidants and polymer dispersants.
  • Nanoparticles containing luminescent nanocrystals 1-1-1 Hollow particle-encapsulating luminescent particles
  • the nanoparticles containing luminescent nanoparticles in the present invention may be particles themselves composed of luminescent nanoparticles, but have a structure for protecting the luminescent nanoparticles from oxygen, heat, moisture, and the like. It is preferable to provide.
  • particles containing luminescent nanocrystals in hollow particles will be described.
  • the luminescent particles 91 shown in FIG. 1 are semiconductor nanocrystals 911 (semiconductor nanocrystals 911) composed of hollow particles 912 having hollow portions 912a and pores 912b communicating with the hollow portions 912a, and metal halides contained in the hollow portions 912a and having light emission.
  • semiconductor nanocrystals 911 semiconductor nanocrystals 911
  • hollow particles 912 having hollow portions 912a and pores 912b communicating with the hollow portions 912a
  • metal halides contained in the hollow portions 912a and having light emission
  • Such luminescent particles 91 can be obtained, for example, by precipitating nanocrystals 911 in the hollow portion 912a of the hollow particles 912.
  • the nanocrystals 911 are protected by the hollow particles 912, excellent stability against heat and oxygen can be obtained, and as a result, excellent
  • the luminescent particles 91 are luminescent particles 90 having a surface thereof provided with a polymer layer 92 made of a hydrophobic polymer (hereinafter, may be referred to as “polymer-coated luminescent particles”).
  • polymer-coated luminescent particles 90 By providing the polymer-coated luminescent particles 90 with the polymer layer 92, the stability against heat and oxygen can be further improved, and excellent particle dispersibility can be obtained. Therefore, the polymer-coated luminescent particles 90 have better luminescent properties when used as an optical conversion layer. Can be obtained.
  • the nanocrystal 911 is composed of an II-VI group compound, a III-V group compound, an IV-VI group compound, an IV group compound, a complex composed of two or more of these, a metal halide compound, and the like, and absorbs excitation light to fluoresce. Alternatively, it is a nano-sized crystal (nano-crystal particles) that emits phosphorescence.
  • the nanocrystal 911 is preferably a luminescent nanocrystal made of metal halide because it can be adjusted to an appropriate particle size relatively easily.
  • the nanocrystal 911 is, for example, a crystal having a maximum particle size of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope.
  • the nanocrystal 911 can be excited by, for example, light energy or electrical energy of a predetermined wavelength and emit fluorescence or phosphorescence.
  • the nanocrystal 911 composed of a metal halide is a compound represented by the general formula: A a M b X c .
  • A is at least one of an organic cation and a metal cation.
  • the organic cation include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea and the like, and examples of the metal cation include cations such as Cs, Rb, K, Na and Li.
  • M is at least one metal cation. Metal cations are selected from Group 1, Group 2, Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, and Group 15. Examples include cations.
  • X is at least one anion.
  • the anion include at least one halogen such as chloride ion, bromide ion, iodide ion, and cyanide ion.
  • a is 1 to 7
  • b is 1 to 4, and c is an integer of 3 to 16.
  • the compounds represented by the general formula A a M b X c are specifically AMX, A 4 MX, AMX 2 , AMX 3 , A 2 MX 3 , AM 2 X 3 , A 2 MX 4 , A 2 MX 5 . , A 3 MX 5 , A 3 M 2 X 5 , A 3 MX 6 , A 4 MX 6 , AM 2 X 6 , A 2 MX 6 , A 4 M 2 X 6 , A 3 MX 8 , A 3 M 2 X Compounds represented by 9 , A 3 M 3 X 9 , A 2 M 2 X 10 , and A 7 M 3 X 16 are preferable.
  • A is at least one of an organic cation and a metal cation.
  • the organic cation include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea and the like, and examples of the metal cation include cations such as Cs, Rb, K, Na and Li.
  • M is at least one metal cation. Specifically, one kind of metal cation (M 1 ), two kinds of metal cations (M 1 ⁇ M 2 ⁇ ), three kinds of metal cations (M 1 ⁇ M 2 ⁇ M 3 ⁇ ), and four kinds of metals.
  • Metal cations are selected from Group 1, Group 2, Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, and Group 15. Examples include cations.
  • X is an anion containing at least one halogen.
  • halogen anion X 1
  • X 2 ⁇ halogen anion
  • the anion include chloride ion, bromide ion, iodide ion, cyanide ion and the like, and include at least one halogen.
  • the compound composed of the metal halide represented by the general formula A a M b X c is different from the metal cation used for the M site in order to improve the emission characteristics, and is different from Bi, Mn, Ca, Eu, Sb, Yb. It may be one to which a metal ion such as is added (doped).
  • the compound having a perovskite type crystal structure adjusts the type and abundance ratio of the metal cations constituting the M site, and further adjusts the X site. It is particularly preferable to use it as a luminescent nanocrystal in that the emission wavelength (emission color) can be controlled by adjusting the type and abundance ratio of the constituent anions.
  • compounds represented by AMX 3 , A 3 MX 5 , A 3 MX 6 , A 4 MX 6 , and A 2 MX 6 are preferable.
  • A, M and X in the formula are as described above.
  • the compound having a perovskite-type crystal structure was added (doped) with metal ions such as Bi, Mn, Ca, Eu, Sb, and Yb, which are different from the metal cations used for the M site. It may be a thing.
  • the emission wavelength can be controlled by adjusting the abundance ratio of halogen atoms. Since this adjustment operation can be easily performed, the perovskite type semiconductor nanocrystal has a feature that the emission wavelength is easier to control and therefore the productivity is higher than that of the conventional core-shell type semiconductor nanocrystal. ing.
  • A is Cs, Rb, K, Na, Li
  • M is one kind of metal cation (M 1 ) or two kinds, in order to show better emission characteristics. It is a metal cation (M 1 ⁇ M 2 ⁇ ), and X is preferably a chloride ion, a bromide ion, or an iodide ion.
  • M may be selected from Ag, Au, Bi, Cu, Eu, Fe, Ge, K, In, Na, Mn, Pb, Pd, Sb, Si, Sn, Yb, Zn, and Zr. preferable.
  • nanocrystal particles using Pb as M such as CsPbBr 3 , CH 3 NH 3 PbBr 3 , and CHN 2 H 4 PbBr 3 are described as nanocrystal particles. It is preferable because it has excellent light intensity and quantum efficiency. Further, luminescent nanocrystal particles using a metal cation other than Pb as M such as CsSnBr 3, CsEuBr 3 , and CsYbI 3 are preferable because they have low toxicity and have little influence on the environment.
  • red light emitting crystals that emit light having an emission peak in the wavelength range of 605 to 665 nm (red light)
  • green light emitting light that emits light having an emission peak in the wavelength range of 500 to 560 nm
  • Crystals and blue light emitting crystals that emit light (blue light) having an emission peak in the wavelength range of 420 to 480 nm can be selected and used. Further, in one embodiment, a plurality of these nanocrystals may be used in combination.
  • the wavelength of the emission peak of the nanocrystal 911 can be confirmed, for example, in the fluorescence spectrum or the phosphorescence spectrum measured by using an absolute PL quantum yield measuring device.
  • the red-emitting nanocrystals 911 are 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less, 640 nm or less, 637 nm or less, 635 nm or less.
  • 628 nm or more 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more, 610 nm or more, 607 nm or more or 605 nm or more.
  • Green luminescent nanocrystals 911 have emission peaks in the wavelength range of 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less, or 530 nm or less.
  • an emission peak in the wavelength range of 528 nm or more, 525 nm or more, 523 nm or more, 520 nm or more, 515 nm or more, 510 nm or more, 507 nm or more, 505 nm or more, 503 nm or more, or 500 nm or more.
  • Blue luminescent nanocrystals 911 have emission peaks in the wavelength range of 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm or less, or 450 nm or less.
  • an emission peak in a wavelength range of 450 nm or more, 445 nm or more, 440 nm or more, 435 nm or more, 430 nm or more, 428 nm or more, 425 nm or more, 422 nm or more, or 420 nm or more.
  • the shape of the nanocrystal 911 is not particularly limited, and may be any geometric shape or any irregular shape.
  • Examples of the shape of the nanocrystal 911 include a rectangular parallelepiped shape, a cubic shape, a spherical shape, a regular tetrahedron shape, an ellipsoidal shape, a pyramidal shape, a disk shape, a branch shape, a net shape, a rod shape and the like.
  • the shape of the nanocrystals 911 is preferably rectangular parallelepiped, cubic, or spherical.
  • the average particle size (volume average diameter) of the nanocrystals 911 is preferably 40 nm or less, more preferably 30 nm or less, and further preferably 20 nm or less.
  • the average particle size of the nanocrystals 911 is preferably 1 nm or more, more preferably 1.5 nm or more, and even more preferably 2 nm or more. Nanocrystals 911 having such an average particle size are preferable because they easily emit light having a desired wavelength.
  • the average particle size of the nanocrystal 911 is obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
  • the hollow particles 912 may have a hollow portion 912a, which is a space capable of accommodating nanocrystals 911 inside, and pores 912b communicating with the hollow portion 912a, and the overall shape may be a rectangular parallelepiped or a cube.
  • Particles such as a shape, a spherical shape (substantially true spherical shape), an elongated spherical shape (elliptical spherical shape), and a honeycomb shape (a shape in which cylinders having a hexagonal cross section and open at both ends are arranged without gaps) can be used.
  • a rectangular parallelepiped, cubic, substantially true spherical, or elliptical hollow particle is a particle having a balloon structure or a hollow structure.
  • These hollow particles having a balloon structure or a hollow structure can more reliably obtain stability against heat and oxygen by covering the entire nanocrystals 911 contained in the hollow portion 912a. preferable. Further, in the obtained luminescent nanoparticles 90, since the hollow particles 912 are interposed between the luminescent nanoparticles 90 and the polymer layer 92 described later, the stability of the nanocrystals 911 against oxygen gas and moisture is also improved.
  • the hollow portion 912a may accommodate one nanocrystal 911, or may accommodate a plurality of nanocrystals 911. Further, the hollow portion 912a may be entirely occupied by one or a plurality of nanocrystals 911, or may be partially occupied.
  • the hollow particles may be any material as long as they can protect the nanocrystals 911.
  • the hollow particles include hollow silica particles, which are hollow inorganic nanoparticles, hollow alumina particles, hollow titanium oxide particles, or hollow polystyrene particles, which are hollow polymer particles, and hollow PMMA. It is preferably particles, more preferably hollow silica particles or hollow alumina particles. Hollow silica particles are more preferable because the surface treatment of the particles is easy.
  • the average outer diameter of the hollow particles 912 is not particularly limited, but is preferably 5 to 300 nm, more preferably 6 to 100 nm, still more preferably 8 to 50 nm, and even more preferably 10 to 25 nm. Is particularly preferred. Hollow particles 912 of such size can sufficiently enhance the stability of nanocrystals 911 to oxygen, moisture and heat.
  • the average inner diameter of the hollow particles 912 is not particularly limited, but is preferably 1 to 250 nm, more preferably 2 to 100 nm, still more preferably 3 to 50 nm. It is particularly preferably 5 to 15 nm. If the average inner diameter of the hollow particles 912 is excessively small, the nanocrystals 911 may not precipitate in the hollow portion 912a, and if the average inner diameter is excessively large, the nanocrystals 911 may excessively aggregate in the hollow portion 91a to emit light. May decrease. If the hollow particles 912 have an average inner diameter in the above range, nanocrystals 911 can be precipitated while suppressing aggregation.
  • the size of the pores 912b is not particularly limited, but is preferably 0.5 to 10 nm, more preferably 1 to 5 nm. In this case, the solution containing the raw material compound of the nanocrystals 911 can be smoothly and surely permeated into the hollow portion 912a.
  • the hollow particles are impregnated with the solution (Z) containing the raw material compound of the semiconductor nanocrystals ((d) in FIG. 1) and dried to form the hollow portions 912a of the hollow particles.
  • Semiconductor nanocrystals made of luminescent metal halides are precipitated ((d) in FIG. 1), and luminescent particles (hollow particle-encapsulating luminescent particles) 91 can be obtained.
  • the obtained luminescent particles 91 can be made into a dispersion liquid containing the luminescent particles 91 by adding to a photopolymerizable compound described later, specifically, for example, isobornyl methacrylate.
  • the solution (Z) containing the raw material compound of the semiconductor nanocrystals is preferably a solution having a solid content concentration of 0.5 to 20% by mass from the viewpoint of impregnation to the hollow particles 912.
  • the organic solvent may be a good solvent with nanocrystals 911, but in particular, dimethyl sulfoxide, N, N-dimethylformamide, N-methylformamide, ethanol, methanol, 2-propanol, ⁇ -butyrolactone, ethyl acetate, etc. Water and a mixed solvent thereof are preferable from the viewpoint of compatibility.
  • the raw material compound and the organic solvent in the reaction vessel under the atmosphere of an inert gas such as argon.
  • the temperature condition at this time is preferably room temperature to 350 ° C., and the stirring time at the time of mixing is preferably 1 minute to 10 hours.
  • the raw material compound for semiconductor nanocrystals for example, when preparing a lead cesium tribromide solution, it is preferable to mix cesium bromide and lead (II) bromide with the organic solvent. At this time, the addition amounts of cesium bromide are adjusted to 0.5 to 200 parts by mass and lead (II) bromide is adjusted to 0.5 to 200 parts by mass with respect to 1000 parts by mass of a good solvent. Is preferable.
  • the hollow portion 912a of the hollow silica particles 912 is impregnated with the lead tribromide cesium solution. Then, by filtering the solution in the reaction solution, the excess lead tribromide cesium solution is removed and the solid substance is recovered. Then, the obtained solid matter is dried under reduced pressure at ⁇ 50 to 200 ° C. As described above, the luminescent particles 91 in which the perovskite-type semiconductor nanocrystals 911 are precipitated in the hollow portion 912a of the hollow silica particles 911 can be obtained.
  • the hollow particle-encapsulating luminescent particles 91 are located between the wall surface of the hollow portion 912a of the hollow particles 92 and the semiconductor nanocrystals 911, and are coordinated with the surface of the semiconductor nanocrystals 911. It is preferable to include an intermediate layer 913 composed of the same ligands.
  • the luminescent particles 91 shown in FIG. 2A are intermediate in that oleic acid, oleylamine, etc. are coordinated as ligands on the surface of nanocrystals 911 containing Pb cations (indicated by black circles in the figure) as M sites. Layer 913 is formed.
  • FIG. 1 the luminescent particles 91 shown in FIG. 2A are intermediate in that oleic acid, oleylamine, etc. are coordinated as ligands on the surface of nanocrystals 911 containing Pb cations (indicated by black circles in the figure) as M sites. Layer 913 is formed.
  • Pb cations indicated by black circles in the figure
  • the light emitting particles 91 provided with the intermediate layer 913 can further enhance the stability of the nanocrystals 911 against oxygen, moisture, heat, etc. by the intermediate layer 913.
  • the ligand is added to the solution containing the raw material compound of the nanocrystal 911, and this solution is impregnated into the hollow silica particles 912 and dried. Can be obtained by doing.
  • the ligand is preferably a compound having a binding group that binds to a cation contained in nanocrystal 911.
  • the binding group include a carboxyl group, a carboxylic acid anhydride group, an amino group, an ammonium group, a mercapto group, a phosphin group, a phosphin oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group and a boron. It is preferably at least one of the acid groups, more preferably at least one of the carboxyl and amino groups. Examples of such a ligand include a carboxyl group or an amino group-containing compound, and one of these can be used alone, or two or more thereof can be used in combination.
  • Examples of the carboxyl group-containing compound include linear or branched aliphatic carboxylic acids having 1 to 30 carbon atoms.
  • amino group-containing compound examples include linear or branched aliphatic amines having 1 to 30 carbon atoms.
  • a ligand having a reactive group for example, 3-aminopropyltrimethoxysilane
  • a ligand having a reactive group for example, 3-aminopropyltrimethoxysilane
  • it is composed of a ligand located between the hollow particle 912 and the nanocrystal 911 and coordinated on the surface of the nanocrystal 911, and the molecules of the ligand form a siloxane bond with each other.
  • the mother particle 91 having the forming intermediate layer 913 According to such a configuration, the nanocrystals 911 can be firmly fixed by the hollow particles 912 via the intermediate layer 913.
  • the ligand having a reactive group is preferably a compound having a bonding group that binds to a cation contained in nanocrystal 911 and a reactive group that contains Si and forms a siloxane bond.
  • the reactive group can also react with the hollow particles 912.
  • the binding group examples include a carboxyl group, a carboxylic acid anhydride group, an amino group, an ammonium group, a mercapto group, a phosphin group, a phosphin oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group and a boron.
  • acid groups examples include acid groups.
  • the binding group is preferably at least one of a carboxyl group and an amino group. These binding groups have a higher affinity (reactivity) for the cations contained in the nanocrystal 911 than the reactive groups. Therefore, the ligand can coordinate with the binding group on the nanocrystal 911 side to more easily and surely form the intermediate layer 913.
  • a hydrolyzable silyl group such as a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms is preferable because a siloxane bond is easily formed.
  • Such ligands include carboxyl group- or amino group-containing silicon compounds, and one of these can be used alone or two or more thereof can be used in combination.
  • the light emitting particles 90 having a polymer layer 92 made of a hydrophobic polymer on the surface of the hollow particle-encapsulating light emitting particles 91 may be described. There is.) Is more preferable.
  • the polymer-coated luminescent particles 90 By providing the polymer-coated luminescent particles 90 with the polymer layer 92, the stability against heat and oxygen can be further improved, and excellent particle dispersibility can be obtained. Therefore, the polymer-coated luminescent particles 90 have better luminescent properties when used as an optical conversion layer. Can be obtained.
  • Silica-coated luminescent particles Another form of nanoparticles containing luminescent nanoparticles in the present invention is, as the luminescent particles 91 shown in FIG. 3A, a perovskite-type semiconductor nanocrystal having luminescence (hereinafter, simply “nanocrystals”). 911 ”) and a surface layer 914 composed of ligands coordinated on the surface of the nanocrystal 911, and further formed by forming siloxane bonds between molecules that are silane compounds among the ligands. (Hereinafter, it may be referred to as "silica-coated luminescent particles 91").
  • the luminescent particles 91 are, for example, mixed with a ligand such as a precursor of the nanocrystal 911, oleic acid, or oleylamine and a ligand having a siloxane bondable site to precipitate the nanocrystal 911, and at the same time, the arrangement thereof. It can be obtained by coordinating the ligand on the surface of the nanocrystal 911 and then subsequently forming a siloxane bond. Since the nanocrystals 911 are protected by the silica surface layer 914, the luminescent particles 91 can obtain excellent stability against heat and oxygen, and as a result, excellent luminescent properties can be obtained.
  • a ligand such as a precursor of the nanocrystal 911, oleic acid, or oleylamine and a ligand having a siloxane bondable site to precipitate the nanocrystal 911, and at the same time, the arrangement thereof. It can be obtained by coordinating the ligand on the surface of the nanocrystal
  • the luminescent particles 90 having a polymer layer 92 made of a hydrophobic polymer on the surface of the silica-coated luminescent particles 91 (hereinafter referred to as “polymer-coated luminescent particles 90”” will be described. It may be more preferable.).
  • polymer-coated luminescent particles 90 By providing the polymer-coated luminescent particles 90 with the polymer layer 92, the stability against heat and oxygen can be further improved, and excellent particle dispersibility can be obtained. Therefore, the polymer-coated luminescent particles 90 have better luminescent properties when used as an optical conversion layer. Can be obtained.
  • the silica-coated luminescent particles 91 shown in FIG. 3A are composed of the nanocrystal 911 having luminescence and a ligand coordinated to the surface of the nanocrystal 911, and further, a silane compound among the ligands. It has a surface layer 914 in which siloxane bonds are formed between the molecules. Therefore, the silica-coated luminescent particles 91 can maintain excellent luminescent properties because the nanocrystals 911 are protected by the surface layer 914.
  • the silica-coated luminescent particles 91 are a solution containing a solution containing a raw material compound for semiconductor nanocrystals, an aliphatic carboxylic acid, and an aliphatic amine containing a compound containing Si and having a reactive group capable of forming a siloxane bond.
  • a perovskite-type semiconductor nanocrystal having light emission is precipitated, the compound is coordinated on the surface of the semiconductor nanocrystal, and then the reactive group in the coordinated compound is condensed. By doing so, it can be produced by a method of obtaining particles 91 having a surface layer having the siloxane bond formed on the surface of the semiconductor nanocrystal.
  • the silica-coated luminescent particles 91 can be used as luminescent particles by themselves.
  • the surface layer 914 is composed of a ligand containing a compound that can be coordinated to the surface of the nanocrystal 911 and the molecules can form a siloxane bond with each other.
  • the ligand is a compound having a binding group that binds to a cation contained in the nanocrystal 911, and contains a compound having a reactive group that contains Si and forms a siloxane bond.
  • the binding group include a carboxyl group, a carboxylic acid anhydride group, an amino group, an ammonium group, a mercapto group, a phosphin group, a phosphin oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group and the like. It is preferably at least one of the boronic acid groups, more preferably at least one of the carboxyl and amino groups.
  • such a ligand include a carboxyl group or an amino group-containing compound, and one of these can be used alone, or two or more thereof can be used in combination.
  • the compound containing Si and having a reactive group forming a siloxane bond has a binding group that binds to a cation contained in the nanocrystal 911.
  • a hydrolyzable silyl group such as a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms is preferable because a siloxane bond is easily formed.
  • the binding group examples include a carboxyl group, an amino group, an ammonium group, a mercapto group, a phosphin group, a phosphin oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group, a boronic acid group and the like. .. Among them, the binding group is preferably at least one of a carboxyl group, a mercapto group and an amino group. These binding groups have a higher affinity for the cations contained in nanocrystal 911 than the reactive groups described above. Therefore, the ligand can coordinate with the binding group on the nanocrystal 911 side to more easily and surely form the surface layer 914.
  • one or more kinds of silicon compounds containing a binding group may be contained, or two or more kinds may be used in combination.
  • any one of a carboxyl group-containing silicon compound, an amino group-containing silicon compound, and a mercapto group-containing silicon compound is contained, or two or more thereof can be used in combination.
  • carboxyl group-containing silicon compound examples include, for example, 3- (trimethoxysilyl) propionic acid, 3- (triethoxysilyl) propionic acid, 2-, carboxyethylphenylbis (2-methoxyethoxy) silane, N-. [3- (Trimethoxysilyl) propyl] -N'-carboxymethylethylenediamine, N- [3- (trimethoxysilyl) propyl] phthalamide, N- [3- (trimethoxysilyl) propyl] ethylenediamine-N, N' , N'-triacetic acid and the like.
  • amino group-containing silicon compound examples include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-.
  • mercapto group-containing silicon compound examples include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 2-mercaptoethyl.
  • silica-coated luminescent particles 91 shown in FIG. 3A oleic acid, oleylamine, and 3-aminopropyltrimethoxysilane are coordinated as ligands on the surface of nanocrystals 911 containing Pb cations as M sites, and further.
  • the surface layer 914 is formed by reacting with 3-aminopropyltrimethoxysilane.
  • the thickness of the surface layer 914 is preferably 0.5 to 50 nm, more preferably 1.0 to 30 nm.
  • the luminescent particles 91 having the surface layer 914 having such a thickness can sufficiently enhance the heat stability of the nanocrystals 911.
  • the thickness of the surface layer 914 can be changed by adjusting the number of atoms (chain length) of the linking structure that connects the binding group and the reactive group of the ligand.
  • Such a silica-coated luminescent particle 91 contains a solution containing a raw material compound of the nanocrystal 911, a compound having a binding group that binds to a cation contained in the nanocrystal 911, and Si, and can form a siloxane bond. After mixing with a solution containing a compound having a sex group, the reactive group in the compound having a reactive group containing Si coordinated on the surface of the precipitated nanocrystal 911 and capable of forming a siloxane bond is condensed. Therefore, it can be easily produced. At this time, there are a method of manufacturing by heating and a method of manufacturing without heating.
  • a method of heating to produce silica-coated luminescent particles 91 will be described.
  • one of the two solutions contains a compound having a cation-bonding group contained in the nanocrystal 911, and the other solution contains Si and has a reactive group capable of forming a siloxane bond. I'll add it.
  • These are then mixed under an inert gas atmosphere and reacted under temperature conditions of 140-260 ° C.
  • a method of precipitating nanocrystals by cooling to ⁇ 20 to 30 ° C. and stirring is mentioned.
  • the precipitated nanocrystals have a surface layer 914 having a siloxane bond formed on the surface of the nanocrystals 911, and the nanocrystals can be obtained by a conventional method such as centrifugation.
  • Si A method for precipitating nanocrystals by dropping and mixing a compound containing a compound having a reactive group capable of forming a siloxane bond in a solution dissolved in an organic solvent which is a poor solvent for nanocrystals in the atmosphere. Can be mentioned.
  • the amount of the organic solvent used is preferably 10 to 1000 times the mass of the semiconductor nanocrystals.
  • the precipitated nanocrystals have a surface layer 914 having a siloxane bond formed on the surface of the nanocrystals 911, and the nanocrystals can be obtained by a conventional method such as centrifugation.
  • the polymer-coated luminescent particles 90 shown in FIGS. 1, 2 (b) and 3 (b) are based on hollow particle-encapsulating luminescent particles 91 or silica-coated luminescent particles 91 obtained in the above steps.
  • these luminescent particles 91 may be referred to as "mother particles 91”
  • the polymer-coated luminescent particles 90 can impart high stability to oxygen and moisture to the luminescent particles 90, and further improve the dispersion stability of the luminescent particles 90. Can be done.
  • the polymer layer 92 is formed by coating the surface of the particles to be coated (hereinafter, also referred to as “mother particles”) with a hydrophobic polymer.
  • the polymer layer is formed by polymerizing the monomer (M) in the presence of mother particles, a non-aqueous solvent and the polymer (P).
  • the non-aqueous solvent is preferably an organic solvent capable of dissolving the hydrophobic polymer, and more preferably if the luminescent particles 91 can be uniformly dispersed.
  • the hydrophobic polymer can be very easily adsorbed on the luminescent particles 91 to coat the polymer layer 92.
  • the non-aqueous solvent is a low dielectric constant solvent. By using a low dielectric constant solvent, the hydrophobic polymer can be strongly adsorbed on the surface of the luminescent particles 91 and the polymer layer can be coated by simply mixing the hydrophobic polymer and the luminescent particles 91 in the non-aqueous solvent. can.
  • the polymer layer 92 thus obtained is difficult to be removed from the luminescent particles 91 even if the luminescent particles 90 are washed with a solvent as described later.
  • the dielectric constant of the non-aqueous solvent is preferably 10 or less, more preferably 6 or less, and particularly preferably 5 or less.
  • the preferred non-aqueous solvent is preferably an organic solvent containing at least one selected from the group consisting of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent.
  • Examples of the aliphatic hydrocarbon solvent include n-hexane, n-heptane, n-octane, isohexane and the like, and examples of the alicyclic hydrocarbon solvent include cyclopentane, cyclohexane, ethylcyclohexane and the like.
  • Examples of the aromatic hydrocarbon solvent include toluene, xylene and the like.
  • a non-aqueous solvent at least one selected from the group consisting of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent, as long as the effect of the present invention is not impaired.
  • a mixed solvent in which another organic solvent is mixed may be used.
  • Such other organic solvents include, for example, ester solvents such as methyl acetate, ethyl acetate, -n-butyl acetate, amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone.
  • ester solvents such as methyl acetate, ethyl acetate, -n-butyl acetate, amyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone.
  • alcohol solvents such as methanol, ethanol, n-propanol, i-propanol and n-butanol.
  • the amount used at least one of the group consisting of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent may be 50% by mass or more. It is preferably 60% by mass or more, more preferably 60% by mass or more.
  • the polymer (P) is a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent.
  • the polymer (P) contains an alkyl (meth) acrylate (A1) having an alkyl group having 4 or more carbon atoms, a (meth) acrylate having a polymerizable functional group at the terminal (meth) acrylate (A2), and a polymerizable unsaturated group.
  • a monomer or a macromonomer composed of a copolymer of a monomer having a polymerizable unsaturated group containing a silicon-containing compound (D) as a main component can be used.
  • alkyl (meth) acrylate (A1) examples include n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate.
  • Isodecyl (meth) acrylate Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl Examples include (meth) acrylate.
  • Examples of the (meth) acrylate (A2) having a polymerizable functional group at the terminal include dimethylamino (meth) acrylate and diethylamino (meth) acrylate; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. And a diester compound of a monovalent alcohol can be mentioned.
  • (meth) acrylate means both methacrylate and acrylate. The same applies to the expression "(meth) acryloyl”.
  • Examples of the fluorine-containing compound (B) having a polymerizable unsaturated group include methacrylates represented by the following formulas (B1-1) to (B1-7) and the following formulas (B1-8) to (B1-15). Examples include acrylates and the like. It should be noted that these compounds may be used alone or in combination of two or more.
  • Examples of the fluorine-containing compound (C) having a polymerizable unsaturated group include a poly (perfluoroalkylene ether) chain and a compound having a polymerizable unsaturated group at both ends thereof.
  • fluorine-containing compound (C) examples include compounds represented by the following formulas (C-1) to (C-13).
  • "-PFPE-” in the following formulas (C-1) to (C-13) is a poly (perfluoroalkylene ether) chain.
  • the fluorine-containing compound (C) is represented by the above formulas (C-1), (C-2), (C-5) or (C-6) from the viewpoint of easy industrial production.
  • Acryloyl is applied to both ends of the poly (perfluoroalkylene ether) chain represented by the above formula (C-1) because a compound is preferable and a polymer (P) that is easily entangled with the surface of the mother particle 91 can be synthesized.
  • a compound having a group or a compound having a methacryloyl group at both ends of the poly (perfluoroalkylene ether) chain represented by the above formula (C-2) is more preferable.
  • examples of the silicon-containing compound (D) having a polymerizable unsaturated group include a compound represented by the following general formula (D1).
  • P is a polymerizable functional group
  • Xa is SiR 11 R 22
  • Rd is a hydrogen atom, a fluorine atom, a methyl group, an acryloyl group or a methacryloyl group (where R 11 and R 22 are. It is a methyl group, or a Si (CH 3 ) group, an amino group, or a glycidyl group, where m is an integer of 0 to 100 and n is an integer of 0 to 4).
  • silicon-containing compound (D) examples include compounds represented by the following formulas (D-1) to (D-13).
  • the polymer (P) the above-mentioned alkyl (meth) acrylate (A1), a (meth) acrylate compound (A2) having a polymerizable functional group at the terminal, a fluorine-containing compound (B, C) and a silicon-containing compound (D).
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, pt-butylstyrene, and vinyltoluene
  • examples thereof include (meth) acrylate compounds such as (meth) acrylate.
  • These compounds have a random copolymer weight with an alkyl (meth) acrylate (A1), a (meth) acrylate having a polymerizable functional group at the terminal (A2), a fluorine-containing compound (B, C) or a silicon-containing compound (D). It is preferable to use it as a coalescence. Thereby, the solubility of the obtained polymer (P) in a non-aqueous solvent can be sufficiently enhanced.
  • alkyl (meth) acrylates (A1) having a linear or branched alkyl group having 4 to 12 carbon atoms such as n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl methacrylate are used. It is preferable to use it.
  • a copolymer (P) can be obtained by introducing a polymerizable unsaturated group into the copolymer after obtaining a copolymer of the compound by polymerizing these compounds by a conventional method.
  • a carboxylic acid group-containing polymerizable monomer such as acrylic acid or methacrylic acid, or an amino group such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide
  • a copolymer having a carboxylic acid group or an amino group is obtained by blending and copolymerizing the containing polymerizable monomer, and then the carboxylic acid group or the amino group is combined with a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group. Examples thereof include a method of reacting a monomer having.
  • the monomer (M) is a polymerizable unsaturated monomer that is soluble in a non-aqueous solvent and becomes insoluble or sparingly soluble after polymerization.
  • Examples of the monomer (M) include vinyl-based monomers having no reactive polar group (functional group), amide bond-containing vinyl-based monomers, (meth) acryloyloxyalkyl phosphates, and (meth) acrylic.
  • vinyl-based monomers having no reactive polar group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate.
  • examples thereof include (meth) acrylates, (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, olefins such as vinylidene fluoride and the like.
  • amide bond-containing vinyl-based monomers include (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, and dimethylamino.
  • examples thereof include propylacrylamide, alkoxylated N-methylolated (meth) acrylamides and the like.
  • (meth) acryloyloxyalkyl phosphates include dialkyl [(meth) acryloyloxyalkyl] phosphates, (meth) acryloyloxyalkyl acid phosphates, and the like.
  • (meth) acryloyloxyalkyl phosphites include dialkyl [(meth) acryloyloxyalkyl] phosphites, (meth) acryloyloxyalkyl acid phosphites, and the like.
  • the phosphorus atom-containing vinyl-based monomers include alkylene oxide adducts of the above-mentioned (meth) acryloyloxyalkyl acid phosphates or (meth) acryloyloxyalkyl acid phosphites, glycidyl (meth) acrylate, and the like.
  • Examples thereof include ester compounds of an epoxy group-containing vinyl-based monomer such as methylglycidyl (meth) acrylate with phosphoric acid, phosphite or acidic esters thereof, 3-chloro-2-acid phosphoxypropyl (meth) acrylate and the like. Be done.
  • hydroxyl group-containing polymerizable unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (.
  • polymerizable unsaturated carboxylic acids such as monobutyl fumarate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate or adducts of these with ⁇ -caprolactone; (meth) acrylic acid.
  • Crotonic acid maleic acid, fumaric acid, itaconic acid, citraconic acid and other unsaturated mono- or dicarboxylic acids, polymerizable unsaturated carboxylic acids such as monoesters of dicarboxylic acid and monovalent alcohol; Hydroxyalkyl esters of saturated carboxylic acids and anhydrides of polycarboxylic acids (maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, hensentricarboxylic acid, benzenetetracarboxylic acid, "hymic acid”, tetra Monoglycidyl esters of various unsaturated carboxylic acids such as additives with chlorphthalic acid, dodecynyl succinic acid, etc.
  • Hydroxyalkyl esters of saturated carboxylic acids and anhydrides of polycarboxylic acids maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydr
  • dialkylaminoalkyl (meth) acrylates include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • epoxy group-containing polymerizable unsaturated monomer examples include, for example, a polymerizable unsaturated carboxylic acid, an equimolar adduct of a hydroxyl group-containing vinyl monomer and the anhydride of the polycarboxylic acid (mono-2- (mono-2- ().
  • Epoxide group-containing polymerization obtained by adding various polyepoxide compounds having at least two epoxy groups in one molecule to various unsaturated carboxylic acids such as meta) acryloyloxymonoethylphthalate) at an equimolar ratio. Examples thereof include sex compounds, glycidyl (meth) acrylate, ( ⁇ -methyl) glucidyl (meth) acrylate, and (meth) allyl glucidyl ether.
  • isocyanate group-containing ⁇ , ⁇ -ethylenically unsaturated monomers include, for example, an equimolar adduct of 2-hydroxyethyl (meth) acrylate and hexamethylene diisocyanate, and isocyanate ethyl (meth) acrylate.
  • examples thereof include monomers having an isocyanate group and a vinyl group.
  • alkoxysilyl group-containing polymerizable unsaturated monomers include silicone-based monomers such as vinylethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and trimethylsiloxyethyl (meth) acrylate. Be done.
  • carboxyl group-containing ⁇ , ⁇ -ethylenic unsaturated monomers include unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
  • ⁇ , ⁇ -Ethenyl unsaturated carboxylic acids such as monoesters of acids, dicarboxylic acids and monovalent alcohols; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Meta) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl ⁇ , ⁇ -Unsaturated carboxylic acid hydroalkyl esters such as fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol mono (meth) acrylate and maleic acid, succinic acid, phthalic acid, hexahydrophthal Examples thereof include additions of polycarboxylic acids such as acids, tetrahydrophthalic acid, benzenetricarboxy
  • the monomer (M) is preferably an alkyl (meth) acrylate having an alkyl group having 3 or less carbon atoms, such as methyl (meth) acrylate and ethyl (meth) acrylate.
  • the polymer layer 92 made of a hydrophobic polymer is formed by polymerizing the monomer (M) in the presence of luminescent particles 91, a non-aqueous solvent and the polymer (P). It is preferable that the luminescent particles 91 and the polymer (P) are mixed before the polymerization is carried out.
  • a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill and the like can be used.
  • the form of the luminescent particles 91 used is not particularly limited and may be any of slurry, wet cake, powder and the like.
  • the luminescent particles 91 and the polymer (P) After mixing the luminescent particles 91 and the polymer (P), the monomer (M) and the polymerization initiator described later are further mixed and polymerized to obtain the polymer (P) and the monomer (M).
  • the polymer layer 92 composed of the polymer of the above is formed. As a result, the luminescent particles 90 are obtained.
  • the number average molecular weight of the polymer (P) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000, and more preferably 3,000 to 100,000. Is even more preferable.
  • the polymer (P) having a molecular weight in such a range the surface of the luminescent particles 91 can be satisfactorily coated with the polymer layer 92.
  • the amount of the polymer (P) used is appropriately set according to the purpose and is not particularly limited, but is usually 0.5 to 50 parts by mass with respect to 100 parts by mass of the luminescent particles 91. It is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass.
  • the amount of the monomer (M) used is also appropriately set according to the purpose and is not particularly limited, but is usually 0.5 to 40 parts by mass with respect to 100 parts by mass of the luminescent particles 91. It is preferably 1 to 35 parts by mass, more preferably 2 to 30 parts by mass.
  • the amount of the hydrophobic polymer finally covering the surface of the luminescent particles 91 is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the luminescent particles 91. It is preferably 3 to 40 parts by mass, and more preferably 3 to 40 parts by mass.
  • the amount of the monomer (M) is usually preferably 10 to 100 parts by mass, more preferably 30 to 90 parts by mass with respect to 100 parts by mass of the polymer (P). , 50-80 parts by mass is more preferable.
  • the thickness of the polymer layer 92 is preferably 0.5 to 100 nm, more preferably 0.7 to 50 nm, and even more preferably 1 to 30 nm. If the thickness of the polymer layer 92 is less than 0.5 nm, dispersion stability is often not obtained. If the thickness of the polymer layer 92 exceeds 100 nm, it is often difficult to contain the luminescent particles 91 at a high concentration. By coating the luminescent particles 91 with the polymer layer 92 having such a thickness, the stability of the luminescent particles 90 against oxygen and moisture can be further improved.
  • the polymerization of the monomer (M) in the presence of the luminescent particles 91, the non-aqueous solvent and the polymer (P) can be carried out by a known polymerization method, but is preferably carried out in the presence of a polymerization initiator.
  • a polymerization initiator include dimethyl-2,2-azobis (2-methylpropionate), azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile), and the like.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the polymerization initiator which is sparingly soluble in a non-aqueous solvent, is added to the mixed solution containing the luminescent particles 91 and the polymer (P) in a state of being dissolved in the monomer (M).
  • the monomer (M) or the monomer (M) in which the polymerization initiator is dissolved may be added to the mixed solution having reached the polymerization temperature by a dropping method and polymerized, but at room temperature before the temperature rise. It is stable and preferable to add it to the mixed solution, mix it sufficiently, and then raise the temperature to polymerize it.
  • the polymerization temperature is preferably in the range of 60 to 130 ° C, more preferably in the range of 70 to 100 ° C. If the monomer (M) is polymerized at such a polymerization temperature, morphological changes (for example, alteration, crystal growth, etc.) of the nanocrystals 911 can be suitably prevented.
  • the polymer not adsorbed on the surface of the luminescent particles 91 is removed to obtain luminescent particles (polymer-coated luminescent particles) 90 in which the polymer layer 92 is formed on the surface of the luminescent particles 91. ..
  • Examples of the method for removing the polymer that has not been adsorbed include centrifugal sedimentation and ultrafiltration. In the centrifugal sedimentation, the dispersion liquid containing the polymer-coated luminescent particles 90 and the unadsorbed polymer is rotated at high speed, and the polymer-coated luminescent particles 90 in the dispersion liquid are settled to separate the unadsorbed polymer.
  • a dispersion containing the polymer-coated luminescent particles 90 and the non-adsorbed polymer is diluted with an appropriate solvent, and the diluted solution is passed through a filtration membrane having an appropriate pore size to pass the unadsorbed polymer and polymer. Separates from the coated luminescent particles 90.
  • the polymer-coated luminescent particles 90 can be obtained.
  • the polymer-coated luminescent particles 90 may be stored in a state of being dispersed in a dispersion medium, a resin or a polymerizable compound (that is, as a dispersion liquid), or the dispersion medium may be removed to remove the powder (aggregation of the polymer-coated luminescent particles 90). It may be saved as a body).
  • the content of the polymer-coated luminescent particles 90 is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. It is preferably 1 to 10% by mass, and more preferably 1 to 10% by mass.
  • the luminescent particle-containing ink composition contains nanocrystals 911 not coated with the polymer layer 92, hollow particle-encapsulating luminescent particles 91, and silica-coated luminescent particles 91
  • the content of the luminescent particles 91 is 0.1. It is preferably about 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass.
  • the content of the polymer-coated luminescent particles 90 (or luminescent particles 91) in the luminescent particle-containing ink composition is set to the above range, when the luminescent particle-containing ink composition is ejected by an inkjet printing method, the ejection thereof is performed. Stability can be further improved. Further, the light emitting particles 90 (or the light emitting particles 91) are less likely to aggregate with each other, and the external quantum efficiency of the obtained light emitting layer (light conversion layer) can be increased.
  • the ink composition may contain two or more of red luminescent particles, green luminescent particles, and blue luminescent particles as the luminescent particles 90 (or luminescent particles 91) containing luminescent nanocrystals, but these particles may be contained. It is preferable to contain only one of them.
  • the content of the green luminescent particles and the content of the blue luminescent particles are preferably 5% by mass or less, more preferably 0% by mass, based on the total mass of the luminescent particles. Is.
  • the content of the red luminescent particles and the flow rate of the blue luminescent particles are preferably 5% by mass or less, more preferably 0% by mass, based on the total mass of the luminescent particles. Is.
  • the ink composition contains light-scattering particles.
  • the light-scattering particles are preferably, for example, optically inactive inorganic fine particles.
  • the light-scattering particles can scatter the light from the light source portion irradiated to the light emitting layer (light conversion layer).
  • Materials that make up the light-scattering particles include, for example, single metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; silica, barium sulfate, barium carbonate, calcium carbonate.
  • Metal oxides such as talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide; Metal carbonates such as magnesium, barium carbonate, bismuth hypocarbonate, calcium carbonate; metal hydroxides such as aluminum hydroxide; barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, etc. Examples thereof include composite oxides and metal salts such as bismuth subnitrate.
  • a material constituting the light-scattering particles at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate and silica from the viewpoint of being more excellent in the effect of reducing leakage light. It preferably contains seeds, more preferably contains at least one selected from the group consisting of titanium oxide, barium sulfate and calcium carbonate, and particularly preferably titanium oxide.
  • titanium oxide When titanium oxide is used, it is preferably surface-treated titanium oxide from the viewpoint of dispersibility.
  • a surface treatment method for titanium oxide There is a known method as a surface treatment method for titanium oxide, but it is more preferable that the surface treatment contains at least alumina.
  • Titanium oxide that has been surface-treated to contain alumina means a treatment that precipitates at least alumina on the surface of titanium oxide particles, and silica or the like can be used in addition to alumina.
  • Alumina or silica also contains their hydrates.
  • the surface of the titanium oxide particles is uniformly surface-coated by performing the surface treatment containing alumina in the titanium oxide particles, and at least when the titanium oxide particles surface-treated with alumina are used, the titanium oxide particles are dispersed.
  • the sex becomes good.
  • the alumina and silica treatment may be performed at the same time, and in particular, the alumina treatment may be performed first, and then the silica treatment may be performed.
  • the amount of alumina and silica to be treated is preferably more silica than that of alumina.
  • titanium oxide particles surface-treated with alumina or silica can be produced as follows.
  • Titanium oxide particles (number average primary particle diameter: 200 to 400 nm) are dispersed in water at a concentration of 50 to 350 g / L to form an aqueous slurry, to which a water-soluble silicate or a water-soluble aluminum compound is added. Then, an alkali or an acid is added to neutralize the particles, and silica or alumina is deposited on the surface of the titanium oxide particles. Subsequently, it is filtered, washed and dried to obtain the desired surface-treated titanium oxide.
  • sodium silicate is used as the water-soluble silicate, it can be neutralized with an acid such as sulfuric acid, nitric acid, or hydrochloric acid.
  • aluminum sulfate is used as the water-soluble aluminum compound, it can be neutralized with an alkali such as sodium hydroxide or potassium hydroxide.
  • a polymer dispersant can be used to enhance the dispersibility of light-scattering particles.
  • the polymer dispersant it is preferable to use a polymer dispersant having an amine value.
  • Disparon (registered trademark) DA-325 amine value: 14 mgKOH / g
  • Disparon DA-234 amine value: 20 mgKOH / g
  • DA-703-50 amine value: 40 mgKOH / g
  • Ajispar (registered trademark) PB821 (amine value: 10 mgKOH / g), Ajisper PB822 (amine value: 17 mgKOH / g), Ajisper PB824 (amine value: 17 mgKOH / g), Ajisper PB881 (amine value: 17 mgKOH / g) g) (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), Efka (registered trademark) PU4046 (amine value: 19 mgKOH / g), Efka PX4300 (amine value: 56 mgKOH / g), Efka PX4320 (amine value: 28 mgKOH / g), Efka PX4330 (amine value: 28 mgKOH / g), Efka PX4350 (amine value: 12 mgKOH / g), Efka PX4700 (amine value: 60 mgKOH / g), Efka P
  • the shape of the light scattering particles various shapes such as spherical, filamentary, and indefinite shapes can be used.
  • the light-scattering particles it is possible to use particles having less directionality as the particle shape (for example, particles having a spherical shape, a regular tetrahedron shape, etc.), so that the uniformity, fluidity, and light scattering of the light emitting particle-containing ink composition can be obtained. It is preferable in that the sex can be further enhanced.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the luminescent particle-containing ink composition is 0.05 ⁇ m or more, 0.2 ⁇ m or more, and 0.3 ⁇ m or more from the viewpoint of being superior in the effect of reducing leakage light. Is preferable.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the luminescent particle-containing ink composition is 1.0 ⁇ m or less, 0.6 ⁇ m or less, 0. It is preferably 4 ⁇ m or less.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the luminescent particle-containing ink composition is 0.05 to 1.0 ⁇ m, 0.05 to 0.6 ⁇ m, 0.05 to 0.4 ⁇ m, and 0.
  • the average particle diameter (volume average diameter) of the light-scattering particles used is preferably 50 nm or more and 1000 nm or less.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the luminescent particle-containing ink 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 to be used can be obtained by measuring the particle diameter of each particle with, for example, a transmission electron microscope or a scanning electron microscope, and calculating the volume average diameter.
  • a ball mill for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like is used.
  • a ball mill for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like is used.
  • a ball mill for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like is used.
  • the content of the light-scattering particles is 0.1% by mass or more, 1% by mass or more, and 5% by mass or more, based on the mass of the non-volatile content of the light-emitting particle-containing ink composition, from the viewpoint of being more excellent in the effect of reducing leakage light. , 7% by mass or more, preferably 10% by mass or more, and preferably 12% by mass or more.
  • the content of the light-scattering particles is 60% by mass or less and 50% by mass or less based on the mass of the non-volatile content of the light-emitting particle-containing ink composition from the viewpoint of excellent effect of reducing leakage light and excellent ejection stability.
  • the light-emitting particle-containing ink composition contains a polymer dispersant, the light-scattering particles can be satisfactorily dispersed even when the content of the light-scattering particles is within the above range.
  • the mass ratio of the content of the light-scattering particles to the content of the light-emitting particles 90 is 0.1 or more and 0 from the viewpoint of being more excellent in reducing light leakage. It is preferably 2 or more and 0.5 or more.
  • the mass ratio (nanoparticles containing light-scattering particles / luminescent nanoparticles) is 5.0 or less, 2.0 or less, and 1 from the viewpoint of excellent light leakage reduction effect and continuous ejection property during inkjet printing. It is preferably 5.5 or less.
  • the reduction of leaked light by the light-scattering particles is considered to be due to the following mechanism.
  • the backlight light in the absence of the 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 light-emitting particles 90.
  • the backlight light when the light-scattering particles are present in the same pixel portion as the light-emitting particles 90, the backlight light is scattered in all directions in the pixel portion, and the light-emitting particles 90 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 considered that such a mechanism makes it possible to prevent light leakage.
  • the content of the light-scattering particles is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, and 2 to 8% by mass, based on the total mass of the ink composition. It is particularly preferable to have.
  • Photopolymerizable compound contained in the ink composition of the present invention is a compound that functions as a binder in a cured product and is polymerized by irradiation with light (active energy rays), and is a photopolymerizable monomer or a photopolymerizable compound.
  • Monomers can be used. These are basically used together with a photopolymerization initiator.
  • the photopolymerizable compound a radical polymerizable compound, a cationically polymerizable compound, an anionic polymerizable compound and the like can be used, but from the viewpoint of quick curability, it is preferable to use a radically polymerizable compound.
  • the radically polymerizable compound is, for example, a compound having an ethylenically unsaturated group.
  • the ethylenically unsaturated group means a group having an ethylenically unsaturated bond (polymerizable carbon-carbon double bond).
  • the number of ethylenically unsaturated bonds (for example, the number of ethylenically unsaturated groups) in the compound having an ethylenically unsaturated group is, for example, 1 to 4.
  • Examples of the compound having an ethylenically unsaturated group include a compound having an ethylenically unsaturated group such as a vinyl group, a vinylene group, a vinylidene group, and a (meth) acryloyl group. From the viewpoint of further improving the external quantum efficiency, a compound having a (meth) acryloyl group is preferable, a monofunctional or polyfunctional (meth) acrylate is more preferable, and a monofunctional or bifunctional (meth) acrylate is further preferable. preferable.
  • "(meth) acryloyl group” means "acryloyl group” and the corresponding "methacryloyl group”.
  • the monofunctional (meth) acrylate means a (meth) acrylate having one (meth) acryloyl group
  • the polyfunctional (meth) acrylate has two or more (meth) acryloyl groups
  • Meta means acrylate.
  • 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 is a bifunctional (meth) acrylate, a trifunctional (meth) acrylate, a tetrafunctional (meth) acrylate, a pentafunctional (meth) acrylate, a hexafunctional (meth) acrylate, or the like.
  • 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.
  • Acrylate or the like can be used.
  • bifunctional (meth) acrylate examples include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di (meth) acrylate.
  • Di (meth) acrylate substituted with an oxy group Two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol were substituted with a (meth) acryloyloxy group.
  • Di (meth) acrylate Di (meth) acrylate in which the two hydroxyl groups of the diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A are substituted with (meth) acryloyloxy groups, 1 mol.
  • Di (meth) acrylate in which two hydroxyl groups of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to trimethylolpropane in the above are substituted with (meth) acryloyloxy groups, and 4 mol in 1 mol of bisphenol A.
  • Examples thereof include di (meth) acrylate in which the two hydroxyl groups of the above ethylene oxide or the diol obtained by adding the propylene oxide are substituted with a (meth) acryloyloxy group.
  • trifunctional (meth) acrylate examples include, for example, trimethylolpropane tri (meth) acrylate, glycerin triacrylate, pentaerythritol tri (meth) acrylate, 1 mol of trimethylolpropane and 3 mol or more of ethylene oxide or propylene.
  • examples thereof include tri (meth) acrylate in which the three hydroxyl groups of triol obtained by adding an oxide are substituted with a (meth) acryloyloxy group.
  • tetrafunctional (meth) acrylate examples include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.
  • pentafunctional (meth) acrylate examples include dipentaerythritol penta (meth) acrylate and the like.
  • hexafunctional (meth) acrylate examples include dipentaerythritol hexa (meth) acrylate and the like.
  • the photopolymerizable compound when the curable component is composed of only a photopolymerizable compound or a main component thereof, the photopolymerizable compound has two or more polymerizable functional groups in one molecule 2 It is more preferable to use a photopolymerizable compound having a functionality or higher as an essential component because the durability (strength, heat resistance, etc.) of the cured product can be further enhanced.
  • the molecular weight of the photopolymerizable compound is, for example, 50 or more, and may be 100 or more or 150 or more.
  • the molecular weight of the photopolymerizable compound is, for example, 500 or less, and may be 400 or less or 300 or less. From the viewpoint of easily achieving both the viscosity of the inkjet ink and the volatility of the ink after ejection, it is preferably 50 to 500, and more preferably 100 to 400.
  • the cyclic structure may be an aromatic ring structure or a non-aromatic ring structure.
  • the number of cyclic structures (total number of aromatic rings and non-aromatic rings) is 1 or 2 or more, but preferably 3 or less.
  • the number of carbon atoms constituting the cyclic structure is, for example, 4 or more, and preferably 5 or more or 6 or more.
  • the number of carbon atoms is, for example, 20 or less, preferably 18 or less.
  • the aromatic ring structure is preferably a structure having an aromatic ring having 6 to 18 carbon atoms.
  • the aromatic ring having 6 to 18 carbon atoms include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring and the like.
  • the aromatic ring structure may be a structure having an aromatic heterocycle. Examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a pyran ring, a pyridine ring and the like.
  • the number of aromatic rings may be 1 or 2 or more, but is preferably 3 or less.
  • the organic group may have a structure (for example, a biphenyl structure) in which two or more aromatic rings are bonded by a single bond.
  • the non-aromatic ring structure is preferably a structure having, for example, an alicyclic having 5 to 20 carbon atoms.
  • the alicyclic ring having 5 to 20 carbon atoms include a cycloalkane ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring, a cycloalkene ring such as a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.
  • a cycloalkane ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring
  • a cycloalkene ring such as a cyclopenten
  • the alicyclic ring may be a fused ring such as a bicycloundecane ring, a decahydronaphthalene ring, a norbornene ring, a norbornadiene ring, or an isobornyl ring.
  • the non-aromatic ring structure may be a structure having a non-aromatic heterocycle. Examples of the non-aromatic heterocycle include a tetrahydrofuran ring, a pyrrolidine ring, a tetrahydropyran ring, a piperidine ring and the like.
  • the radically polymerizable compound having a cyclic structure is preferably a monofunctional or polyfunctional (meth) acrylate having a cyclic structure, and more preferably a monofunctional (meth) acrylate having a cyclic structure.
  • phenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, biphenyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and the like are available. It is preferably used.
  • the content of the radically polymerizable compound having a cyclic structure is from the viewpoint of easily suppressing the stickiness (tack) of the surface of the ink composition, and from the viewpoint of easily obtaining an appropriate viscosity as an inkjet ink and easily obtaining excellent ejection properties.
  • Based on the total mass of the photopolymerizable compound in the ink composition it is preferably 3 to 85% by mass, more preferably 5 to 65% by mass, and further preferably 10 to 45% by mass. It is preferably 15 to 35% by mass, and particularly preferably 15 to 35% by mass.
  • a radically polymerizable compound having a linear structure having 3 or more carbon atoms as the ink composition, and having a linear structure having 4 or more carbon atoms. It is more preferable to use a radically polymerizable compound.
  • the linear structure represents a hydrocarbon chain having 3 or more carbon atoms.
  • a hydrogen atom directly connected to a carbon atom constituting the linear structure may be substituted with a methyl group or an ethyl group, but the number of substitutions may be 3 or less. preferable.
  • the radically polymerizable compound having a linear structure having 4 or more carbon atoms preferably has a structure in which atoms other than hydrogen atoms are connected without branching, and other than carbon atoms and hydrogen atoms. In addition, it may have a hetero atom such as an oxygen atom. That is, the linear structure is not limited to a structure in which three or more carbon atoms are linearly continuous, and is a structure in which three or more carbon atoms are linearly connected via a hetero atom such as an oxygen atom. May be good.
  • the linear structure may have unsaturated bonds, but preferably consists only of saturated bonds.
  • the number of carbon atoms constituting the linear structure is preferably 5 or more, more preferably 6 or more, and further preferably 7 or more.
  • the number of carbon atoms constituting the linear structure is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.
  • radical polymerization having a linear structure in which the total number of carbon atoms is 3 or more is not included in the number.
  • the sex compound preferably does not have a cyclic structure from the viewpoint of ejection property.
  • the linear structure is preferably, for example, a structure having a linear alkyl group having 4 or more carbon atoms.
  • the linear alkyl group having 4 or more carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group.
  • an alkyl (meth) acrylate in which the linear alkyl group is directly bonded to the (meth) acryloyloxy group is preferably used.
  • the linear structure is preferably, for example, a structure having a linear alkylene group having 4 or more carbon atoms.
  • the linear alkylene group having 4 or more carbon atoms include a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group and a pentadecylene group.
  • a butylene group a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group and a pentadecylene
  • an alkylene glycol di (meth) acrylate in which two (meth) acryloyloxy groups are bonded by the above-mentioned linear alkylene group is preferably used.
  • the linear structure is preferably, for example, a structure in which a linear alkyl group and one or more linear alkylene groups are bonded via an oxygen atom (a structure having an alkyl (poly) oxyalkylene group).
  • the number of linear alkylene groups is 2 or more, preferably 6 or less. When the number of linear alkylene groups is 2 or more, the 2 or more alkylene groups may be the same or different.
  • the number of carbon atoms of the linear alkyl group and the linear alkylene group may be 1 or more, may be 2 or more or 3 or more, but is preferably 4 or less.
  • linear alkyl group examples include the above-mentioned linear alkyl group having 4 or more carbon atoms, as well as a methyl group, an ethyl group and a propyl group.
  • linear alkylene group examples include the above-mentioned linear alkylene group having 4 or more carbon atoms, a methylene group, an ethylene group and a propylene group.
  • an alkyl (poly) oxyalkylene (meth) acrylate in which the above-mentioned alkyl (poly) oxyalkylene group is directly bonded to the (meth) acryloyloxy group is preferably used.
  • the content of the radically polymerizable compound having a linear structure having 3 or more carbon atoms is excellent in the viewpoint that an appropriate viscosity can be easily obtained as an ink jet ink, an excellent ejection property can be easily obtained, and the curability of the ink composition is excellent.
  • it is preferably 10 to 90% by mass, preferably 15 to 80% by mass, based on the total mass of the photopolymerizable compound in the ink composition. It is more preferably%, and particularly preferably 20 to 70% by mass.
  • the photopolymerizable compound it is preferable to use two or more kinds of radically polymerizable compounds from the viewpoint of excellent surface uniformity of the pixel portion, and the above-mentioned radically polymerizable compound having a cyclic structure and the above-mentioned number of carbon atoms are used. It is more preferable to use in combination with a radically polymerizable compound having a linear structure of 3 or more.
  • the amount of nanoparticles containing luminescent nanocrystals is increased in order to improve the external quantum efficiency, the uniformity of the surface of the pixel portion may decrease. Even in such a case, the above-mentioned light According to the combination of the polymerizable compounds, there is a tendency to obtain a pixel portion having excellent surface uniformity.
  • the content M of the radically polymerizable compound having a cyclic structure is used.
  • the mass ratio ( ML / MC) of the content ML of the radically polymerizable compound having a linear structure having 3 or more carbon atoms to C is 0 . It is preferably 05 to 5, more preferably 0.1 to 3.5, and particularly preferably 0.1 to 2.
  • the photopolymerizable compound is preferably alkali-insoluble from the viewpoint that a highly reliable pixel portion (cured product of the ink composition) can be easily obtained.
  • the fact that the photopolymerizable compound is alkali-insoluble means that the amount of the photopolymerizable compound dissolved in 1% by mass of potassium hydroxide aqueous solution at 25 ° C. is 30 based on the total mass of the photopolymerizable compound. It means that it is not more than% by mass.
  • the dissolved amount of the photopolymerizable compound is preferably 10% by mass or less, more preferably 3% by mass or less.
  • the content of the photopolymerizable compound contained in the ink composition is from the viewpoint that an appropriate viscosity can be easily obtained as an inkjet ink, from the viewpoint of improving the curability of the ink composition, and the pixel portion (ink composition). From the viewpoint of improving the solvent resistance and abrasion resistance of the cured product, and from the viewpoint of obtaining better optical characteristics (for example, external quantum efficiency), 70 to 95 mass based on the total mass of the ink composition. %, More preferably 75 to 93% by mass, and even more preferably 80 to 90% by mass.
  • Photopolymerization Initiator examples of the photopolymerization initiator used in the ink composition of the present invention include a photoradical polymerization initiator.
  • a 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-dimethylamino-1.
  • -(4-Morphorinophenyl) -butane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide Etc. are preferably used.
  • molecular cleavage type photoradical polymerization initiators include 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 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, 4-benzoyl-4'-methyl-diphenylsulfide and the like.
  • a molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.
  • the photopolymerization initiator used in the ink composition of the present invention preferably contains at least one acylphosphine oxide-based compound.
  • at least one acylphosphine oxide-based compound it has a narrow spectrum in the ⁇ 15 nanometer range centered on a specific wavelength, such as 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers. It is suitable and preferable for an ultraviolet light emitting diode (UV-LED) having an output.
  • UV-LED ultraviolet light emitting diode
  • an acylphosphine oxide-based compound when used as the photopolymerization initiator, it is more preferable to use one or more monoacylphosphine phosphine oxide-based compounds and one or more bisacylphosphine phosphine oxide-based compounds in combination. By using these in combination, it is possible to surely achieve both reduction of ink viscosity and suppression of precipitation of the photopolymerizable initiator.
  • the monoacylphosphine phosphine oxide-based compound is not particularly limited, and is, for example, 2,4,6-trimethylbenzoyldiphenylphosphine phosphine oxide, ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine phosphine oxide, 2,4.
  • Examples thereof include 6-triethylbenzoyldiphenylphosphine oxide and 2,4,6-triphenylbenzoyldiphenylphosphine oxide.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable.
  • Monoacylphosphine oxide compounds include, for example, Omnirad (registered trademark) TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) and Omnirad TPO-L (ethoxyphenyl (2,4,6-). Trimethylbenzoyl) phosphine oxide) (above, manufactured by IGM Resins BV).
  • the bisacylphosphine oxide-based compound is not particularly limited, and is, for example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl.
  • Examples include phosphine oxide.
  • bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is preferable.
  • bisacylphosphine oxide compounds examples include Omnirad 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide) (manufactured by IGM Resins BV).
  • the content of the photopolymerization initiator is determined from the viewpoint of solubility in a photopolymerizable compound, the viewpoint of curability of the ink composition, and the stability over time of the pixel portion (cured product of the ink composition) (maintenance and stability of external quantum efficiency). From the viewpoint of property), it is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 1 to 10% by mass with respect to 100% by mass of the photopolymerizable compound. It is more preferably present, and particularly preferably 3 to 7% by mass.
  • the reactive silicone compound in the present invention is a silicone compound having a polymerizable functional group. Specifically, it has one or more radically polymerizable functional groups and has a dimethylsiloxane structure as a repeating unit. Didimethylpolysiloxane is also called polydimethylsiloxane.
  • the reactive silicone compound is preferably a silicone compound having a structural unit represented by the following formula (I) and having a polymerizable functional group at at least one end of the structural unit via a spacer group.
  • the spacer group represents a divalent linking group. Examples of the divalent linking group include -O-, -N-, an alkylene group, an alkyl ether group, and an alkyl ester group.
  • the reactive silicone compound is preferably a silicone compound in which the reactive silicone compound has a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). ..
  • X represents a linear or branched alkylene group having 1 to 30 carbon atoms, but one of the alkylene groups-CH 2 -or two or more non-adjacent groups-.
  • CH 2- may be independently substituted with a group selected from -O-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, and the alkylene thereof. Any hydrogen atom in the group may be substituted with a hydroxy group, where R 1 represents a hydrogen atom or a polymerizable functional group.
  • the reactive silicone compound contains a plurality of structural units represented by the formula (II), the plurality of R 1s may be the same as or different from each other.
  • the structural unit represented by the above formula (I) and the structural unit represented by the formula (II) may be randomly arranged.
  • an acryloyl group and a methacryloyl group are preferable from the viewpoint of being easily immobilized in the coating film by a curing process in an ink composition containing a radically polymerizable photopolymerizable compound.
  • the reactive silicone compound may contain one or more of the reactive silicone compounds in the ink composition.
  • the number of polymerizable groups in the reactive silicone compound is preferably a bifunctional or higher functional compound for the purpose of improving the crosslink density, and the reactive silicone compound has an acryloyl group or a methacryloyl group at both ends, or a reaction.
  • a compound having an acryloyl group or a methacryloyl group at the end of the side chain of the sex silicone compound is more preferable.
  • reactive silicone compound for example, polymers represented by the following formulas (2a) and (2b) are preferable.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms
  • R 4 and R 5 are carbons which may independently have a substituent.
  • An alkylene group having 1 to 3 atoms and an alkyleneoxy group having 1 to 3 carbon atoms are represented, and R 6 and R 7 independently represent a methacryloyl group and an acryloyl group, respectively.
  • Z 1 and Z 2 represent a linear or branched alkylene group having 1 to 10 carbon atoms, which may be independently substituted with a hetero atom containing an oxygen atom, a nitrogen atom and a sulfur atom, respectively. , Z 1 and Z 2 may appear the same or different from each other.
  • n1 and n1 independently represent an integer of 1 to 100
  • m2 represents an integer of 1 to 75
  • p1 and q1 each independently represent an integer of 0 to 10, but satisfy p1 + q1> 0.
  • S1 and s2 each independently represent an integer of 0 to 20.
  • the reactive silicone compound represented by the general formula (2a) specifically, from the viewpoint that the hydroxy group derived from the alkylene ether group or the glycidyl group existing in the side chain has excellent compatibility with the photopolymerizable compound, specifically. It is preferably represented by the following general formulas (2a-1) and (2a-2).
  • R 8 represents a hydrogen atom or a methyl group
  • p11 represents an integer of 10 to 15
  • q11 represents an integer of 0 to 5
  • m11 represents 20.
  • n11 represents an integer of 1 to 5
  • m12 represents an integer of 1 to 5
  • n12 represents an integer of 1 to 5.
  • Examples of the reactive silicone compound represented by the general formula (2a-1) include Tego® Rad2300 (molecular weight 2000-4500, viscosity 200-700 mPa ⁇ s) and Tego Rad2200N (molecular weight 2000-4500, viscosity 700). 2,500 mPa ⁇ s), Tego Rad2250 (molecular weight 1500-4500, viscosity 250-700 mPa ⁇ s) and the like.
  • Examples of the reactive silicone compound represented by the general formula (2a-2) include Tego Rad2100 (molecular weight 1000-2500, viscosity 590 mPa ⁇ s) and Tego Rad2500 (molecular weight 1000-2500, viscosity 150 mPa ⁇ s) (above, Degusa) and the like.
  • the reactive silicone compound represented by the general formula (2b) is specifically described by the following general formula (from the viewpoint that the alkyl group or alkylene ether group present in the main chain has excellent compatibility with the photopolymerizable compound. It is preferably represented by 2b-1).
  • R 9 represents a hydrogen atom or a methyl group
  • X 12 and X 22 each independently represent an alkylene group having 2 to 6 carbon atoms and a single bond.
  • One -CH 2- or two or more non-adjacent -CH 2- in an alkylene group is independently selected from -O-, -CO-, -COO-, and -OCO-, respectively.
  • Z 12 and Z 22 independently represent —O—, —N—, an alkylene group, a single bond
  • m21 represents an integer from 1 to 75
  • s21 and s22 represent, respectively. Independently represents an integer from 1 to 100.
  • Examples of the reactive silicone compound represented by the general formula (2b-1) include X-22-164B (molecular weight 3200, viscosity 54 mPa ⁇ s), X-22-164C (molecular weight 4800, viscosity 88 mPa ⁇ s).
  • X-24-164E molecular weight 7200, viscosity 184 mPa ⁇ s
  • X-22-2445 molecular weight 3200, viscosity 54 mPa ⁇ s) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
  • BYK-UV3500 molecular weight 5000, viscosity 470 mPa ⁇ s).
  • BYK-UV3570 molecular weight 3000
  • the viscosity of the reactive silicone compound at 25 ° C. is preferably 50 mPa ⁇ s or more, 100 mPa ⁇ s or more, 500 mPa ⁇ s or more, and preferably 5000 mPa ⁇ s or less, or 3000 mPa ⁇ s or less.
  • the viscosity of the reactive silicone compound at 25 ° C. is measured by an E-type viscometer.
  • the weight average molecular weight Mw of the reactive silicone compound may be 1000 or more, 2000 or more, 5000 or more, or 10000 or more, and may be 500,000 or less, 100,000 or less, or 50,000 or less.
  • the molecular weight of the reactive silicone compound is a weight average molecular weight (Mw), which means a weight average molecular weight determined in terms of polystyrene as measured by gel permeation chromatography (GPC).
  • the content of the reactive silicone compound is 0.001% by mass or more with respect to the total amount of the non-volatile content of the ink composition from the viewpoint of further excellent compatibility with the inkjet process, optical properties and its reproducibility. It is preferably 0.01% by mass or more, and particularly preferably 0.02% by mass or more.
  • the content of the reactive silicone compound is based on the total amount of non-volatile components of the ink composition from the viewpoint of making the viscosity of the ink composition containing high-concentration luminescent nanocrystal particles more suitable for inkjet and the surface tension. It is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.
  • the content of the reactive silicone compound is the above-mentioned upper limit value from the viewpoint of suppressing the reaction of the reactive silicone compound with the photopolymerizable compound and the interaction with the luminescent nanocrystal particles to increase the viscosity.
  • the following is preferable.
  • the ink composition may further contain components other than the above-mentioned components as long as the effects of the present invention are not impaired.
  • examples of such components include antioxidants, polymerization inhibitors, sensitizers, dispersants, chain transfer agents, thermoplastic resins and the like.
  • Antioxidants Ink compositions may contain compounds that function as antioxidants as long as they do not interfere with the effects of the present invention.
  • examples of such compounds include conventionally known compounds such as phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • phenol-based antioxidants amine-based antioxidants
  • phosphorus-based antioxidants phosphorus-based antioxidants
  • sulfur-based antioxidants it is preferable to use a phenol-based antioxidant and a phosphoric acid ester-based antioxidant because they tend to further suppress the decrease in external quantum efficiency.
  • the phenolic antioxidant is preferably a hindered phenolic compound.
  • Specific examples of the hindered phenolic compound include, for example, "2,4,6-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylen" (product name: Adecastab (registered trademark).
  • phosphoric acid ester-based antioxidant examples include "tris phosphite” marketed as Adecastab 1178 (product name, manufactured by ADEKA Co., Ltd.), JP-351 (product name, manufactured by Johoku Chemical Industry Co., Ltd.) and the like.
  • Undecane "(melting point 237 ° C, molecular weight 633), Adecastab TPP (product name, manufactured by ADEKA Co., Ltd.), JP-360 (product) Commercially available as "Triphenylphosphite” (melting point 25 ° C., molecular weight 310), JP-351 (product name, manufactured by Johoku Chemical Industry Co., Ltd.), etc.
  • Trisnonylphenyl phosphite (melting point 20 ° C or less, molecular weight 689), JP-3CP “tricresylphosphite” (melting point 20 ° C or less, molecular weight 352), JP-302 (product name, manufactured by Johoku Chemical Industry Co., Ltd.) ) Etc.
  • Tridecylphosfite (melting point 20 ° C.) commercially available as 20 ° C. or lower, molecular weight 419), JP-310 (product name, manufactured by Johoku Chemical Industry Co., Ltd.), Adecastab 3010 (product name, manufactured by ADEKA Co., Ltd.), etc.
  • trilauryl phosphite (melting point 20 ° C. or lower, molecular weight 589)
  • JP-333 product name, Johoku
  • JP-312L product name, manufactured by Johoku Chemical Industry Co., Ltd.
  • Tris (tridecyl) phosphite (melting point 20 ° C or less, molecular weight 629), JP-318-O (product name, manufactured by Johoku Chemical Industry Co., Ltd.), etc.
  • Trioleyl phosphite (melting point 20 ° C or less, molecular weight 833), JPM-308 (product name, manufactured by Johoku Chemical Industry Co., Ltd.), Adecaster C (product name, manufactured by ADEKA Co., Ltd.), etc. are commercially available.
  • “Diphenylmonodecylphosphite” (melting point) commercially available as “diphenylmono (2-ethylhexyl) phosphite” (melting point 20 ° C. or less, molecular weight 346), JPM-311 (product name, manufactured by Johoku Chemical Industry Co., Ltd.), etc. 18 ° C, molecular weight 375), "diphenylmono (tridecyl) phosphite” (melting point 20 ° C or less, molecular weight 416), JA-805, which is commercially available as JPM-313 (product name, manufactured by Johoku Chemical Industry Co., Ltd.).
  • Tristearyl phosphite (melting point 45-52 ° C., molecular weight 839), HOSTANOX (registered trademark) P-EPQ (product name, manufactured by Clarianto Chemicals Co., Ltd.), etc.
  • Di-tert-butylphenyl) -1,1-biphenyl-4,4'-diylbisphosphonite "(melting point 85-100 ° C., molecular weight 1035) , GSY-P100 (product name, manufactured by Sakai Chemical Industry Co., Ltd.), etc.
  • the phosphoric acid ester-based antioxidant is preferably a phosphoric acid diester-based compound from the viewpoint of storage stability of the ink composition and suppression of a decrease in external quantum efficiency due to heat of the photoconversion layer.
  • the content of the antioxidant is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the ink composition, from the viewpoint that the decrease in external quantum efficiency is more likely to be suppressed. It is more preferably 1% by mass or more, and particularly preferably 5% by mass or more.
  • the content of the antioxidant is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, based on the total mass of the ink composition. It is particularly preferably 3% by mass or less.
  • the ink composition may further contain a polymerization inhibitor.
  • the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amine-based compounds, thioether-based compounds, N-oxyl compounds, nitroso-based compounds and the like.
  • the content of the polymerization inhibitor is preferably 0.01 to 1.0% by mass, preferably 0.02 to 0.5% by mass, based on the total amount of the photopolymerizable compounds contained in the ink composition. Is more preferable.
  • Sensitizer As the sensitizer, amines that do not cause an addition reaction with the photopolymerizable compound can be used. Examples of the sensitizer include trimethylamine, methyldimethylamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, 4, Examples thereof include 4'-bis (diethylamino) benzophenone.
  • Dispersant is not particularly limited as long as it is a compound capable of improving the dispersion stability of nanoparticles containing luminescent nanoparticles in the ink composition. Dispersants are classified into small molecule dispersants and high molecular dispersants. In the present specification, "small molecule” means a molecule having a weight average molecular weight (Mw) of 5,000 or less, and “polymer” means a molecule having a weight average molecular weight (Mw) of more than 5,000. Means. In the present specification, the value measured by gel permeation chromatography (GPC) using polystyrene as a standard material can be adopted as the "weight average molecular weight (Mw)".
  • GPC gel permeation chromatography
  • Examples of the low molecular weight dispersant include oleic acid; triethyl phosphate, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphine.
  • Phosphorus atom-containing compounds such as acid (OPA); nitrogen atom-containing compounds such as oleylamine, octylamine, trioctylamine, hexadecylamine; sulfur atoms such as 1-decanethiol, octanethiol, dodecanethiol, amylsulfide. Examples include contained compounds.
  • examples of the polymer dispersant include acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether resin, phenol resin, silicone resin, polyurea resin, amino resin, and polyamine resin.
  • Resins polyethyleneimine, polyallylamine, etc.
  • epoxy resins polyimide resins
  • wood rosins gum rosins
  • natural rosins such as tall oil rosins
  • polymerized rosins such as tall oil rosins
  • disproportionated rosins hydrogenated rosins
  • oxide rosins maleated rosins.
  • examples thereof include modified rosin, rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin derivatives such as rosin-modified phenol, and the like.
  • polymer dispersants include, for example, DISPERBYK (registered trademark) series manufactured by Big Chemie, TEGO Dispers series manufactured by Ebonic, EFKA series manufactured by BASF, and SOLSPERSE (registered trademark) series manufactured by Japan Lubrizol. , Ajinomoto Fine Techno Co., Ltd.'s Ajispar series, Kusumoto Kasei's DISPARLON (registered trademark) series, Kyoeisha Chemical Co., Ltd.'s Floren series, etc. can be used.
  • the blending amount of the dispersant is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the luminescent fine particles 910 and 90, respectively.
  • Chain transfer agent is a component used for the purpose of further improving the adhesion of the ink composition to the substrate.
  • chain transfer agent examples include aromatic hydrocarbons, halogenated hydrocarbons, mercaptan compounds, sulfide compounds and the like.
  • the amount of the chain transfer agent added is preferably 0.1 to 10% by mass, more preferably 1.0 to 5% by mass, based on the total amount of the photopolymerizable compound contained in the ink composition. ..
  • thermoplastic resin examples include urethane resin, acrylic resin, polyamide resin, polyimide resin, styrene maleic acid resin, styrene anhydride maleic acid resin, polyester acrylate resin and the like.
  • Viscosity of Ink Composition The viscosity of the ink composition according to the present invention is preferably 2 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, for example, from the viewpoint of ejection stability during inkjet printing. It is more preferably 7 mPa ⁇ s or more.
  • the viscosity of the ink composition is preferably 20 mPa ⁇ s or less, more preferably 15 mPa ⁇ s or less, and even more preferably 12 mPa ⁇ s or less.
  • the viscosity of the ink composition When the viscosity of the ink composition is 2 mPa ⁇ s or more, the meniscus shape of the ink composition at the tip of the ink ejection hole of the ejection head is stable, so that the ejection control of the ink composition (for example, the ejection amount and the ejection timing) Control) becomes easy.
  • the viscosity when the viscosity is 20 mPa ⁇ s or less, the ink composition can be smoothly ejected from the ink ejection holes.
  • the viscosity of the ink composition 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 ink composition is measured, for example, by an E-type viscometer.
  • the viscosity of the ink composition can be adjusted to a desired range by changing, for example, a photopolymerizable compound, a photopolymerization initiator, or the like.
  • the surface tension of the ink composition according to the present invention is preferably a surface tension suitable for an inkjet method, specifically, preferably in the range of 20 to 40 mN / m, 25. It is more preferably ⁇ 35 mN / m.
  • the flight bending means that when the ink composition is ejected from the ink ejection holes, the landing position of the ink composition deviates from the target position by 30 ⁇ m or more.
  • the surface tension is 40 mN / m or less, the meniscus shape at the tip of the ink ejection hole is stable, so that ejection control of the ink composition (for example, control of ejection amount and ejection timing) becomes easy.
  • the surface tension is 20 mN / m or less, the occurrence of flight bending can be suppressed. That is, a pixel portion may not be landed accurately on the pixel portion forming region to be landed, and the ink composition may be insufficiently filled, or a pixel portion forming region (or pixel portion) adjacent to the pixel portion forming region to be landed may be generated.
  • the ink composition does not land on the surface and the color reproducibility does not deteriorate.
  • the surface tension of the ink composition can be adjusted to a desired range by using, for example, the above-mentioned silicone-based surfactant, fluorine-based surfactant, or the like in combination.
  • an active energy ray-curable ink composition can be prepared by blending the above-mentioned components, and can be used as an ink for inkjet. ..
  • a specific method for preparing an ink composition for inkjet is to synthesize the luminescent particles 90 or luminescent particles 91 in an organic solvent, remove the organic solvent from the precipitate separated by centrifugation, and then obtain a photopolymerizable compound. Disperse.
  • Dispersion of the luminescent particles 90 or the luminescent particles 91 can be performed by using, for example, a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, a disperser such as an ultrasonic wave. Further, it can be prepared by adding a photopolymerization initiator and an antioxidant to this dispersion and stirring and mixing them.
  • a mill base is separately prepared by mixing the light-scattering particles and the polymer dispersant and dispersing the light-scattering particles in the photopolymerizable compound by a bead mill, and the photopolymerizable compound together with the light-emitting particles.
  • the ink composition can be obtained, for example, by mixing the constituent components of the above-mentioned ink composition and performing a dispersion treatment. Further, it can be obtained by individually mixing the constituent components, preparing a dispersion liquid having been subjected to a dispersion treatment as necessary, and mixing the respective dispersion liquids.
  • a method for producing an ink composition a method for producing an ink composition further containing light-scattering particles and a polymer dispersant will be described.
  • the dispersion liquid of the light scattering particles can be prepared by mixing the light scattering particles, the polymer dispersant and the photopolymerizable compound and performing the dispersion treatment.
  • the mixing and dispersion treatment can be performed using a dispersion device such as a bead mill, a paint conditioner, and a planetary stirrer.
  • a dispersion device such as a bead mill, a paint conditioner, and a planetary stirrer.
  • the method for preparing the ink composition may further include a step of preparing a dispersion liquid of luminescent particles containing luminescent particles and a photopolymerizable compound before the second step.
  • the dispersion liquid of the light-scattering particles, the dispersion liquid of the light-emitting particles, the photopolymerization initiator, and the antioxidant are mixed.
  • the luminescent particles can be sufficiently dispersed. Therefore, the leakage light in the pixel portion can be reduced, and an ink composition having excellent ejection stability can be easily obtained.
  • the luminescent particles and the photopolymerizable compound may be mixed and dispersed using the same dispersion device as in the step of preparing the dispersion liquid of the light scattering particles.
  • the ink composition of the present embodiment is used as an ink composition for an inkjet method, it is preferable to apply it to a piezojet type inkjet recording device using a mechanical ejection mechanism using a piezoelectric element.
  • the ink composition is not instantaneously exposed to a high temperature at the time of ejection, and deterioration of the light emitting particles is unlikely to occur. Therefore, a color filter pixel portion (light conversion layer) having desired light emission characteristics is obtained. be able to.
  • the ink composition of the above-described embodiment can be used, for example, by a photolithography method in addition to the inkjet method.
  • the ink composition contains an alkali-soluble resin as the binder polymer.
  • the ink composition When the ink composition is used by a photolithography method, the ink composition is first applied onto a substrate, and when the ink composition contains a solvent, the ink composition is further dried to form a coating film.
  • the coating film thus obtained is soluble in an alkaline developer and is patterned by being treated with an alkaline developer.
  • the alkaline developer is mostly an aqueous solution from the viewpoint of ease of waste liquid treatment of the developer, the coating film of the ink composition is treated with the aqueous solution.
  • the luminescent particles quantum dots or the like
  • the luminescent particles are unstable with respect to water, and the luminescence (for example, fluorescence) is impaired by water. Therefore, in this embodiment, an inkjet method that does not need to be treated with an alkaline developer (aqueous solution) is preferable.
  • the coating film of the ink composition is preferably alkali-insoluble. That is, the ink composition of the present embodiment is preferably an ink composition capable of forming an alkali-insoluble coating film.
  • Such an ink composition can be obtained by using an alkali-insoluble photopolymerizable compound as the photopolymerizable compound.
  • the coating film of the ink composition is alkaline insoluble means that the amount of the coating film of the ink composition dissolved at 25 ° C. in 1% by mass of the potassium hydroxide aqueous solution is based on the total mass of the coating film of the ink composition. It means that it is 30% by mass or less.
  • the dissolved amount of the coating film of the ink composition is preferably 10% by mass or less, and more preferably 3% by mass or less.
  • the fact that the ink composition is an ink composition capable of forming an alkali-insoluble coating film means that after the ink composition is applied on a substrate, it is dried at 80 ° C. for 3 minutes when it contains a solvent. It can be confirmed by measuring the above-mentioned dissolution amount of the obtained coating film having a thickness of 1 ⁇ m.
  • Emission Particle-Containing Ink Composition forms a film on a substrate by various methods such as an inkjet printer, photolithography, and a spin coater, and the film is heated and cured. A cured product can be obtained by allowing the particles to be obtained.
  • a case where the color filter pixel portion of the light emitting element provided with the blue organic LED backlight is formed of the light emitting particle-containing ink composition will be described as an example.
  • FIG. 3 is a cross-sectional view showing an embodiment of the light emitting device of the present invention
  • FIGS. 4 and 5 are schematic views showing the configuration of an active matrix circuit, respectively.
  • FIG. 3 for convenience, the dimensions of each part and their ratios are exaggerated and may differ from the actual ones. Further, the materials, dimensions, etc. shown below are examples, and the present invention is not limited thereto, and can be appropriately changed without changing the gist thereof.
  • the upper side of FIG. 3 is referred to as “upper side” or “upper side”, and the upper side is referred to as “lower side” or “lower side”. Further, in FIG. 3, in order to avoid complicating the drawing, the description of the hatching showing the cross section is omitted.
  • the light emitting element 100 includes a lower substrate 1, an EL light source unit 200, a packed layer 10, a protective layer 11, and a light conversion layer 12 containing light emitting particles 90 and acting as a light emitting layer. It has a structure in which the upper substrate 13 is laminated in this order.
  • the light emitting particles 90 contained in the light conversion layer 12 may be polymer-coated light emitting particles 90 or may be light emitting particles 91 not coated with the polymer layer 92.
  • the EL light source unit 200 includes an anode 2, an EL layer 14 composed of a plurality of layers, a cathode 8, a polarizing plate (not shown), and a sealing layer 9 in this order.
  • the EL layer 14 includes a hole injection layer 3 sequentially laminated from the anode 2 side, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7.
  • the light emitting element 100 is a photoluminescence element that absorbs and re-emits or transmits the light emitted from the EL light source unit 200 (EL layer 14) by the light conversion layer 12 and takes it out from the upper substrate 13 side to the outside. .. At this time, the light is converted into light of a predetermined color by the light emitting particles 90 contained in the light conversion layer 12.
  • each layer will be described in sequence.
  • the lower substrate 1 and the upper substrate 13 each have a function of supporting and / or protecting each layer constituting the light emitting element 100.
  • the upper substrate 13 is composed of a transparent substrate.
  • the lower substrate 1 is composed of a transparent substrate.
  • the transparent substrate means a substrate capable of transmitting light having a wavelength in the visible light region, and the transparency includes colorless transparent, colored transparent, and translucent.
  • the transparent substrate examples include quartz glass, Pylex (registered trademark) glass, a transparent glass substrate such as a synthetic quartz plate, a quartz substrate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyether sulfone (PES).
  • a plastic substrate (resin substrate) made of polyimide (PI), polycarbonate (PC) or the like, a metal substrate made of iron, stainless steel, aluminum, copper or the like, a silicon substrate, a gallium arsenic substrate or the like can be used.
  • PI polyimide
  • PC polycarbonate
  • metal substrate made of iron, stainless steel, aluminum, copper or the like
  • silicon substrate a gallium arsenic substrate or the like
  • the lower substrate 1 and the upper substrate 13 have a plastic substrate (a substrate composed of a polymer material as a main material) and a relatively small thickness, respectively.
  • the metal substrate is selected.
  • the thickness of the lower substrate 1 and the upper substrate 13 is not particularly limited, but is preferably in the range of 100 to 1,000 ⁇ m, and more preferably in the range of 300 to 800 ⁇ m.
  • either or both of the lower substrate 1 and the upper substrate 13 may be omitted depending on the usage pattern of the light emitting element 100.
  • a signal line drive circuit C1 and a scanning line drive circuit C2 for controlling the supply of current to the anode 2 constituting the pixel electrode PE represented by R, G, and B are provided.
  • a control circuit C3 for controlling the operation of these circuits, a plurality of signal lines 706 connected to the signal line drive circuit C1, and a plurality of scan lines 707 connected to the scan line drive circuit C2 are provided.
  • a capacitor 701, a drive transistor 702, and a switching transistor 708 are provided in the vicinity of the intersection of each signal line 706 and each scanning line 707.
  • one electrode is connected to the gate electrode of the drive transistor 702, and the other electrode is connected to the source electrode of the drive transistor 702.
  • the gate electrode is connected to one electrode of the capacitor 701
  • the source electrode is connected to the other electrode of the capacitor 701 and the power supply line 703 that supplies the drive current
  • the drain electrode is the anode 4 of the EL light source unit 200. It is connected to the.
  • the gate electrode is connected to the scanning line 707
  • the source electrode is connected to the signal line 706, and the drain electrode is connected to the gate electrode of the drive transistor 702.
  • the common electrode 705 constitutes the cathode 8 of the EL light source unit 200.
  • the drive transistor 702 and the switching transistor 708 can be configured by, for example, a thin film transistor or the like.
  • the scanning line drive circuit C2 supplies or cuts off the scanning voltage according to the scanning signal to the gate electrode of the switching transistor 708 via the scanning line 707, and turns the switching transistor 708 on or off. As a result, the scanning line driving circuit C2 adjusts the timing at which the signal line driving circuit C1 writes the signal voltage.
  • the signal line drive circuit C1 supplies or cuts off the signal voltage corresponding to the video signal to the gate electrode of the drive transistor 702 via the signal line 706 and the switching transistor 708, and supplies the signal current to the EL light source unit 200. Adjust the amount.
  • the scanning voltage is supplied from the scanning line drive circuit C2 to the gate electrode of the switching transistor 708, and when the switching transistor 708 is turned on, the signal voltage is supplied from the signal line driving circuit C1 to the gate electrode of the switching transistor 708.
  • the drain current corresponding to this signal voltage is supplied to the EL light source unit 200 as a signal current from the power supply line 703.
  • the EL light source unit 200 emits light according to the supplied signal current.
  • the anode 2 has a function of supplying holes from an external power source toward the light emitting layer 5.
  • the constituent material (anode material) of the anode 2 is not particularly limited, but for example, a metal such as gold (Au), a halogenated metal such as copper iodide (CuI), indium zinc oxide (ITO), and oxidation. Examples thereof include metal oxides such as tin (SnO 2 ) and zinc oxide (ZnO). These may be used alone or in combination of two or more.
  • the thickness of the anode 2 is not particularly limited, but is preferably in the range of 10 to 1,000 nm, and more preferably in the range of 10 to 200 nm.
  • the anode 2 can be formed by, for example, a dry film forming method such as a vacuum vapor deposition method or a sputtering method. At this time, the anode 2 having a predetermined pattern may be formed by a photolithography method or a method using a mask.
  • the cathode 8 has a function of supplying electrons from an external power source toward the light emitting layer 5.
  • the constituent material (cathode material) of the cathode 8 is not particularly limited, and is, for example, lithium, sodium, magnesium, aluminum, silver, sodium-potassium alloy, magnesium / aluminum mixture, magnesium / silver mixture, magnesium / indium mixture, aluminum. / Aluminum oxide (Al 2 O 3 ) mixture, rare earth metals and the like can be mentioned. These may be used alone or in combination of two or more.
  • the thickness of the cathode 8 is not particularly limited, but is preferably in the range of 0.1 to 1,000 nm, and more preferably in the range of 1 to 200 nm.
  • the cathode 3 can be formed by, for example, a dry film forming method such as a vapor deposition method or a sputtering method.
  • the hole injection layer 3 has a function of receiving the holes supplied from the anode 2 and injecting them into the hole transport layer 4.
  • the hole injection layer 3 may be provided as needed and may be omitted.
  • the constituent material (hole injection material) of the hole injection layer 3 is not particularly limited, but is, for example, a phthalocyanine compound such as copper phthalocyanine; 4,4', 4''-tris [phenyl (m-tolyl) amino.
  • Triphenylamine derivatives such as triphenylamine; 1,4,5,8,9,12-hexazatriphenylene hexacarbonitrile, 2,3,5,6-tetrafluoro-7,7,8,8- Cyan compounds such as tetracyano-quinodimethane; vanadium oxide, metal oxides such as molybdenum oxide; amorphous carbon; polyaniline (emeraldine), poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT) -PSS), polymers such as polypyrrole, and the like.
  • the hole injection material a polymer is preferable, and PEDOT-PSS is more preferable.
  • the above-mentioned hole injection material may be used alone or in combination of two or more.
  • the thickness of the hole injection layer 3 is not particularly limited, but is preferably in the range of 0.1 to 500 mm, more preferably in the range of 1 to 300 nm, and further preferably in the range of 2 to 200 nm. preferable.
  • the hole injection layer 3 may have a single-layer structure or a laminated structure in which two or more layers are laminated.
  • Such a hole injection layer 4 can be formed by a wet film forming method or a dry film forming method.
  • a wet film forming method an ink containing the hole injection material described above is usually applied by various coating methods, and the obtained coating film is dried.
  • the coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, and a nozzle printing printing method. Can be mentioned.
  • a vacuum vapor deposition method, a sputtering method or the like can be preferably used.
  • the hole transport layer 4 has a function of receiving holes from the hole injection layer 3 and efficiently transporting them to the light emitting layer 6. Further, the hole transport layer 4 may have a function of preventing the transport of electrons. The hole transport layer 4 may be provided as needed and may be omitted.
  • the constituent material (hole transport material) of the hole transport layer 4 is not particularly limited, but for example, TPD (N, N'-diphenyl-N, N'-di (3-methylphenyl) -1,1'. -Biphenyl-4,4'diamine), ⁇ -NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4, 4', 4''- Low molecular weight triphenylamine derivatives such as tris (3-methylphenylphenylamino) triphenylamine); polyvinylcarbazole; poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) -Benzidine] (poly-TPA), polyfluorene (PF), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) -benzidine (Poly
  • the hole transporting material is preferably a triphenylamine derivative or a polymer compound obtained by polymerizing a triphenylamine derivative having a substituent introduced therein, and is preferably a bird having a substituent introduced therein. It is more preferable that it is a polymer compound obtained by polymerizing a phenylamine derivative.
  • the hole transporting material described above may be used alone or in combination of two or more.
  • the thickness of the hole transport layer 4 is not particularly limited, but is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 300 nm, and even more preferably in the range of 10 to 200 nm.
  • the hole transport layer 4 may have a single-layer structure or a laminated structure in which two or more layers are laminated.
  • Such a hole transport layer 4 can be formed by a wet film forming method or a dry film forming method.
  • a wet film forming method an ink containing the hole transport material described above is usually applied by various coating methods, and the obtained coating film is dried.
  • the coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, and a nozzle printing printing method. Can be mentioned.
  • a vacuum vapor deposition method, a sputtering method or the like can be preferably used.
  • the electron injection layer 7 has a function of receiving electrons supplied from the cathode 8 and injecting them into the electron transport layer 6.
  • the electron injection layer 7 may be provided as needed and may be omitted.
  • the constituent material (electron injection material) of the electron injection layer 7 is not particularly limited, and for example, alkali metal chalcogenides such as Li 2O , LiO, Na 2S, Na 2 Se , and NaO; CaO, BaO, SrO, and the like.
  • Alkali earth metal chalcogenides such as BeO, BaS, MgO, CaSe; alkali metal halides such as CsF, LiF, NaF, KF, LiCl, KCl, NaCl; alkalis such as 8-hydroxyquinolinolatrithium (Liq).
  • Metal salts examples include alkaline earth metal halides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 , BeF 2 .
  • alkali metal chalcogenides, alkaline earth metal halides, and alkali metal salts are preferable.
  • the above-mentioned electron injection material may be used alone or in combination of two or more.
  • the thickness of the electron injection layer 7 is not particularly limited, but is preferably in the range of 0.1 to 100 nm, more preferably in the range of 0.2 to 50 nm, and in the range of 0.5 to 10 nm. Is even more preferable.
  • the electron injection layer 7 may have a single-layer structure or a laminated structure in which two or more layers are laminated.
  • Such an electron injection layer 7 can be formed by a wet film forming method or a dry film forming method.
  • an ink containing the above-mentioned electron injection material is usually applied by various coating methods, and the obtained coating film is dried.
  • the coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, and a nozzle printing printing method. Can be mentioned.
  • a vacuum vapor deposition method, a sputtering method or the like can be applied.
  • the electron transport layer 8 has a function of receiving electrons from the electron injection layer 7 and efficiently transporting them to the light emitting layer 5. Further, the electron transport layer 8 may have a function of preventing the transport of holes. The electron transport layer 8 may be provided as needed and may be omitted.
  • the constituent material (electron transport material) of the electron transport layer 8 is not particularly limited, and for example, tris (8-quinolinate) aluminum (Alq3), tris (4-methyl-8-quinolinolate) aluminum (Almq3), bis ( 10-Hydroxybenzo [h] quinolinate) beryllium (BeBq2), bis (2-methyl-8-quinolinolate) (p-phenylphenolate) aluminum (BAlq), bis (8-quinolinolate) quinoline such as zinc (Znq) Metal complex with skeleton or benzoquinoline skeleton; metal complex with benzoxazoline skeleton such as bis [2- (2'-hydroxyphenyl) benzoxazolate] zinc (Zn (BOX) 2); bis [2- ( 2'-Hydroxyphenyl) benzothiazolate] Metal complex with a benzothiazolin skeleton such as zinc (Zn (BTZ) 2); 2- (4-biphenylyl) -5- (4-
  • the electron transport material is preferably an imidazole derivative, a pyridine derivative, a pyrimidine derivative, a triazine derivative, or a metal oxide (inorganic oxide).
  • the above-mentioned electron transport materials may be used alone or in combination of two or more.
  • the thickness of the electron transport layer 7 is not particularly limited, but is preferably in the range of 5 to 500 nm, and more preferably in the range of 5 to 200 nm.
  • the electron transport layer 6 may be a single layer or a stack of two or more.
  • Such an electron transport layer 7 can be formed by a wet film forming method or a dry film forming method.
  • an ink containing the above-mentioned electron transport material is usually applied by various coating methods, and the obtained coating film is dried.
  • the coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, and a nozzle printing printing method. Can be mentioned.
  • a vacuum vapor deposition method, a sputtering method or the like can be applied.
  • the light emitting layer 5 has a function of generating light emission by utilizing the energy generated by the recombination of holes and electrons injected into the light emitting layer 5.
  • the light emitting layer 5 of the present embodiment emits blue light having a wavelength in the range of 400 to 500 nm, and more preferably in the range of 420 to 480 nm.
  • the light emitting layer 5 preferably contains a light emitting material (guest material or dopant material) and a host material.
  • a light emitting material guest material or dopant material
  • the mass ratio of the host material and the light emitting material is not particularly limited, but is preferably in the range of 10: 1 to 300: 1.
  • the light emitting material a compound capable of converting singlet excitation energy into light or a compound capable of converting triplet excitation energy into light can be used.
  • the light emitting material preferably contains at least one selected from the group consisting of an organic small molecule fluorescent material, an organic polymer fluorescent material and an organic phosphorescent material.
  • Examples of the compound capable of converting the singlet excitation energy into light include an organic low molecular weight fluorescent material or an organic high molecular weight fluorescent material that emits fluorescence.
  • a compound having an anthracene structure, a tetracene structure, a chrysene structure, a phenanthrene structure, a pyrene structure, a perylene structure, a stylben structure, an acridone structure, a coumarin structure, a phenoxazine structure or a phenothiazine structure is preferable.
  • organic low molecular weight fluorescent material examples include, for example, 5,6-bis [4- (10-phenyl-9-anthryl) phenyl] -2,2'-bipyridine and 5,6-bis [4'-(. 10-Phenyl-9-anthril) biphenyl-4-yl] -2,2'-bipyridine (, N, N'-bis [4- (9H-carbazole-9-yl) phenyl] -N, N'-diphenyl Stilben-4,4'-diamine, 4- (9H-carbazole-9-yl) -4'-(10-phenyl-9-anthril) triphenylamine, 4- (9H-carbazole-9-yl) -4 '-(9,10-diphenyl-2-anthryl) triphenylamine, N, 9-diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazol
  • organic polymer fluorescent material examples include homopolymers consisting of units based on fluorene derivatives, copolymers consisting of units based on fluorene derivatives and units based on tetraphenylphenylenediamine derivatives, and units based on tarphenyl derivatives. Homopolymers, homopolymers consisting of units based on diphenylbenzofluorene derivatives, and the like.
  • an organic phosphorescent material that emits phosphorescence is preferable.
  • the organic phosphorescent material include, for example, a metal containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadrinium, palladium, silver, gold and aluminum. Examples include complexes.
  • a metal complex containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadrinium and palladium is preferable, and iridium, rhodium and platinum are preferable.
  • a metal complex containing at least one metal atom selected from the group consisting of and ruthenium is more preferable, and an iridium complex or a platinum complex is further preferable.
  • the host material it is preferable to use at least one compound having an energy gap larger than the energy gap of the light emitting material. Further, when the light emitting material is a phosphorescent material, it is possible to select a compound having a triplet excitation energy larger than the triplet excitation energy (energy difference between the ground state and the triplet excited state) of the light emitting material as the host material. preferable.
  • Examples of the host material include tris (8-quinolinolato) aluminum (III), tris (4-methyl-8-quinolinolato) aluminum (III), bis (10-hydroxybenzo [h] quinolinato) berylium (II), and bis.
  • the thickness of the light emitting layer 5 is not particularly limited, but is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 50 nm.
  • Such a light emitting layer 5 can be formed by a wet film forming method or a dry film forming method.
  • a wet film forming method an ink containing the above-mentioned light emitting material and host material is usually applied by various coating methods, and the obtained coating film is dried.
  • the coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, and a nozzle printing printing method. Can be mentioned.
  • a dry film forming method a vacuum vapor deposition method, a sputtering method or the like can be applied.
  • the EL light source unit 200 may further have, for example, a bank (partition wall) for partitioning the hole injection layer 3, the hole transport layer 4, and the light emitting layer 5.
  • the height of the bank is not particularly limited, but is preferably in the range of 0.1 to 5 ⁇ m, more preferably in the range of 0.2 to 4 ⁇ m, and further preferably in the range of 0.2 to 3 ⁇ m. preferable.
  • the width of the opening of the bank is preferably in the range of 10 to 200 ⁇ m, more preferably in the range of 30 to 200 ⁇ m, and even more preferably in the range of 50 to 100 ⁇ m.
  • the length of the bank opening is preferably in the range of 10 to 400 ⁇ m, more preferably in the range of 20 to 200 ⁇ m, and even more preferably in the range of 50 to 200 ⁇ m.
  • the inclination angle of the bank is preferably in the range of 10 to 100 °, more preferably in the range of 10 to 90 °, and further preferably in the range of 10 to 80 °.
  • the light conversion layer 12 converts the light emitted from the EL light source unit 200 and re-emits it, or transmits the light emitted from the EL light source unit 200.
  • a first pixel unit 20a that converts light having a wavelength in the above range to emit red light
  • a second pixel unit 20a that converts light having a wavelength in the above range to emit green light
  • 20b and a third pixel portion 20c that transmits light having a wavelength in the above range.
  • a plurality of first pixel portions 20a, second pixel portions 20b, and third pixel portions 20c are arranged in a grid pattern so as to repeat in this order.
  • a light-shielding portion 30 that shields light is provided between the 20c and the first pixel portion 20a. In other words, these adjacent pixel portions are separated from each other by the light-shielding portion 30.
  • the first pixel portion 20a and the second pixel portion 20b may include a coloring material corresponding to each color.
  • the first pixel portion 20a and the second pixel portion 20b each contain a cured product of the luminescent particle-containing ink composition of the above-described embodiment. It is preferable that the cured product contains the luminescent particles 90 and the cured component as essential, and further contains light-scattering particles in order to scatter the light and surely take it out to the outside.
  • the curing component is a cured product of a thermosetting resin, for example, a cured product obtained by polymerizing a resin containing an epoxy group. That is, the first pixel portion 20a includes a first curing component 22a, a first light emitting particle 90a and a first light scattering particle 21a dispersed in the first curing component 22a, respectively.
  • the second pixel portion 20b includes a second curing component 22b, a first light emitting particle 90b and a first light scattering particle 21b dispersed in the second curing component 22b, respectively.
  • the first curing component 22a and the second curing component 22b may be the same or different, and may be the same as or different from the first light scattering particles 22a. It may be the same as or different from the second light-scattering particle 22b.
  • the first light emitting particle 90a is a red light emitting particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having a light emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel portion 20a may be paraphrased as a red pixel portion for converting blue light into red light.
  • the second light emitting particle 90b is a green light emitting particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having a light emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 20b may be paraphrased as a green pixel portion for converting blue light into green light.
  • the content of the luminescent particles 90 in the pixel portions 20a and 20b containing the cured product of the luminescent particle-containing ink composition is a luminescent particle-containing ink composition from the viewpoint of being excellent in the effect of improving the external quantum efficiency and being able to obtain excellent luminescent intensity. It is preferably 0.1% by mass or more based on the total mass of the cured product of the product. From the same viewpoint, the content of the luminescent particles 90 is 1% by mass or more, 2% by mass or more, 3% by mass or more, and 5% by mass or more, based on the total mass of the cured product of the luminescent particles-containing ink composition. Is preferable.
  • the content of the luminescent particles 90 is preferably 30% by mass or less based on the total mass of the luminescent particles-containing ink composition from the viewpoint of excellent reliability of the pixel portions 20a and 20b and excellent luminescence intensity. be. From the same viewpoint, the content of the luminescent particles 90 is 25% by mass or less, 20% by mass or less, 15% by mass or less, and 10% by mass or less based on the total mass of the cured product of the luminescent particles-containing ink composition. It is preferable to have.
  • the content of the light-scattering particles 21a and 21b in the pixel portions 20a and 20b containing the cured product of the luminescent particle-containing ink composition is the total mass of the cured product of the ink composition from the viewpoint of being more excellent in the effect of improving the external quantum efficiency. As a reference, it is preferably 0.1% by mass or more, 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, and 12% by mass or more.
  • the content of the light-scattering particles 21a and 21b is 60% by mass or less based on the total mass of the cured product of the ink composition from the viewpoint of excellent effect of improving the external quantum efficiency and excellent reliability of the pixel portion 20. , 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, and preferably 15% by mass or less.
  • the third pixel portion 20c 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 20c 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 20c contains, for example, a cured product of the composition containing the thermosetting resin described above.
  • the cured product contains 22 cc of a third cured component.
  • the third curing component 22c is a cured product of a thermosetting resin, and specifically, is a cured product obtained by polymerizing a resin containing an epoxy group. That is, the third pixel portion 20c contains the third curing component 22c.
  • the composition containing the thermosetting resin emits the above-mentioned light emission as long as the transmittance for light having a wavelength in the range of 420 to 480 nm is 30% or more.
  • the transmittance of the third pixel unit 20c can be measured by a microspectroscopy device.
  • the thickness of the pixel portion is not particularly limited, but is preferably 1 ⁇ m or more, 2 ⁇ m or more, and 3 ⁇ m or more, for example.
  • the thickness of the pixel portion is preferably, for example, 30 ⁇ m or less, 25 ⁇ m or less, and 20 ⁇ m or less.
  • the optical conversion layer 12 including the first to third pixel portions 20a to 20c can be formed by drying, heating and curing the coating film formed by the wet film forming method.
  • the first pixel portion 20a and the second pixel portion 20b can be formed by using the luminescent particle-containing ink composition of the present invention, and the third pixel portion 20c is included in the luminescent particle-containing ink composition. It can be formed by using an ink composition that does not contain luminescent particles 90.
  • the method for forming a coating film using the luminescent particle-containing ink composition of the present invention will be described in detail, but the same can be performed when the luminescent particle-containing ink composition of the present invention is used.
  • the coating method for obtaining the coating film of the luminescent particle-containing ink composition of the present invention is not particularly limited, and is, for example, an inkjet printing method (piezo method or thermal method droplet ejection method), a spin coat method, or a casting method. , LB method, letterpress printing method, gravure printing method, screen printing method, nozzle printing printing method and the like.
  • the nozzle print printing method is a method of applying a light emitting particle-containing ink composition as a liquid column from a nozzle hole in a striped shape.
  • an inkjet printing method is preferable as the coating method.
  • the heat load when ejecting the light-emitting particle-containing ink composition can be reduced, and deterioration of the light-emitting particles 90 due to heat can be prevented.
  • the ejection amount of the luminescent particle-containing ink composition is not particularly limited, but is preferably 1 to 50 pL / time, more preferably 1 to 30 pL / time, and further preferably 1 to 20 pL / time. ..
  • the opening diameter of the nozzle hole is preferably in the range of 5 to 50 ⁇ m, and more preferably in the range of 10 to 30 ⁇ m. This makes it possible to improve the ejection accuracy of the luminescent particle-containing ink composition while preventing clogging of the nozzle holes.
  • the temperature at which the coating film is formed is not particularly limited, but is preferably in the range of 10 to 50 ° C, more preferably in the range of 15 to 40 ° C, and preferably in the range of 15 to 30 ° C. More preferred. By ejecting the droplets at such a temperature, crystallization of various components contained in the luminescent particle-containing ink composition can be suppressed.
  • the relative humidity at the time of forming the coating film is also not particularly limited, but is preferably in the range of 0.01 ppm to 80%, more preferably in the range of 0.05 ppm to 60%, and 0.1 ppm. It is more preferably in the range of ⁇ 15%, particularly preferably in the range of 1 ppm to 1%, and most preferably in the range of 5 to 100 ppm.
  • the relative humidity is at least the above lower limit value, it becomes easy to control the conditions when forming the coating film.
  • the relative humidity is not more than the above upper limit value, the amount of water adsorbed on the coating film which may adversely affect the obtained light conversion layer 12 can be reduced.
  • the organic solvent is contained in the luminescent particle-containing ink composition
  • the drying may be carried out by leaving it at room temperature (25 ° C.) or by heating, but it is preferably carried out by heating from the viewpoint of productivity.
  • the drying temperature is not particularly limited, but it is preferably a temperature in consideration of the boiling point and the vapor pressure of the organic solvent used in the luminescent particle-containing ink composition.
  • the drying temperature is preferably 50 to 130 ° C., more preferably 60 to 120 ° C., and particularly preferably 70 to 110 ° C. as a prebaking step for removing the organic solvent in the coating film.
  • the drying temperature is 50 ° C. or lower, the organic solvent may not be removed, while if the drying temperature is 130 ° C. or higher, the organic solvent may be removed instantaneously and the appearance of the coating film may be significantly deteriorated, which is not preferable.
  • the drying is preferably performed under reduced pressure, more preferably under reduced pressure of 0.001 to 100 Pa.
  • the drying time is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, and particularly preferably 1 to 10 minutes.
  • the luminescent particle-containing ink composition of the present invention can be cured by irradiation with active energy rays (for example, ultraviolet rays).
  • active energy rays for example, ultraviolet rays.
  • the irradiation source for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like is used, but the LED is preferable from the viewpoint of reducing the heat load on the coating film and low power consumption.
  • the wavelength of the irradiated light is preferably 250 nm to 440 nm, more preferably 300 nm to 400 nm. When an LED is used, it is preferably 350 nm or more and 400 nm or less, for example, from the viewpoint of sufficiently curing a film thickness of 10 ⁇ m or more.
  • the light intensity is preferably 0.2 to 2 kW / cm 2 , more preferably 0.4 to 1 kW / cm 2 . A light intensity of less than 0.2 kW / cm 2 cannot sufficiently cure the coating film, and a light intensity of 2 kW / cm 2 or more causes unevenness in the curing degree between the surface and the inside of the coating film, resulting in smoothness of the coating film surface.
  • the irradiation amount (exposure amount) of light is preferably 10 mJ / cm 2 or more, and more preferably 4000 mJ / cm 2 or less.
  • the coating film can be cured in the air or in an inert gas, but more preferably in an inert gas in order to suppress oxygen inhibition on the surface of the coating film and oxidation of the coating film.
  • the inert gas include nitrogen, argon, carbon dioxide and the like.
  • the light-emitting particle ink composition of the present invention is excellent in heat stability, good light emission can be realized even in the pixel portion 20 which is a molded product after thermosetting. Furthermore, since the luminescent particle composition of the present invention is excellent in dispersibility, it is possible to obtain a flat pixel portion 20 with excellent dispersibility of the luminescent particles 90.
  • the light emitting particles 90 contained in the first pixel portion 20a and the second pixel portion 20b contain semiconductor nanocrystals having a perovskite type, the absorption in the wavelength region of 300 to 500 nm is large. Therefore, in the first pixel portion 20a and the second pixel portion 20b, the blue light incident on the first pixel portion 20a and the second pixel portion 20b is transmitted to the upper substrate 13 side, that is, the blue light is on the upper side. It is possible to prevent leakage to the substrate 13 side. Therefore, according to the first pixel unit 20a and the second pixel unit 20b of the present invention, it is possible to extract red light and green light having high color purity without mixing blue light.
  • the light-shielding portion 30 is a so-called black matrix provided for the purpose of separating adjacent pixel portions 20 to prevent color mixing and for the purpose of preventing light leakage from a light source.
  • the material constituting the light-shielding portion 30 is not particularly limited, and the curing of an ink composition containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a 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 resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein and cellulose, photosensitive resin, and O / W.
  • An emulsion-type ink composition (for example, an emulsion of reactive silicone) or the like can be used.
  • the thickness of the light-shielding portion 30 is preferably, for example, 1 ⁇ m or more and 15 ⁇ m or less.
  • the light emitting element 100 can be configured as a bottom emission type instead of the top emission type. Further, the light emitting element 100 may use another light source instead of the EL light source unit 200.
  • the light-emitting particle-containing ink composition of the present invention a method for producing the same, and a light-emitting element provided with a light conversion layer manufactured by using the ink composition have been described above.
  • the luminescent particles, the luminescent particle dispersion, the luminescent particle-containing ink composition, and the luminescent device of the present invention may each have any other additional configuration in the configuration of the above-described embodiment. , May be replaced with any configuration that performs a similar function.
  • the method for producing luminescent particles of the present invention may have other arbitrary steps of interest in the configuration of the above-described embodiment, or may be replaced with any step of exhibiting the same effect. good.
  • the operation of producing luminescent particles and the operation of producing an ink composition containing luminescent particles were performed in a glove box filled with nitrogen or in a flask with the atmosphere blocked and a nitrogen stream.
  • all the raw materials exemplified below were used after replacing the atmosphere in the container with the nitrogen gas introduced into the container.
  • the liquid material was used after replacing the dissolved oxygen in the liquid material with the nitrogen gas introduced into the container.
  • the isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, and 1,6-hexanediol dimethacrylate used below were previously dehydrated with molecular sieves (using 3A or 4A) for 48 hours or more. Titanium oxide was heated at 120 ° C. for 2 hours under a reduced pressure of 1 mmHg and allowed to cool in a nitrogen gas atmosphere before use.
  • ⁇ Preparation of luminescent particle dispersion> (Preparation of luminescent particle dispersion liquid 1) First, 0.12 g of cesium carbonate, 5 mL of 1-octadecene and 0.5 mL of oleic acid were mixed to obtain a mixed solution. Next, this mixed solution was dried under reduced pressure at 120 ° C. for 30 minutes, and then heated at 150 ° C. under an argon atmosphere. This gave a cesium-oleic acid solution.
  • the luminescent particles X-1 were perovskite-type lead cesium bromide crystals having a surface layer, and the average particle size was 10 nm as observed by a transmission electron microscope.
  • the surface layer was a layer composed of 3-aminopropyltriethoxysilane, and its thickness was about 1 nm. That is, the luminescent particles X-1 are particles coated with silica.
  • a luminescent particle dispersion liquid 1 in which the luminescent particles X-1 were dispersed was obtained.
  • the luminescent particles X-2 were perovskite-type lead cesium tribromide crystals having a surface layer, and the average particle size was 11 nm as observed by a transmission electron microscope.
  • the surface layer was a layer composed of 3-aminopropyltriethoxysilane, and its thickness was about 1 nm. That is, the luminescent particles X-2 are particles coated with silica.
  • a luminescent particle dispersion liquid 2 in which the luminescent particles X-2 were dispersed was obtained.
  • the mixed solution in the four-necked flask was stirred at room temperature for 30 minutes, then heated to 80 ° C., and the reaction was continued at the same temperature for 15 hours.
  • the polymer that was not adsorbed on the luminescent particles A in the reaction solution was separated by centrifugation, and then the precipitated particles were vacuum dried at room temperature for 2 hours to obtain the luminescent particles X-2 as mother particles.
  • Polymer-coated luminescent particles X-3 having a surface coated with a polymer layer made of a hydrophobic polymer were obtained.
  • the obtained polymer-coated luminescent particles X-3 were observed with a transmission electron microscope, a polymer layer having a thickness of about 10 nm was formed on the surface of the luminescent particles X-3. Then, the obtained polymer-coated luminescent particles X-3 were dispersed in isobornyl methacrylate so that the solid content concentration was 2.5% by mass to obtain a luminescent particle dispersion liquid 3.
  • silica particles of "SiliNax (registered trademark) SP-PN (b)" manufactured by Nittetsu Mining Co., Ltd. were used.
  • the hollow particles are entirely rectangular parallelepiped and are silica particles having a hollow structure, and have an average outer diameter of 100 nm and an average inner diameter of 80 nm.
  • the hollow silica particles were dried under reduced pressure at 150 ° C. for 8 hours.
  • 200.0 parts by mass of the dried hollow silica particles were weighed in a Kiriyama funnel.
  • the hollow silica particles are supplied to the three-necked flask, the obtained lead tribromide solution is impregnated into the hollow silica particles, and then the excess lead tribromide cesium solution is removed by filtration to form a solid. I recovered the thing. Then, the obtained solid material was dried under reduced pressure at 120 ° C. for 1 hour to obtain luminescent particles X-4 in which nanocrystals composed of perovskite-type lead cesium tribromide were encapsulated in hollow silica particles.
  • the luminescent particles X-4 are hollow particle-encapsulating luminescent particles.
  • a luminescent particle dispersion liquid 4 in which the luminescent particles X-4 were dispersed was obtained.
  • the luminescent particles X-4 as the mother particles are made of a hydrophobic polymer in the same manner as the polymer-coated luminescent particles X-3, except that the luminescent particles X-4 are used instead of the luminescent particles X-1.
  • Polymer-coated luminescent particles X-5 coated with a layer were obtained.
  • the light emitting particle dispersion liquid 5 was obtained in the same manner as the light emitting particle dispersion liquid 3 except that the polymer-coated light emitting particles X-5 were used instead of the polymer-coated light emitting particles X-3 as the light emitting particles.
  • Preparation of light-scattering particle dispersion liquid 1 In a container filled with nitrogen gas, 10.0 parts by mass of titanium oxide (“CR60-2” manufactured by Ishihara Sangyo Co., Ltd.) and polymer dispersant “Efka PX4701” (amine value: 40.0 mgKOH / g, BASF Japan) 1.0 part by mass of phenoxyethyl methacrylate (light ester PO; manufactured by Kyoeisha Chemical Co., Ltd.) 14.0 parts by mass was mixed.
  • titanium oxide CR60-2” manufactured by Ishihara Sangyo Co., Ltd.
  • polymer dispersant “Efka PX4701” amine value: 40.0 mgKOH / g, BASF Japan
  • zirconia beads (diameter: 1.25 mm) were added to the obtained formulation, the container was sealed tightly, and the mixture was shaken for 2 hours using a paint conditioner to disperse the formulation, resulting in light-scattering particles. Dispersion 1 was obtained. The average particle size of the light-scattering particles after the dispersion treatment was 0.245 ⁇ m as measured by using NANOTRAC WAVE II.
  • 0.05 parts by mass and BYK-UV3500 (manufactured by Big Chemie Japan Co., Ltd.) 0.01 parts by mass as a reactive silicone compound are mixed in a container filled with argon gas. After uniformly dissolving, the dissolved compound was filtered in a glove box with a filter having a pore size of 5 ⁇ m. Further, argon gas was introduced into a container containing the obtained filtered substance, and the inside of the container was saturated with argon gas. Next, the ink composition (1) was obtained by reducing the pressure and removing the argon gas. The content of the luminescent particles was 1.5% by mass, and the content of IB-X was 58.5% by mass.
  • the LM content is 7.4% by mass
  • the PO content is 4.2% by mass
  • the 1,6-HX content is 20.0% by mass
  • TPO-H The content of is 3.0% by mass
  • the content of 819 is 1.0% by mass
  • the content of P-EPQ is 0.5% by mass
  • the content of Irganox 1010 is 0.5% by mass.
  • the content of the reactive silicone compound is 0.1% by mass.
  • the content of the light-scattering particles was 3.0% by mass
  • the content of the polymer dispersant was 0.3% by mass. The content is based on the total mass of the ink composition.
  • Example 1 ⁇ Nozzle plate liquid repellent >> As an evaluation of suitability for the inkjet process, the liquid repellency to the nozzle plate was evaluated. Specifically, the nozzle plate of an inkjet head (MH5421F) manufactured by Ricoh Co., Ltd. was brought into contact with the ink composition (1) and allowed to stand for 5 minutes. After that, the nozzle plate was pulled up vertically and the ink on the nozzle plate was slid off. When the initial liquid repellency to the nozzle plate was evaluated by observing the area of the ink remaining on the nozzle plate after being pulled up vertically, the area of the remaining ink was less than 20%, which was very good. rice field.
  • MH5421F inkjet head manufactured by Ricoh Co., Ltd.
  • the nozzle plate was allowed to stand at 50 ° C. for one week with the nozzle plate in contact with the ink composition (1), and then the plate was pulled up vertically and the ink was slid down in the same manner as described above.
  • the area of the residual ink was less than 20%, which was very good.
  • Inkjet ejection property evaluation >> The ink composition (1) was continuously ejected for 10 minutes using an inkjet printer (manufactured by Fujifilm Dimatics, "DMP-2831"). As a result, among the 16 nozzles, there were 10 or more nozzles that could normally eject after continuous ejection, and the ejection performance was good. In addition, 16 nozzles are formed in the head portion for ejecting ink of this inkjet printer, and the ejection amount of the ink composition ejected from one nozzle at one ejection is set to 10 pL. Evaluation was performed. [Evaluation criteria] A (Very good): Of the 16 nozzles, 13 or more nozzles can be ejected normally.
  • B (good): Of the 16 nozzles, 9 to 12 nozzles can be ejected normally.
  • D (defective): 5 to 0 nozzles that can be ejected normally out of 16 nozzles.
  • UV irradiation is performed with a UV irradiation device using an LED lamp having a main wavelength of 395 nm so that the integrated light amount is 1500 mJ / cm 2 , and a coating film (light conversion layer) made of a cured product of the ink composition is applied onto a glass substrate.
  • a coating film (light conversion layer) made of a cured product of the ink composition is applied onto a glass substrate.
  • step 2 These steps 1 and 2 were repeated 10 times to obtain 10 coating film samples (optical conversion layers) for evaluating the reproducibility of inkjet printing. When the optical density (OD) of these 10 coating film samples was measured and the variation was evaluated, the variation was less than 3%.
  • the method of measuring OD was as follows.
  • a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd. was used as a surface emission light source, and a light conversion filter was installed on this light source with the glass substrate side facing down.
  • An integrating sphere was connected to a radiation spectrophotometer (trade name "MCPD-9800") manufactured by Otsuka Electronics Co., Ltd., and the integrating sphere was brought close to the optical conversion filter installed on the blue LED.
  • the blue LED was turned on, and the intensity Is of the observed blue light (wavelength range of 380 to 500 nm) was measured.
  • the intensity I 0 of the blue light when only the glass substrate was installed was also measured.
  • the optical density (OD) is expressed by the following equation and represents the degree of blue light absorbed by the optical conversion filter.
  • a large OD means that the light conversion filter absorbs blue light well, that is, it is a good light conversion layer with less leakage light.
  • OD -log (Is / I 0 )
  • ⁇ Bleed test >> The obtained light conversion layer 1 was allowed to stand at 60 ° C. for 30 days, and then allowed to stand at 25 ° C. for 1 day, and the surface of the obtained coating film was visually observed, and the presence or absence of bleeding (from the coating film) was observed. Whether or not the eluted components ooze out on the surface of the coating film) was confirmed. [Evaluation criteria] ⁇ : No bleed ⁇ : With bleed (no whitening due to eluted components) ⁇ : With bleeding (with whitening due to eluted components)
  • Example 2 to 12 Using the ink compositions (2) to (12) of the present invention, the nozzle plate liquid repellency, inkjet ejection property, and optical characteristics reproducibility of the ink compositions (2) to (12) are the same as in Example 1. , Bleed resistance was evaluated.
  • Comparative Examples 1 to 3 Using the comparative ink compositions (C1) to (C3), the nozzle plates of the comparative ink compositions (C1) to (C3) have the same liquid repellency, inkjet ejection property, and optical properties as in Example 1. Reproducibility and bleed resistance were evaluated.
  • the ink compositions of Examples 1 to 12 and Comparative Examples 1 to 3 and the light conversion layer prepared by using them will be examined.
  • the ink composition of Comparative Example 1 containing neither a reactive silicone compound nor a non-reactive silicone compound has poor liquid repellency of the nozzle plate and poor inkjet ejection property.
  • the optical conversion layer formed by using the ink composition of Comparative Example 1 has a large variation in optical characteristics and low reproducibility of optical characteristics. ..
  • the ink compositions of Comparative Examples 2 and 3 containing the non-reactive silicone compound have poor liquid repellency of the nozzle plate and poor inkjet ejection property. It is clear that the optical conversion layer formed by using the ink compositions of Comparative Examples 2 and 3 cannot withstand actual use because the optical characteristics vary greatly and the bleed resistance is also inferior.
  • the ink compositions of Examples 1 to 12 containing the reactive silicone compound contain the reactive silicone compound, they are excellent in the liquid repellency of the nozzle plate and the ejection property of the inkjet, and also.
  • the optical conversion layer formed from the ink compositions of Examples 1 to 12 is used, the variation in optical characteristics is small and the bleed resistance is also good.
  • the ink compositions of Examples 1 to 12 have better inkjet suitability as compared with Comparative Examples 1 to 3, and when they form an optical conversion layer, there is little variation in optical characteristics. It is clear that it is an excellent optical conversion layer without bleeding of the surface conditioner. Therefore, when the color filter pixel portion of the light emitting element is configured by using these light conversion layers, it can be expected that excellent light emission characteristics can be obtained.
  • Light emitting element 200 EL light source part 1 Lower substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode 9 Sealing layer 10 Filling layer 11 Protective layer 12 Optical conversion layer 13 Upper substrate 14 EL layer 20 pixel part, 20a 1st pixel part 20b 2nd pixel part 20c 3rd pixel part 21a 1st light-scattering particle 21b 2nd light-scattering particle 21c 3rd light-scattering particle 22a 1st hardening component 22b second 2 Curing component 22c 3rd curing component 90a 1st light emitting particle 90b 1st light emitting particle 30 light shielding part 90 light emitting particle, polymer coated particle 91 light emitting particle 911 nanocrystal 912 hollow nanoparticle 912a hollow part 912b pore 913 intermediate Layer 914 Surface layer 92 Polymer layer 701 Condenser 702 Drive transistor 705 Common electrode 706 Signal line 707 Scan

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  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Luminescent Compositions (AREA)
  • Optical Filters (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention vise à fournir une composition d'encre très appropriée pour un procédé à jet d'encre et pouvant former un film de revêtement à caractéristiques optiques et reproductibilité supérieures, et à fournir un produit durci, une couche de conversion de lumière et un filtre coloré dans lequel ladite composition d'encre est utilisée. La présente invention concerne à cet effet une composition d'encre comprenant : des nanoparticules qui comprennent des nanocristaux produisant de la lumière ; des particules diffusant la lumière ; un composé photopolymérisable ; un initiateur de photopolymérisation ; et un composé de silicone réactif.
PCT/JP2021/040510 2020-11-19 2021-11-04 Composition d'encre, couche de conversion de lumière et filtre coloré Ceased WO2022107598A1 (fr)

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JP2022563685A JP7311055B2 (ja) 2020-11-19 2021-11-04 インク組成物、光変換層およびカラーフィルタ
KR1020237014370A KR20230107797A (ko) 2020-11-19 2021-11-04 잉크 조성물, 광 변환층 및 컬러 필터
CN202180067395.5A CN116323827A (zh) 2020-11-19 2021-11-04 墨液组合物、光转换层及滤色器

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KR20250026630A (ko) 2023-08-17 2025-02-25 현대모비스 주식회사 차량용 램프

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CN116323827A (zh) 2023-06-23
KR20230107797A (ko) 2023-07-18

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