WO2022107601A1 - Composition d'encre pour jet d'encre, couche de conversion de lumière et filtre coloré - Google Patents

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

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WO2022107601A1
WO2022107601A1 PCT/JP2021/040513 JP2021040513W WO2022107601A1 WO 2022107601 A1 WO2022107601 A1 WO 2022107601A1 JP 2021040513 W JP2021040513 W JP 2021040513W WO 2022107601 A1 WO2022107601 A1 WO 2022107601A1
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Prior art keywords
ink composition
particles
acrylate
meth
group
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PCT/JP2021/040513
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English (en)
Japanese (ja)
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浩一 延藤
良夫 青木
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Dic株式会社
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Priority to JP2022503524A priority Critical patent/JP7151929B1/ja
Priority to KR1020237014369A priority patent/KR102557679B1/ko
Priority to CN202180067336.8A priority patent/CN116249756A/zh
Publication of WO2022107601A1 publication Critical patent/WO2022107601A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • 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

Definitions

  • the present invention relates to an ink jet ink composition, a light conversion layer, and a color filter.
  • Patent Document 1 discloses an ink jet ink composition containing luminescent nanocrystal particles made of core / shell type semiconductor nanocrystals, and a wavelength conversion member made of a cured film of the composition.
  • Luminescent nanocrystal particles such as semiconductor nanocrystals are prone to deterioration due to light irradiation in the presence of water vapor, oxygen, etc.
  • the light conversion layer is heated by strong light from the backlight, there is a problem that the luminescent nanocrystal particles are deteriorated by light irradiation at a high temperature and the light emission intensity is lowered.
  • a technique for enhancing the light resistance of the obtained cured film in a high temperature environment by adding a hindered amine compound to a curable composition containing core / shell type semiconductor nanocrystals has been developed. It has been proposed (see Patent Document 2).
  • 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 set. It also has the advantage of being small.
  • the problem to be solved by the present invention is an ink composition for inkjet containing semiconductor nanocrystals made of metal halide, which can form a cured film having excellent light resistance at high temperatures, and light conversion using the ink composition. It is an object of the present invention to provide a layer and a color filter.
  • the present inventors have obtained a cured film having excellent light resistance at high temperatures when the hindered amine compound has a specific structure in an ink composition for inkjet containing semiconductor nanocrystals made of metal halide. We found that it can be formed and came up with the present invention.
  • the ink composition for inkjet of the present invention has a structure represented by the following formula (1), which is a luminescent particle containing semiconductor nanocrystal particles made of metal halide, a photopolymerizable compound, and a photopolymerization initiator. It is characterized by containing a NOR-type hindered amine compound.
  • R 1 to R 5 each independently represent a hydrocarbon group, and * indicates a bond.
  • the melting point of the NOR type hindered amine compound is 70 ° C. or higher.
  • the molecular weight of the NOR-type hindered amine compound is preferably 1000 or more.
  • the luminescent particles are particles having a surface layer formed on the surface of the semiconductor nanocrystal particles, and the surface layer is a silane having a binding group and a hydrolyzable silyl group that can be bonded to the surface of the semiconductor nanocrystal particles. It preferably contains a polymer of the compound.
  • the luminescent particles further include an inner space capable of accommodating the semiconductor nanocrystal particles and hollow particles having pores communicating with the inner space, and the semiconductor nanocrystal particles are accommodated in the inner space. You may.
  • the SP value of the photopolymerizable compound is preferably 10.0 or less. It is preferable that the photopolymerizable compound has a cyclic structure.
  • the ink composition preferably further contains light-scattering particles.
  • the ink composition preferably further contains a polymer dispersant.
  • the viscosity of the ink composition at 30 ° C. is preferably 7 to 12 mPa ⁇ s.
  • Another aspect of the present invention includes a plurality of pixel portions and a light-shielding portion provided between the plurality of pixel portions, and the plurality of pixel portions emit light including a cured product of the ink jet ink composition.
  • the present invention relates to an optical conversion layer having a sex pixel portion.
  • Another aspect of the present invention relates to a color filter including the above-mentioned optical conversion layer.
  • an ink jet ink composition capable of forming a cured film having excellent light resistance at high temperatures.
  • an optical conversion layer and a color filter using the ink composition for inkjet.
  • FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.
  • the ink composition includes luminescent particles containing semiconductor nanocrystal particles made of metal halide (hereinafter, also simply referred to as “nanocrystal particles”), a photopolymerizable compound, a photopolymerization initiator, and a description below. It contains a NOR-type hindered amine compound represented by the formula (1).
  • the ink composition is, for example, an ink composition for forming an optical conversion layer (for example, for forming a color filter pixel portion) used for forming an optical conversion layer (pixel portion of the optical conversion layer) of a color filter or the like. May be.
  • the ink composition is a composition (inkjet ink) used in an ultraviolet curable inkjet method.
  • Luminous particles include nanocrystalline particles.
  • Nanocrystal particles are nano-sized crystals (nanocrystal particles) composed of metal halides, which absorb excitation light and emit fluorescence or phosphorescence.
  • a luminescent nanocrystal made of a metal halide for example, a quantum dot having a perovskite-type crystal structure described later is widely known.
  • the nanocrystal particles are, for example, crystals having a maximum particle size of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope.
  • the nanocrystal particles can be excited by, for example, light energy or electrical energy of a predetermined wavelength and emit fluorescence or phosphorescence.
  • the nanocrystal particles made of metal halide are compounds 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 chloride ion, bromide ion, iodide ion, cyanide ion and the like, and include at least one halogen.
  • a is 1 to 7
  • b is 1 to 4, and c is 3 to 16.
  • the emission wavelength (emission color) of such nanocrystal particles can be controlled by adjusting the particle size, the type of anion constituting the X-site, and the abundance ratio.
  • 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 9 , A 3 M 3 X 9 , A 2 M 2 X 10 , A 7 M 3 X 16 are preferred.
  • A is at least one of an organic cation and a metal cation.
  • 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. Examples thereof include cations (M 1 ⁇ M 2 ⁇ M 3 ⁇ M 4 ⁇ ).
  • 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 is adjusted by adjusting its particle size, the type and abundance ratio of the metal cations constituting the M site.
  • the emission wavelength can be controlled by adjusting the type and abundance ratio of the anions constituting the X-site, which is particularly preferable for use as a luminescent nanocrystal. 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.
  • 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.
  • 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, 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.
  • the nanocrystal particles may be red light emitting crystals that emit light having an emission peak in the wavelength range of 605 to 665 nm (red light), and may emit light having an emission peak in the wavelength range of 500 to 560 nm (green light). It may be a green luminescent crystal that emits light, or may be a blue luminescent crystal that emits light (blue light) having an emission peak in the wavelength range of 420 to 480 nm. Further, in one embodiment, a combination of these nanocrystal particles may be used. The wavelength of the emission peak of the nanocrystal particles 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 nanocrystal particles 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-emitting nanocrystal particles 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-emitting nanocrystal particles 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 particles is not particularly limited, and may be any geometric shape or any irregular shape.
  • Examples of the shape of the nanocrystal particles include a rectangular parallelepiped shape, a cubic shape, a spherical shape, a regular tetrahedron shape, an ellipsoidal shape, a pyramidal shape, a disc shape, a branch shape, a net shape, a rod shape and the like.
  • the shape of the nanocrystal particles is preferably a rectangular parallelepiped shape, a cube shape, or a spherical shape.
  • the average particle diameter (volume average diameter) of the nanocrystal particles 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 nanocrystal particles is preferably 1 nm or more, more preferably 1.5 nm or more, and further preferably 2 nm or more. Nanocrystal particles having such an average particle size are preferable because they easily emit light having a desired wavelength.
  • the average particle size of the nanocrystal particles is obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
  • the luminescent particles are preferably particles further comprising a surface layer formed on the surface of the nanocrystal particles.
  • the surface layer preferably contains a polymer of a silane compound having a bondable group and a hydrolyzable silyl group that can be bonded to the surface of the semiconductor nanocrystal particles.
  • the binding group that can be bound to the surface of the nanocrystal particles may be a binding group that binds (coordinates) to a cation contained in the nanocrystal particles.
  • the binding group 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. ..
  • the binding group is preferably at least one of a carboxyl group, a mercapto group and an amino group.
  • binding groups have a higher affinity for the cations contained in the nanocrystal particles than the hydrolyzable silyl group described above. Therefore, the silane compound can be coordinated with the binding group on the nanocrystal particle side to more easily and surely form nanocrystal particles having a surface layer.
  • the silane compound is formed by a reaction between precursor compounds having a binding group and a hydrolyzable silyl group.
  • the hydrolyzable silyl group can easily form a siloxane bond.
  • As the hydrolyzable silyl group a silanol group and an alkoxysilyl group having 1 to 6 carbon atoms are preferable.
  • a silane compound having a binding group and a hydrolyzable silyl group may be used alone, or two or more kinds may be used in combination.
  • the precursor compound may contain one or more compounds selected from the group consisting of a carboxyl group-containing silicon compound, an amino group-containing silicon compound, and a mercapto group-containing silicon compound.
  • 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- (2).
  • mercapto group-containing silicon compound examples include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 2-mercaptoethyl.
  • the thickness of the surface layer is preferably 0.5 to 50 nm, more preferably 1.0 to 30 nm. Luminescent particles having a surface layer having such a thickness can sufficiently enhance the heat stability of the nanocrystal particles.
  • the thickness of the surface layer can be changed by adjusting the number of atoms (chain length) of the linking structure in which the binding group and the hydrolyzable silyl group of the precursor compound are linked.
  • the surface layer comprises mixing a solution containing a raw material compound for nanocrystal particles and a solution containing a precursor compound, and then condensing a hydrolyzable silyl group coordinated with the surface of the precipitated nanocrystal particles.
  • the luminescent particles may further include an inner space containing the nanocrystal particles and hollow particles having pores communicating with the inner space. Since the nanocrystal particles are contained inside the hollow particles, the stability of the luminescent particles with respect to oxygen gas and moisture can be further improved.
  • the hollow particles may have a spherical shape (true spherical shape), an elongated spherical shape (elliptical spherical shape), or a cubic shape (including a rectangular parallelepiped and a cube). Hollow particles can also be referred to as particles having a balloon structure.
  • One nanocrystal particle may be present in the inner space, or a plurality of nanocrystal particles may be present. Further, the inner space may be entirely occupied by one or a plurality of nanocrystal particles, or may be partially occupied.
  • the hollow particles may be any material as long as they can protect the nanocrystal particles. From the viewpoint of ease of synthesis, permeability, cost and the like, the hollow particles are preferably hollow silica particles, hollow alumina particles, hollow titanium oxide particles or hollow polymer particles, and are hollow silica particles or hollow alumina particles. More preferably, hollow silica particles are further preferable.
  • the average outer diameter of the hollow particles is not particularly limited, but is preferably 5 to 300 nm, more preferably 6 to 100 nm, further preferably 8 to 50 nm, and particularly preferably 10 to 25 nm. preferable.
  • the average inner diameter of the hollow silica particles is also not particularly limited, but is preferably 1 to 250 nm, more preferably 2 to 100 nm, still more preferably 3 to 50 nm, and 5 to 15 nm. Is particularly preferable. Hollow particles of this size can sufficiently enhance the heat stability of the nanocrystal particles.
  • the size of the pores is not particularly limited, but is preferably 0.5 to 10 nm, and more preferably 1 to 5 nm. In this case, the solution containing the raw material compound of the nanocrystal particles can be smoothly and surely filled in the inner space.
  • hollow silica particles can also be used for the hollow silica particles.
  • examples of such commercially available products include "SiliNax (registered trademark) SP-PN (b)” manufactured by Nittetsu Mining Co., Ltd.
  • the hollow particles are preferably hollow silica particles from the viewpoint of luminescence and dispersion characteristics in ink and the like, in addition to stabilizing the semiconductor nanocrystal particles.
  • the luminescent particles may further comprise a polymer layer containing a hydrophobic polymer.
  • the polymer layer may be located on the outermost layer of the luminescent particles, including the nanocrystal particles.
  • the polymer layer may be a layer that covers at least a portion of the surface layer.
  • the polymer layer may be a layer that covers at least a portion of the hollow silica.
  • the nanocrystal particles have a polymer layer, high stability to oxygen and moisture can be imparted to the luminescent particles.
  • the ink composition is prepared using the luminescent particles having a polymer layer, the dispersion stability of the luminescent particles can be improved.
  • the polymer layer is provided, the luminescent particles are less likely to aggregate when the ink composition is prepared, and the emission characteristics are less likely to be deteriorated due to the aggregation.
  • the polymer layer 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 mother particles can be uniformly dispersed.
  • the hydrophobic polymer can be very easily adsorbed on the mother particles to coat the polymer layer.
  • 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 mother particles and the polymer layer can be coated only by mixing the hydrophobic polymer and the mother particles in the non-aqueous solvent.
  • the polymer layer thus obtained is difficult to be removed from the mother particles even if the luminescent particles are washed with a solvent.
  • the dielectric constant of the non-aqueous solvent is preferably 10 or less, more preferably 6 or less, and particularly preferably 5 or less.
  • Preferred non-aqueous solvents are an aliphatic hydrocarbon solvent and an alicyclic hydrocarbon solvent, and an organic solvent containing at least one of them is preferable.
  • aliphatic hydrocarbon solvent or the alicyclic hydrocarbon solvent examples include n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and the like. Further, as long as the effect of the present invention is not impaired, a mixed solvent in which at least one of the aliphatic hydrocarbon solvent and the alicyclic hydrocarbon solvent is mixed with another organic solvent may be used as the non-aqueous solvent. good.
  • organic solvents examples include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, -n-butyl acetate and amyl acetate; acetone, methyl ethyl ketone and methyl isobutyl.
  • Ketone solvents such as ketones, methylamylketones and cyclohexanones
  • alcoholic solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol and the like can be mentioned.
  • the amount of at least one of the aliphatic hydrocarbon solvent and the alicyclic hydrocarbon solvent is preferably 50% by mass or more, more preferably 60% by mass or more. preferable.
  • the polymer (P) is a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent.
  • the polymer (P) is polymerizable unsaturated, mainly composed of an alkyl (meth) acrylate (A) having an alkyl group having 4 or more carbon atoms or a fluorine-containing compound (B, C) having a polymerizable unsaturated group.
  • a polymer in which a polymerizable unsaturated group is introduced into a monomer copolymer, an alkyl (meth) acrylate (A) having an alkyl group having 4 or more carbon atoms, or a fluorine-containing compound having a polymerizable unsaturated group A macromonomer made of a copolymer of a polymerizable unsaturated monomer containing B and C) as a main component can be used.
  • alkyl (meth) acrylate (A) examples include n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate.
  • 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.
  • fluorine-containing compound (C) having a polymerizable unsaturated group examples include a poly (perfluoroalkylene ether) chain and a compound having a polymerizable unsaturated group at both ends thereof.
  • Specific examples of the fluorine-containing compound (C) 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 groups are used at both ends of the poly (perfluoroalkylene ether) chain represented by the above formula (C-1) because the compound is preferable and the polymer (P) that is easily entangled with the surface of the mother particles can be synthesized.
  • a compound having methacryloyl groups at both ends of the poly (perfluoroalkylene ether) chain represented by the above formula (C-2) is more preferable.
  • polymer (P) examples include styrene, ⁇ -methylstyrene, pt-butylstyrene, and vinyl as compounds other than the above-mentioned alkyl (meth) acrylate (A) and fluorine-containing compound (B, C).
  • Aromatic vinyl compounds such as toluene; (meth) acrylates such as benzyl (meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate.
  • the compound that can be used as the polymer (P) one type may be used alone or two or more types may be used in combination.
  • the alkyl (meth) acrylate (A) 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 is used. It is preferable to use it.
  • a polymer (P) can be obtained by introducing a polymerizable unsaturated group into the copolymer.
  • 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 copolymerization component in advance.
  • a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group are added to the carboxylic acid group or the amino 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.
  • Specific examples of (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.
  • Specific examples of the epoxy group-containing polymerizable unsaturated monomer 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.
  • various unsaturated carboxylic acids such as meta) acryloyloxymonoethylphthalate
  • 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 is formed by polymerizing the monomer (M) in the presence of mother particles, a non-aqueous solvent and the polymer (P). It is preferable that the mother particles 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 mother particles used when forming the polymer layer is not particularly limited, and may be any of slurry, wet cake, powder and the like.
  • the monomer (M) and the polymerization initiator described later are further mixed and polymerized to obtain the polymer (P) and the monomer (M).
  • a polymer layer composed of the polymer is formed. As a result, luminescent particles 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 surface of the mother particles can be satisfactorily coated with the polymer layer.
  • the amount of the polymer (P) used is appropriately set according to the intended 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 mother particles. 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 mother particle. 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 mother particles 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 mother particles. It is 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 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 is less than 0.5 nm, dispersion stability is often not obtained.
  • the thickness of the polymer layer exceeds 100 nm, it is often difficult to contain the mother particles at a high concentration.
  • the stability of the luminescent particles with respect to oxygen and moisture can be further improved.
  • the polymerization of the monomer (M) in the presence of the mother particles, 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-methylbutyronitrile), and benzoyl.
  • examples thereof include peroxide, t-butyl perbenzoate, t-butyl-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like.
  • 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 preferably added to the mixture containing the mother particles 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 nanocrystal particles can be suitably prevented.
  • the polymer not adsorbed on the surface of the mother particles is removed to obtain luminescent particles.
  • the method for removing the polymer that has not been adsorbed include centrifugal sedimentation and ultrafiltration. In centrifugal sedimentation, the dispersion liquid containing the mother particles and the polymer that has not been adsorbed is rotated at high speed, the mother particles in the dispersion liquid are settled, and the polymer that has not been adsorbed is separated.
  • a dispersion containing the mother particles 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 separate the unadsorbed polymer and the mother particles.
  • a filtration membrane having an appropriate pore size to separate the unadsorbed polymer and the mother particles.
  • luminescent particles having a polymer layer can be obtained.
  • the luminescent particles may be stored in a state of being dispersed in a dispersion medium or a photopolymerizable compound (that is, as a dispersion liquid), or the dispersion medium may be removed and stored as a powder (aggregate of luminescent particles alone). You may.
  • the content of the luminescent particles in the ink composition is preferably 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and is 20% by mass or less, 15% by mass or less, or 10% by mass. It is less than mass%.
  • the ink composition may contain two or more of red luminescent particles, green luminescent particles, and blue luminescent particles as the luminescent particles, but may contain only one of these particles. Is more preferable.
  • the content of the green luminescent particles and the content of the blue luminescent particles are preferably 5% by mass or less, more preferably, based on the total mass of the luminescent particles. Is 0% by mass.
  • the content of the red luminescent particles and the content of the blue luminescent particles are preferably 5% by mass or less, more preferably, based on the total mass of the luminescent particles. Is 0% by mass.
  • the ink composition contains a NOR type hindered amine compound represented by the following formula (1).
  • the hindered amine compound is a compound having an imino group (NOR type hindered amino group) in which a hydrocarbon group (R) is bonded via an oxygen atom (O) as a hindered amino group.
  • the NOR-type hindered amine compound may be a compound having one NOR-type hindered amino group, or may be a compound having a plurality of (for example, two or more) NOR-type hindered amino groups. Then, the ink composition may be used with only one kind as the NOR type hindered amine compound, or two or more kinds may be used.
  • R 1 to R 5 each independently represent a hydrocarbon group, and * indicates a bond.
  • the number of carbon atoms of the hydrocarbon group as R 1 and R 4 is, for example, 1 or more or 2 or more, and preferably 8 or less or 7 or less.
  • R1 is preferably, for example, an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the alkyl group may be linear or branched.
  • the cycloalkyl group may be, for example, a cyclohexyl group.
  • the hydrocarbon group as R2 to R5 and R6 to R10 may be, for example, an alkyl group.
  • the number of carbon atoms of the hydrocarbon group as R 2 to R 5 may be, for example, 1 or more, or 8 or less.
  • R2 to R5 may be, for example, a methyl group.
  • * Represents a bond, and may be, for example, a binding site with a carbon atom, a nitrogen atom, or an oxygen atom.
  • the ink composition of the present embodiment is contained in the ink composition as compared with the case where the NR type hindered amine compound is contained. It is possible to form a cured film having excellent solubility in a photopolymerizable compound and excellent light resistance at high temperatures.
  • the photopolymerizable compound used as the ink composition is preferably a compound having a low polarity in terms of compatibility with light emitting particles, and more preferably a NOR type hindered amine compound.
  • the NOR type hindered amine compound has better light resistance than the NR type hindered amine compound because it is more difficult to coordinate to the surface of the semiconductor nanotie and the photostabilizing action of the hindered amine compound is not hindered. Will be done.
  • the NR-type hindered amine compound means a compound having a structure represented by "-N-R” instead of the structure represented by "-N-OR” of the NOR-type hindered amine compound. Is a hydrogen or alkyl group.
  • the NOR-type hindered amine compound may be a compound further having a 1,3,5-triazine ring which may have a substituent.
  • the structure represented by the formula (1) may be bonded to the 1,3,5-triazine ring directly or via another atom (for example, a nitrogen atom).
  • the NOR type hindered amine compound for example, a compound that is liquid at 20 ° C or solid at 20 ° C can also be used. However, considering that the cured product of the ink composition may be heated to, for example, about 50 ° C. by light irradiation, it is preferable that the melting point of the NOR type hindered amine compound is high, and it is 70 ° C. or higher, 80 ° C. or higher, or It is preferably 85 ° C. or higher. When a NOR-type hindered amine compound having a melting point of 70 ° C.
  • the hindered amine compound does not liquefy. It is possible to prevent the phenomenon of the hindered amine compound oozing out on the surface of the cured product (bleeding phenomenon) (bleeding resistance).
  • the melting point of the NOR-type hindered amine compound is preferably 180 ° C. or lower.
  • the molecular weight (or molar mass) or mass average molecular weight of the NOR type hindered amine compound may be 1000 or more.
  • the value measured by gel permeation chromatography (GPC) using polystyrene as a standard material can be adopted as the “mass average molecular weight”.
  • the NOR type hindered amine compound is preferably a compound represented by the following formula (1a), the following formula (1b), the following formula (1c), the following formula (1d) or the following formula (1e). From the viewpoint of further excellent curability and further excellent light resistance at high temperature, the NOR type hindered amine compound is more preferably a compound represented by the following formula (1a) or the following formula (1b).
  • n represents an integer from 1 to 15.
  • R is the following formula (1b-R): Indicates a group represented by.
  • * indicates a binding site with a nitrogen atom.
  • TINUVIN registered trademark
  • NOR371 melting point: 91 to 104 ° C., mass average molecular weight: 2800 to 4000, BASF Japan stock, which has a structure represented by the above formula (1a)
  • Flamestab NOR116FF melting point: 108 to 123 ° C., molecular weight: 2261, manufactured by BASF Japan Co., Ltd.
  • TINUVIN registered trademark
  • the content of the NOR-type hindered amine compound is 0.1% by mass or more, 0.2% by mass or more, based on the total mass of the ink composition, from the viewpoint of further excellent light resistance at high temperature. Alternatively, it may be 0.3% by mass or more.
  • the content of the NOR type hindered amine compound may be, for example, 5.0% by mass or less, 3.0% by mass or less, or 2.0% by mass or less.
  • the ink composition contains a photopolymerizable compound.
  • the photopolymerizable compound is preferably a photoradical polymerizable compound that polymerizes by irradiation with light, and may be a photopolymerizable monomer or oligomer. These are used with photopolymerization initiators.
  • One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.
  • the photopolymerizable compound preferably contains a monofunctional monomer having one photopolymerizable group and a polyfunctional monomer having two or more photopolymerizable groups.
  • the mass ratio of the monofunctional monomer to the polyfunctional monomer in the photopolymerizable compound may be 1.0, 5.0 or 10.0.
  • the mass ratio of the monofunctional monomer to the polyfunctional monomer is within this range, the ink viscosity is suitable for inkjet suitability, and the cured film has excellent curability, so that the cured film (light conversion layer) emits light. The characteristics will be even better.
  • Examples of the photopolymerizable compound include (meth) acrylate compounds.
  • the (meth) acrylate compound includes a methacrylate compound having a methacryloyl group and an acrylate compound having an acryloyl group.
  • the (meth) acrylate compound may be a monofunctional (meth) acrylate having one (meth) acryloyl group, or may be a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups.
  • Monofunctional (meth) acrylates are used from the viewpoints of excellent fluidity when preparing an ink composition, excellent ejection stability, and suppression of deterioration of smoothness due to curing shrinkage during the production of a cured film. It is preferable to use it in combination with a functional (meth) 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 may be a bifunctional (meth) acrylate, a trifunctional (meth) acrylate, a tetrafunctional (meth) acrylate, a pentafunctional (meth) acrylate, a hexafunctional (meth) acrylate, or the like, and may be, for example.
  • 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 two hydroxyl groups of a diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A are replaced with a (meth) acryloyloxy group, 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 trimethylol propane is substituted with a (meth) acryloyloxy group, and 4 mol is added to 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 the like.
  • 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 polyfunctional (meth) acrylate may be a poly (meth) acrylate in which a plurality of hydroxyl groups of dipentaerythritol such as dipentaerythritol hexa (meth) acrylate are substituted with (meth) acryloyloxy groups.
  • the (meth) acrylate compound may be an ethylene oxide-modified phosphoric acid (meth) acrylate, an ethylene oxide-modified alkyl phosphoric acid (meth) acrylate, or the like, which has a phosphoric acid group.
  • the photopolymerizable compound as described above has two or more polymerizable functional groups in one molecule. It is more preferable to use a polyfunctional photopolymerizable compound having two or more functionalities 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 viscosity of the monofunctional (meth) acrylate is, for example, 2 mPa ⁇ s or more, and 3 mPa ⁇ s or more or. It may be 5 mPa ⁇ s or more.
  • the viscosity of the monofunctional (meth) acrylate is, for example, 50 or less, and may be 20 or less or 10 or less.
  • the viewpoint of easily achieving both viscosity, ejection property and viscosity stability as an inkjet ink it is preferably 2 to 50 mPa ⁇ s, more preferably 3 to 20 mPa ⁇ s, and 5 to 10 mPa ⁇ s. Is particularly preferable.
  • Examples of the monofunctional (meth) acrylate compound having a viscosity of 2 to 50 mPa ⁇ s at room temperature include lauryl acrylate (viscosity 4 to 5 mPa ⁇ s) and isostearyl acrylate (viscosity 17 mPa ⁇ s, viscosity 4 to 5 mPa ⁇ s).
  • Isodecyl acrylate (viscosity 2.7 mPa ⁇ s), isobornyl acrylate (viscosity 7.7 mPa ⁇ s), cyclohexyl acrylate (viscosity 2.5 mPa ⁇ s), benzyl acrylate (viscosity 2.2 mPa ⁇ s), phenoxy Ethyl acrylate (viscosity 9 mPa ⁇ s), dicyclopentenyl acrylate (viscosity 8-18 mPa ⁇ s), dicyclopentenyloxyethyl acrylate (viscosity 15-25 mPa ⁇ s), dicyclopentanyl acrylate (viscosity 7-17 mPa ⁇ s) , (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (viscosity 5.1 mPa ⁇ s), (2
  • 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 10 to 80% by mass, and further preferably 20 to 75% by mass. It is preferably 30 to 70% by mass, and particularly preferably 30 to 70% 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 heteroatom 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 nanocrystal particles containing luminescent nanocrystals is increased in order to improve the external quantum efficiency, the uniformity of the surface of the pixel portion may decrease. According to the combination of the photopolymerizable compounds, there is a tendency to obtain a pixel portion having excellent surface uniformity.
  • the SP value of the photopolymerizable compound is preferably 10.0 or less.
  • the SP value of the photopolymerizable compound may be, for example, 9.75 or less, or 9.50 or less, and may be 8.50 or more or 8.70 or more.
  • the solubility of the NOR-type hindered amine compound, the storage stability of the ink, and the optical properties are further improved.
  • the content of the photopolymerizable compound is from the viewpoint of excellent storage stability of the ink and excellent optics. From the viewpoint of obtaining characteristics (for example, external quantum efficiency), it is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, based on the total mass of the photopolymerizable compound in the ink composition. It is preferably 0 to 5% by mass.
  • the SP value (solubility parameter / unit: ((cal / cm 3 ) 0.5 ) in the present invention is described in RF Fedors, Polymer Engineering Science, 14, p147 (1974), so-called. It refers to the solubility parameter calculated by the Fedors method. In the Fedors method, it is considered that the aggregation energy density and the molar molecular weight depend on the type and number of substituents, and the solubility parameter is expressed by the following formula (1).
  • the solubility parameter is a value unique to each compound.
  • ⁇ Ecoh indicates the aggregation energy
  • ⁇ V indicates the molar molecular content
  • the SI unit of the SP value is (J / cm 3 ) 0.5 or (MPa) 0.5 , but here, (cal / cm 3 ) 0.5 , which is conventionally used conventionally, is used.
  • the unit of the SP value can be converted by the following formula: 1 (cal / cm 3 ) 0.5 ⁇ 2.05 (J / cm 3 ) 0.5 ⁇ 2.05 (MPa) 0.5 .
  • Examples of the (meth) acrylate compound having an SP value of 10.0 or less include lauryl acrylate (SP value: 8.70), isostearyl acrylate (SP value: 8.59), and isodecyl acrylate (SP value: 8).
  • the photopolymerizable compound as described above has two or more polymerizable functional groups in one molecule. It is more preferable to use a polyfunctional photopolymerizable compound having two or more functionalities as an essential component because the durability (strength, heat resistance, etc.) of the cured product can be further enhanced.
  • 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 that the curability of the ink composition is good, and the pixel portion (curing of the ink composition).
  • the photopolymerization initiator is preferably at least one selected from the group consisting of alkylphenone-based compounds, acylphosphine oxide-based compounds and oxime ester-based compounds.
  • alkylphenone-based photopolymerization initiator include compounds represented by the formula (b-1).
  • R1a represents a group selected from the following formulas (R 1a -1) to (R 1a -6), and R 2a , R 2b and R 2c independently represent the following formula (R 2 ).
  • the compounds represented by the following formulas (b-1-1) to (b-1-6) are preferable, and the following formula (b-1) is preferable.
  • the compound represented by the formula (b-1-5) or the formula (b-1-6) is more preferable.
  • Examples of the acylphosphine oxide-based photopolymerization initiator include compounds represented by the formula (b-2).
  • R 24 represents an alkyl group, an aryl group or a heterocyclic group
  • R 25 and R 26 each independently represent an alkyl group, an aryl group, a heterocyclic group or an alkanoyl group. May be substituted with an alkyl group, a hydroxyl group, a carboxyl group, a sulfon group, an aryl group, an alkoxy group, or an arylthio group.
  • the compounds represented by the above formula (b-2) are preferable, and the following formula (b-2) is preferable.
  • a compound represented by -1) or the formula (b-2-5) is more preferable.
  • Examples of the oxime ester-based photopolymerization initiator include compounds represented by the following formula (b-3-1) or formula (b-3-2).
  • R 27 to R 31 each independently represent a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group. May be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and a phenyl group, where X1 represents an oxygen atom or a nitrogen atom and X2 is oxygen. It represents an atom or NR, and R represents an alkyl group having 1 to 6 carbon atoms.
  • the content of the photopolymerization initiator is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, based on the total amount of the photopolymerizable compounds contained in the ink composition. It is preferably 1 to 6% by mass, and more preferably 1 to 6% by mass.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the ink composition containing the photopolymerization initiator in such an amount sufficiently maintains the photosensitivity at the time of photocuring, and the crystals of the photopolymerization initiator are less likely to precipitate when the cured film is dried, so that the physical properties of the cured film are deteriorated. Can be suppressed.
  • the photopolymerization initiator When dissolving the photopolymerization initiator in the ink composition, it is preferable to dissolve it in the photopolymerizable compound in advance before use. In order to dissolve the photopolymerizable compound, it is preferable to uniformly dissolve the photopolymerizable compound by adding a photopolymerization initiator while stirring so that the reaction due to heat is not started.
  • the dissolution temperature of the photopolymerization initiator may be appropriately adjusted in consideration of the solubility of the photopolymerization initiator used in the photopolymerizable compound and the thermal polymerizable property of the photopolymerizable compound, but the polymerization of the photopolymerizable compound may be appropriately adjusted.
  • the temperature is preferably 10 to 50 ° C., more preferably 10 to 40 ° C., and even more preferably 10 to 30 ° C. from the viewpoint of not starting the polymerization.
  • the ink composition may further contain 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 a surface treatment containing alumina on 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.
  • the content of the light-scattering particles may be 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, based on the total mass of the ink composition, and may be 10% by mass or less, 9% by mass or less, or. It may be 8% by mass or less.
  • the ink composition may further contain a polymer dispersant.
  • the polymer dispersant is a molecule having a weight average molecular weight (Mw) of more than 5,000, and is a compound capable of improving the dispersion stability of light-scattering particles in an ink composition.
  • the polymer dispersant also contributes to the dispersion stability of the luminescent particles.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • polymer dispersant examples include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyether resins, phenol resins, silicone resins, polyurea resins, amino resins, and polyamine resins ( Polyethylene imine, polyallylamine, etc.), epoxy resins, polyimide resins, wood rosins, gum rosins, natural rosins such as tall oil rosins, polymerized rosins, disproportionated rosins, hydrogenated rosins, oxide rosins, maleated rosins, etc.
  • 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.
  • Examples of commercially available polymer dispersants include DISPERBYK (registered trademark) series manufactured by Big Chemie, TEGO (registered trademark) Dispers series manufactured by Ebony, EFKA (registered trademark) series manufactured by BASF, and Japan Lubrizol.
  • SOLSPERSE (registered trademark) series manufactured by Zol, Ajinomoto Fine-Techno's Azispar (registered trademark) series, DISPARLON (registered trademark) series manufactured by Kusumoto Kasei, Floren series manufactured by Kyoeisha Chemical Co., Ltd., and the like can be used.
  • the polymer dispersant is a block copolymer.
  • the effect of applying the block copolymer to the polymer dispersant is that the block copolymer is composed of a hydrophilic region and a pigment adsorption region, so that high dispersibility can be obtained and a random copolymer weight can be obtained. It is possible to obtain better dispersibility than coalescence or cross-copolymer.
  • the monomer monomer constituting the copolymer has a high probability of being sterically or electrically stably arranged in the copolymer at the time of polymer formation.
  • Monomer Since the portion (molecule) in which the monomer is stably arranged is sterically or electrically stable, it often becomes an obstacle when adsorbing on the pigment surface.
  • the block copolymer type polymer dispersant having a controlled molecular arrangement the portion that hinders the adsorption of the dispersant to the pigment may be arranged at a position away from the adsorption portion between the pigment and the dispersant. can.
  • the polymer dispersant according to the present invention is not limited as long as it has the above characteristics, and a block copolymer synthesized using a known ethylenically unsaturated monomer can be applied, and the ethylenically unsaturated monomer can be used. , For example, the following can be mentioned.
  • Stylines and styrene derivatives such as ⁇ -methylstyrene or vinyltoluene; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate; vinyl halides; ethylenically unsaturated monocarboxylic acids and dicarboxylic acids such as acrylic acids, Monoalkyl esters with methacrylic acid, itaconic acid, maleic acid or fumaric acid, and the above-mentioned alkanols of dicarboxylic acids (preferably those having 1 to 4 carbon atoms), derivatives of the above-mentioned monoalkyl esters, and their derivatives.
  • vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate
  • vinyl halides vinyl halides
  • ethylenically unsaturated monocarboxylic acids and dicarboxylic acids such as acrylic acids, Monoalkyl esters with methacrylic acid, itaconic acid, maleic acid or fumaric acid
  • N-substituted derivatives, aryl esters, and derivatives thereof N-substituted derivatives, aryl esters, and derivatives thereof; amides of unsaturated carboxylic acids such as acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide, N-alkylacrylamide; ethylenic monomers containing sulfonic acid groups and theirs.
  • Ammonium or alkali metal salts such as vinyl sulfonic acid, vinyl benzene sulfonic acid, ⁇ -acrylamide methyl propane sulfonic acid, 2-sulfoethylene methacrylate; vinyl amine amides such as vinyl formamide, vinyl acetamide; second, third or second An unsaturated ethylenic monomer containing a quaternary amino group or a nitrogen-containing heterocyclic group, such as vinylpyridine, vinylimidazole, aminoalkyl (meth) acrylate, aminoalkyl (meth) acrylamide, acrylic acid or dimethylaminoethyl methacrylate, acrylic.
  • a block copolymer can be synthesized according to a known method, for example, a synthesis method such as JP-A-2005-60669 and JP-A-2007-314617.
  • a (meth) acrylic block copolymer for example, JP-A-60-89452, JP-A-9-62002, P.I. Lutz, P. et al. Massonetal, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrewsetal, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K. et al. Ute, et al, Polym. J. 17,977 (1985), K.K. Hatada, K. et al. Ute, et al, Polym. J.
  • the polymer dispersant used in the present invention has a basic polar group, and the basic functional groups include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and pyridine, pyrimidine, pyrazine, and the like. Examples thereof include nitrogen-containing heterocyclic groups such as imidazole and triazole.
  • the amine value of the polymer dispersant is preferably 6 to 90 mgKOH / g, more preferably 7 to 70 mgKOH / g, and even more preferably 8 to 50 mgKOH / g.
  • the amine value of the polymer dispersant is smaller than 6 mgKOH / g, the adsorptivity of the polymer dispersant to the light diffusing particles is low, and when the amine value is larger than 90 mgKOH / g, the polarity is high, and aggregation and storage stability are achieved. It tends to cause deterioration, and the dispersibility of the luminescent particles also deteriorates due to the influence.
  • the content of the polymer dispersant is preferably 0.5 to 50% by mass, more preferably 2 to 30% by mass, and 3 to 20 parts by mass with respect to 100% by mass of the light-scattering particles. Is particularly preferable.
  • the ink composition may contain other components other than luminescent particles, photopolymerizable compounds, photopolymerization initiators, light-scattering particles, and polymer dispersants as long as the effects of the present invention are not impaired.
  • examples of such other components include polymerization inhibitors, antioxidants, leveling agents, chain transfer agents, dispersion aids, thermoplastic resins, sensitizers and the like.
  • Polymerization inhibitor examples include p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, and 2,2'-methylenebis (4-methyl-6-t-).
  • antioxidant examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (product name "IRGANOX® 1010”)) and thiodiethylenebis [3-.
  • Tridecylphosphite product name" JP-310 "), Trilaurylphosphite (product name” JP-312L "), Tris (tridecyl) phosphite (product name” JP-333 "), Trio Rail phosphite (product name "JP-318-O"), diphenylmono (2-ethylhexyl) phosphite (product name "JPM-308"), diphenylmonodecylphosphite (product name "JPM-311") ", Diphenylmono (tridecyl) phosphite (product name "JPM-313"), bis (decyl) pentaerythritol diphosphite (product name "JPE-10”), tristearylphosphite (product name "JP-318E”) (Manufactured by Johoku Chemical Industry Co., Ltd.); Butylated hydroxytol
  • the leveling agent is not particularly limited, but a compound capable of reducing film thickness unevenness when forming a thin film of luminescent particles is preferable.
  • leveling agents include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, and fluoroalkylethylene oxide derivatives. , Polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like.
  • the amount of the leveling agent added is preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the photopolymerizable compound contained in the ink composition. preferable.
  • the chain transfer agent is a component used for the purpose of further improving the adhesion of the ink composition to the substrate.
  • Examples of the chain transfer agent include aromatic hydrocarbons, halogenated hydrocarbons, mercaptan compounds, thiol 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.
  • Sensitizer As the sensitizer, a thioxanthone-based compound, a benzophenone-based compound, a quinone-based compound, amines and the like can be used.
  • sensitizers examples include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-ethylanthraquinone, trimethylamine, methyldimethylamine, and triethanolamine.
  • Viscosity of ink composition is preferably in the range of 2 to 20 mPa ⁇ s, more preferably in the range of 5 to 15 mPa ⁇ s, and 7 to 7 to 7 to s, from the viewpoint of ejection stability during inkjet printing. It is more preferably in the range of 12 mPa ⁇ s.
  • the ejection control of the ink composition (for example, the control of the ejection amount and the ejection timing) becomes easy.
  • the ink composition can be smoothly ejected from the ink ejection holes.
  • the viscosity of the ink composition can be measured by, for example, an E-type viscometer.
  • the viscosity increase rate of the ink composition may be 5% or less, 1% or less, or 0.5% or less, and may be 0.01% or more.
  • the viscosity increase rate of the ink composition is a value calculated by the following formula. Equation: ( ⁇ 1 - ⁇ 0 ) / ⁇ 0 ⁇ 100
  • ⁇ 1 indicates the viscosity of the ink composition after storage at 40 ° C. for 1 week at 30 ° C.
  • ⁇ 0 indicates the viscosity of the ink composition of the ink composition before storage.
  • the surface tension of the ink composition is preferably a surface tension suitable for the inkjet printing method.
  • the specific value of the surface tension is preferably in the range of 20 to 40 mN / m, and more preferably in the range of 25 to 35 mN / m.
  • the ink composition as described above can be prepared, for example, by dispersing luminescent particles in a solution in which a NOR-type hindered amine compound and, if necessary, a photopolymerizable compound and a photopolymerization initiator are mixed.
  • Dispersion of luminescent particles 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.
  • the ink composition set of one embodiment includes the ink composition of the above-described embodiment.
  • the ink composition set may include an ink composition (non-luminescent ink composition) containing no luminescent particles in addition to the ink composition (luminescent ink composition) of the above-described embodiment.
  • the non-emissive ink composition is, for example, a curable ink composition.
  • the non-emission ink composition may be a conventionally known ink composition, and has the same composition as the ink composition (emissive ink composition) of the above-described embodiment except that it does not contain luminescent particles. You may.
  • the non-luminescent ink composition does not contain luminescent particles, when light is incident on the pixel portion formed by the non-luminescent ink composition (the pixel portion containing the cured product of the non-luminescent ink composition).
  • the light emitted from the pixel portion has substantially the same wavelength as the incident light. Therefore, the non-emissive ink composition is preferably used to form a pixel portion having the same color as the light from the light source.
  • the pixel portion formed by the non-emissive ink composition can be a blue pixel portion.
  • the non-luminescent ink composition preferably contains light-scattering particles.
  • the pixel portion formed by the non-emission ink composition can scatter the light incident on the pixel portion, whereby the pixel It is possible to reduce the difference in light intensity of the light emitted from the unit at the viewing angle.
  • optical conversion layer and color filter> Another embodiment of the present invention is an optical conversion layer and a color filter.
  • the details of the light conversion layer and the color filter obtained by using the ink composition or the ink composition set of the above-described embodiment will be described with reference to the drawings.
  • the following embodiment is an embodiment when the ink composition contains light-scattering particles.
  • the same reference numerals will be used for the same or equivalent elements, and duplicate description will be omitted.
  • FIG. 1 is a schematic cross-sectional view of the color filter of one embodiment.
  • the color filter 100 includes a base material 40 and a light conversion layer 30 provided on the base material 40.
  • the light conversion layer 30 includes a plurality of pixel units 10 and a light-shielding unit 20.
  • the optical conversion layer 30 has a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c as the pixel unit 10.
  • the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c are arranged in a grid pattern so as to repeat in this order.
  • the light-shielding portion 20 is located between adjacent pixel portions, that is, between the first pixel portion 10a and the second pixel portion 10b, between the second pixel portion 10b and the third pixel portion 10c, and the third. It is provided between the pixel portion 10c of the above and the first pixel portion 10a. In other words, these adjacent pixel portions are separated from each other by the light-shielding portion 20.
  • the first pixel portion 10a and the second pixel portion 10b are luminescent pixel portions (light emitting pixel portions) containing a cured product of the ink composition of the above-described embodiment, respectively.
  • the cured product shown in FIG. 1 contains luminescent particles, a curing component, and light scattering particles.
  • the first pixel portion 10a includes a first curing component 13a, a first luminescent particle 11a and a first light scattering particle 12a dispersed in the first curing component 13a, respectively.
  • the second pixel portion 10b includes a second curing component 13b and a second luminescent particle 11b and a second light scattering particle 12b dispersed in the second curing component 13b, respectively. ..
  • the curing component is a component obtained by polymerizing a photopolymerizable compound, and includes a polymer of the photopolymerizable compound.
  • the curing component may contain a component other than the organic solvent contained in the ink composition.
  • the first curing component 13a and the second curing component 13b may be the same or different, and may be the same as or different from the first light scattering particles 12a. It may be the same as or different from the second light-scattering particle 12b.
  • the first luminescent particles 11a are red luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel portion 10a may be paraphrased as a red pixel portion for converting blue light into red light.
  • the second luminescent particle 11b is a green luminescent nanocrystal particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having a emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 10b may be paraphrased as a green pixel portion for converting blue light into green light.
  • the content of the luminescent particles in the luminescent pixel portion is preferably based on the total mass of the cured product of the luminescent ink composition from the viewpoint of being superior in the effect of improving the external quantum efficiency and obtaining excellent emission intensity. 1% by mass or more, 2% by mass or more, or 3% by mass or more.
  • the content of the luminescent particles is preferably 15% by mass or less based on the total mass of the cured product of the luminescent ink composition from the viewpoint of excellent reliability of the pixel portion and excellent emission intensity. It is 10% by mass or less, or 7% by mass or less.
  • the content of the light-scattering particles in the luminescent pixel portion is 0.1% by mass or more and 1% by mass based on the total mass of the cured product of the luminescent ink composition from the viewpoint of being more excellent in the effect of improving the external quantum efficiency. It may be more than or equal to 3% by mass or more.
  • the content of the light-scattering particles is 30% by mass or less, 25, based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of improving the effect of improving the external quantum efficiency and the reliability of the pixel portion. It may be mass% or less, 20 parts by mass or less, 15 parts by mass or less, or 10% by mass or less.
  • the third pixel portion 10c is a non-light emitting pixel portion (non-light emitting pixel portion) containing a cured product of the above-mentioned non-light emitting ink composition.
  • the cured product does not contain luminescent particles, but contains light-scattering particles and a cured component. That is, the third pixel portion 10c includes a third curing component 13c and a third light scattering particle 12c dispersed in the third curing component 13c.
  • the third curing component 13c is, for example, a component obtained by polymerizing a polymerizable compound and contains a polymer of the polymerizable compound.
  • the third light-scattering particle 12c may be the same as or different from the first light-scattering particle 12a and the second light-scattering particle 12b.
  • the third pixel portion 10c has a transmittance of 30% or more with respect to light having a wavelength in the range of, for example, 420 to 480 nm. Therefore, the third pixel unit 10c functions as a blue pixel unit when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the transmittance of the third pixel unit 10c can be measured by a microspectroscopy device.
  • the content of the light-scattering particles in the non-emissive pixel portion is 1% by mass based on the total mass of the cured product of the non-emission ink composition from the viewpoint that the difference in light intensity at the viewing angle can be further reduced. It may be more than 5% by mass, or it may be 10% by mass or more.
  • the content of the light-scattering particles may be 80% by mass or less, and 75% by mass or less, based on the total mass of the cured product of the non-emissive ink composition from the viewpoint of further reducing light reflection. It may be 70% by mass or less.
  • the thickness of the pixel portion may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. You may.
  • the thickness of the pixel portion may be, for example, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less. You may.
  • the light-shielding portion 20 is a so-called black matrix provided for the purpose of separating adjacent pixel portions to prevent color mixing and for the purpose of preventing light leakage from a light source.
  • the material constituting the light-shielding portion 20 is not particularly limited, and the curing of the resin composition containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the binder polymer in addition to a metal such as chromium. Objects and the like can be used.
  • the binder polymer used here includes one or a mixture of one or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, photosensitive resin, and O / W.
  • An emulsion-type resin composition (for example, an emulsion of a reactive silicone) or the like can be used.
  • the thickness of the light-shielding portion 20 may be, for example, 0.5 ⁇ m or more, and may be 10 ⁇ m or less.
  • the base material 40 is a transparent base material having light transmission, and is, for example, a transparent glass substrate such as quartz glass, Pylex (registered trademark) glass, a synthetic quartz plate, a transparent resin film, an optical resin film, or the like.
  • a flexible base material or the like can be used.
  • a glass substrate made of non-alkali glass that does not contain an alkaline component in the glass.
  • "7059 glass”, “1737 glass”, “Eagle 200” and “Eagle XG” manufactured by Corning Inc., "AN100” manufactured by Asahi Glass Co., Ltd., "OA-10G” and “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. OA-11 ” is suitable. These are materials with a small thermal expansion rate and are excellent in dimensional stability and workability in high temperature heat treatment.
  • the color filter 100 provided with the above optical conversion layer 30 is suitably used when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the color filter 100 can be manufactured, for example, by forming the light-shielding portion 20 in a pattern on the base material 40 and then forming the pixel portion 10 in the pixel portion-forming region partitioned by the light-shielding portion 20 on the base material 40. ..
  • the pixel portion 10 has a step of selectively adhering the ink composition (inkjet ink) to the pixel portion forming region on the base material 40 by an inkjet method, and irradiates the ink composition with active energy rays (for example, ultraviolet rays). It can be formed by a method comprising a step of curing an ink composition to obtain a light emitting pixel portion.
  • a luminescent pixel portion can be obtained by using the above-mentioned luminescent ink composition as the ink composition, and a non-luminescent pixel portion can be obtained by using the non-luminescent ink composition.
  • the method of forming the light-shielding portion 20 is to form a metal thin film such as chromium or a thin film of a resin composition containing light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material 40.
  • a method of patterning this thin film and the like can be mentioned.
  • the metal thin film can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like, and the thin film of the resin composition containing the light-shielding particles can be formed, for example, by a method such as coating or printing. Examples of the method for patterning include a photolithography method.
  • Examples of the inkjet method include a bubble jet (registered trademark) method using an electric heat converter as an energy generating element, a piezo jet method using a piezoelectric element, and the like.
  • the ink composition can be cured by using, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like. LEDs are 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 to 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. It is not preferable because it is inferior in sex.
  • 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 it is more preferably performed 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 conversion layer is a pixel portion containing a cured product of a luminescent ink composition containing blue-emitting nanocrystal particles in place of the third pixel portion 10c or in addition to the third pixel portion 10c ( It may be provided with a blue pixel portion).
  • the light conversion layer includes a pixel portion (for example, a yellow pixel portion) containing a cured product of a luminescent ink composition containing nanocrystal particles that emit light of colors other than red, green, and blue. good. In these cases, it is preferable that each of the luminescent particles contained in each pixel portion of the optical conversion layer has an absorption maximum wavelength in the same wavelength range.
  • At least a part of the pixel portion of the light conversion layer may contain a cured product of a composition containing a pigment other than luminescent particles.
  • the color filter may be provided with an ink-repellent layer made of a material having an ink-repellent property narrower than that of the light-shielding portion on the pattern of the light-shielding portion.
  • an ink-repellent layer instead of providing an ink-repellent layer, a photocatalyst-containing layer as a wettable variable layer is formed in a solid coating shape in a region including a pixel portion forming region, and then light is applied to the photocatalyst-containing layer via a photomask. Irradiation may be performed for exposure to selectively increase the parental ink property of the pixel portion forming region.
  • the photocatalyst include titanium oxide and zinc oxide.
  • the color filter may be provided with an ink receiving layer containing hydroxypropyl cellulose, polyvinyl alcohol, gelatin, etc. between the base material and the pixel portion.
  • the color filter may be provided with a protective layer on the pixel portion.
  • This protective layer flattens the color filter and prevents the components contained in the pixel portion, or the components contained in the pixel portion and the components contained in the photocatalyst-containing layer from elution into the liquid crystal layer. It is provided.
  • a material used as a known protective layer for a color filter can be used.
  • the pixel portion of the light conversion layer of the present embodiment may further contain a pigment having substantially the same color as the luminescent color of the luminescent particles.
  • the pigment may be contained in the ink composition.
  • one or two types of luminescent pixel portions are luminescent particles. It may be a pixel portion containing a coloring material without containing the above.
  • a known color material can be used.
  • a diketopyrrolopyrrole pigment and / or an anionic red organic dye is used. Can be mentioned.
  • Examples of the coloring material used for the green pixel portion (G) include at least one selected from the group consisting of a halogenated copper phthalocyanine pigment, a phthalocyanine-based green dye, and a mixture of a phthalocyanine-based blue dye and an azo-based yellow organic dye.
  • Examples of the coloring material used for the blue pixel portion (B) include an ⁇ -type copper phthalocyanine pigment and / or a cationic blue organic dye. The amount of these coloring materials used is 1 to 5 mass based on the total mass of the pixel portion (cured product of the ink composition) from the viewpoint of preventing a decrease in transmittance when contained in the optical conversion layer. % Is preferable.
  • the following compound was prepared as the hindered amine compound (A).
  • A-2) TINUVIN (registered trademark) NOR371 NOR type, melting point 91 to 104 ° C., molecular weight 2800 to 4000
  • A-3) TINUVIN (registered trademark) 123 NOR type, melting point ⁇ 20 ° C.
  • antioxidant (C) As the antioxidant (C), (C-1) IRGANOX (registered trademark) 1010 (phenolic) and (C-2) Hostanox (registered trademark) P-EPQ (phosphorus) were prepared.
  • D-1 Isobornyl methacrylate (light ester IB-X, monofunctional, cyclic, viscosity: 6 mPa ⁇ s / 25 ° C.)
  • D-2) Lauryl methacrylate (light ester L, monofunctional, chain, viscosity: 3-8 mPa ⁇ s / 25 ° C.)
  • D-3) Phenoxyethyl methacrylate (light ester PO, monofunctional, cyclic, viscosity: 7 mPa ⁇ s / 25 ° C.)
  • D-4) 1,6-Hexanediol dimethacrylate (light ester 1,6-HX, bifunctional, chain, viscosity: 5-6 mPa ⁇ s / 25 ° C.)
  • D-1) to (D-4) are all manufactured by Kyoeisha Chemical Co., Ltd.
  • Titanium oxide (CR60-2) was prepared as light-scattering particles (F).
  • the reaction solution was stirred under the atmosphere (23 ° C., humidity 45%) for 60 minutes, and then 20 mL of ethanol was added.
  • the obtained suspension was centrifuged (3,000 rpm, 5 minutes) to recover the solid matter, and luminescent particles X-1 were obtained.
  • the luminescent particles X-1 were perovskite-type lead cesium tribromide 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 1 nm. That is, the luminescent particles X-1 were silica-coated particles.
  • the luminescent particles X-1 were dispersed in isobornyl methacrylate so that the solid content concentration was 2.9% by mass to obtain a luminescent particle dispersion liquid 1 in which the luminescent particles X-1 were dispersed. ..
  • ⁇ Preparation of light-scattering particle dispersion> 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. Further, zirconia beads (diameter: 1.25 mm) are added to the obtained compound, and the container is sealed and shaken for 2 hours using a paint conditioner to disperse the compound to disperse light-diffusing particles. I got body 1. The average particle size of the light diffusing particles after the dispersion treatment was 0.245 ⁇ m as measured by using NANOTRAC WAVE II.
  • the ink composition (1) was obtained.
  • the content of luminescent particles is 1.5% by mass
  • the content of IB-X is 50.0% by mass
  • the content of LM is 16.0% by mass
  • the content of PO is 4. It is 2% by mass
  • the content of 1,6-HX is 20.0% by mass
  • the content of TPO-H is 3.0% by mass
  • the content of O-819 is 1.5% by mass.
  • the content of Irganox 1010 is 0.5% by mass
  • the content of P-EPQ is 0.5% by mass
  • the content of light-scattering particles is 3.0% by mass
  • the polymer is dispersed.
  • the content of the agent was 0.3% by mass. The content is based on the total mass of the ink composition.
  • ink compositions (2) to (9) and (C1) to (C3) Luminous particle dispersion, light scattering particle dispersion, photopolymerizable compounds D-2 and D-3, photopolymerization initiators E-1 and E-2, light stabilizers A-1 to A-5, antioxidant
  • the ink compositions (2) of Examples 2 to 9 were prepared under the same conditions as the preparation of the ink composition (1) except that the addition amounts of the agents C-1 and C-2 were changed to the addition amounts shown in Table 1 below. )-(9) and the ink compositions (C1)-(C3) of Comparative Examples 1 to 3.
  • ⁇ Preparation of optical conversion layer (sample for evaluation)>
  • the obtained ink composition was applied onto a glass substrate (“EagleXG” manufactured by Corning Inc.) with a spin coater so that the film thickness after drying was 15 ⁇ m.
  • the obtained film was irradiated with ultraviolet light having an LED lamp wavelength of 395 nm under a nitrogen atmosphere at an exposure amount of 10 J / cm 2 .
  • the ink composition was cured to form a layer made of the cured product of the ink composition on the glass substrate, which was used as a light conversion layer.
  • ⁇ Evaluation of ink composition and optical conversion layer> (Example 1) ⁇ Viscosity of ink composition> The viscosity (initial viscosity) of the ink composition at 30 ° C. was measured using an E-type viscometer. ⁇ Cure film curability> When the surface of the obtained light conversion layer 1 was evaluated by palpation using a cotton swab according to the following criteria, the surface was not scratched and there was no tack feeling. ⁇ Evaluation criteria ⁇ ⁇ : The surface of the optical conversion layer 1 is not scratched and there is no tack feeling. ⁇ : The surface of the optical conversion layer 1 is not scratched and there is a slight tack feeling, but there is no problem in practical use. The surface of 1 is slightly scratched and has a tacky feeling. ⁇ : The surface of the optical conversion layer 1 is scratched and a part of the cured film adheres to the cotton swab.
  • ⁇ Bleed test> The obtained optical conversion layer 1 was allowed to stand at 60 ° C. for 30 days, then allowed to stand at 25 ° C. for another day, and then the surface of the optical conversion layer 1 was visually observed to show the presence or absence of bleeding (optical conversion layer 1). It was confirmed whether or not the components eluted from the inside ooze out on the surface) and whether or not whitening (whether or not the surface of the light conversion layer 1 was whitened by the eluted components).
  • ⁇ There is bleeding and there is whitening.
  • the external quantum efficiency is a value indicating how much of the light (photons) incident on the optical conversion layer is emitted to the observer side as fluorescence. Therefore, if this value is large, it indicates that the light conversion layer is excellent in light emission characteristics, which is an important evaluation index.
  • EQE means that the larger the value, the smaller the deterioration of the semiconductor nanocrystals due to ultraviolet rays in the curing step of the coating film, that is, the better the stability against ultraviolet rays.
  • the EQE is preferably 20% or more, more preferably 25% or more, which means that it is excellent.
  • the EQE measured immediately after the optical conversion layer was produced was set to the initial external quantum efficiency EQE 0 , and the EQE 0 was measured and found to be 32%.
  • the ink compositions of Examples 1 to 9 containing the NOR-type hindered amine compound have the above-mentioned ink viscosities and excellent curability, and are therefore suitable as ink composition for inkjet. be. Since the cured products of the ink compositions of Examples 1 to 9 are excellent in light resistance at high temperatures, the ink compositions are suitable for use in the light conversion layer.
  • the ink compositions of Examples 1 to 4 and 7 to 8 containing the NOR-type hindered amine compound having a melting point of more than 90 ° C. are particularly preferable because the surface of the light conversion layer 1 does not bleed or whiten.

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Abstract

La présente invention aborde le problème de la fourniture : d'une composition d'encre pour jet d'encre qui contient des nanocristaux semi-conducteurs composés d'un halogénure métallique et à partir de laquelle un film durci ayant une excellente résistance à la lumière à une température élevée peut être formé ; et d'une couche de conversion de lumière et d'un filtre coloré qui utilisent ladite composition d'encre. Le problème peut être résolu par une composition d'encre pour jet d'encre selon la présente invention, la composition d'encre comprenant : des particules électroluminescentes comprenant des particules de nanocristal semi-conducteur composées d'un halogénure de métal ; un composé photopolymérisable ; un initiateur de photopolymérisation ; et un composé d'amine encombrée de type NOR ayant une structure représentée par la formule (1). [Dans la formule (1), R1 à R5 représentent chacun indépendamment un groupe hydrocarboné, et * représente une liaison pendante.]
PCT/JP2021/040513 2020-11-17 2021-11-04 Composition d'encre pour jet d'encre, couche de conversion de lumière et filtre coloré WO2022107601A1 (fr)

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KR1020237014369A KR102557679B1 (ko) 2020-11-17 2021-11-04 잉크젯용 잉크 조성물, 광 변환층 및 컬러 필터
CN202180067336.8A CN116249756A (zh) 2020-11-17 2021-11-04 喷墨用油墨组合物、光转换层及滤色器

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JP2016011370A (ja) * 2014-06-30 2016-01-21 キヤノン株式会社 インク、インクカートリッジ、及びインクジェット記録方法
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