WO2019017423A1 - Ink composition, method for producing same, light conversion layer and color filter - Google Patents

Ink composition, method for producing same, light conversion layer and color filter Download PDF

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Publication number
WO2019017423A1
WO2019017423A1 PCT/JP2018/027064 JP2018027064W WO2019017423A1 WO 2019017423 A1 WO2019017423 A1 WO 2019017423A1 JP 2018027064 W JP2018027064 W JP 2018027064W WO 2019017423 A1 WO2019017423 A1 WO 2019017423A1
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Prior art keywords
ink composition
light
less
mass
particles
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PCT/JP2018/027064
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French (fr)
Japanese (ja)
Inventor
佐々木　博友
直 義原
崇之 三木
育郎 清都
穣 田淵
亜弥 石塚
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Dic株式会社
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Priority to JP2019530590A priority Critical patent/JP7124827B2/en
Publication of WO2019017423A1 publication Critical patent/WO2019017423A1/en

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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 composition and a method for producing the same, a light conversion layer, and a color filter.
  • a color filter pixel portion in a display such as a liquid crystal display device uses, for example, a curable resist material containing red organic pigment particles or green organic pigment particles and an alkali soluble resin and / or an acrylic monomer. , Has been manufactured by photolithography.
  • the method of manufacturing a color filter by the photolithography method has a disadvantage that the resist material other than the pixel portion including the relatively expensive light emitting nanocrystal particles is wasted because of the characteristic of the manufacturing method.
  • the resist material other than the pixel portion including the relatively expensive light emitting nanocrystal particles is wasted because of the characteristic of the manufacturing method.
  • thermosetting resin In such an ink composition, it is known to use various ones as a thermosetting resin, and there are many high viscosity liquid or solid ones as this thermosetting resin so that handling becomes easy. There are many forms in which it is dissolved or dispersed in an organic solvent. There is no knowledge that it is possible to reduce the defects of the light conversion layer consisting of the cured product by selecting and using an organic solvent that specifically satisfies any of the properties, and any thermosetting resin and organic solvent may be used. The light conversion layer was formed by curing using the above, and the light conversion layer was measured for various characteristic items, and it was actually confirmed that the presence or absence of a defect was confirmed through trial and error.
  • Patent Document 1 discloses a formulation containing a solvent saturated or supersaturated with an inert gas, and a functional organic material, and also discloses a formulation in which the total amount of oxygen and moisture is below a certain level.
  • this patent document 1 does not describe using a thermosetting resin. Moreover, no actual data of water content was shown, and it was unclear how much the water content would affect.
  • the influence of the atmosphere is shown in the examples for the organic light emitting material for OLED, there is no disclosure of whether or not the specific technical effect is expressed with respect to the quantum dot consisting of light emitting nanocrystal particles, the quantum dot It was unclear how much the technical effect would be.
  • the light emitting material for OLED shown by the Example does not have a wavelength conversion function, and can not divert it to the light conversion layer by a quantum dot.
  • a solvent saturated or supersaturated with an inert gas is used, bubbles are generated in the flow path of the coating liquid when the coating liquid is fed using a pump up to the coater head or nozzle for coating, Air bubbles are mixed into the coating solution to cause problems such as defects in the coated material.
  • air bubbles are generated in the printing head of the ink jet printer, resulting in a serious problem that discharge failure occurs.
  • Patent Document 2 discloses a composition containing quantum dots substantially free of water.
  • the measured data of the water content is not shown, and it is unclear whether the water content is effective.
  • the IJ method is not described, and the application of the light conversion layer to a color filter (CF) for LCD is not described.
  • CF color filter
  • ink is ejected from the nozzles of a printing head into the atmosphere, exposed to moisture in the air, and exposed to the atmosphere even after printing. Since the CF substrate has a large area, setting the vicinity of the head portion and the printing surface on the printing substrate to a moisture-free inert gas atmosphere has a problem that the device cost and the running cost increase significantly.
  • Patent Document 3 discloses that an inert gas is introduced to drive out dissolved oxygen to degas the oxygen, and degassing by depressurization. And, it is disclosed that the light emission of the quantum dot (QD) composition which does not contain oxygen is less likely to deteriorate.
  • QD quantum dot
  • Patent Documents 2 to 3 describe that acrylate monomers and oligomers can be used as the photocurable compound, the monomers actually used in the experiment have a length such as dodecanediol di (meth) acrylate. Only di (meth) acrylates that contain chain alkylene groups. These are not thermosetting resins.
  • the ink composition using the light-emitting nanocrystal particles and the light conversion layer using the ink composition are unstable with respect to moisture in the air, it is necessary to improve the stability.
  • the present invention provides the inventions of the following embodiments, respectively.
  • the organic solvent in the specific Log P value range is used as the organic solvent, no problem occurs in the cured product, and, for example, the stability in the air can be improved. .
  • a light conversion layer comprising a cured product of the ink composition according to any one of the above 1 to 3. 13. The light conversion layer in which the light conversion layer which consists of hardened
  • the plurality of pixel units are It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm.
  • the first pixel portion It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light in the wavelength range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm.
  • the light conversion layer according to any one of 12 to 14, which has a second pixel portion. 16. 12.
  • a color filter comprising the light conversion layer according to any one of 12 to 16.
  • FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.
  • the ink composition of the embodiment contains luminescent nanocrystal particles, a thermosetting resin, and an organic solvent,
  • the LogP value of the organic solvent is -1.0 or more and 6.5 or less.
  • the ink composition of one embodiment is, for example, an ink composition for a color filter, which is used to form a pixel portion of a color filter by a method such as a photolithography method or an inkjet method.
  • the ink composition of one embodiment is suitably used for the application which forms a color filter pixel part by an inkjet system.
  • the color filter pixel portion is formed by, for example, an inkjet method using a conventional ink composition, there is a problem that the light conversion layer is deteriorated when exposed to moisture in the air.
  • the ink composition of the present embodiment such a problem can be improved.
  • ink composition for color filters (ink jet ink for color filters) used for an inkjet system is mentioned as an example, and is demonstrated.
  • the light-emitting nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and for example, the maximum particle diameter measured by a transmission electron microscope or a scanning electron microscope is 100 nm or less It is a crystal.
  • the luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength, for example, by absorbing light of a predetermined wavelength.
  • the light-emitting nanocrystal particles may be red light-emitting nanocrystal particles that emit light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and light having an emission peak wavelength in the range of 500 to 560 nm It may be a green light emitting nanocrystal particle which emits (green light), and may be a blue light emitting nanocrystal particle which emits light (blue light) having an emission peak wavelength in the range of 420 to 480 nm .
  • the ink composition comprises at least one of these luminescent nanocrystal particles.
  • the light absorbed by the light-emitting nanocrystal particles may be, for example, light with a wavelength in the range of 400 nm to less than 500 nm (blue light) or light with a wavelength in the range of 200 nm to 400 nm (ultraviolet light).
  • the emission peak wavelength of the luminescent nanocrystal particle can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using an ultraviolet-visible spectrophotometer.
  • the red light emitting nanocrystalline particles have a wavelength of 665 nm or less, 663 nm or less, 660 nm or less, 658 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
  • the emission peak wavelength is preferably 632 nm or less or 630 nm or less, and the emission peak wavelength is preferably 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.
  • These upper limit value and lower limit value can be arbitrarily combined. Also in the following similar descriptions, the upper limit value and the lower limit value described individually can be arbitrarily combined.
  • Green light-emitting nanocrystal particles have an emission peak wavelength at 560 nm or less, 557 nm or less, 555 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 537 nm or less, 535 nm or less, 532 nm or less or 530 nm or less
  • the emission peak wavelength is preferably 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 light emitting nanocrystal particles have a light emission peak wavelength at 480 nm, 477 nm, 475 nm, 470 nm, 467 nm, 465 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm or 450 nm or less
  • the light emission peak wavelength is preferably 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 wavelength (emission color) of light emitted from the luminescent nanocrystal particle depends on the size (for example, particle diameter) of the luminescent nanocrystal particle according to the solution of the Schrodinger wave equation of the well potential model, but the luminescent nano It also depends on the energy gap of the crystal particles. Therefore, the emission color can be selected by changing the constituent material and the size of the luminescent nanocrystal particle to be used.
  • the luminescent nanocrystal particles may be luminescent nanocrystal particles (luminescent semiconductor nanocrystal particles) including a semiconductor material.
  • a luminescent semiconductor nanocrystal particle a quantum dot (it is also called the following "QD"), a quantum rod, etc. are mentioned.
  • QD quantum dot
  • quantum rod etc. are mentioned.
  • quantum dots are preferable from the viewpoint of easy control of the emission spectrum and reduction of production cost and improvement of mass productivity after securing reliability.
  • the light emitting semiconductor nanocrystal particle may be composed only of the core containing the first semiconductor material, and contains the core containing the first semiconductor material and the second semiconductor material different from the first semiconductor material, And a shell covering at least a part of the core.
  • the structure of the light emitting semiconductor nanocrystal particle may be a structure consisting only of the core (core structure), or may be a structure consisting of the core and the shell (core / shell structure).
  • the light-emitting semiconductor nanocrystal particles contain a third semiconductor material different from the first and second semiconductor materials, It may further have a shell (second shell) covering at least a part.
  • the structure of the light-emitting semiconductor nanocrystal particle may be a structure (core / shell / shell structure) composed of the core, the first shell and the second shell.
  • Each of the core and the shell may be a mixed crystal (for example, CdSe + CdS, CIS + ZnS, etc.) containing two or more semiconductor materials.
  • the luminescent nanocrystal particles are selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors and I-II-IV-VI semiconductors as semiconductor materials Preferably, it comprises at least one semiconductor material.
  • Specific semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnTe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe.
  • CdZnTe CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgZnTe, CdHgZnTe, CdHgSeg, CdH, CdHgSe, CdHgSe, CdHgSe, CdHgZnTe, CdHgSeg, CdH, CdHgSe, CdHgSe, CdHgSe: CdHgSe: CdHgSe: CdHgSe: Cd: InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, Ga Sb, AlNP, AlNAs, AlPAs, AlPAs, AlPSb, InPS, InNAs, InNSb, InPAs, InPAs, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNs, GaAl
  • the light-emitting semiconductor nanocrystal particles are easy to control the emission spectrum, secure reliability, reduce production cost, and can improve mass productivity, and CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS 2 , AgInSe 2 , AgInTe 2 , AgInTe 2 , AgGaS 2 , AgGaSe 2 , AgGaTe 2 , CuInS 2 , CuInSe 2 , CuInTe 2 , CuInTe 2 , CuInTe 2 , CuInTe 2 , CuInTe 2 , CuInTe 2 , CuInTe 2 It is preferable to include at least one selected from the group consisting of CuGaS 2 , CuGaSe 2 , CuGaTe 2
  • red light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe, rod-like nanocrystalline particles of CdSe, and rod-like nanocrystalline particles having a core-shell structure, and the shell portion is CdS, A nanocrystalline particle having an inner core part of CdSe, a rod-like nanocrystalline particle having a core-shell structure, wherein the shell part is a CdS nanocrystalline particle having an inner core part of ZnSe, a core-shell structure Nanocrystalline particles, wherein the shell part is CdS and the inner core part is CdSe, the nanocrystalline particle having a core-shell structure, the shell part is CdS, and the inner core part Of nanocrystalline particles of ZnSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, rod-like nanocrystalline particles of mixed crystals of CdSe and ZnS, Nanocrystalline particles of nP, nanocrystalline particles of InP, rod-like nanocrystalline particles of InP, nanocrystalline particles of mixed crystals of CdSe and C
  • green light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe, rod-like nanocrystalline particles of CdSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, and rod-like crystals of mixed crystals of CdSe and ZnS The nanocrystalline particles of
  • blue light emitting semiconductor nanocrystal particles include nanocrystalline particles of ZnSe, rodlike nanocrystalline particles of ZnSe, nanocrystalline particles of ZnS, rodlike nanocrystalline particles of ZnS, and nanocrystals having a core-shell structure.
  • the semiconductor nanocrystal particle can change the color to be emitted from the particle to be either red or green by changing the average particle size of the semiconductor chemical particle with the same chemical composition.
  • semiconductor nanocrystal particles containing cadmium, selenium or the like are used as light-emitting nanocrystal particles, it is possible to select semiconductor nanocrystal particles containing the above elements (cadmium, selenium or the like) as little as possible, or use them alone or It is preferable to use in combination with other luminescent nanocrystal particles so as to reduce as much as possible.
  • the shape of the luminescent nanocrystal particles is not particularly limited, and may be any geometric shape or any irregular shape.
  • the shape of the luminescent nanocrystal particle may be, for example, a sphere, an ellipsoid, a pyramid, a disc, a branch, a net, a rod, or the like.
  • the light-emitting nanocrystal particles it is possible to further improve the uniformity and fluidity of the ink composition by using particles with less directivity (for example, particles such as spheres and tetrahedra) as the particle shape. Preferred.
  • the average particle diameter (volume average diameter) of the light-emitting nanocrystal particles may be 1 nm or more, 1.5 nm, from the viewpoint that light emission of a desired wavelength is easily obtained, and from the viewpoint of excellent dispersibility and storage stability. Or more, and may be 2 nm or more. From the viewpoint of easily obtaining a desired emission wavelength, it may be 40 nm or less, 30 nm or less, or 20 nm or less.
  • the average particle diameter (volume average diameter) of the luminescent nanocrystal particles can be obtained by measuring the volume average diameter by measurement using a transmission electron microscope or a scanning electron microscope.
  • the luminescent nanocrystal particles preferably have an organic ligand on the surface from the viewpoint of dispersion stability.
  • the organic ligand may, for example, be coordinated to the surface of the luminescent nanocrystal particle.
  • the surface of the luminescent nanocrystal particle may be passivated by the organic ligand.
  • the luminescent nanocrystal particles may have a polymer dispersant on the surface thereof.
  • the polymer dispersant on the surface of the luminescent nanocrystal particle May be combined.
  • a polymer dispersant be blended to the light emitting nanocrystal particles in which the organic ligand remains coordinated.
  • organic ligands examples include TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (for example, HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).
  • TOP trioctylphosphine
  • TOPO trioctylphosphine oxide
  • oleic acid oleylamine
  • octylamine trioctylamine
  • hexadecylamine octanethiol
  • dodecanethiol dodecanethiol
  • hexylphosphonic acid for example, HPA
  • TDPA tetradecylphospho
  • the light-emitting nanocrystal particles those dispersed in an organic solvent in the form of colloid can be used. It is preferable that the surface of the luminescent nanocrystal particles in the dispersed state in the organic solvent be passivated by the above-mentioned organic ligand.
  • the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or a mixture thereof.
  • a commercial item can be used as a luminescent nanocrystal particle.
  • Examples of commercially available light emitting nanocrystal particles include indium phosphorus / zinc sulfide, D-dots, CuInS / ZnS manufactured by NN-Labs, and InP / ZnS manufactured by Aldrich.
  • the content of the light-emitting nanocrystal particles may be 5% by mass or more, or 10% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent in the reduction effect of leakage light.
  • the content may be 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more.
  • the content of the light-emitting nanocrystal particles may be 70% by mass or less, 60% by mass or less, based on the mass of the non-volatile component of the ink composition, from the viewpoint of excellent ejection stability.
  • the content may be less than or equal to 50% by mass.
  • the “mass of nonvolatile component of ink composition” refers to the mass of the ink composition excluding the mass of the organic solvent.
  • the luminescent nanocrystal particles have surface atoms that can be coordination sites, they have high reactivity. Luminescent nanocrystalline particles tend to cause aggregation of the particles because of having such high reactivity and having a large surface area as compared to general pigments. Since the luminescent nanocrystal particles emit light due to the quantum size effect, when aggregation of the particles occurs, a quenching phenomenon occurs, leading to a decrease in fluorescence quantum yield, and a decrease in luminance and color reproducibility. On the other hand, in the present embodiment, since the ink composition contains a polymer dispersant, it is difficult for the light-emitting nanocrystal particles to aggregate. Therefore, in the present embodiment, the content of the light-emitting nanocrystal particles can be set to the above range.
  • the ink composition of one embodiment may contain light scattering particles.
  • a color filter pixel portion (hereinafter, also simply referred to as "pixel portion") is formed of an ink composition using luminescent nanocrystal particles, light from a light source is not absorbed by the luminescent nanocrystal particles, and the pixel portion is not absorbed. May leak from the Since such leaked light reduces the color reproducibility of the pixel portion, when the pixel portion is used as the light conversion layer, it is preferable to reduce the leaked light as much as possible.
  • the light scattering particles are preferably used in order to prevent light leakage from the pixel portion.
  • the light scattering particles are, for example, optically inactive inorganic fine particles. The light scattering particles can scatter the light from the light source irradiated to the color filter pixel portion.
  • Examples of the material constituting the light scattering particles include single metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum and gold; silica, barium sulfate, barium carbonate, calcium carbonate, 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, metal oxides such as zinc oxide; magnesium carbonate, Metal carbonates such as barium carbonate, bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, Secondary nitrate And metal salts of the mass, and the like.
  • single metals such as tungsten, zirconium, titanium, platinum, bismuth, rh
  • the light scattering particles preferably contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate and silica, from the viewpoint of being superior in the light leakage reducing effect. It is more preferable to include at least one selected from the group consisting of titanium oxide, barium sulfate and calcium carbonate.
  • the shape of the light scattering particles may be spherical, filamentous, indeterminate or the like.
  • using particles with less directivity as particle shape for example, particles of spherical shape, tetrahedron shape, etc. makes the ink composition more uniform, flowable, and light scattering. It is preferable in that it is enhanced.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 ⁇ m or more, or 0.2 ⁇ m or more, from the viewpoint of being excellent by the reduction effect of leakage light. It may be 0.3 ⁇ m or more.
  • the average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 1.0 ⁇ m or less, 0.6 ⁇ m or less, or 0 from the viewpoint of excellent ejection stability. .4 ⁇ m or less.
  • the average particle diameter (volume average diameter) of the light scattering particles in the ink composition is 0.05 to 1.0 ⁇ m, 0.05 to 0.6 ⁇ m, 0.05 to 0.4 ⁇ m, 0.2 to 1 And 0.2 to 0.6 ⁇ m, 0.2 to 0.4 ⁇ m, 0.3 to 1.0 ⁇ m, 0.3 to 0.6 ⁇ m, or 0.3 to 0.4 ⁇ m. From the viewpoint of easily obtaining such an average particle diameter (volume average diameter), the average particle diameter (volume average diameter) of the light scattering particles to be used may be 50 nm or more and 1000 nm or less.
  • the average particle diameter (volume average diameter) of the light scattering particles is obtained by measuring with a dynamic light scattering nanotrack particle size distribution analyzer and calculating the volume average diameter.
  • the average particle diameter (volume average diameter) of the light scattering particles to be used can be obtained, for example, by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
  • the content of the light scattering particles may be 0.1% by mass or more, or 1% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent in the reduction effect of leakage light. It may be 5% by mass or more, 7% by mass or more, 10% by mass or more, and 12% by mass or more.
  • the content of the light scattering particles may be 60% by mass or less, 50% by mass, based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light and from the viewpoint of excellent ejection stability. Or less, or 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less, or 15% by mass It may be the following.
  • the ink composition contains a polymer dispersant, the light scattering particles can be well dispersed even when the content of the light scattering particles is in the above range.
  • the mass ratio of the content of the light scattering particles to the content of the light emitting nanocrystal particles is 0.1 to 5.0.
  • the mass ratio (light scattering particles / luminescent nanocrystal particles) may be 0.2 or more, or 0.5 or more, from the viewpoint of being more excellent in the reduction effect of the leaked light.
  • the mass ratio (light scattering particles / luminescent nanocrystal particles) may be 2.0 or less, or 1.5 or less, from the viewpoint of being excellent in the reduction effect of leakage light and excellent in continuous dischargeability at the time of ink jet printing.
  • the mass ratio (light scattering particles / luminescent nanocrystal particles) is 0.1 to 2.0, 0.1 to 1.5, 0.2 to 5.0, 0.2 to 2.0, 0. It may be 2 to 1.5, 0.5 to 5.0, 0.5 to 2.0, or 0.5 to 1.5.
  • grains is based on the following mechanisms. That is, when light scattering particles do not exist, it is considered that the backlight only travels almost straight through the inside of the pixel portion, and there is little chance of being absorbed by the light emitting nanocrystal particles.
  • the ink composition of one embodiment preferably contains a polymer dispersant.
  • the polymeric dispersant can uniformly disperse light scattering particles in the ink.
  • the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity to the light scattering particles, and has a function of dispersing the light scattering particles.
  • the polymer dispersant is adsorbed to the light scattering particles through the functional group having affinity to the light scattering particles, and electrostatic repulsion and / or steric repulsion between the polymer dispersants causes Light scattering particles are dispersed in the ink composition.
  • the polymer dispersant is preferably bonded to the surface of the light scattering particle and adsorbed to the light scattering particle, but is bonded to the surface of the light emitting nanocrystal particle and adsorbed to the light emitting nanoparticle. It may also be free in the ink composition.
  • Examples of functional groups having affinity to light scattering particles include acidic functional groups, basic functional groups and nonionic functional groups.
  • the acidic functional group has dissociative protons, and may be neutralized by a base such as an amine or hydroxide ion, and the basic functional group is neutralized by an acid such as an organic acid or inorganic acid. May be
  • the acidic functional group a carboxyl group (-COOH), a sulfo group (-SO 3 H), sulfuric acid group (-OSO 3 H), a phosphonic acid group (-PO (OH) 3), phosphoric acid group (-OPO ( OH) 3 ), phosphinic acid group (-PO (OH)-), mercapto group (-SH) can be mentioned.
  • Examples of basic functional groups include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.
  • nonionic functional group a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO 2- ), a carbonyl group, a formyl group, an ester group, a carbonate group, an amide group, A carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group and a phosphine sulfide group can be mentioned.
  • the acidic functional As a group, a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used, and as a basic functional group, an amino group is preferably used.
  • a carboxyl group, a phosphonic acid group and an amino group are more preferably used, and most preferably an amino group.
  • the polymeric dispersant having an acidic functional group has an acid value.
  • the acid value of the polymer dispersant having an acidic functional group is preferably 1 to 150 mg KOH / g in terms of solid content. When the acid value is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the acid value is 150 or less, the storage stability of the pixel portion (cured product of the ink composition) does not easily decrease. .
  • the polymer dispersant having a basic functional group has an amine value.
  • the amine value of the polymer dispersant having a basic functional group is preferably 1 to 200 mg KOH / g in terms of solid content. When the amine number is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the amine number is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) does not easily decrease. .
  • the polymer dispersant may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of monomers. Further, the polymer dispersant may be any of a random copolymer, a block copolymer or a graft copolymer. When the polymer dispersant is a graft copolymer, it may be a comb graft copolymer or a star graft copolymer.
  • the polymer dispersant includes, for example, acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, polyamine such as polyethyleneimine and polyallylamine, epoxy resin, polyimide, etc. May be there.
  • DISPERBYK-130 As a commercial item, for example, "DISPERBYK-130", “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-164", “DISPERBYK-164", “DISPERBYK-166”, “DISPERBYK-166”, “DISPERBYK-130”, made by BIC Chemie, Inc.
  • a cationic monomer having a basic group and / or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and optionally, other monomers Those synthesized by copolymerizing (nonionic monomers, monomers having a hydrophilic group, etc.) can be used.
  • the anionic monomer, the monomer having a hydrophobic group, and the other monomers monomers described in paragraphs 0034 to 0036 of JP-A No. 2004-250502 can be mentioned.
  • the weight average molecular weight of the polymer dispersant may be 750 or more and 1000 or more from the viewpoint of being able to disperse the light scattering particles well and to further improve the reduction effect of the leaked light. It may be 2000 or more, or 3000 or more.
  • the weight average molecular weight of the polymer dispersant can well disperse the light scattering particles, can further improve the effect of reducing leaked light, and can eject the viscosity of the inkjet ink, which is suitable for stable ejection. From the viewpoint of viscosity, it may be 100,000 or less, 50,000 or less, or 30,000 or less.
  • the weight average molecular weight is a weight average molecular weight in terms of polystyrene, which is measured by GPC (gel permeation chromatography, gel permeation chromatography).
  • the content of the polymer dispersant may be 0.5 parts by mass or more and 2 parts by mass or more based on 100 parts by mass of the light scattering particles from the viewpoint of dispersibility of the light scattering particles. It may be 5 parts by mass or more.
  • the content of the polymer dispersion may be 50 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the light scattering particles, from the viewpoint of wet heat stability of the pixel portion (cured product of ink composition) Or 10 parts by mass or less.
  • thermosetting resin is a resin which functions as a binder in a cured product and which is crosslinked and cured by heat.
  • the thermosetting resin has a curable group.
  • the curable group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxyl group and a methylol group, and the like, and a light shielding portion (the light resistance portion and the storage stability of the cured product of the ink composition are excellent)
  • an epoxy group is preferable from the viewpoint of excellent adhesion to a black matrix) and a substrate.
  • the thermosetting resin may have one type of curable group, and may have two or more types of curable groups.
  • thermosetting resins there are photoradically polymerizable resins (polymerized by irradiation with light when used together with a photoradical polymerization initiator) and photocationic polymerizates (photocationic polymerization). Included are resins that polymerize upon irradiation with light when used with an initiator.
  • the thermosetting resin may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of monomers.
  • the thermosetting resin may be any of a random copolymer, a block copolymer or a graft copolymer.
  • thermosetting resin a compound having two or more thermosetting functional groups in one molecule is used, and is usually used in combination with a curing agent.
  • a catalyst hardening accelerator capable of promoting a thermosetting reaction may be further added.
  • the ink composition may contain a thermosetting component including a thermosetting resin (as well as a curing agent and a curing accelerator which is optionally used).
  • a polymer which itself is not polymerizable may be further used.
  • an epoxy resin having two or more epoxy groups in one molecule may be used as a compound having two or more thermosetting functional groups in one molecule.
  • Epoxy resin includes both monomeric epoxy resin and polymeric epoxy resin.
  • the number of epoxy groups that the multifunctional epoxy resin has in one molecule is preferably 2 to 50, and more preferably 2 to 20.
  • the epoxy group may be a structure having an oxirane ring structure, and may be, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group and the like.
  • an epoxy resin the well-known polyvalent epoxy resin which can be hardened
  • Such an epoxy resin is widely disclosed, for example, in "Epoxy resin handbook” published by M. Shinbo, published by Nikkan Kogyo Shimbun (Showa 62), etc., and these can be used.
  • thermosetting resin having an epoxy group including a polyfunctional epoxy resin
  • a polymer of a monomer having an oxirane ring structure a copolymer of a monomer having an oxirane ring structure and another monomer (for example, an acrylic monomer) It can be mentioned.
  • Examples of such monomers include various epoxy group-containing monomers such as glycidyl (meth) acrylate, ⁇ -methyl glycidyl (meth) acrylate, glycidyl vinyl ether and allyl glycidyl ether; (2-oxo-1,3-oxolane ) (2-Oxo-1,3-oxolane) group-containing vinyl monomers such as methyl (meth) acrylate; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate And various alicyclic epoxy group-containing vinyl monomers such as 3,4-epoxycyclohexylethyl (meth) acrylate.
  • epoxy group-containing monomers such as glycidyl (meth) acrylate, ⁇ -methyl glycidyl (meth) acrylate, glycidyl vinyl ether and allyl glycidy
  • the ethylenically unsaturated double bond-containing monomer for example, various aromatic vinyls such as styrene, ⁇ -methylstyrene and vinyltoluene; such as methyl acrylate, ethyl acrylate, butyl acrylate and cyclohexyl acrylate, Various acrylic acid esters; Various methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate; ethylene, propylene, butene-1 Various ⁇ -olefins such as: vinyl chloride, various halogenated olefins other than fluoroolefin such as vinylidene chloride (halo / olefins); dimethyl fumarate
  • polyfunctional epoxy resins include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl Examples include methacrylate copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.
  • the compounds described in paragraphs 0044 to 0066 of JP-A-2014-56248 can also be used.
  • a homopolymer or copolymer of a monomer having such an oxirane ring structure is preferably a two-dimensional (linear) copolymer from the viewpoint of ease of handling and production, for example, without a solvent Or ethylenic unsaturation such as aromatic vinyl or (meth) acrylic acid ester which is a commonly known copolymerizable ethylenic unsaturated monomer containing glycidyl (meth) acrylate as an essential component in an organic solvent It can be obtained by polymerizing together a monomer containing one double bond and, if necessary, a monomer containing two or more ethylenically unsaturated double bonds.
  • a copolymer having a desired epoxy group content can also be obtained by adjusting the combined use ratio of glycidyl (meth) acrylate and other ethylenically unsaturated monomers, and a copolymerizable ethylenically unsaturated singlet can be obtained.
  • the refractive index of the copolymer, the glass transition temperature, the flexibility, the transparency, the solubility in organic solvents, etc. are selected depending on what kind of monomer is selected and used and how the average molecular weight of the whole is made. It can be adjusted.
  • the copolymerization ratio of a monomer containing an aromatic ring such as aromatic vinyl is, for example, the refractive index of the formed copolymer, and the alkyl chain length of (meth) acrylic acid ester is the flexibility or support of the formed copolymer. Affects adhesion to etc.
  • a copolymer is, for example, a conventional copolymerizable ethylenically unsaturated unitary monomer containing, as an essential component, the above glycidyl (meth) acrylate in an organic solvent in the specific Log P value range of the present invention described later.
  • the body can also be easily obtained, for example, by polymerization until the desired intended molecular weight is obtained so that the glycidyl group does not open.
  • the copolymer may be prepared in an organic solvent having a specific LogP value range which will be described later, and the organic solvent may be substituted with an organic solvent which is in a specific LogP value range which will be described later. .
  • a polyfunctional epoxy resin for example, bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy Resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, dicyclopentadiene Phenolic epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol A cored polyol epoxy resin, polypropylene glycol epoxy resin Resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
  • bisphenol A type epoxy resin such as trade name "epi coat 828" (made by Japan Epoxy Resins Co., Ltd.), bisphenol F epoxy resin such as trade name "YDF-175S” (made by Tohto Kasei Co., Ltd.), trade name Brominated bisphenol A type epoxy resin such as "YDB-715" (made by Tohto Kasei Co., Ltd.), bisphenol S type epoxy resin such as "EPICLON EXA 1514" (made by DIC Corporation), trade name "YDC-1312” Hydroquinone type epoxy resins such as Toto Kasei Co., Ltd.), Naphthalene type epoxy resins such as “EPICLON EXA 4032”, “HP-4770”, “HP-4700”, “HP-5000” (manufactured by DIC Corporation), Brand name "Epicoat YX4000H” (made by Japan Epoxy Resins Co.) Biphenyl type epoxy resin, bisphenol A type novolac epoxy resin such as trade name "Epikot
  • FINEDIC A-247S made by DIC Corporation, "FINEDIC A-254", “FINEDIC A-253", “FINEDIC A-229-30A”, FINE DICK A-261, FINE DICK A 249, FINE DICK A-266, FINE DICK A-241, FINE DICK M-8020, EPICLON N-740, EPICLON N-770, "Epiclon N-865" (trade name) can be used.
  • thermosetting resin When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermosetting resin, the epoxy group is replenished in the ink composition (ink jet ink), the reaction point concentration of the epoxy becomes high, and the crosslinking density is increased. it can.
  • the polyfunctional epoxy resins it is preferable to use an epoxy resin (a tetrafunctional or higher polyfunctional epoxy resin) having four or more epoxy groups in one molecule from the viewpoint of increasing the crosslinking density.
  • an epoxy resin a tetrafunctional or higher polyfunctional epoxy resin
  • a thermosetting resin having a weight average molecular weight of 10000 or less in order to improve the ejection stability from the ejection head in the ink jet method, the strength and hardness of the pixel portion (cured product of the ink composition) decrease.
  • thermosetting resin having an epoxy group a multicomponent copolymer of a monomer having an oxirane ring structure and another monomer is less in coloration, more excellent in transparency, and enhanced in crosslink density and excellent in chemical resistance and flexibility It is preferable compared with other polyfunctional epoxy resins from the viewpoint that it is easy to obtain a cured product having the above advantages.
  • the excellent optical properties and film physical properties as such a cured product indicate that it is suitable for use in, for example, optical material applications, in particular, light conversion layers expected to have long-term reliability.
  • thermosetting resin any of known and commonly used ones which can be dissolved or dispersed in the above-mentioned organic solvent can be used, for example, 4-methylhexahydro Phthalic anhydride, triethylenetetramine, diaminodiphenylmethane, phenol novolak resin, tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1 , 1-dimethylurea and the like.
  • 4-methylhexahydro Phthalic anhydride triethylenetetramine, diaminodiphenylmethane, phenol novolak resin, tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1 , 1-dimethylurea and the like.
  • phenol novolak resin compared to polymers such as phenol novolak resin, it is liquid at normal temperature or has excellent solubility in the above organic solvents and can be made low in viscosity, and curing at a lower temperature and in a shorter time is easier It is preferable to use a low molecular weight curing agent and a curing accelerator, which are less colored of the cured product.
  • the thermosetting resin may be alkali-insoluble from the viewpoint of easily obtaining a color filter pixel portion excellent in reliability.
  • the amount of the thermosetting resin dissolved in a 1% by mass aqueous potassium hydroxide solution is 30% by mass or less based on the total mass of the thermosetting resin. It means that.
  • the above-mentioned dissolution amount of the thermosetting resin is preferably 10% by mass or less, more preferably 3% by mass or less.
  • the weight average molecular weight of the thermosetting resin is a viewpoint from which an appropriate viscosity is easily obtained as an inkjet ink, a viewpoint from which the curability of the ink composition becomes good, and a solvent resistance of the pixel portion (cured product of the ink composition) And from the viewpoint of improving the wear resistance, it may be 750 or more, 1000 or more, or 2000 or more. From the viewpoint of achieving an appropriate viscosity as an inkjet ink, it may be 500000 or less, 300000 or less, or 200000 or less. However, the molecular weight after crosslinking is not limited to this.
  • the content of the thermosetting resin is from the viewpoint that an appropriate viscosity as an inkjet ink can be easily obtained, from the viewpoint that the curability of the ink composition becomes good, and the solvent resistance of the pixel portion (cured product of the ink composition) From the viewpoint of improving the abrasion resistance, the content may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the mass of the nonvolatile component of the ink composition.
  • the content of the thermosetting resin is based on the mass of the nonvolatile matter of the ink composition from the viewpoint that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. It may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
  • the organic solvent in the present invention is an organic solvent having a specific LogP value range described later.
  • Examples of the organic solvent contained in the ink composition in the present invention include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate and dimethyl malonate.
  • diethyl malonate dimethyl succinate, diethyl succinate, 1,4-butanediol diacetate, glyceryl triacetate and the like.
  • the boiling point of the organic solvent is preferably 180 ° C. or more from the viewpoint of the continuous ejection stability of the inkjet ink. Moreover, since it is necessary to remove the solvent from the ink composition before curing the ink composition when forming the pixel portion, the boiling point of the solvent is preferably 300 ° C. or less from the viewpoint of easy removal of the solvent.
  • the present invention from the viewpoint of preparing the ink composition to be uniform, and from the viewpoint of forming the color filter pixel portion (light conversion layer) with less unevenness by enhancing the fluidity of the ink composition, etc. It is preferable to use
  • the ink composition of the present invention is characterized most in using an organic solvent having a specific LogP value range, and for example, an organic solvent having a specific LogP value range is selected from the organic solvents exemplified above. Can be used as an essential ingredient.
  • the cured product of the ink composition can be made less susceptible to problems by using the organic solvent having such a specific LogP value range.
  • the log P value represents the logarithm value of the 1-octanol / water partition coefficient of the organic solvent, "Journal of Pharmaceutical Sciences, page 83, volume 84, No. 1, 1995" (WILLIAM M. MEYLAN Calculated by the method described in PHILIP H. HOWARD).
  • the log P value is a numerical value generally used to evaluate the relative hydrophobicity of organic compounds.
  • the logarithmic value of the 1-octanol / water partition coefficient can also be measured based on JIS Z 7260-117, but the values obtained by the above calculation method have a very good correlation with many measured results. It is shown in the above-mentioned literature to show.
  • the LogP value of the organic solvent is -1.0 or more and 6.5 or less, and the technical effect of the present invention is not impaired if necessary.
  • the LogP value may contain an organic solvent outside this range.
  • the LogP value of the organic solvent may be 5.0 or less, 4.0 or less, or 3.0 or less, from the viewpoint of suppressing the deterioration of the luminescent nanocrystals due to moisture. It may be the following. Further, from the viewpoint of suppressing the water absorbency of the ink composition containing the light emitting nanocrystals, it may be ⁇ 0.5 or more, 0.0 or more, or 1.0 or more.
  • the LogP value contains an organic solvent outside the range of -1.0 or more to 6.5 or less in the above range, the organic solvent suppresses deterioration of the luminescent nanocrystal due to oxygen or moisture in the air, In the ink, it may be 30% by mass or less, 20% by mass or less, 10% by mass, 5% by mass or less, or 2% by mass or less.
  • the ink composition of the present invention is a thermosetting ink composition using a thermosetting resin, it is possible to suppress, for example, the deterioration of light-emitting nanocrystal particles caused by photocuring.
  • the ink composition of the present embodiment can be applied as an ink used in a well-known and commonly used method of manufacturing a color filter, but without consuming waste materials such as relatively expensive light-emitting nanocrystal particles and solvent.
  • the color filter pixel portion (light conversion layer) can be formed only by using the necessary amount in the necessary places, so that it can be properly prepared and used so as to be compatible with the inkjet method rather than the photolithography method. preferable.
  • the viscosity of the ink composition may be, for example, 2 mPa ⁇ s or more, 5 mPa ⁇ s or more, or 7 mPa ⁇ s or more from the viewpoint of discharge stability during inkjet printing.
  • the viscosity of the ink composition may be 20 mPa ⁇ s or less, 15 mPa ⁇ s or less, or 12 mPa ⁇ s or less.
  • the ink composition can be smoothly discharged from the ink discharge hole.
  • the viscosity of the ink composition is 2 to 20 mPa ⁇ s, 2 to 15 mPa ⁇ s, 2 to 12 mPa ⁇ s, 5 to 20 mPa ⁇ s, 5 to 15 mPa ⁇ 2 to 20 mPa ⁇ s, 7 to 15 mPa ⁇ s, 7 to 12 mPa S, s, or 7 to 12 mPa ⁇ s may be used.
  • the viscosity of the ink composition is measured, for example, by an E-type viscometer.
  • the surface tension of the ink composition is preferably a surface tension suitable for the ink jet system, specifically, preferably in the range of 20 to 40 mN / m, and more preferably 25 to 35 mN / m. .
  • flying means that when the ink composition is discharged from the ink discharge hole, the landing position of the ink composition causes a shift of 30 ⁇ m or more with respect to the target position.
  • the surface tension is 40 mN / m or less, the meniscus shape at the tip of the ink discharge hole is stabilized, and the discharge control of the ink composition (for example, control of discharge amount and discharge timing) becomes easy.
  • the surface tension is 20 mN / m or less
  • the occurrence of flight deflection can be suppressed. That is, a pixel portion which is not sufficiently landed in the pixel portion formation region to be landed and insufficiently filled with the ink composition is generated, or a pixel portion formation region (or pixel portion) adjacent to the pixel portion formation region to be landed
  • the ink composition does not land on the surface, and the color reproducibility does not decrease.
  • the ink composition further contains components other than the luminescent nanocrystal particles, the light scattering particles, the thermosetting resin, the polymer dispersant, and the organic ligand, as long as the effects of the present invention are not impaired. It is also good.
  • a photopolymerizable compound, a polymerization initiator, a sensitizer etc. are mentioned, for example.
  • the water content of the ink composition can be measured by a Karl Fischer moisture meter (for example, Mitsubishi Chemical Co., Ltd., model number CA-06, vaporization unit is VA-06 manufactured by the same company).
  • the water content in the ink composition may be 90 ppm or less, 50 ppm or less, 20 ppm or less, 9 ppm or less, or 4 ppm or less from the viewpoint of suppressing deterioration of the luminescent nanocrystals. It may be 2 ppm or less and 1 ppm or less.
  • the ink composition of the present invention using an organic solvent having a specific Log P value range and setting the above-described water content range further degrades the light-emitting nanocrystals, which hardly causes a problem due to a cured product. It is more preferable from the viewpoint of being able to be effectively suppressed. In the case of the ink composition for inkjet, the best technical effect can be expected together with the discharge method.
  • the water content of the ink composition raw material such as the ink composition and the organic solvent can be controlled to the above-mentioned specific content value range by the following method.
  • molecular sieves are added to prepare an ink composition using a dehydrated organic solvent, or molecular sieves are added to a mixture of a thermosetting resin and an organic solvent, molecular sieves are added to the ink composition, and filtration is performed after dehydration. How to If necessary, the filtration as described in the left does not have to be performed.
  • the dehydration treatment time is not particularly limited, but since molecular sieves take time to adsorb water molecules contained in the ink composition raw material such as the ink composition and the organic solvent, it is necessary to add the molecular sieves after addition. It may be dehydrated for 12 hours or more, may be dehydrated for 24 hours or more, and may be dehydrated for 48 hours or more. Under the present circumstances, although it may be air
  • a heating temperature may be 200 degreeC or more, 250 degreeC or more, and 300 degreeC or more. The temperature may be 350 ° C. or higher. Depressurizing at the time of heating is also preferable in view of removing adsorbed water molecules, and may be 0.1 mmHg or less, 0.01 mmHg, or 0.001 mmHg or less. Since solid materials such as light scattering particles can adsorb water molecules, they may be dehydrated prior to use, and may be superheated to remove water in the atmosphere or in an inert gas atmosphere or under reduced pressure. .
  • the ink composition raw material may be dehydrated before preparing the ink composition, or the ink composition may be prepared without dewatering the ink composition raw material.
  • the ink composition may be dewatered.
  • the ink composition may be further dehydrated after each of the ink composition raw materials is dehydrated to prepare the ink composition.
  • the dissolved oxygen concentration of the ink composition raw material such as the ink composition and the organic solvent can be reduced by exposing the ink or the organic solvent to an inert gas flow such as nitrogen or argon or blowing an inert gas.
  • an inert gas flow such as nitrogen or argon or blowing an inert gas.
  • solid raw materials such as light scattering particles
  • the inside of the container is filled with a nitrogen stream, and the mixture is stored under a nitrogen atmosphere, whereby the mixing of oxygen into the ink composition can be suppressed.
  • the dissolved oxygen concentration is a value obtained by measuring the dissolved oxygen of the ink composition using an optical type and a solvent-resistant dissolved oxygen analyzer, and specifically, for example, using a Visiferm manufactured by Hamilton, an ink composition Dissolved oxygen concentration can be measured.
  • the oxygen scavenger may be any agent as long as it reacts with dissolved oxygen to reduce the oxygen concentration, for example, L-ascorbic acid, erythorbic acid, gallic acid, and These salts, pyrogallol, galacetophenone and the like can be mentioned.
  • the content of the oxygen scavenger in the ink composition may be 0.01% by mass or more and 0.1% by mass or more from the viewpoint of suppressing deterioration of the light-emitting nanocrystals. May be 0.5% by mass or more, 1% by mass or more, and 30% by mass or less, or 20% by mass or less from the viewpoint of avoiding coloring of the cured ink film. And 10% by mass or less, and may be 5% by mass or less.
  • both the dissolved gas concentration and the water concentration are low by performing the method of removing the dissolved gas containing dissolved oxygen in the ink composition described above and the method of dewatering the ink composition described above. It is more preferable from the viewpoint of being able to prepare the composition and more effectively suppressing the defects of the cured product and the deterioration of the luminescent nanocrystals.
  • the ink composition of embodiment mentioned above can also be used by a photolithographic system other than an inkjet system, for example.
  • the ink composition contains an alkali soluble resin as a binder polymer.
  • the ink composition When the ink composition is used in the photolithography method, first, the ink composition is applied on a substrate, and when the ink composition contains a solvent, the ink composition is further dried to form a coating film.
  • the coating film thus obtained is soluble in an alkaline developer and is patterned by being treated with the alkaline developer.
  • the alkaline developing solution is mainly an aqueous solution from the viewpoint of easiness of waste liquid processing of the developing solution etc.
  • the coating film of the ink composition is treated with the aqueous solution.
  • the ink composition using light emitting nanocrystal particles are unstable to water, and the light emitting property (for example, fluorescence) is impaired by water.
  • an inkjet method which does not require treatment with an alkaline developer (aqueous solution) is preferable.
  • the coating film of the ink composition is preferably alkali insoluble. That is, the ink composition of the present embodiment is preferably an ink composition capable of forming an alkali-insoluble coating film.
  • Such an ink composition can be obtained by using an alkali-insoluble thermosetting resin as the thermosetting resin.
  • the coating film of the ink composition is alkali insoluble means that the amount of dissolution of the coating film of the ink composition at 25 ° C. in a 1% by mass aqueous solution of potassium hydroxide is based on the total mass of the coating film of the ink composition. It means that it is 30 mass% or less.
  • the dissolution amount of the coating film of the ink composition is preferably 10% by mass or less, more preferably 3% by mass or less. If the ink composition is an ink composition capable of forming an alkali-insoluble coating film, the ink composition is applied on a substrate and then dried under conditions of 80 ° C. for 3 minutes when it contains a solvent. It can confirm by measuring the said melt
  • the method for producing an ink composition includes, for example, a first step of preparing a dispersion of light scattering particles containing light scattering particles and a polymer dispersant, a dispersion of light scattering particles, and a luminescent nano And d) mixing the crystal particles.
  • the dispersion of the light scattering particles may further contain a thermosetting resin and an organic solvent having a specific Log P value range as described above as an essential component, and in the second step, the thermosetting resin May be further mixed. According to this method, the light scattering particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leaked light in the pixel portion can be easily obtained.
  • the dispersion of light scattering particles is carried out by mixing the light scattering particles, the polymer dispersant, and optionally, the thermosetting resin, and performing dispersion treatment. May be prepared.
  • the mixing and dispersing process may be performed using a dispersing apparatus such as a bead mill, a paint conditioner, a planetary stirrer, or the like. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light scattering particles is good and the average particle diameter of the light scattering particles can be easily adjusted to a desired range.
  • the method for producing an ink composition may further comprise, prior to the second step, a step of preparing a dispersion of light-emitting nanocrystal particles containing light-emitting nanocrystal particles and a thermosetting resin. Good.
  • the dispersion of light scattering particles and the dispersion of light emitting nanocrystal particles are mixed. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leaked light in the pixel portion can be easily obtained.
  • step of preparing the dispersion of light-emitting nanocrystal particles mixing and dispersion of the light-emitting nanocrystal particles and the thermosetting resin using the same dispersion apparatus as the step of preparing the dispersion of light-scattering particles You may process it.
  • the ink composition thus obtained is prepared to have a specific water content as described above.
  • the ink composition of the present embodiment is used as an ink composition for an inkjet system
  • the ink composition is not instantaneously exposed to a high temperature upon discharge, so that the light-emitting nanocrystal particles are not easily degraded, and the light emission characteristics as expected for the color filter pixel portion (light conversion layer) Is easier to obtain.
  • FIG. 1 is a schematic cross-sectional view of a color filter according to one embodiment.
  • the color filter 100 includes a base 40 and a light conversion layer 30 provided on the base 40.
  • the light conversion layer 30 includes a plurality of pixel units 10 and a light shielding unit 20.
  • the light conversion layer 30 includes, as the pixel unit 10, a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c.
  • the first pixel unit 10a, the second pixel unit 10b, and the third pixel unit 10c are arranged in a grid so as to be repeated in this order.
  • the light shielding unit 20 is disposed between adjacent pixel units, that is, between the first pixel unit 10a and the second pixel unit 10b, between the second pixel unit 10b and the third pixel unit 10c, or the third. Are provided between the first pixel unit 10a and the second pixel unit 10c. In other words, these adjacent pixel portions are separated by the light shielding portion 20.
  • the first pixel unit 10a and the second pixel unit 10b each include a cured product of the ink composition of the above-described embodiment.
  • the cured product contains luminescent nanocrystal particles, light scattering particles, and a curing component.
  • the curing component is a cured product of a thermosetting resin, and specifically, a cured product obtained by crosslinking of a thermosetting resin. That is, the first pixel portion 10a includes the first curing component 13a and the first light emitting nanocrystal particles 11a and the first light scattering particles 12a respectively dispersed in the first curing component 13a. Including.
  • the second pixel portion 10 b includes a second curing component 13 b and a second light emitting nanocrystal particle 11 b and a second light scattering particle 12 b respectively dispersed in the second curing component 13 b.
  • the first curing component 13a and the second curing component 13b may be the same or different, and the first light scattering particles 12a and The second light scattering particles 12 b may be the same as or different from each other.
  • the first light-emitting nanocrystal particles 11a are red light-emitting nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel unit 10a may be rephrased as a red pixel unit for converting blue light into red light.
  • the second light-emitting nanocrystal particles 11b are green light-emitting nanocrystal particles that absorb light having a wavelength of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel unit 10b may be reworded as a green pixel unit for converting blue light into green light.
  • the content of the light-emitting nanocrystal particles in the pixel portion containing the cured product of the ink composition is 5% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of being superior by the leakage light reduction effect. 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, It is also good.
  • the content of the light-emitting nanocrystal particles may be 70% by mass or less and 60% by mass or less based on the total mass of the cured product of the ink composition, from the viewpoint of excellent reliability of the pixel portion. It may be 55% by mass or less, or 50% by mass or less.
  • the content of the light scattering particles in the pixel portion containing the cured product of the ink composition is 0.1% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light. It may be 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more. May be The content of the light scattering particles may be 60% by mass or less, based on the total mass of the cured product of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light and from the viewpoint of excellent reliability of the pixel portion.
  • the content of the light scattering particles is 0.1 to 60% by mass, 0.1 to 50% by mass, 0.1 to 40% by mass, or 0.1 to 60% by mass, based on the total mass of the cured product of the ink composition.
  • the third pixel unit 10c has a transmittance of 30% or more to light of wavelengths in the range of 420 to 480 nm. Therefore, the third pixel unit 10c functions as a blue pixel unit when using a light source that emits light in the wavelength range of 420 to 480 nm.
  • the third pixel portion 10c includes, for example, a cured product of a composition containing the above-mentioned thermosetting resin.
  • the cured product contains the third cured component 13c.
  • the third curing component 13c is a cured product of a thermosetting resin, and specifically, a cured product obtained by crosslinking of the thermosetting resin. That is, the third pixel unit 10c includes the third curing component 13c.
  • the composition containing a thermosetting resin can be used as the above-described ink as long as the transmittance to light in the wavelength range of 420 to 480 nm is 30% or more.
  • the components contained in the composition components other than the thermosetting resin may be further contained.
  • the transmittance of the third pixel unit 10c can be measured by a microspectroscope.
  • the thickness of the pixel portion (the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c) may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. May be The thickness of the pixel unit (the first pixel unit 10a, the second pixel unit 10b, and the third pixel unit 10c) may be, for example, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less. May be
  • 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 which comprises the light-shielding part 20 is not specifically limited, In addition to metals, such as chromium, hardening of the resin composition which made the binder polymer contain light-shielding particles, such as carbon particulates, a metal oxide, an inorganic pigment, and an organic pigment, A thing etc. can be used.
  • a binder polymer used here what mixed 1 type, or 2 or more types of resin, such as a polyimide resin, an acrylic resin, an epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, a cellulose, photosensitive resin, O / W
  • An emulsion type resin composition (for example, one obtained by emulsifying a reactive silicone) 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 transmittance, and for example, transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, transparent resin films, optical resin films, etc.
  • transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, transparent resin films, optical resin films, etc.
  • a flexible substrate or the like can be used.
  • a glass substrate made of non-alkali glass containing no alkali component in the glass Specifically, “7059 glass”, “1737 glass”, “Eagle 200” and “Eagle XG” manufactured by Corning, "AN 100" manufactured by Asahi Glass, “OA-10G” manufactured by Nippon Electric Glass, and " OA-11 "is preferred. These are materials having a small thermal expansion coefficient, and are excellent in dimensional stability and workability in high-temperature heat treatment.
  • the color filter 100 including the light conversion layer 30 described above is suitably used in the case of using a light source that emits light in the wavelength range of 420 to 480 nm.
  • the ink composition of the above-described embodiment is formed in the pixel portion forming region partitioned by the light shielding portion 20 on the base material
  • the ink composition can be manufactured by a method in which an ink-jet ink is selectively deposited by an ink-jet method, and the ink composition is cured by irradiation with an active energy ray or heating.
  • a thin film of a metal thin film such as chromium or a thin film of a resin composition containing light shielding particles is formed in a region serving as a boundary between a plurality of pixel portions on one surface side of the substrate 40 And a method of patterning this thin film.
  • the metal thin film can be formed, for example, by a sputtering method, a vacuum evaporation 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. A photolithography method etc. are mentioned as a method of patterning.
  • Examples of the inkjet method include a bubble jet (registered trademark) method using an electrothermal transducer as an energy generating element, and a piezo jet method using a piezoelectric element.
  • the ink composition When curing of the ink composition is performed by irradiation with active energy rays (for example, ultraviolet light), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like may be used.
  • active energy rays for example, ultraviolet light
  • the wavelength of light to be irradiated may be, for example, 200 nm or more and 440 nm or less.
  • the exposure dose may be, for example, 10 mJ / cm 2 or more, and may be 4000 mJ / cm 2 or less.
  • the heating temperature may be, for example, 110 ° C. or more and 250 ° C. or less.
  • the heating time may be, for example, 10 minutes or more and 120 minutes or less.
  • the light conversion layer is a pixel portion including a cured product of an ink composition containing blue light-emitting nanocrystal particles in place of or in addition to the third pixel portion 10c. (Blue pixel portion) may be provided.
  • the light conversion layer may be provided with a pixel portion (for example, a yellow pixel portion) including a cured product of an ink composition containing nanocrystal particles that emits light of colors other than red, green and blue.
  • each of the luminescent nanocrystal particles contained in each pixel portion of the light conversion layer preferably 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 the luminescent nanocrystal particles.
  • the color filter may be provided with an ink repellent layer made of a material having ink repellent property narrower than the light shielding portion on the pattern of the light shielding portion.
  • the photocatalyst containing layer as the wettability variable layer is formed in a solid form in the area including the pixel portion forming area instead of providing the ink repellent layer, and then light is applied to the photocatalyst containing layer through the photomask. The exposure may be performed by irradiation to selectively increase the parent ink property of the pixel portion formation region.
  • the photocatalyst include titanium oxide and the like.
  • the color filter may be provided with an ink receiving layer containing hydroxypropyl cellulose or the like between the base and the pixel portion.
  • the color filter may include a protective layer on the pixel portion.
  • the protective layer planarizes the color filter and prevents the components contained in the pixel section or the components contained in the pixel section and the components contained in the photocatalyst containing layer from eluting into the liquid crystal layer. It is provided.
  • materials constituting the protective layer those used as known protective layers for color filters can be used.
  • the pixel portion may be formed not by the inkjet method but by the photolithography method.
  • the ink composition is applied in layers to the substrate to form an ink composition layer.
  • the ink composition layer is exposed in a pattern, and then developed using a developer.
  • a pixel portion made of the cured product of the ink composition is formed.
  • the developing solution is usually alkaline, an alkali-soluble polymer is used as a binder polymer.
  • the inkjet method is superior to the photolithography method. This is because the photolithography method, in principle, removes about 2/3 or more of the material, and the material is wasted. Therefore, in the present embodiment, it is preferable to form the pixel portion by an inkjet method using an inkjet ink.
  • 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 nanocrystal particles.
  • a pigment having substantially the same color as the luminescent color of the luminescent nanocrystal particles.
  • blue light or quasi-white light having a peak at 450 nm as light from a light source
  • concentration of the luminescent nanocrystal particles in the pixel portion is not sufficient, light from the light source is transmitted through the light conversion layer when the liquid crystal display element is driven.
  • a pigment may be contained in the pixel portion of the light conversion layer from the viewpoint of preventing the decrease in color reproducibility due to the occurrence of such color mixing.
  • the pigment may be contained in the ink composition in order to contain the pigment in the pixel portion.
  • one or two or more of the red pixel portion (R), the green pixel portion (G), and the blue pixel portion (B) in the light conversion layer of the present embodiment do not contain the luminescent nanocrystal particles. It may be a pixel portion containing a coloring material.
  • a coloring material which can be used here a well-known coloring material can be used, for example, as a coloring material used for a red pixel part (R), a diketopyrrolopyrrole pigment and / or anionic red organic dye are It can be mentioned.
  • Examples of the color material used for the green pixel portion (G) include at least one selected from the group consisting of a halogenated copper phthalocyanine dye, a phthalocyanine green dye, and a mixture of a phthalocyanine blue dye and an azo yellow organic dye.
  • a coloring material used for a blue pixel part (B) (epsilon) type copper phthalocyanin pigment and / or a cationic blue organic dye are mentioned.
  • the amount of the coloring material used is 1 to 5 mass based on the total mass of the pixel portion (cured product of ink composition) from the viewpoint of preventing a decrease in transmittance when it is contained in the light conversion layer. % Is preferred.
  • chloroform, ethanol, hexane, toluene, 1,4-butanediol diacetate used in the following are pre-made with molecular sieves (basically using 3A, hexane, toluene, butanediol diacetate using 4A). It was used after being dehydrated and dried over time. Before use, titanium oxide was heated at 120 ° C. under a reduced pressure of 1 mmHg for 2 hours, and allowed to cool under a nitrogen gas atmosphere.
  • trioctyl phosphine Indium phosphide
  • a stock solution is prepared by mixing 42.9 ml of a 1 M solution of diethyl zinc in hexane and 92.49 g of a 9.09% by weight solution of bistrimethylsilyl sulfide in 92 g of trioctylphosphine in a glove box. After the inside of the flask was replaced with a nitrogen atmosphere, the temperature of the flask was set to 180 ° C., and when reaching 80 ° C., 15 ml of the above stock solution was added, and thereafter 15 ml was added every 10 minutes. (Flask temperature maintained at 180 ° C.). After the final addition, the reaction was terminated by maintaining the temperature for an additional 10 minutes.
  • the solution was cooled to room temperature, and 500 ml of toluene and 2000 ml of ethanol were added to aggregate the nanocrystals. After precipitating the nanocrystals using a centrifuge, discard the supernatant and dissolve the precipitate again in chloroform so that the concentration of nanocrystals in the solution becomes 20% by mass, InP / ZnS core-shell nanocrystals Chloroform solution was obtained.
  • Triethylene glycol monomethyl ether ester triethylene glycol monomethyl ether mercaptopropionate (TEGMEMP) of 3-mercaptopropanoic acid was synthesized with reference to JP-A-2002-121549.
  • QD dispersion 1 above InP / ZnS core-shell nanocrystal (red light emitting property)
  • 80 g of a chloroform solution in which 8 g of TEGMEMP synthesized above was dissolved were mixed and heated at 80 ° C. for 2 hours
  • the ligand exchange was carried out by stirring and cooled to room temperature. Then, while stirring at 40 ° C.
  • toluene / chloroform was evaporated and concentrated until the liquid volume reached 100 ml.
  • Four-fold weight n-hexane was added to this dispersion to aggregate QD, and the supernatant was removed by centrifugation and decantation.
  • the precipitate was added with 50 g of toluene and redispersed with ultrasound. This washing operation was performed a total of three times to remove free ligand components remaining in the solution.
  • the precipitate after decantation was vacuum dried at room temperature for 2 hours to obtain 2 g of a powder of TEGMEMP modified QD (QD-TEGMEMP).
  • Example 1 Preparation of Ink Composition
  • the mixture is filtered with a filter with a pore size of 5 ⁇ m in a glove box and nitrogen gas is further added into the ink It was introduced to saturate nitrogen gas.
  • the ink composition was obtained by reducing pressure and removing nitrogen gas. The following materials were used.
  • Example 2 [Preparation of Ink Composition] In the same manner as in Example 1, an ink composition was obtained using QD dispersion 2 (the above-mentioned InP / ZnS core-shell nanocrystal (green light emitting property)) instead of QD dispersion 1.
  • QD dispersion 2 the above-mentioned InP / ZnS core-shell nanocrystal (green light emitting property)
  • Comparative Example 1 An ink composition sealed in nitrogen gas and prepared in the same manner as in Example 1 using decylbenzene as an organic solvent was stirred in the air to obtain an ink composition. An increase in dissolved oxygen concentration was observed.
  • the ink composition obtained above was applied on a glass substrate in the air with a spin coater so that the film thickness after drying was 3.5 ⁇ m.
  • the coating film was heated at 180 ° C. in nitrogen for curing to form a layer (light conversion layer) comprising a cured product of the ink composition on a glass substrate.
  • the light conversion filter was obtained by the above operation.
  • E (Blue), P (Red), and P (Gleen) respectively represent the following.
  • h represents Planck's constant and c represents the speed of light. (This is a value corresponding to the number of observed photons.)
  • P (Gleen) It represents the total value in this wavelength range of "illuminance x wavelength ⁇ hc" at the measurement wavelength of 590 to 780 nm. (Corresponding to the number of observed photons)
  • EQE was calculated, EQE of Example 2 was set to 10, and EQE of the measured sample was evaluated as follows using relative values. ⁇ Evaluation criteria> Less than 10: D 10: C More than 10 and less than 100: B More than 100: A
  • a substrate (BM substrate) having a light shielding portion called a black matrix (BM) was produced in the following procedure. That is, after a black resist ("CFPR BK” manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on a glass substrate ("OA-10G” manufactured by Nippon Electric Glass Co., Ltd.) made of alkali free glass, prebaking, pattern exposure, development and By performing post-baking, a patterned light shielding portion was formed. The exposure was performed by irradiating the black resist with ultraviolet light at an exposure amount of 250 mJ / cm 2 .
  • the pattern of the light shielding portion was a pattern having an opening portion corresponding to a 200 ⁇ m ⁇ 600 ⁇ m sub-pixel, the line width was 20 ⁇ m, and the thickness was 2.6 ⁇ m.
  • the red light emitting ink composition obtained in Example 1 was printed on the opening portion on the BM substrate by an inkjet method, then irradiated with ultraviolet light, and then heated at 150 ° C. for 30 minutes under a nitrogen atmosphere.
  • the ink composition was cured to form a pixel portion made of a cured product of the ink composition.
  • the obtained pixel part is a pixel part which converts blue light into red light.
  • the thickness of the pixel portion was 2.1 ⁇ m.
  • a patterned light conversion filter was obtained by the above operation.
  • Example 4 In the same manner as in Example 3, a BM substrate was prepared. Subsequently, the red light emitting ink composition obtained in Example 1 and the green light emitting ink composition obtained in Example 2 are printed on the opening portion on the BM substrate by an inkjet method, and then the ultraviolet ray is irradiated. The ink composition was cured in the same manner. Thus, on the BM substrate, a pixel portion that converts blue light to red light and a pixel portion that converts blue light to green light are formed. By the above-described operation, a patterned light conversion filter including a plurality of types of pixel units is obtained.

Abstract

The present invention provides: an ink composition that is characterized by containing light-emitting nanocrystalline particles, a thermosetting resin and an organic solvent, with the LogP value of the organic solvent being -1.0 to -6.5; an ink composition that is characterized by containing light-emitting nanocrystalline particles, a thermosetting resin and an organic solvent, with the LogP value of the organic solvent being -1.0 to -6.5 and the content of moisture (H2O), obtained using a Karl Fischer moisture meter, being 90 ppm or less; a light conversion layer having a plurality of pixels, wherein the plurality of pixels include pixels containing a cured product of the ink composition; and a color filter comprising the light conversion layer.

Description

インク組成物及びその製造方法、光変換層並びにカラーフィルタInk composition and method for producing the same, light conversion layer and color filter
　本発明は、インク組成物及びその製造方法、光変換層並びにカラーフィルタに関する。 The present invention relates to an ink composition and a method for producing the same, a light conversion layer, and a color filter.
　従来、液晶表示装置等のディスプレイにおけるカラーフィルタ画素部は、例えば、赤色有機顔料粒子又は緑色有機顔料粒子と、アルカリ可溶性樹脂及び／又はアクリル系単量体とを含有する硬化性レジスト材料を用いて、フォトリソグラフィ法により製造されてきた。 Conventionally, a color filter pixel portion in a display such as a liquid crystal display device uses, for example, a curable resist material containing red organic pigment particles or green organic pigment particles and an alkali soluble resin and / or an acrylic monomer. , Has been manufactured by photolithography.
　近年、ディスプレイの低消費電力化が強く求められるようになり、上記赤色有機顔料粒子又は緑色有機顔料粒子に代えて、例えば量子ドット、量子ロッド、その他の無機蛍光体粒子等の発光性ナノ結晶粒子を用いて、赤色画素、緑色画素といったカラーフィルタ画素部を形成させる方法が、活発に研究されている。 In recent years, reduction in power consumption of a display is strongly demanded, and light emitting nanocrystal particles such as quantum dots, quantum rods, and other inorganic phosphor particles are substituted for the above red organic pigment particles or green organic pigment particles. Active research is being conducted on methods of forming color filter pixel portions such as red pixels and green pixels using
　ところで、上記フォトリソグラフィ法でのカラーフィルタの製造方法では、その製造方法の特徴から、比較的高価な発光性ナノ結晶粒子を含めた画素部以外のレジスト材料が無駄になるという欠点があった。このような状況下、上記のようなレジスト材料の無駄をなくすため、インクジェット法により、光変換基板画素部を形成することが検討され始めている。 By the way, the method of manufacturing a color filter by the photolithography method has a disadvantage that the resist material other than the pixel portion including the relatively expensive light emitting nanocrystal particles is wasted because of the characteristic of the manufacturing method. Under such circumstances, in order to eliminate the waste of the resist material as described above, it has begun to be studied to form the light conversion substrate pixel portion by the ink jet method.
　この様なインク組成物においては、熱硬化性樹脂として種々ものを用いることが知られており、この熱硬化性樹脂としては高粘度の液状或いは固体状のものが多く、取扱いが容易となるよう、それを有機溶剤に溶解または分散させた形態のものが多い。具体的にどの様な特性を満足する有機溶剤を選択して用いると、その硬化物からなる光変換層の不具合を軽減できるのか、といった知見はなく、それぞれ任意の熱硬化性樹脂と有機溶剤とを用いて硬化させて光変換層を形成させて、当該光変換層につき、種々特性項目について測定を行い、試行錯誤の上で、不具合の有無を確認しているのが実情であった。 In such an ink composition, it is known to use various ones as a thermosetting resin, and there are many high viscosity liquid or solid ones as this thermosetting resin so that handling becomes easy. There are many forms in which it is dissolved or dispersed in an organic solvent. There is no knowledge that it is possible to reduce the defects of the light conversion layer consisting of the cured product by selecting and using an organic solvent that specifically satisfies any of the properties, and any thermosetting resin and organic solvent may be used. The light conversion layer was formed by curing using the above, and the light conversion layer was measured for various characteristic items, and it was actually confirmed that the presence or absence of a defect was confirmed through trial and error.
　例えば、発光性ナノ結晶粒子からなる量子ドットインクには空気中の水分が溶け込み、劣化する問題があった。
　特許文献１には、不活性ガスにより飽和または過飽和された溶媒、及び機能性有機材料を含む調合物を開示するとともに、酸素と水分の総量を一定レベル以下とした調合物を開示している。
　しかしながら、この特許文献１には、熱硬化性樹脂を用いることは記載されていない。
　しかも、水分量の実測データが示されておらず、どの程度の水分量がどの程度影響するか不明であった。
　また、ＯＬＥＤ用有機発光材料について、実施例で大気の影響を示しているが、発光性ナノ結晶粒子からなる量子ドットに関して具体的な技術的効果が発現するか否かの開示がなく、量子ドットについて具体的にどの程度の技術的効果があるか不明であった。また実施例に示されたＯＬＥＤ用発光材料は波長変換機能がなく、量子ドットによる光変換層に転用できない。
　また、不活性ガスを飽和または過飽和させた溶剤を用いた場合、塗布のためのコーターヘッドやノズルまでポンプを用いて塗布液を送液する際に、塗布液の流路内に気泡が生じ、塗布液に気泡が混入して塗布物が不良となる等の問題を生じる。またインクジェットインクとして用いると、インクジェットプリンターの印刷用ヘッド内で気泡が発生し、吐出不良が発生するという大きな問題があった。 For example, there is a problem that moisture in the air dissolves into the quantum dot ink composed of light emitting nanocrystal particles, resulting in deterioration.
Patent Document 1 discloses a formulation containing a solvent saturated or supersaturated with an inert gas, and a functional organic material, and also discloses a formulation in which the total amount of oxygen and moisture is below a certain level.
However, this patent document 1 does not describe using a thermosetting resin.
Moreover, no actual data of water content was shown, and it was unclear how much the water content would affect.
In addition, although the influence of the atmosphere is shown in the examples for the organic light emitting material for OLED, there is no disclosure of whether or not the specific technical effect is expressed with respect to the quantum dot consisting of light emitting nanocrystal particles, the quantum dot It was unclear how much the technical effect would be. Moreover, the light emitting material for OLED shown by the Example does not have a wavelength conversion function, and can not divert it to the light conversion layer by a quantum dot.
When a solvent saturated or supersaturated with an inert gas is used, bubbles are generated in the flow path of the coating liquid when the coating liquid is fed using a pump up to the coater head or nozzle for coating, Air bubbles are mixed into the coating solution to cause problems such as defects in the coated material. In addition, when used as an ink jet ink, air bubbles are generated in the printing head of the ink jet printer, resulting in a serious problem that discharge failure occurs.
　特許文献２には、水分を実質的に含まない量子ドットを含む組成物が開示されている。しかし水分量の実測データが示されておらず、どの程度の水分量が有効か不明である。
　またＩＪ法について述べられておらず、光変換層のＬＣＤ用のカラーフィルタ（ＣＦ）への適用についても述べられていない。
　ＩＪ法では印刷用ヘッドのノズルからインクが大気中に吐出され、空気中の水分に晒され、印刷後も大気中に晒される。ＣＦ基板は大面積であるため、ヘッド部分近傍や印刷基材上の印刷面を水分のない不活性ガス雰囲気とすることは、装置価格とランニングコストが大幅に増大する問題がある。このため、大気中の湿気にインクが晒されても、量子ドットの性能劣化の少ないインクが望まれていた。
　従って、量子ドットの劣化の少ない、かつ、送液時やＩＪヘッド内で気泡発生の少ないインクが求められていた。 Patent Document 2 discloses a composition containing quantum dots substantially free of water. However, the measured data of the water content is not shown, and it is unclear whether the water content is effective.
Also, the IJ method is not described, and the application of the light conversion layer to a color filter (CF) for LCD is not described.
In the IJ method, ink is ejected from the nozzles of a printing head into the atmosphere, exposed to moisture in the air, and exposed to the atmosphere even after printing. Since the CF substrate has a large area, setting the vicinity of the head portion and the printing surface on the printing substrate to a moisture-free inert gas atmosphere has a problem that the device cost and the running cost increase significantly. For this reason, even if the ink is exposed to the moisture in the atmosphere, an ink with less deterioration in the performance of the quantum dot has been desired.
Therefore, there is a need for an ink which causes less deterioration of the quantum dots and generates less air bubbles at the time of liquid feeding or in the IJ head.
　尚、特許文献３には、不活性ガスを導入して溶存酸素を追い出して酸素を脱気すること、減圧により脱気することを開示している。そして酸素を含まない量子ドット（ＱＤ）組成物の発光が劣化しにくいことを開示している。
　しかし、ＩＪ印刷用インクやインク硬化膜が大気中に晒された場合には、ＱＤが大気中の水分に晒されることになる。こうした場合、公知の方法では劣化を抑制することができず、ＩＪ印刷にとって有利なＱＤ組成物やその硬化物が望まれている。 Patent Document 3 discloses that an inert gas is introduced to drive out dissolved oxygen to degas the oxygen, and degassing by depressurization. And, it is disclosed that the light emission of the quantum dot (QD) composition which does not contain oxygen is less likely to deteriorate.
However, when the IJ printing ink or the cured ink film is exposed to the atmosphere, the QD is exposed to moisture in the atmosphere. In such a case, a known method can not suppress deterioration, and a QD composition or its cured product advantageous for IJ printing is desired.
　特許文献２～３では、光硬化性化合物として、アクリレートモノマーやオリゴマーを用いることできることが記載されているものの、実際に実験で用いられているモノマーは、ドデカンジオールジ（メタ）アクリレートの様な長鎖アルキレン原子団を含有する様なジ（メタ）アクリレートのみである。これらは熱硬化性樹脂ではない。 Although Patent Documents 2 to 3 describe that acrylate monomers and oligomers can be used as the photocurable compound, the monomers actually used in the experiment have a length such as dodecanediol di (meth) acrylate. Only di (meth) acrylates that contain chain alkylene groups. These are not thermosetting resins.
特表２０１６－５０１４３０公報Special table 2016-501430 gazette 米国公開特許２０１４／００２７６７３明細書US Patent Publication 2014/0027673 ＷＯ２０１３／１２２８２０公報WO2013 / 122820 gazette
　発光性ナノ結晶粒子を用いたインク組成物や、該インク組成物を用いた光変換層が、大気中の水分に対し不安定であるため、安定性を改善する必要がある。 Since the ink composition using the light-emitting nanocrystal particles and the light conversion layer using the ink composition are unstable with respect to moisture in the air, it is necessary to improve the stability.
　水分に対する安定性を向上させたインク組成物及びその製造方法、並びに該インク組成物を用いた光変換層及びカラーフィルタを提供することを目的とする。
It is an object of the present invention to provide an ink composition having improved stability to moisture, a method for producing the same, and a light conversion layer and a color filter using the ink composition.
　本発明は、以下の実施態様の発明をそれぞれ提供するものである。
　下記１のインク組成物によれば、有機溶剤として特定ＬｏｇＰ値範囲の有機溶剤を用いているので、その硬化物に不具合が発生せず、例えば、大気中での安定性を向上させることができる。 The present invention provides the inventions of the following embodiments, respectively.
According to the ink composition of the following 1, since the organic solvent in the specific Log P value range is used as the organic solvent, no problem occurs in the cured product, and, for example, the stability in the air can be improved. .
１．発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であることを特徴とするインク組成物。
２．発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であり、
カールフィッシャー水分計に基づく水分（Ｈ２Ｏ）含有率が、９０ｐｐｍ以下であることを特徴とするインク組成物。
３．発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であり、
カールフィッシャー水分計に基づく水分（Ｈ２Ｏ）含有率が、９０ｐｐｍ以下であることを特徴とするインクジェット用インク組成物。
４．前記インク組成物の製造方法であって、前記インク組成物を減圧し溶存ガスを除去することを特徴とする、前記３記載のインクジェット用インク組成物の製造方法。
５．前記水分（Ｈ２Ｏ）含有率が、２０ｐｐｍ以下であることを前記３記載のインクジェット用インク組成物。
６．前記熱硬化性樹脂が、アルカリ不溶性である、前記３または５のいずれか一項記載のインクジェット用インク組成物。
７．アルカリ不溶性の塗布膜を形成可能である、前記３、５または６のいずれか一項記載のインクジェット用インク組成物。
８．表面張力が２０～４０ｍＮ／ｍである、前記３、５、６または７のいずれか一項記載のインクジェット用インク組成物。
９．粘度が２～２０ｍＰａ・ｓである、前記３、５、６、７または８のいずれか一項記載のインクジェット用インク組成物。
１０．沸点が１８０℃以上である溶剤を更に含有する、前記３、５、６、７、８または９のいずれか一項記載のインクジェット用インク組成物。
１１．カラーフィルタ用である、前記３、５、６、７、８、９または１０のいずれか一項記載のインクジェット用インク組成物。 1. Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
An ink composition wherein the LogP value of the organic solvent is -1.0 or more and 6.5 or less.
2. Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
The LogP value of the organic solvent is -1.0 or more and 6.5 or less,
An ink composition having a water (H 2 O) content based on a Karl Fischer moisture meter of 90 ppm or less.
3. Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
The LogP value of the organic solvent is -1.0 or more and 6.5 or less,
An ink composition for inkjet according to claim 1, wherein a water content (H 2 O) content based on a Karl Fischer moisture meter is 90 ppm or less.
4. The method for producing an ink composition according to the above 3, wherein in the method for producing the ink composition, the pressure of the ink composition is reduced to remove the dissolved gas.
5. The ink composition for inkjet according to the above 3, wherein the water (H 2 O) content is 20 ppm or less.
6. 5. The ink composition for inkjet according to any one of 3 or 5, wherein the thermosetting resin is alkali insoluble.
7. The inkjet ink composition according to any one of 3, 5 or 6, which is capable of forming an alkali-insoluble coating film.
8. The inkjet ink composition according to any one of 3, 5, 6 or 7, which has a surface tension of 20 to 40 mN / m.
9. The ink composition for inkjet according to any one of 3, 5, 6, 7 or 8, which has a viscosity of 2 to 20 mPa · s.
10. The ink composition for ink jet according to any one of 3, 5, 6, 7, 8 or 9, which further contains a solvent having a boiling point of 180 ° C. or higher.
11. The ink composition for inkjet according to any one of 3, 5, 6, 7, 8, 9 or 10, which is for color filters.
１２．前記１～３のいずれか一項記載のインク組成物の硬化物からなる光変換層。
１３．前期１～３のいずれか一項記載のインク組成物の硬化物からなる光変換層がアルカリ不溶性である光変換層。
１４．複数の画素部を備える光変換層であって、
　前記複数の画素部は、前記３、５、６、７、８、９または１０のいずれか一項記載のインクジェット用インク組成物の硬化物を含む画素部を有する、光変換層。
１５．前記複数の画素部間に設けられた遮光部を更に備え、
　前記複数の画素部は、
　前記硬化物を含み、且つ、前記発光性ナノ結晶粒子として、４２０～４８０ｎｍの範囲
の波長の光を吸収し６０５～６６５ｎｍの範囲に発光ピーク波長を有する光を発する発光
性ナノ結晶粒子を含有する、第１の画素部と、
　前記硬化物を含み、且つ、前記発光性ナノ結晶粒子として、４２０～４８０ｎｍの範囲
の波長の光を吸収し５００～５６０ｎｍの範囲に発光ピーク波長を有する光を発する発光
性ナノ結晶粒子を含有する、第２の画素部と、を有する、前記１２～１４のいずれか一項記載の光変換層。
１６．前記複数の画素部は、４２０～４８０ｎｍの範囲の波長の光に対する透過率が３０％以上である第３の画素部を更に有する、前記１２～１５のいずれか一項記載の光変換層。
１７．前記１２～１６のいずれか一項記載の光変換層を備える、カラーフィルタ。 12. A light conversion layer comprising a cured product of the ink composition according to any one of the above 1 to 3.
13. The light conversion layer in which the light conversion layer which consists of hardened | cured material of the ink composition as described in any one of said 1-3 is alkali-insoluble.
14. A light conversion layer comprising a plurality of pixel portions, wherein
The light conversion layer which has a pixel part containing the hardened | cured material of the ink composition for inkjet as described in any one of said 3, 5, 6, 7, 8, 9 or 10 as said several pixel part.
15. It further comprises a light shielding part provided between the plurality of pixel parts,
The plurality of pixel units are
It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. , The first pixel portion,
It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light in the wavelength range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. The light conversion layer according to any one of 12 to 14, which has a second pixel portion.
16. 12. The light conversion layer according to any one of 12 to 15, wherein the plurality of pixel portions further have a third pixel portion having a transmittance of 30% or more to light having a wavelength of 420 to 480 nm.
17. A color filter comprising the light conversion layer according to any one of 12 to 16.
　大気中での安定性を向上させたインク組成物及びその製造方法、並びに該インク組成物を用いた光変換層及びカラーフィルタを提供することができる。 It is possible to provide an ink composition having improved stability in air, a method for producing the same, and a light conversion layer and a color filter using the ink composition.
図１は、本発明の一実施形態のカラーフィルタの模式断面図である。FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.
　以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜インク組成物＞
　実施形態のインク組成物は、発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であることを特徴とする。 <Ink composition>
The ink composition of the embodiment contains luminescent nanocrystal particles, a thermosetting resin, and an organic solvent,
The LogP value of the organic solvent is -1.0 or more and 6.5 or less.
　一実施形態のインク組成物は、例えば、フォトリソグラフィ方式、インクジェット方式等の方法によりカラーフィルタの画素部を形成するために用いられる、カラーフィルタ用インク組成物である。 The ink composition of one embodiment is, for example, an ink composition for a color filter, which is used to form a pixel portion of a color filter by a method such as a photolithography method or an inkjet method.
　一実施形態のインク組成物は、インクジェット方式でカラーフィルタ画素部を形成する用途に好適に用いられる。
　従来のインク組成物を用いて、例えば、インクジェット方式でカラーフィルタ画素部を形成する場合、大気中の水分に曝されると、光変換層が劣化する問題があった。
　一方、本実施形態のインク組成物によれば、このような問題を改善することができる。 The ink composition of one embodiment is suitably used for the application which forms a color filter pixel part by an inkjet system.
When the color filter pixel portion is formed by, for example, an inkjet method using a conventional ink composition, there is a problem that the light conversion layer is deteriorated when exposed to moisture in the air.
On the other hand, according to the ink composition of the present embodiment, such a problem can be improved.
　以下では、インクジェット方式に用いられるカラーフィルタ用インク組成物（カラーフィルタ用インクジェットインク）を例に挙げて説明する。 Below, the ink composition for color filters (ink jet ink for color filters) used for an inkjet system is mentioned as an example, and is demonstrated.
［発光性ナノ結晶粒子］
　発光性ナノ結晶粒子は、励起光を吸収して蛍光又は燐光を発光するナノサイズの結晶体であり、例えば、透過型電子顕微鏡又は走査型電子顕微鏡によって測定される最大粒子径が１００ｎｍ以下である結晶体である。 [Luminescent nanocrystalline particles]
The light-emitting nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and for example, the maximum particle diameter measured by a transmission electron microscope or a scanning electron microscope is 100 nm or less It is a crystal.
　発光性ナノ結晶粒子は、例えば、所定の波長の光を吸収することにより、吸収した波長とは異なる波長の光（蛍光又は燐光）を発することができる。発光性ナノ結晶粒子は、６０５～６６５ｎｍの範囲に発光ピーク波長を有する光（赤色光）を発する、赤色発光性のナノ結晶粒子であってよく、５００～５６０ｎｍの範囲に発光ピーク波長を有する光（緑色光）を発する、緑色発光性のナノ結晶粒子であってよく、４２０～４８０ｎｍの範囲に発光ピーク波長を有する光（青色光）を発する、青色発光性のナノ結晶粒子であってもよい。一実施形態では、インク組成物がこれらの発光性ナノ結晶粒子のうちの少なくとも一種を含むことが好ましい。また、発光性ナノ結晶粒子が吸収する光は、例えば、４００ｎｍ以上５００ｎｍ未満の範囲の波長の光（青色光）、又は、２００ｎｍ～４００ｎｍの範囲の波長の光（紫外光）であってよい。なお、発光性ナノ結晶粒子の発光ピーク波長は、例えば、紫外可視分光光度計を用いて測定される蛍光スペクトル又は燐光スペクトルにおいて確認することできる。 The luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength, for example, by absorbing light of a predetermined wavelength. The light-emitting nanocrystal particles may be red light-emitting nanocrystal particles that emit light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and light having an emission peak wavelength in the range of 500 to 560 nm It may be a green light emitting nanocrystal particle which emits (green light), and may be a blue light emitting nanocrystal particle which emits light (blue light) having an emission peak wavelength in the range of 420 to 480 nm . In one embodiment, it is preferred that the ink composition comprises at least one of these luminescent nanocrystal particles. The light absorbed by the light-emitting nanocrystal particles may be, for example, light with a wavelength in the range of 400 nm to less than 500 nm (blue light) or light with a wavelength in the range of 200 nm to 400 nm (ultraviolet light). In addition, the emission peak wavelength of the luminescent nanocrystal particle can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using an ultraviolet-visible spectrophotometer.
　赤色発光性のナノ結晶粒子は、６６５ｎｍ以下、６６３ｎｍ以下、６６０ｎｍ以下、６５８ｎｍ以下、６５５ｎｍ以下、６５３ｎｍ以下、６５１ｎｍ以下、６５０ｎｍ以下、６４７ｎｍ以下、６４５ｎｍ以下、６４３ｎｍ以下、６４０ｎｍ以下、６３７ｎｍ以下、６３５ｎｍ以下、６３２ｎｍ以下又は６３０ｎｍ以下に発光ピーク波長を有することが好ましく、６２８ｎｍ以上、６２５ｎｍ以上、６２３ｎｍ以上、６２０ｎｍ以上、６１５ｎｍ以上、６１０ｎｍ以上、６０７ｎｍ以上又は６０５ｎｍ以上に発光ピーク波長を有することが好ましい。これらの上限値及び下限値は、任意に組み合わせることができる。なお、以下の同様の記載においても、個別に記載した上限値及び下限値は任意に組み合わせ可能である。 The red light emitting nanocrystalline particles have a wavelength of 665 nm or less, 663 nm or less, 660 nm or less, 658 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 The emission peak wavelength is preferably 632 nm or less or 630 nm or less, and the emission peak wavelength is preferably 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. These upper limit value and lower limit value can be arbitrarily combined. Also in the following similar descriptions, the upper limit value and the lower limit value described individually can be arbitrarily combined.
　緑色発光性のナノ結晶粒子は、５６０ｎｍ以下、５５７ｎｍ以下、５５５ｎｍ以下、５５０ｎｍ以下、５４７ｎｍ以下、５４５ｎｍ以下、５４３ｎｍ以下、５４０ｎｍ以下、５３７ｎｍ以下、５３５ｎｍ以下、５３２ｎｍ以下又は５３０ｎｍ以下に発光ピーク波長を有することが好ましく、５２８ｎｍ以上、５２５ｎｍ以上、５２３ｎｍ以上、５２０ｎｍ以上、５１５ｎｍ以上、５１０ｎｍ以上、５０７ｎｍ以上、５０５ｎｍ以上、５０３ｎｍ以上又は５００ｎｍ以上に発光ピーク波長を有することが好ましい。 Green light-emitting nanocrystal particles have an emission peak wavelength at 560 nm or less, 557 nm or less, 555 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 537 nm or less, 535 nm or less, 532 nm or less or 530 nm or less The emission peak wavelength is preferably 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.
　青色発光性のナノ結晶粒子は、４８０ｎｍ以下、４７７ｎｍ以下、４７５ｎｍ以下、４７０ｎｍ以下、４６７ｎｍ以下、４６５ｎｍ以下、４６３ｎｍ以下、４６０ｎｍ以下、４５７ｎｍ以下、４５５ｎｍ以下、４５２ｎｍ以下又は４５０ｎｍ以下に発光ピーク波長を有することが好ましく、４５０ｎｍ以上、４４５ｎｍ以上、４４０ｎｍ以上、４３５ｎｍ以上、４３０ｎｍ以上、４２８ｎｍ以上、４２５ｎｍ以上、４２２ｎｍ以上又は４２０ｎｍ以上に発光ピーク波長を有することが好ましい。 Blue light emitting nanocrystal particles have a light emission peak wavelength at 480 nm, 477 nm, 475 nm, 470 nm, 467 nm, 465 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm or 450 nm or less The light emission peak wavelength is preferably 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.
　発光性ナノ結晶粒子が発する光の波長（発光色）は、井戸型ポテンシャルモデルのシュレディンガー波動方程式の解によれば、発光性ナノ結晶粒子のサイズ（例えば粒子径）に依存するが、発光性ナノ結晶粒子が有するエネルギーギャップにも依存する。そのため、使用する発光性ナノ結晶粒子の構成材料及びサイズを変更することにより、発光色を選択することができる。 The wavelength (emission color) of light emitted from the luminescent nanocrystal particle depends on the size (for example, particle diameter) of the luminescent nanocrystal particle according to the solution of the Schrodinger wave equation of the well potential model, but the luminescent nano It also depends on the energy gap of the crystal particles. Therefore, the emission color can be selected by changing the constituent material and the size of the luminescent nanocrystal particle to be used.
　発光性ナノ結晶粒子は、半導体材料を含む、発光性ナノ結晶粒子（発光性半導体ナノ結晶粒子）であってよい。発光性半導体ナノ結晶粒子としては、量子ドット（以下「ＱＤ」ともいう）、量子ロッド等が挙げられる。これらの中でも、発光スペクトルの制御が容易であり、信頼性を確保した上で、生産コストを低減し、量産性を向上させることができる観点から、量子ドットが好ましい。 The luminescent nanocrystal particles may be luminescent nanocrystal particles (luminescent semiconductor nanocrystal particles) including a semiconductor material. As a luminescent semiconductor nanocrystal particle, a quantum dot (it is also called the following "QD"), a quantum rod, etc. are mentioned. Among them, quantum dots are preferable from the viewpoint of easy control of the emission spectrum and reduction of production cost and improvement of mass productivity after securing reliability.
　発光性半導体ナノ結晶粒子は、第一の半導体材料を含むコアのみからなっていてよく、第一の半導体材料を含むコアと、第一の半導体材料とは異なる第二の半導体材料を含み、上記コアの少なくとも一部を被覆するシェルと、を有していてもよい。換言すれば、発光性半導体ナノ結晶粒子の構造は、コアのみからなる構造（コア構造）であってよく、コアとシェルからなる構造（コア／シェル構造）であってもよい。また、発光性半導体ナノ結晶粒子は、第二の半導体材料を含むシェル（第一のシェル）の他に、第一及び第二の半導体材料とは異なる第三の半導体材料を含み、上記コアの少なくとも一部を被覆するシェル（第二のシェル）を更に有していてもよい。換言すれば、発光性半導体ナノ結晶粒子の構造は、コアと第一のシェルと第二のシェルとからなる構造（コア／シェル／シェル構造）であってもよい。コア及びシェルのそれぞれは、２種以上の半導体材料を含む混晶（例えば、ＣｄＳｅ＋ＣｄＳ、ＣＩＳ＋ＺｎＳ等）であってよい。 The light emitting semiconductor nanocrystal particle may be composed only of the core containing the first semiconductor material, and contains the core containing the first semiconductor material and the second semiconductor material different from the first semiconductor material, And a shell covering at least a part of the core. In other words, the structure of the light emitting semiconductor nanocrystal particle may be a structure consisting only of the core (core structure), or may be a structure consisting of the core and the shell (core / shell structure). In addition to the shell containing the second semiconductor material (first shell), the light-emitting semiconductor nanocrystal particles contain a third semiconductor material different from the first and second semiconductor materials, It may further have a shell (second shell) covering at least a part. In other words, the structure of the light-emitting semiconductor nanocrystal particle may be a structure (core / shell / shell structure) composed of the core, the first shell and the second shell. Each of the core and the shell may be a mixed crystal (for example, CdSe + CdS, CIS + ZnS, etc.) containing two or more semiconductor materials.
　発光性ナノ結晶粒子は、半導体材料として、ＩＩ－ＶＩ族半導体、ＩＩＩ－Ｖ族半導体、Ｉ－ＩＩＩ－ＶＩ族半導体、ＩＶ族半導体及びＩ－ＩＩ－ＩＶ－ＶＩ族半導体からなる群より選択される少なくとも一種の半導体材料を含むことが好ましい。 The luminescent nanocrystal particles are selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors and I-II-IV-VI semiconductors as semiconductor materials Preferably, it comprises at least one semiconductor material.
　具体的な半導体材料としては、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＺｎＯ、ＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＣｄＳｅＳ、ＣｄＳｅＴｅ、ＣｄＳＴｅ、ＺｎＳｅＳ、ＺｎＳｅＴｅ、ＺｎＳＴｅ、ＨｇＳｅＳ、ＨｇＳｅＴｅ、ＨｇＳＴｅ、ＣｄＺｎＳ、ＣｄＺｎＳｅ、ＣｄＺｎＴｅ、ＣｄＨｇＳ、ＣｄＨｇＳｅ、ＣｄＨｇＴｅ、ＨｇＺｎＳ、ＨｇＺｎＳｅ、ＣｄＨｇＺｎＴｅ、ＣｄＺｎＳｅＳ、ＣｄＺｎＳｅＴｅ、ＣｄＺｎＳＴｅ、ＣｄＨｇＳｅＳ、ＣｄＨｇＳｅＴｅ、ＣｄＨｇＳＴｅ、ＨｇＺｎＳｅＳ、ＨｇＺｎＳｅＴｅ、ＨｇＺｎＳＴｅ；ＧａＮ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＡｌＳｂ、ＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＮＰ、ＧａＮＡｓ、ＧａＮＳｂ、ＧａＰＡｓ、ＧａＰＳｂ、ＡｌＮＰ、ＡｌＮＡｓ、ＡｌＮＳｂ、ＡｌＰＡｓ、ＡｌＰＳｂ、ＩｎＮＰ、ＩｎＮＡｓ、ＩｎＮＳｂ、ＩｎＰＡｓ、ＩｎＰＳｂ、ＧａＡｌＮＰ、ＧａＡｌＮＡｓ、ＧａＡｌＮＳｂ、ＧａＡｌＰＡｓ、ＧａＡｌＰＳｂ、ＧａＩｎＮＰ、ＧａＩｎＮＡｓ、ＧａＩｎＮＳｂ、ＧａＩｎＰＡｓ、ＧａＩｎＰＳｂ、ＩｎＡｌＮＰ、ＩｎＡｌＮＡｓ、ＩｎＡｌＮＳｂ、ＩｎＡｌＰＡｓ、ＩｎＡｌＰＳｂ；ＳｎＳ、ＳｎＳｅ、ＳｎＴｅ、ＰｂＳ、ＰｂＳｅ、ＰｂＴｅ、ＳｎＳｅＳ、ＳｎＳｅＴｅ、ＳｎＳＴｅ、
ＰｂＳｅＳ、ＰｂＳｅＴｅ、ＰｂＳＴｅ、ＳｎＰｂＳ、ＳｎＰｂＳｅ、ＳｎＰｂＴｅ、ＳｎＰｂＳＳｅ、ＳｎＰｂＳｅＴｅ、ＳｎＰｂＳＴｅ；Ｓｉ、Ｇｅ、ＳｉＣ、ＳｉＧｅ、ＡｇＩｎＳｅ２、ＣｕＧａＳｅ２、ＣｕＩｎＳ２、ＣｕＧａＳ２、ＣｕＩｎＳｅ２、ＡｇＩｎＳ２、ＡｇＧａＳｅ２、ＡｇＧａＳ２、Ｃ、Ｓｉ及びＧｅが挙げられる。発光性半導体ナノ結晶粒子は、発光スペクトルの制御が容易であり、信頼性を確保した上で、生産コストを低減し、量産性を向上させることができる観点から、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＺｎＯ、ＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｇＩｎＳ２、ＡｇＩｎＳｅ２、ＡｇＩｎＴｅ２、ＡｇＧａＳ２、ＡｇＧａＳｅ２、ＡｇＧａＴｅ２、ＣｕＩｎＳ２、ＣｕＩｎＳｅ２、ＣｕＩｎＴｅ２、ＣｕＧａＳ２、ＣｕＧａＳｅ２、ＣｕＧａＴｅ２、Ｓｉ、Ｃ、Ｇｅ及びＣｕ２ＺｎＳｎＳ４からなる群より選択される少なくとも１種を含むことが好ましい。 Specific semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnTe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe. CdZnTe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgZnTe, CdHgZnTe, CdHgSeg, CdH, CdHgSe, CdHgSe, CdHgSe, CdHgSe: CdHgSe: CdHgSe: CdHgSe: CdHgSe: Cd: InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, Ga Sb, AlNP, AlNAs, AlPAs, AlPAs, AlPSb, InPS, InNAs, InNSb, InPAs, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNs, GaAlPAs, GaAlPSb, GaAlPSb, GaInNAs, GaInNAs, GaInNSb, GaInPSb, InAlNP, InAlNIns, AlIns InAlPSb: SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe,
PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe 2 , CuGaSe 2 , CuInS 2 , CuGaS 2 , CuInSe 2 , AgInS 2 , AgGaSe 2 , AgGaS 2 , C, Si and Ge can be mentioned. The light-emitting semiconductor nanocrystal particles are easy to control the emission spectrum, secure reliability, reduce production cost, and can improve mass productivity, and CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS 2 , AgInSe 2 , AgInTe 2 , AgInTe 2 , AgGaS 2 , AgGaSe 2 , AgGaTe 2 , CuInS 2 , CuInSe 2 , CuInTe 2 It is preferable to include at least one selected from the group consisting of CuGaS 2 , CuGaSe 2 , CuGaTe 2 , Si, C, Ge and Cu 2 ZnSnS 4 .
　赤色発光性の半導体ナノ結晶粒子としては、例えば、ＣｄＳｅのナノ結晶粒子、ＣｄＳｅのロッド状のナノ結晶粒子、コアシェル構造を備えたロッド状のナノ結晶粒子であって、該シェル部分がＣｄＳであり内側のコア部がＣｄＳｅであるナノ結晶粒子、コアシェル構造を備えたロッド状のナノ結晶粒子であって、該シェル部分がＣｄＳであり内側のコア部がＺｎＳｅであるナノ結晶粒子、コアシェル構造を備えたナノ結晶粒子であって、該シェル部分がＣｄＳであり内側のコア部がＣｄＳｅであるナノ結晶粒子、コアシェル構造を備えたナノ結晶粒子であって、該シェル部分がＣｄＳであり内側のコア部がＺｎＳｅであるナノ結晶粒子、ＣｄＳｅとＺｎＳとの混晶のナノ結晶粒子、ＣｄＳｅとＺｎＳとの混晶のロッド状のナノ結晶粒子、ＩｎＰのナノ結晶粒子、ＩｎＰのナノ結晶粒子、ＩｎＰのロッド状のナノ結晶粒子、ＣｄＳｅとＣｄＳとの混晶のナノ結晶粒子、ＣｄＳｅとＣｄＳとの混晶のロッド状のナノ結晶粒子、ＺｎＳｅとＣｄＳとの混晶のナノ結晶粒子、ＺｎＳｅとＣｄＳとの混晶のロッド状のナノ結晶粒子などが挙げられる。 Examples of red light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe, rod-like nanocrystalline particles of CdSe, and rod-like nanocrystalline particles having a core-shell structure, and the shell portion is CdS, A nanocrystalline particle having an inner core part of CdSe, a rod-like nanocrystalline particle having a core-shell structure, wherein the shell part is a CdS nanocrystalline particle having an inner core part of ZnSe, a core-shell structure Nanocrystalline particles, wherein the shell part is CdS and the inner core part is CdSe, the nanocrystalline particle having a core-shell structure, the shell part is CdS, and the inner core part Of nanocrystalline particles of ZnSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, rod-like nanocrystalline particles of mixed crystals of CdSe and ZnS, Nanocrystalline particles of nP, nanocrystalline particles of InP, rod-like nanocrystalline particles of InP, nanocrystalline particles of mixed crystals of CdSe and CdS, rod-like nanocrystalline particles of mixed crystals of CdSe and CdS, ZnSe and Nanocrystal particles of mixed crystals with CdS, rod-like nanocrystal particles of mixed crystals of ZnSe and CdS, and the like can be mentioned.
　緑色発光性の半導体ナノ結晶粒子としては、例えば、ＣｄＳｅのナノ結晶粒子、ＣｄＳｅのロッド状のナノ結晶粒子、ＣｄＳｅとＺｎＳとの混晶のナノ結晶粒子、ＣｄＳｅとＺｎＳとの混晶のロッド状のナノ結晶粒子等が挙げられる。 Examples of green light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe, rod-like nanocrystalline particles of CdSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, and rod-like crystals of mixed crystals of CdSe and ZnS The nanocrystalline particles of
　青色発光性の半導体ナノ結晶粒子としては、例えば、ＺｎＳｅのナノ結晶粒子、ＺｎＳｅのロッド状のナノ結晶粒子、ＺｎＳのナノ結晶粒子、ＺｎＳのロッド状のナノ結晶粒子、コアシェル構造を備えたナノ結晶粒子であって、該シェル部分がＺｎＳｅであり内側のコア部がＺｎＳであるナノ結晶粒子、コアシェル構造を備えたロッド状のナノ結晶であって、該シェル部分がＺｎＳｅであり内側のコア部がＺｎＳであるナノ結晶粒子、ＣｄＳのナノ結晶粒子、ＣｄＳのロッド状のナノ結晶粒子等が挙げられる。半導体ナノ結晶粒子は、同一の化学組成で、それ自体の平均粒子径を変えることにより、当該粒子から発光させるべき色を赤色にも緑色にも変えることができる。また、半導体ナノ結晶粒子は、それ自体として、人体等に対する悪影響が極力低いものを用いることが好ましい。カドミウム、セレン等を含有する半導体ナノ結晶粒子を発光性ナノ結晶粒子として用いる場合は、上記元素（カドミウム、セレン等）が極力含まれない半導体ナノ結晶粒子を選択して単独で用いるか、上記元素が極力少なくなるようにその他の発光性ナノ結晶粒子と組み合わせて用いることが好ましい。 Examples of blue light emitting semiconductor nanocrystal particles include nanocrystalline particles of ZnSe, rodlike nanocrystalline particles of ZnSe, nanocrystalline particles of ZnS, rodlike nanocrystalline particles of ZnS, and nanocrystals having a core-shell structure. A particle, wherein the shell part is ZnSe, and the inner core part is a nanocrystal particle having ZnS, and a rod-like nanocrystal provided with a core-shell structure, wherein the shell part is ZnSe and the inner core part is Examples include nanocrystalline particles of ZnS, nanocrystalline particles of CdS, rod-like nanocrystalline particles of CdS, and the like. The semiconductor nanocrystal particle can change the color to be emitted from the particle to be either red or green by changing the average particle size of the semiconductor chemical particle with the same chemical composition. In addition, it is preferable to use, as the semiconductor nanocrystal particles, those which have as little adverse effect on the human body as possible. When semiconductor nanocrystal particles containing cadmium, selenium or the like are used as light-emitting nanocrystal particles, it is possible to select semiconductor nanocrystal particles containing the above elements (cadmium, selenium or the like) as little as possible, or use them alone or It is preferable to use in combination with other luminescent nanocrystal particles so as to reduce as much as possible.
　発光性ナノ結晶粒子の形状は特に限定されず、任意の幾何学的形状であってもよく、任意の不規則な形状であってもよい。発光性ナノ結晶粒子の形状は、例えば、球状、楕円体状、角錐形状、ディスク状、枝状、網状、ロッド状等であってもよい。しかしながら、発光性ナノ結晶粒子としては、粒子形状として方向性の少ない粒子（例えば、球状、正四面体状等の粒子）を用いることが、インク組成物の均一性及び流動性をより高められる点で好ましい。 The shape of the luminescent nanocrystal particles is not particularly limited, and may be any geometric shape or any irregular shape. The shape of the luminescent nanocrystal particle may be, for example, a sphere, an ellipsoid, a pyramid, a disc, a branch, a net, a rod, or the like. However, as the light-emitting nanocrystal particles, it is possible to further improve the uniformity and fluidity of the ink composition by using particles with less directivity (for example, particles such as spheres and tetrahedra) as the particle shape. Preferred.
　発光性ナノ結晶粒子の平均粒子径（体積平均径）は、所望の波長の発光が得られやすい観点、並びに、分散性及び保存安定性に優れる観点から、１ｎｍ以上であってよく、１．５ｎｍ以上であってよく、２ｎｍ以上であってもよい。所望の発光波長が得られやすい観点から、４０ｎｍ以下であってよく、３０ｎｍ以下であってよく、２０ｎｍ以下であってもよい。発光性ナノ結晶粒子の平均粒子径（体積平均径）は、透過型電子顕微鏡又は走査型電子顕微鏡により測定し、体積平均径を算出することにより得られる。 The average particle diameter (volume average diameter) of the light-emitting nanocrystal particles may be 1 nm or more, 1.5 nm, from the viewpoint that light emission of a desired wavelength is easily obtained, and from the viewpoint of excellent dispersibility and storage stability. Or more, and may be 2 nm or more. From the viewpoint of easily obtaining a desired emission wavelength, it may be 40 nm or less, 30 nm or less, or 20 nm or less. The average particle diameter (volume average diameter) of the luminescent nanocrystal particles can be obtained by measuring the volume average diameter by measurement using a transmission electron microscope or a scanning electron microscope.
　発光性ナノ結晶粒子は、分散安定性の観点から、その表面に有機リガンドを有することが好ましい。有機リガンドは、例えば、発光性ナノ結晶粒子の表面に配位結合されていてよい。換言すれば、発光性ナノ結晶粒子の表面は、有機リガンドによってパッシベーションされていてよい。また、発光性ナノ結晶粒子は、その表面に高分子分散剤を有していてもよい。一実施形態では、例えば、上述の有機リガンドを有する発光性ナノ結晶粒子から有機リガンドを除去し、有機リガンドと高分子分散剤とを交換することで発光性ナノ結晶粒子の表面に高分子分散剤を結合させてよい。ただし、インクジェットインクにした際の分散安定性の観点では、有機リガンドが配位したままの発光性ナノ結晶粒子に対して高分子分散剤が配合されることが好ましい。 The luminescent nanocrystal particles preferably have an organic ligand on the surface from the viewpoint of dispersion stability. The organic ligand may, for example, be coordinated to the surface of the luminescent nanocrystal particle. In other words, the surface of the luminescent nanocrystal particle may be passivated by the organic ligand. In addition, the luminescent nanocrystal particles may have a polymer dispersant on the surface thereof. In one embodiment, for example, by removing the organic ligand from the luminescent nanocrystal particle having the above-mentioned organic ligand, and exchanging the organic ligand and the polymer dispersant, the polymer dispersant on the surface of the luminescent nanocrystal particle May be combined. However, from the viewpoint of dispersion stability when used as an inkjet ink, it is preferable that a polymer dispersant be blended to the light emitting nanocrystal particles in which the organic ligand remains coordinated.
　有機リガンドとしては、例えば、ＴＯＰ（トリオクチルフォスフィン）、ＴＯＰＯ（トリオクチルフォスフィンオキサイド）、オレイン酸、オレイルアミン、オクチルアミン、トリオクチルアミン、ヘキサデシルアミン、オクタンチオール、ドデカンチオール、ヘキシルホスホン酸（ＨＰＡ）、テトラデシルホスホン酸（ＴＤＰＡ）、及びオクチルホスフィン酸（ＯＰＡ）が挙げられる。 Examples of organic ligands include TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (for example, HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).
　発光性ナノ結晶粒子としては、有機溶剤の中にコロイド形態で分散しているものを用いることができる。有機溶剤中で分散状態にある発光性ナノ結晶粒子の表面は、上述の有機リガンドによってパッシベーションされていることが好ましい。有機溶剤としては、例えば、シクロヘキサン、ヘキサン、ヘプタン、クロロホルム、トルエン、オクタン、クロロベンゼン、テトラリン、ジフェニルエーテル、プロピレングリコールモノメチルエーテルアセテート、ブチルカルビトールアセテート、又はそれらの混合物が挙げられる。 As the light-emitting nanocrystal particles, those dispersed in an organic solvent in the form of colloid can be used. It is preferable that the surface of the luminescent nanocrystal particles in the dispersed state in the organic solvent be passivated by the above-mentioned organic ligand. Examples of the organic solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or a mixture thereof.
　発光性ナノ結晶粒子としては、市販品を用いることができる。発光性ナノ結晶粒子の市販品としては、例えば、ＮＮ－ラボズ社の、インジウムリン／硫化亜鉛、Ｄ－ドット、ＣｕＩｎＳ／ＺｎＳ、アルドリッチ社の、ＩｎＰ／ＺｎＳ等が挙げられる。 A commercial item can be used as a luminescent nanocrystal particle. Examples of commercially available light emitting nanocrystal particles include indium phosphorus / zinc sulfide, D-dots, CuInS / ZnS manufactured by NN-Labs, and InP / ZnS manufactured by Aldrich.
　発光性ナノ結晶粒子の含有量は、漏れ光の低減効果により優れる観点から、インク組成物の不揮発分の質量を基準として、５質量％以上であってよく、１０質量％以上であってもよく、１５質量％以上であってもよく、２０質量％以上であってもよく、３０質量％以上であってもよく、４０質量％以上であってもよい。発光性ナノ結晶粒子の含有量は、吐出安定性に優れる観点から、インク組成物の不揮発分の質量を基準として、７０質量％以下であってよく、６０質量％以下であってもよく、５５質量％以下であってもよく、５０質量％以下であってもよい。なお、本明細書中、「インク組成物の不揮発分の質量」とは、インク組成物の全質量から有機溶剤の質量を除いた質量を指す。 The content of the light-emitting nanocrystal particles may be 5% by mass or more, or 10% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent in the reduction effect of leakage light. The content may be 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more. The content of the light-emitting nanocrystal particles may be 70% by mass or less, 60% by mass or less, based on the mass of the non-volatile component of the ink composition, from the viewpoint of excellent ejection stability. The content may be less than or equal to 50% by mass. In the present specification, the “mass of nonvolatile component of ink composition” refers to the mass of the ink composition excluding the mass of the organic solvent.
　ところで、発光性ナノ結晶粒子は、配位サイトとなりうる表面原子を有するため、高い反応性を有している。発光性ナノ結晶粒子は、このような高い反応性を有すること、及び、一般の顔料に比べ大きい表面積を有することから、粒子の凝集を起こしやすい。発光性ナノ結晶粒子は量子サイズ効果によって発光を生じるものであるため、粒子の凝集が発生した場合には消光現象が生じ、蛍光量子収率の低下を招き、輝度及び色再現性が低下する。これに対し、本実施形態では、インク組成物が高分子分散剤を含むため、発光性ナノ結晶粒子が凝集し難い。そのため、本実施形態では、発光性ナノ結晶粒子の含有量を上記範囲とすることができる。 By the way, since the luminescent nanocrystal particles have surface atoms that can be coordination sites, they have high reactivity. Luminescent nanocrystalline particles tend to cause aggregation of the particles because of having such high reactivity and having a large surface area as compared to general pigments. Since the luminescent nanocrystal particles emit light due to the quantum size effect, when aggregation of the particles occurs, a quenching phenomenon occurs, leading to a decrease in fluorescence quantum yield, and a decrease in luminance and color reproducibility. On the other hand, in the present embodiment, since the ink composition contains a polymer dispersant, it is difficult for the light-emitting nanocrystal particles to aggregate. Therefore, in the present embodiment, the content of the light-emitting nanocrystal particles can be set to the above range.
［光散乱性粒子］
　一実施形態のインク組成物は、光散乱性粒子を含有してよい。発光性ナノ結晶粒子を用いたインク組成物によりカラーフィルタ画素部（以下、単に「画素部」ともいう。）を形成した場合、光源からの光が発光性ナノ結晶粒子に吸収されずに画素部から漏れることがある。このような漏れ光は、画素部の色再現性を低下させるため、光変換層として上記画素部を用いる場合には、その漏れ光を可能な限り低減することが好ましい。上記光散乱性粒子は、画素部の漏れ光を防止するために、好適には用いられる。光散乱性粒子は、例えば、光学的に不活性な無機微粒子である。光散乱性粒子は、カラーフィルタ画素部に照射された光源からの光を散乱させることができる。 [Light-scattering particles]
The ink composition of one embodiment may contain light scattering particles. When a color filter pixel portion (hereinafter, also simply referred to as "pixel portion") is formed of an ink composition using luminescent nanocrystal particles, light from a light source is not absorbed by the luminescent nanocrystal particles, and the pixel portion is not absorbed. May leak from the Since such leaked light reduces the color reproducibility of the pixel portion, when the pixel portion is used as the light conversion layer, it is preferable to reduce the leaked light as much as possible. The light scattering particles are preferably used in order to prevent light leakage from the pixel portion. The light scattering particles are, for example, optically inactive inorganic fine particles. The light scattering particles can scatter the light from the light source irradiated to the color filter pixel portion.
　光散乱性粒子を構成する材料としては、例えば、タングステン、ジルコニウム、チタン、白金、ビスマス、ロジウム、パラジウム、銀、スズ、プラチナ、金等の単体金属；シリカ、硫酸バリウム、炭酸バリウム、炭酸カルシウム、タルク、酸化チタン、クレー、カオリン、硫酸バリウム、炭酸バリウム、炭酸カルシウム、アルミナホワイト、酸化チタン、酸化マグネシウム、酸化バリウム、酸化アルミニウム、酸化ビスマス、酸化ジルコニウム、酸化亜鉛等の金属酸化物；炭酸マグネシウム、炭酸バリウム、次炭酸ビスマス、炭酸カルシウム等の金属炭酸塩；水酸化アルミニウム等の金属水酸化物；ジルコン酸バリウム、ジルコン酸カルシウム、チタン酸カルシウム、チタン酸バリウム、チタン酸ストロンチウム等の複合酸化物、次硝酸ビスマス等の金属塩などが挙げられる。光散乱性粒子は、漏れ光の低減効果により優れる観点から、酸化チタン、アルミナ、酸化ジルコニウム、酸化亜鉛、炭酸カルシウム、硫酸バリウム及びシリカからなる群より選択される少なくとも１種を含むことが好ましく、酸化チタン、硫酸バリウム及び炭酸カルシウムからなる群より選択される少なくとも一種を含むことがより好ましい。 Examples of the material constituting the light scattering particles include single metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum and gold; silica, barium sulfate, barium carbonate, calcium carbonate, 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, metal oxides such as zinc oxide; magnesium carbonate, Metal carbonates such as barium carbonate, bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, Secondary nitrate And metal salts of the mass, and the like. The light scattering particles preferably contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate and silica, from the viewpoint of being superior in the light leakage reducing effect. It is more preferable to include at least one selected from the group consisting of titanium oxide, barium sulfate and calcium carbonate.
　光散乱性粒子の形状は、球状、フィラメント状、不定形状等であってよい。しかしながら、光散乱性粒子としては、粒子形状として方向性の少ない粒子（例えば、球状、正四面体状等の粒子）を用いることが、インク組成物の均一性、流動性及び光散乱性をより高められる点で好ましい。 The shape of the light scattering particles may be spherical, filamentous, indeterminate or the like. However, as the light scattering particles, using particles with less directivity as particle shape (for example, particles of spherical shape, tetrahedron shape, etc.) makes the ink composition more uniform, flowable, and light scattering. It is preferable in that it is enhanced.
　インク組成物中での光散乱性粒子の平均粒子径（体積平均径）は、漏れ光の低減効果により優れる観点から、０．０５μｍ以上であってよく、０．２μｍ以上であってもよく、０．３μｍ以上であってもよい。インク組成物中での光散乱性粒子の平均粒子径（体積平均径）は、吐出安定性に優れる観点から、１．０μｍ以下であってもよく、０．６μｍ以下であってもよく、０．４μｍ以下であってもよい。インク組成物中での光散乱性粒子の平均粒子径（体積平均径）は、０．０５～１．０μｍ、０．０５～０．６μｍ、０．０５～０．４μｍ、０．２～１．０μｍ、０．２～０．６μｍ、０．２～０．４μｍ、０．３～１．０μｍ、０．３～０．６μｍ、又は０．３～０．４μｍであってもよい。このような平均粒子径（体積平均径）が得られやすい観点から、使用する光散乱性粒子の平均粒子径（体積平均径）は、５０ｎｍ以上であってよく、１０００ｎｍ以下であってよい。光散乱性粒子の平均粒子径（体積平均径）は、動的光散乱式ナノトラック粒度分布計により測定し、体積平均径を算出することにより得られる。また、使用する光散乱性粒子の平均粒子径（体積平均径）は、例えば透過型電子顕微鏡又は走査型電子顕微鏡により各粒子の粒子径を測定し、体積平均径を算出することにより得られる。 The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 0.05 μm or more, or 0.2 μm or more, from the viewpoint of being excellent by the reduction effect of leakage light. It may be 0.3 μm or more. The average particle diameter (volume average diameter) of the light-scattering particles in the ink composition may be 1.0 μm or less, 0.6 μm or less, or 0 from the viewpoint of excellent ejection stability. .4 μm or less. The average particle diameter (volume average diameter) of the light scattering particles in the ink composition is 0.05 to 1.0 μm, 0.05 to 0.6 μm, 0.05 to 0.4 μm, 0.2 to 1 And 0.2 to 0.6 μm, 0.2 to 0.4 μm, 0.3 to 1.0 μm, 0.3 to 0.6 μm, or 0.3 to 0.4 μm. From the viewpoint of easily obtaining such an average particle diameter (volume average diameter), the average particle diameter (volume average diameter) of the light scattering particles to be used may be 50 nm or more and 1000 nm or less. The average particle diameter (volume average diameter) of the light scattering particles is obtained by measuring with a dynamic light scattering nanotrack particle size distribution analyzer and calculating the volume average diameter. The average particle diameter (volume average diameter) of the light scattering particles to be used can be obtained, for example, by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
　光散乱性粒子の含有量は、漏れ光の低減効果により優れる観点から、インク組成物の不揮発分の質量を基準として、０．１質量％以上であってよく、１質量％以上であってもよく、５質量％以上であってもよく、７質量％以上であってもよく、１０質量％以上であってもよく、１２質量％以上であってもよい。光散乱性粒子の含有量は、漏れ光の低減効果により優れる観点及び吐出安定性に優れる観点から、インク組成物の不揮発分の質量を基準として、６０質量％以下であってよく、５０質量％以下であってもよく、４０質量％以下であってもよく、３０質量％以下であってもよく、２５質量％以下であってもよく、２０質量％以下であってもよく、１５質量％以下であってもよい。本実施形態では、インク組成物が高分子分散剤を含むため、光散乱性粒子の含有量を上記範囲とした場合であっても光散乱性粒子の良好に分散させることができる。 The content of the light scattering particles may be 0.1% by mass or more, or 1% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent in the reduction effect of leakage light. It may be 5% by mass or more, 7% by mass or more, 10% by mass or more, and 12% by mass or more. The content of the light scattering particles may be 60% by mass or less, 50% by mass, based on the mass of the non-volatile component of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light and from the viewpoint of excellent ejection stability. Or less, or 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less, or 15% by mass It may be the following. In the present embodiment, since the ink composition contains a polymer dispersant, the light scattering particles can be well dispersed even when the content of the light scattering particles is in the above range.
　発光性ナノ結晶粒子の含有量に対する光散乱性粒子の含有量の質量比（光散乱性粒子／発光性ナノ結晶粒子）は、０．１～５．０である。質量比（光散乱性粒子／発光性ナノ結晶粒子）は、漏れ光の低減効果により優れる観点から、０．２以上であってもよく、０．５以上であってもよい。質量比（光散乱性粒子／発光性ナノ結晶粒子）は、漏れ光の低減効果により優れ、インクジェット印刷時の連続吐出性に優れる観点から、２．０以下であってもよく、１．５以下であってもよい。質量比（光散乱性粒子／発光性ナノ結晶粒子）は、０．１～２．０、０．１～１．５、０．２～５．０、０．２～２．０、０．２～１．５、０．５～５．０、０．５～２．０、又は０．５～１．５であってもよい。なお、光散乱性粒子による漏れ光低減は、次のようなメカニズムによると考えられる。すなわち、光散乱性粒子が存在しない場合、バックライト光は画素部内をほぼ直進して通過するのみであり、発光性ナノ結晶粒子に吸収される機会が少ないと考えられる。一方、光散乱性粒子を発光性ナノ結晶粒子と同一の画素部内に存在させると、その画素部内でバックライト光が全方位に散乱され、それを発光性ナノ結晶粒子が受光することができるため、同一のバックライトを用いていても、画素部における光吸収量が増大すると考えられる。結果的に
、このようなメカニズムで漏れ光を防ぐことが可能になったと考えられる。 The mass ratio of the content of the light scattering particles to the content of the light emitting nanocrystal particles (light scattering particles / light emitting nanocrystal particles) is 0.1 to 5.0. The mass ratio (light scattering particles / luminescent nanocrystal particles) may be 0.2 or more, or 0.5 or more, from the viewpoint of being more excellent in the reduction effect of the leaked light. The mass ratio (light scattering particles / luminescent nanocrystal particles) may be 2.0 or less, or 1.5 or less, from the viewpoint of being excellent in the reduction effect of leakage light and excellent in continuous dischargeability at the time of ink jet printing. It may be The mass ratio (light scattering particles / luminescent nanocrystal particles) is 0.1 to 2.0, 0.1 to 1.5, 0.2 to 5.0, 0.2 to 2.0, 0. It may be 2 to 1.5, 0.5 to 5.0, 0.5 to 2.0, or 0.5 to 1.5. In addition, it is thought that the leak light reduction by light-scattering particle | grains is based on the following mechanisms. That is, when light scattering particles do not exist, it is considered that the backlight only travels almost straight through the inside of the pixel portion, and there is little chance of being absorbed by the light emitting nanocrystal particles. On the other hand, when light scattering particles are present in the same pixel portion as the light emitting nanocrystal particles, backlight light is scattered in all directions in the pixel portion, and the light emitting nanocrystal particles can receive light. Even though the same backlight is used, it is considered that the light absorption amount in the pixel portion is increased. As a result, it is considered that such a mechanism makes it possible to prevent light leakage.
［高分子分散剤］
　一実施形態のインク組成物は、高分子分散剤を含有させることが好ましい。高分子分散剤は、光散乱性粒子をインク中に均一分散させることができる。
　本発明において、高分子分散剤は、７５０以上の重量平均分子量を有し、かつ、光散乱性粒子に対し親和性を有する官能基を有する高分子化合物であり、光散乱性粒子を分散させる機能を有する。高分子分散剤は、光散乱性粒子に対し親和性を有する官能基を介して高分子分散剤が光散乱性粒子に吸着し、高分子分散剤同士の静電反発及び／又は立体反発により、光散乱性粒子がインク組成物中に分散される。高分子分散剤は、光散乱性粒子の表面と結合して光散乱性粒子に吸着していることが好ましいが、発光性ナノ結晶粒子の表面に結合して発光性ナノ粒子に吸着していてもよく、インク組成物中に遊離していてもよい。 [Polymer dispersant]
The ink composition of one embodiment preferably contains a polymer dispersant. The polymeric dispersant can uniformly disperse light scattering particles in the ink.
In the present invention, the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity to the light scattering particles, and has a function of dispersing the light scattering particles. Have. In the polymer dispersant, the polymer dispersant is adsorbed to the light scattering particles through the functional group having affinity to the light scattering particles, and electrostatic repulsion and / or steric repulsion between the polymer dispersants causes Light scattering particles are dispersed in the ink composition. The polymer dispersant is preferably bonded to the surface of the light scattering particle and adsorbed to the light scattering particle, but is bonded to the surface of the light emitting nanocrystal particle and adsorbed to the light emitting nanoparticle. It may also be free in the ink composition.
　光散乱性粒子に対し親和性を有する官能基としては、酸性官能基、塩基性官能基及び非イオン性官能基が挙げられる。酸性官能基は解離性のプロトンを有しており、アミン、水酸化物イオン等の塩基により中和されていてもよく、塩基性官能基は有機酸、無機酸等の酸により中和されていてもよい。 Examples of functional groups having affinity to light scattering particles include acidic functional groups, basic functional groups and nonionic functional groups. The acidic functional group has dissociative protons, and may be neutralized by a base such as an amine or hydroxide ion, and the basic functional group is neutralized by an acid such as an organic acid or inorganic acid. May be
　酸性官能基としては、カルボキシル基（－ＣＯＯＨ）、スルホ基（－ＳＯ３Ｈ）、硫酸基（－ＯＳＯ３Ｈ）、ホスホン酸基（－ＰＯ（ＯＨ）３）、リン酸基（－ＯＰＯ（ＯＨ）３）、ホスフィン酸基（－ＰＯ（ＯＨ）－）、メルカプト基（－ＳＨ）、が挙げられる。 The acidic functional group, a carboxyl group (-COOH), a sulfo group (-SO 3 H), sulfuric acid group (-OSO 3 H), a phosphonic acid group (-PO (OH) 3), phosphoric acid group (-OPO ( OH) 3 ), phosphinic acid group (-PO (OH)-), mercapto group (-SH) can be mentioned.
　塩基性官能基としては、一級、二級及び三級アミノ基、アンモニウム基、イミノ基、並
びに、ピリジン、ピリミジン、ピラジン、イミダゾール、トリアゾール等の含窒素ヘテロ
環基等が挙げられる。 Examples of basic functional groups include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.
　非イオン性官能基としては、ヒドロキシ基、エーテル基、チオエーテル基、スルフィニル基（－ＳＯ－）、スルホニル基（－ＳＯ２－）、カルボニル基、ホルミル基、エステル基、炭酸エステル基、アミド基、カルバモイル基、ウレイド基、チオアミド基、チオウレイド基、スルファモイル基、シアノ基、アルケニル基、アルキニル基、ホスフィンオキシド基、ホスフィンスルフィド基が挙げられる。 As the nonionic functional group, a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO 2- ), a carbonyl group, a formyl group, an ester group, a carbonate group, an amide group, A carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group and a phosphine sulfide group can be mentioned.
　光散乱性粒子の分散安定性の観点、発光性ナノ結晶粒子が沈降するという副作用を起こしにくい観点、高分子分散剤の合成の容易性の観点、及び官能基の安定性の観点から、酸性官能基としては、カルボキシル基、スルホ基、ホスホン酸基及びリン酸基が好ましく用いられ、塩基性官能基としては、アミノ基が好ましく用いられる。これらの中でも、カルボキシル基、ホスホン酸基及びアミノ基がより好ましく用いられ、最も好ましくはアミノ基が用いられる。 From the viewpoint of dispersion stability of the light scattering particles, the viewpoint that the light emitting nanocrystal particles hardly cause the side effect of settling, the viewpoint of easiness of synthesis of the polymer dispersant, and the stability of the functional group, the acidic functional As a group, a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used, and as a basic functional group, an amino group is preferably used. Among these, a carboxyl group, a phosphonic acid group and an amino group are more preferably used, and most preferably an amino group.
　酸性官能基を有する高分子分散剤は酸価を有する。酸性官能基を有する高分子分散剤の酸価は、好ましくは、固形分換算で、１～１５０ｍｇＫＯＨ／ｇである。酸価が１以上であると、光散乱性粒子の充分な分散性が得られやすく、酸価が１５０以下であると、画素部（インク組成物の硬化物）の保存安定性が低下しにくい。 The polymeric dispersant having an acidic functional group has an acid value. The acid value of the polymer dispersant having an acidic functional group is preferably 1 to 150 mg KOH / g in terms of solid content. When the acid value is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the acid value is 150 or less, the storage stability of the pixel portion (cured product of the ink composition) does not easily decrease. .
　また、塩基性官能基を有する高分子分散剤はアミン価を有する。塩基性官能基を有する高分子分散剤のアミン価は、好ましくは、固形分換算で、１～２００ｍｇＫＯＨ／ｇである。アミン価が１以上であると、光散乱性粒子の充分な分散性が得られやすく、アミン価が２００以下であると、画素部（インク組成物の硬化物）の保存安定性が低下しにくい。 Moreover, the polymer dispersant having a basic functional group has an amine value. The amine value of the polymer dispersant having a basic functional group is preferably 1 to 200 mg KOH / g in terms of solid content. When the amine number is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the amine number is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) does not easily decrease. .
　高分子分散剤は、単一のモノマーの重合体（ホモポリマー）であってよく、複数種のモノマーの共重合体（コポリマー）であってもよい。また、高分子分散剤は、ランダム共重合体、ブロック共重合体又はグラフト共重合体のいずれであってもよい。また、高分子分散剤がグラフト共重合体である場合、くし形のグラフト共重合体であってよく、星形のグラフト共重合体であってもよい。高分子分散剤は、例えば、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエーテル、フェノール樹脂、シリコーン樹脂、ポリウレア樹脂、アミノ樹脂、ポリエチレンイミン及びポリアリルアミン等のポリアミン、エポキシ樹脂、ポリイミドなどであってよい。 The polymer dispersant may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of monomers. Further, the polymer dispersant may be any of a random copolymer, a block copolymer or a graft copolymer. When the polymer dispersant is a graft copolymer, it may be a comb graft copolymer or a star graft copolymer. The polymer dispersant includes, for example, acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, polyamine such as polyethyleneimine and polyallylamine, epoxy resin, polyimide, etc. May be there.
　前記高分子分散剤として、市販品を使用することも可能であり、市販品としては、味の素ファインテクノ株式会社のアジスパーＰＢシリーズ、ＢＹＫ社製のＤＩＳＰＥＲＢＹＫシリーズ並びにＢＹＫ－シリーズ、ＢＡＳＦ社製のＥｆｋａシリーズ等を使用することができる。 As the above-mentioned polymer dispersant, it is possible to use a commercially available product, and as a commercially available product, Addisper PB series of Ajinomoto Fine Techno Co., Ltd., DISPERBYK series manufactured by BYK, and BYK-series, Efka manufactured by BASF Etc. can be used.
　市販品としては、例えば、ビックケミー社製の「ＤＩＳＰＥＲＢＹＫ－１３０」、「ＤＩＳＰＥＲＢＹＫ－１６１」、「ＤＩＳＰＥＲＢＹＫ－１６２」、「ＤＩＳＰＥＲＢＹＫ－１６３」、「ＤＩＳＰＥＲＢＹＫ－１６４」、「ＤＩＳＰＥＲＢＹＫ－１６６」、「ＤＩＳＰＥＲＢＹＫ－１６７」、「ＤＩＳＰＥＲＢＹＫ－１６８」、「ＤＩＳＰＥＲＢＹＫ－１７０」、「ＤＩＳＰＥＲＢＹＫ－１７１」、「ＤＩＳＰＥＲＢＹＫ－１７４」、「ＤＩＳＰＥＲＢＹＫ－１８０」、「ＤＩＳＰＥＲＢＹＫ－１８２」、「ＤＩＳＰＥＲＢＹＫ－１８３」、「ＤＩＳＰＥＲＢＹＫ－１８４」、「ＤＩＳＰＥＲＢＹＫ－１８５」、「ＤＩＳＰＥＲＢＹＫ－２０００」、「ＤＩＳＰＥＲＢＹＫ－２００１」、「ＤＩＳＰＥＲＢＹＫ－２００８」、「ＤＩＳＰＥＲＢＹＫ－２００９」、「ＤＩＳＰＥＲＢＹＫ－２０２０」、「ＤＩＳＰＥＲＢＹＫ－２０２２」、「ＤＩＳＰＥＲＢＹＫ－２０２５」、「ＤＩＳＰＥＲＢＹＫ－２０５０」、「ＤＩＳＰＥＲＢＹＫ－２０７０」、「ＤＩＳＰＥＲＢＹＫ－２０９６」、「ＤＩＳＰＥＲＢＹＫ－２１５０」、「ＤＩＳＰＥＲＢＹＫ－２１５５」、「ＤＩＳＰＥＲＢＹＫ－２１６３」、「ＤＩＳＰＥＲＢＹＫ－２１６４」、「ＢＹＫ－ＬＰＮ２１１１６」及び「ＢＹＫ－ＬＰＮ６９１９」；ＢＡＳＦ社製の「ＥＦＫＡ４０１０」、「ＥＦＫＡ４０１５」、「ＥＦＫＡ４０４６」、「ＥＦＫＡ４０４７」、「ＥＦＫＡ４０６１」、「ＥＦＫＡ４０８０」、「ＥＦＫＡ４３００」、「ＥＦＫＡ４３１０」、「ＥＦＫＡ４３２０」、「ＥＦＫＡ４３３０」、「ＥＦＫＡ４３４０」、「ＥＦＫＡ４５６０」、「ＥＦＫＡ４５８５」、「ＥＦＫＡ５２０７」、「ＥＦＫＡ１５０１」、「ＥＦＫＡ１５０２」、「ＥＦＫＡ１５０３」及び「ＥＦＫＡ　ＰＸ－４７０１」；ルーブリゾール社製の「ソルスパース３０００」、「ソルスパース９０００」、「ソルスパース１３２４０」、「ソルスパース１３６５０」、「ソルスパース１３９４０」、「ソルスパース１１２００」、「ソルスパース１３９４０」、「ソルスパース１６０００」、「ソルスパース１７０００」、「ソルスパース１８０００」、「ソルスパース２００００」、「ソルスパース２１０００」、「ソルスパース２４０００」、「ソルスパース２６０００」、「ソルスパース２７０００」、「ソルスパース２８０００」、「ソルスパース３２０００」、「ソルスパース３２５００」、「ソルスパース３２５５０」、「ソルスパース３２６００」、「ソルスパース３３０００」、「ソルスパース３４７５０」、「ソルスパース３５１００」、「ソルスパース３５２００」、「ソルスパース３６０００」、「ソルスパース３７５００」、「ソルスパース３８５００」、「ソルスパース３９０００」、「ソルスパース４１０００」、「ソルスパース５４０００」、「ソルスパース７１０００」及び「ソルスパース７６５００」；味の素ファインテクノ株式会社製の「アジスパーＰＢ８２１」、「アジスパーＰＢ８２２」、「アジスパーＰＢ８８１」、「ＰＮ４１１」及び「ＰＡ
１１１」；エボニック社製の「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６５０」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６６０Ｃ」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６６２Ｃ」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６７０」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ６８５」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ７００」、「ＴＥＧＯ　Ｄｉｓｐｅｒｓ７１０」及び「ＴＥＧＯ　Ｄｉｓｐｅｒｓ７６０Ｗ」；楠本化成製の「ディスパロンＤＡ―７０３―５０」、「ＤＡ－７０５」及び「ＤＡ－７２５」などを用いることができる。 As a commercial item, for example, "DISPERBYK-130", "DISPERBYK-161", "DISPERBYK-162", "DISPERBYK-163", "DISPERBYK-164", "DISPERBYK-164", "DISPERBYK-166", "DISPERBYK-166", "DISPERBYK-130", made by BIC Chemie, Inc. 167 "," DISPERBYK-168 "," DISPERBYK-170 "," DISPERBYK-171 "," DISPERBYK-174 "," DISPERBYK-180 "," DISPERBYK-182 "," DISPERBYK-182 "," DISPERBYK-183 "," DISPERBYK-184 " , "DISPERBYK-185", "DISPERBYK-2000", "DISPERBYK-2001", "DISPERBYK-2008", "DISP RBYK-2009 "," DISPERBYK-2020 "," DISPERBYK-2022 "," DISPERBYK-2025 "," DISPERBYK-2050 "," DISPERBYK-2070 "," DISPERBYK-2096 "," DISPERBYK-2150 "," DISPERBYK- " 2155 "," DISPERBYK-2163 "," DISPERBYK-2164 "," BYK-LPN 21116 "and" BYK-LPN 6919 ";" EFKA4010 "," EFKA4015 "," EFKA4046 "," EFKA4047 "," EFKA4061 "manufactured by BASF. , "EFKA 4080", "EFKA 4300", "EFKA 4310", "EFKA 4320", "EFKA 4330", "EFK 4340 ”,“ EFKA 4560 ”,“ EFKA 4585 ”,“ EFKA 5207 ”,“ EFKA 1501 ”,“ EFKA 1502 ”,“ EFKA 1503 ”and“ EFKA PX-4701 ”;“ Sulsparse 3000 ”,“ Sulsparse 9000 ”, manufactured by Lubrizol Solsparse 13240, Solsparse 13650, Solsparse 13940, Solsparse 11200, Solsparse 13940, Solsparse 16000, Solsparse 17000, Solsparse 18000, Solsparse 20000, Solsparse 21000, Solsparse 24000, Solsparse 26000, Solsparse 27000, Solsparse 28000, Solsparse 32000 "Sol spars 32500", "Sols sparse 32550", "Sols sparse 32600", "Sols sparse 33000", "Sols sparse 34750", "Sols sparse 35100", "Sols sparse 35200", "Sols sparse 36000", "Sols sparse 37500", "Sols sparse 38500", "Sol Sparse 39000", "Sol Sparse 41000", "Sol Sparse 54000", "Sol Sparse 71000" and "Sol Sparse 76500";"Ajisper PB 821" made by Ajinomoto Fine Techno Co., "Ajisper PB 822", "Ajisper PB 881", "PN 411" And "PA
111 "Evonik" TEGO Disperss 650 "," TEGO Disperss 660C "," TEGO Disperss 662 C "," TEGO Disperss 670 "," TEGO Disperss 685 "," TEGO Disperss 700 "," TEGO Disperss 710 "and" TEGO Disperss 760 W "; For example, "Disparon DA-703-50", "DA-705" and "DA-725" may be used.
　高分子分散剤としては、上記のような市販品以外にも、塩基性基を含有するカチオン性モノマー及び／又は酸性基を有するアニオン性モノマーと、疎水基を有するモノマーと、必要により他のモノマー（ノニオン性モノマー、親水基を有するモノマー等）とを共重合させて合成したものを用いることができる。カチオン性モノマー、アニオン性モノマー、疎水基を有するモノマー及び他のモノマーの詳細については、特開２００４－２５０５０２号公報の段落００３４～００３６に記載のモノマーを挙げることができる。 As the polymer dispersant, in addition to the commercially available products as described above, a cationic monomer having a basic group and / or an anionic monomer having an acidic group, a monomer having a hydrophobic group, and optionally, other monomers Those synthesized by copolymerizing (nonionic monomers, monomers having a hydrophilic group, etc.) can be used. With respect to the details of the cationic monomer, the anionic monomer, the monomer having a hydrophobic group, and the other monomers, monomers described in paragraphs 0034 to 0036 of JP-A No. 2004-250502 can be mentioned.
　また、例えば、特開昭５４－３７０８２号公報、特開昭６１－１７４９３９号公報などに記載のポリアルキレンイミンとポリエステル化合物を反応させた化合物、特開平９－１６９８２１号公報に記載のポリアリルアミンの側鎖のアミノ基をポリエステルで修飾した化合物、特開平９－１７１２５３号公報に記載のポリエステル型マクロモノマーを共重合成分とするグラフト重合体、特開昭６０－１６６３１８号公報に記載のポリエステルポリオール付加ポリウレタン等が好適に挙げられる。 Further, for example, compounds obtained by reacting a polyalkyleneimine with a polyester compound described in JP-A-54-37082, JP-A-61-174939, etc., and polyallylamine described in JP-A-9-169821. Compound in which side chain amino group is modified with polyester, graft polymer having polyester type macromonomer described in JP-A-9-171253 as copolymer component, added polyester polyol described in JP-A-60-166318 A polyurethane etc. are mentioned suitably.
　高分子分散剤の重量平均分子量は、光散乱性粒子を良好に分散することができ、漏れ光の低減効果をより向上させることができる観点から、７５０以上であってよく、１０００以上であってよく、２０００以上であってよく、３０００以上であってもよい。高分子分散剤の重量平均分子量は、光散乱性粒子を良好に分散することができ、漏れ光の低減効果をより向上させることができ、また、インクジェットインクの粘度を吐出可能で安定吐出に適する粘度とする観点から、１０００００以下であってよく、５００００以下であってもよく、３００００以下であってもよい。本明細書中、重量平均分子量とは、ＧＰＣ（ゲル浸透クロマトグラフィー、Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）によって測定される、ポリスチレン換算の重量平均分子量である。 The weight average molecular weight of the polymer dispersant may be 750 or more and 1000 or more from the viewpoint of being able to disperse the light scattering particles well and to further improve the reduction effect of the leaked light. It may be 2000 or more, or 3000 or more. The weight average molecular weight of the polymer dispersant can well disperse the light scattering particles, can further improve the effect of reducing leaked light, and can eject the viscosity of the inkjet ink, which is suitable for stable ejection. From the viewpoint of viscosity, it may be 100,000 or less, 50,000 or less, or 30,000 or less. In the present specification, the weight average molecular weight is a weight average molecular weight in terms of polystyrene, which is measured by GPC (gel permeation chromatography, gel permeation chromatography).
　高分子分散剤の含有量は、光散乱性粒子の分散性の観点から、光散乱性粒子１００質量部に対して、０．５質量部以上であってよく、２質量部以上であってもよく、５質量部以上であってもよい。高分子分散の含有量は、画素部（インク組成物の硬化物）の湿熱安定性の観点から、光散乱性粒子１００質量部に対して、５０質量部以下であってよく、３０質量部以下であってもよく、１０質量部以下であってもよい。 The content of the polymer dispersant may be 0.5 parts by mass or more and 2 parts by mass or more based on 100 parts by mass of the light scattering particles from the viewpoint of dispersibility of the light scattering particles. It may be 5 parts by mass or more. The content of the polymer dispersion may be 50 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the light scattering particles, from the viewpoint of wet heat stability of the pixel portion (cured product of ink composition) Or 10 parts by mass or less.
［熱硬化性樹脂］
　本実施形態において熱硬化性樹脂とは、硬化物中においてバインダーとして機能する、熱により架橋し硬化する樹脂である。熱硬化性樹脂は、硬化性基を有する。硬化性基としては、エポキシ基、オキセタン基、イソシアネート基、アミノ基、カルボキシル基、メチロール基等が挙げられ、インク組成物の硬化物の耐熱性及び保存安定性に優れる観点、及び、遮光部（例えばブラックマトリックス）及び基材への密着性に優れる観点から、エポキシ基が好ましい。熱硬化性樹脂は、１種の硬化性基を有していてもよく、二種以上の硬化性基を有していてもよい。 [Thermosetting resin]
In the present embodiment, a thermosetting resin is a resin which functions as a binder in a cured product and which is crosslinked and cured by heat. The thermosetting resin has a curable group. Examples of the curable group include an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxyl group and a methylol group, and the like, and a light shielding portion (the light resistance portion and the storage stability of the cured product of the ink composition are excellent) For example, an epoxy group is preferable from the viewpoint of excellent adhesion to a black matrix) and a substrate. The thermosetting resin may have one type of curable group, and may have two or more types of curable groups.
　なお、熱硬化性樹脂の中には、光ラジカル重合性を有する（光ラジカル重合開始剤と共に用いられた場合に光の照射によって重合する）樹脂、及び、光カチオン重合性を有する（光カチオン重合開始剤と共に用いられた場合に光の照射によって重合する）樹脂が含まれる。 Among the thermosetting resins, there are photoradically polymerizable resins (polymerized by irradiation with light when used together with a photoradical polymerization initiator) and photocationic polymerizates (photocationic polymerization). Included are resins that polymerize upon irradiation with light when used with an initiator.
　熱硬化性樹脂は、単一のモノマーの重合体（ホモポリマー）であってよく、複数種のモノマーの共重合体（コポリマー）であってもよい。また、熱硬化性樹脂は、ランダム共重合体、ブロック共重合体又はグラフト共重合体のいずれであってもよい。 The thermosetting resin may be a polymer (homopolymer) of a single monomer, or may be a copolymer (copolymer) of a plurality of monomers. The thermosetting resin may be any of a random copolymer, a block copolymer or a graft copolymer.
　熱硬化性樹脂としては、１分子中に熱硬化性官能基を２個以上有する化合物が用いられ、通常、硬化剤と組み合わせて用いられる。熱硬化性樹脂を用いる場合、熱硬化反応を促進できる触媒（硬化促進剤）を更に添加してもよい。言い換えれば、インク組成物は、熱硬化性樹脂（並びに、必要に応じて用いられる硬化剤及び硬化促進剤）を含む熱硬化性成分を含有していてよい。また、これらに加えて、それ自体は重合反応性のない重合体を更に用いてもよい。 As a thermosetting resin, a compound having two or more thermosetting functional groups in one molecule is used, and is usually used in combination with a curing agent. When a thermosetting resin is used, a catalyst (hardening accelerator) capable of promoting a thermosetting reaction may be further added. In other words, the ink composition may contain a thermosetting component including a thermosetting resin (as well as a curing agent and a curing accelerator which is optionally used). In addition to these, a polymer which itself is not polymerizable may be further used.
　１分子中に熱硬化性官能基を２個以上有する化合物として、例えば、１分子中にエポキシ基を２個以上有するエポキシ樹脂（以下、「多官能エポキシ樹脂」ともいう。）を用いてよい。「エポキシ樹脂」には、モノマー性エポキシ樹脂及びポリマー性エポキシ樹脂の両方が含まれる。多官能性エポキシ樹脂が１分子中に有するエポキシ基の数は、好ましくは２～５０個であり、より好ましくは２～２０個である。エポキシ基は、オキシラン環構造を有する構造であればよく、例えば、グリシジル基、オキシエチレン基、エポキシシクロヘキシル基等であってよい。エポキシ樹脂としては、カルボン酸により硬化しうる公知の多価エポキシ樹脂を挙げることができる。このようなエポキシ樹脂は、例えば、新保正樹編「エポキシ樹脂ハンドブック」日刊工業新聞社刊（昭和６２年）等に広く開示されており、これらを用いることが可能である。 As a compound having two or more thermosetting functional groups in one molecule, for example, an epoxy resin having two or more epoxy groups in one molecule (hereinafter, also referred to as “polyfunctional epoxy resin”) may be used. "Epoxy resin" includes both monomeric epoxy resin and polymeric epoxy resin. The number of epoxy groups that the multifunctional epoxy resin has in one molecule is preferably 2 to 50, and more preferably 2 to 20. The epoxy group may be a structure having an oxirane ring structure, and may be, for example, a glycidyl group, an oxyethylene group, an epoxycyclohexyl group and the like. As an epoxy resin, the well-known polyvalent epoxy resin which can be hardened | cured by carboxylic acid can be mentioned. Such an epoxy resin is widely disclosed, for example, in "Epoxy resin handbook" published by M. Shinbo, published by Nikkan Kogyo Shimbun (Showa 62), etc., and these can be used.
　エポキシ基を有する熱硬化性樹脂（多官能エポキシ樹脂を含む）としては、オキシラン環構造を有するモノマーの重合体、オキシラン環構造を有するモノマーと他のモノマー（例えばアクリルモノマー）との共重合体が挙げられる。当該モノマーとしては、例えばグリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、グリシジルビニルエーテル、アリルグリシジルエーテルの如き、各種のエポキシ基含有単量体類；（２－オキソ－１，３－オキソラン）メチル（メタ）アクリレートの如き、（２－オキソ－１，３－オキソラン）基含有ビニル単量体類；３，４－エポキシシクロヘキシル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３，４－エポキシシクロヘキシルエチル（メタ）アクリレートの如き、各種の脂環式エポキシ基含有ビニル単量体などがある。 As a thermosetting resin having an epoxy group (including a polyfunctional epoxy resin), a polymer of a monomer having an oxirane ring structure, a copolymer of a monomer having an oxirane ring structure and another monomer (for example, an acrylic monomer) It can be mentioned. Examples of such monomers include various epoxy group-containing monomers such as glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, glycidyl vinyl ether and allyl glycidyl ether; (2-oxo-1,3-oxolane ) (2-Oxo-1,3-oxolane) group-containing vinyl monomers such as methyl (meth) acrylate; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate And various alicyclic epoxy group-containing vinyl monomers such as 3,4-epoxycyclohexylethyl (meth) acrylate.
　一方、エチレン性不飽和二重結合含有単量体としては、例えば、スチレン、α－メチルスチレン、ビニルトルエンの如き、各種の芳香族ビニル；メチルアクリレート、エチルアクリレート、ブチルアクリレート、シクロヘキシルアクリレートの如き、各種のアクリル酸エステル類；メチルメタクリレート、エチルメタクリレート、ｎ－ブチルメタクリレート、ｉｓｏ－ブチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレートの如き、各種のメタクリル酸エステル類；エチレン、プロピレン、ブテン－１の如き、各種のα－オレフィン類；塩化ビニル、塩化ビニリデンの如き、フルオロオレフィンを除く各種のハロゲン化オレフィン類（ハロ・オレフィン類）；フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル、フマル酸ジオクチル、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチル、マレイン酸ジオクチル、イタコン酸ジメチル、イタコン酸ジエチル、イタコン酸ジブチル、イタコン酸ジオクチルの如き、各種の不飽和ジカルボン酸と、炭素数が１～１８なる１価アルコールとのジエステル類；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、炭素原子数９なる分岐状（分枝状）脂肪族カルボン酸ビニル、炭素原子数１０なる分岐状脂肪族カルボン酸ビニル、炭素原子数１１なる分岐脂肪族カルボン酸ビニル、ステアリン酸ビニルの如き、各種の脂肪族カルボン酸ビニル類等が挙げられる。 On the other hand, as the ethylenically unsaturated double bond-containing monomer, for example, various aromatic vinyls such as styrene, α-methylstyrene and vinyltoluene; such as methyl acrylate, ethyl acrylate, butyl acrylate and cyclohexyl acrylate, Various acrylic acid esters; Various methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate; ethylene, propylene, butene-1 Various α-olefins such as: vinyl chloride, various halogenated olefins other than fluoroolefin such as vinylidene chloride (halo / olefins); dimethyl fumarate, Various unsaturations such as diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate Diesters of dicarboxylic acids and monohydric alcohols each having 1 to 18 carbon atoms; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, carbon Various types such as a branched (branched) aliphatic carboxylic acid vinyl having 9 atoms, a vinyl branched aliphatic carboxylic acid having 10 carbon atoms, a vinyl branched aliphatic carboxylic acid having 11 carbon atoms, and vinyl stearate Aliphatic carboxylic acid vinyls and the like can be mentioned.
　具体的な多官能エポキシ樹脂としては、ポリグリシジルメタクリレート、メチルメタクリレート－グリシジルメタクリレート共重合体、ベンジルメタクリレート－グリシジルメタクリレート共重合体、ｎ－ブチルメタクリレート－グリシジルメタクリレート共重合体、２－ヒドロキシエチルメタクリレート－グリシジルメタクリレート共重合体、（３－エチル－３－オキセタニル）メチルメタクリレート－グリシジルメタクリレート共重合体、スチレン－グリシジルメタクリレート共重合体等が挙げられる。また、本実施形態の熱硬化性樹脂として、特開２０１４－５６２４８号公報の段落００４４～００６６の記載の化合物を用いることもできる。 Specific examples of polyfunctional epoxy resins include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl Examples include methacrylate copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer. Further, as the thermosetting resin of the present embodiment, the compounds described in paragraphs 0044 to 0066 of JP-A-2014-56248 can also be used.
　この様なオキシラン環構造を有するモノマーの単独重合体や共重合体は、二次元状（リニアー）の共重合体であることが、取り扱いや製造の容易さの観点から好ましく、例えば、溶剤なしにまたは有機溶剤中にて、グリシジル（メタ）アクリレートを必須成分として、公知慣用の共重合可能なエチレン性不飽和単量体である、芳香族ビニルや（メタ）アクリル酸エステル等のエチレン性不飽和二重結合を一つ含有する単量体と、必要に応じてエチレン性不飽和二重結合を二つ以上含有する単量体と、共に重合することで得ることができる。グリシジル（メタ）アクリレートとその他のエチレン性不飽和単量体との併用割合を調整することで所望のエポキシ基含有量の共重合体を得ることもできるし、共重合可能なエチレン性不飽和単量体としてどの様なものを選択して用いるか全体の平均分子量をどの程度とするかにより、共重合体の屈折率、ガラス転移温度、柔軟性、透明性、有機溶剤への溶解性等を調整することができる。芳香族ビニルの様な芳香環を含有するモノマーの共重合割合は、例えば生成共重合体の屈折率に、（メタ）アクリル酸エステルのアルキル鎖長は、生成共重合体の柔軟性や支持体などへの接着性に影響を与える。この様な共重合体は、例えば、後記する本発明の特定ＬｏｇＰ値範囲にある有機溶剤中で、上記グリシジル（メタ）アクリレートを必須成分として、公知慣用の共重合可能なエチレン性不飽和単量体とを、グリジシル基が開環しない様に所望の意図した分子量となるまで重合を行う等によっても容易に得ることができる。勿論、後記する特定ＬｏｇＰ値範囲外にある有機溶剤中で行って前記共重合体の調製を行って、左記有機溶剤を後記する特定ＬｏｇＰ値範囲内にある有機溶剤と置換する様にしても良い。 A homopolymer or copolymer of a monomer having such an oxirane ring structure is preferably a two-dimensional (linear) copolymer from the viewpoint of ease of handling and production, for example, without a solvent Or ethylenic unsaturation such as aromatic vinyl or (meth) acrylic acid ester which is a commonly known copolymerizable ethylenic unsaturated monomer containing glycidyl (meth) acrylate as an essential component in an organic solvent It can be obtained by polymerizing together a monomer containing one double bond and, if necessary, a monomer containing two or more ethylenically unsaturated double bonds. A copolymer having a desired epoxy group content can also be obtained by adjusting the combined use ratio of glycidyl (meth) acrylate and other ethylenically unsaturated monomers, and a copolymerizable ethylenically unsaturated singlet can be obtained. The refractive index of the copolymer, the glass transition temperature, the flexibility, the transparency, the solubility in organic solvents, etc. are selected depending on what kind of monomer is selected and used and how the average molecular weight of the whole is made. It can be adjusted. The copolymerization ratio of a monomer containing an aromatic ring such as aromatic vinyl is, for example, the refractive index of the formed copolymer, and the alkyl chain length of (meth) acrylic acid ester is the flexibility or support of the formed copolymer. Affects adhesion to etc. Such a copolymer is, for example, a conventional copolymerizable ethylenically unsaturated unitary monomer containing, as an essential component, the above glycidyl (meth) acrylate in an organic solvent in the specific Log P value range of the present invention described later. The body can also be easily obtained, for example, by polymerization until the desired intended molecular weight is obtained so that the glycidyl group does not open. Of course, the copolymer may be prepared in an organic solvent having a specific LogP value range which will be described later, and the organic solvent may be substituted with an organic solvent which is in a specific LogP value range which will be described later. .
　また、多官能エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、３官能型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ含核ポリオール型エポキシ樹脂、ポリプロピレングリコール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリオキザール型エポキシ樹脂、脂環型エポキシ樹脂、複素環型エポキシ樹脂などを使用できる。 Moreover, as a polyfunctional epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy Resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, dicyclopentadiene Phenolic epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol A cored polyol epoxy resin, polypropylene glycol epoxy resin Resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
　より具体的には、商品名「エピコート８２８」（ジャパンエポキシレジン社製）などのビスフェノールＡ型エポキシ樹脂、商品名「ＹＤＦ－１７５Ｓ」（東都化成社製）などのビスフェノールＦ型エポキシ樹脂、商品名「ＹＤＢ－７１５」（東都化成社製）などの臭素化ビスフェノールＡ型エポキシ樹脂、商品名「ＥＰＩＣＬＯＮ　ＥＸＡ１５１４」（ＤＩＣ（株）製）などのビスフェノールＳ型エポキシ樹脂、商品名「ＹＤＣ－１３１２」（東都化成社製）などのハイドロキノン型エポキシ樹脂、商品名「ＥＰＩＣＬＯＮ　ＥＸＡ４０３２」、「ＨＰ－４７７０」、「ＨＰ－４７００」、「ＨＰ－５０００」（ＤＩＣ（株）製）などのナフタレン型エポキシ樹脂、商品名「エピコートＹＸ４０００Ｈ」（ジャパンエポキシレジン社製）などのビフェニル型エポキシ樹脂、商品名「エピコート１５７Ｓ７０」（ジャパンエポキシレジン社製）などのビスフェノールＡ型ノボラック系エポキシ樹脂、商品名「エピコート１５４」（ジャパンエポキシレジン社製）、商品名「ＹＤＰＮ－６３８」（東都化成社製）などのフェノールノボラック型エポキシ樹脂、商品名「ＹＤＣＮ－７０１」（東都化成社製）などのクレゾールノボラック型エポキシ樹脂、商品名「ＥＰＩＣＬＯＮ　ＨＰ－７２００」、「ＨＰ－７２００Ｈ」（ＤＩＣ（株）製）などのジシクロペンタジエンフェノール型エポキシ樹脂、商品名「エピコート１０３２Ｈ６０」（ジャパンエポキシレジン社製）などのトリスヒドロキシフェニルメタン型エポキシ樹脂、商品名「ＶＧ３１０１Ｍ８０」（三井化学社製）などの３官能型エポキシ樹脂、商品名「エピコート１０３１Ｓ」（ジャパンエポキシレジン社製）などのテトラフェニロールエタン型エポキシ樹脂、商品名「デナコールＥＸ－４１１」（ナガセ化成工業社製）などの４官能型エポキシ樹脂、商品名「ＳＴ－３０００」（東都化成社製）などの水添ビスフェノールＡ型エポキシ樹脂、商品名「エピコート１９０Ｐ」（ジャパンエポキシレジン社製）などのグリシジルエステル型エポキシ樹脂、商品名「ＹＨ－４３４」（東都化成社製）などのグリシジルアミン型エポキシ樹脂、商品名「ＹＤＧ－４１４」（東都化成社製）などのグリオキザール型エポキシ樹脂、商品名「エポリードＧＴ－４０１」（ダイセル化学社製）などの脂環式多官能エポキシ化合物、トリグリシジルイソシアネート（ＴＧＩＣ）などの複素環型エポキシ樹脂などを例示することができる。また、必要であれば、エポキシ反応性希釈剤として、商品名「ネオトートＥ」（東都化成社製）などを混合することができる。 More specifically, bisphenol A type epoxy resin such as trade name "epi coat 828" (made by Japan Epoxy Resins Co., Ltd.), bisphenol F epoxy resin such as trade name "YDF-175S" (made by Tohto Kasei Co., Ltd.), trade name Brominated bisphenol A type epoxy resin such as "YDB-715" (made by Tohto Kasei Co., Ltd.), bisphenol S type epoxy resin such as "EPICLON EXA 1514" (made by DIC Corporation), trade name "YDC-1312" Hydroquinone type epoxy resins such as Toto Kasei Co., Ltd.), Naphthalene type epoxy resins such as “EPICLON EXA 4032”, “HP-4770”, “HP-4700”, “HP-5000” (manufactured by DIC Corporation), Brand name "Epicoat YX4000H" (made by Japan Epoxy Resins Co.) Biphenyl type epoxy resin, bisphenol A type novolac epoxy resin such as trade name "Epikote 157S70" (made by Japan Epoxy Resins Co., Ltd.), trade name "Epikote 154" (made by Japan Epoxy Resins Co., Ltd.), trade name "YDPN-638" Phenolic novolac epoxy resin such as Toto Kasei Co., Ltd., Cresol novolac epoxy resin such as trade name “YDCN-701” (Toto Kasei Co., Ltd.), trade name “EPICLON HP-7200”, “HP-7200H” Dicyclopentadiene phenol type epoxy resin such as DIC Co., Ltd., trishydroxyphenylmethane type epoxy resin such as trade name "epicoat 1032H60" (made by Japan Epoxy Resins Co., Ltd.) trade name "VG3101M80" (made by Mitsui Chemicals, Inc.) Such as Functional epoxy resin, tetraphenylol ethane type epoxy resin such as trade name "epi coat 1031S" (made by Japan Epoxy Resins Co., Ltd.), and tetrafunctional epoxy resin such as trade name "Denacol EX-411" (made by Nagase Chemical Industry Co., Ltd.) , Hydrogenated bisphenol A type epoxy resin such as trade name "ST-3000" (made by Tohto Kasei Co., Ltd.), glycidyl ester type epoxy resin such as trade name "Epikote 190P" (made by Japan Epoxy Resins Co., Ltd.), trade name "YH- Glycidyl amine type epoxy resin such as 434 "(made by Tohto Kasei Co., Ltd.), Glyoxal type epoxy resin such as trade name" YDG-414 "(made by Toto Kasei Co., Ltd.), trade name" Epolide GT-401 " Aliphatic polyfunctional epoxy compounds such as, triglycidyl isocyanate (TGIC) Etc. can be exemplified. Moreover, if necessary, a trade name "Neototo E" (made by Tohto Kasei Co., Ltd.) can be mixed as an epoxy reactive diluent.
　また、多官能エポキシ樹脂としては、ＤＩＣ（株）製の「ファインディックＡ－２４７Ｓ」、「ファインディックＡ－２５４」、「ファインディックＡ－２５３」、「ファインディックＡ－２２９－３０Ａ」、「ファインディックＡ－２６１」、「ファインディックＡ２４９」、「ファインディックＡ－２６６」、「ファインディックＡ－２４１」「ファインディックＭ－８０２０」、「エピクロンＮ－７４０」、「エピクロンＮ－７７０」、「エピクロンＮ－８６５」（商品名）等を用いることができる。 Moreover, as a polyfunctional epoxy resin, "FINEDIC A-247S" made by DIC Corporation, "FINEDIC A-254", "FINEDIC A-253", "FINEDIC A-229-30A", FINE DICK A-261, FINE DICK A 249, FINE DICK A-266, FINE DICK A-241, FINE DICK M-8020, EPICLON N-740, EPICLON N-770, "Epiclon N-865" (trade name) can be used.
　熱硬化性樹脂として、比較的分子量が小さい多官能エポキシ樹脂を用いると、インク組成物（インクジェットインク）中にエポキシ基が補充されてエポキシの反応点濃度が高濃度となり、架橋密度を高めることができる。 When a polyfunctional epoxy resin having a relatively small molecular weight is used as the thermosetting resin, the epoxy group is replenished in the ink composition (ink jet ink), the reaction point concentration of the epoxy becomes high, and the crosslinking density is increased. it can.
　多官能エポキシ樹脂の中でも、架橋密度を高める観点から、一分子中にエポキシ基を４個以上有するエポキシ樹脂（４官能以上の多官能エポキシ樹脂）を用いることが好ましい。特に、インクジェット方式における吐出ヘッドからの吐出安定性を向上させるために重量平均分子量が１００００以下の熱硬化性樹脂を用いる場合には、画素部（インク組成物の硬化物）の強度及び硬度が低下し易いため、架橋密度を充分に高める観点から、４官能以上の多官能エポキシ樹脂をインク組成物（インクジェットインク）に配合することが好ましい。 Among the polyfunctional epoxy resins, it is preferable to use an epoxy resin (a tetrafunctional or higher polyfunctional epoxy resin) having four or more epoxy groups in one molecule from the viewpoint of increasing the crosslinking density. In particular, in the case of using a thermosetting resin having a weight average molecular weight of 10000 or less in order to improve the ejection stability from the ejection head in the ink jet method, the strength and hardness of the pixel portion (cured product of the ink composition) decrease. It is preferable to blend a tetrafunctional or higher polyfunctional epoxy resin into the ink composition (ink jet ink) from the viewpoint of sufficiently increasing the crosslink density because it is easy to do.
　エポキシ基を有する熱硬化性樹脂として、オキシラン環構造を有するモノマーと他のモノマーとの多元共重合体は、着色が少なく透明性により優れ、かつ架橋密度を高められ耐薬品性や柔軟性により優れるといった長所を兼備する硬化物が得られやすい観点から、その他の多官能エポキシ樹脂に比べると好ましい。この様な硬化物としての優れた光学特性や膜物性は、例えば、光学材料用途、特に長期信頼性が期待される光変換層への適用に好適であることを示している。 As a thermosetting resin having an epoxy group, a multicomponent copolymer of a monomer having an oxirane ring structure and another monomer is less in coloration, more excellent in transparency, and enhanced in crosslink density and excellent in chemical resistance and flexibility It is preferable compared with other polyfunctional epoxy resins from the viewpoint that it is easy to obtain a cured product having the above advantages. The excellent optical properties and film physical properties as such a cured product indicate that it is suitable for use in, for example, optical material applications, in particular, light conversion layers expected to have long-term reliability.
　熱硬化性樹脂を硬化させるために用いられる硬化剤及び硬化促進剤としては、上記した有機溶剤に溶解又は分散し得る公知慣用のものをいずれも用いることができるが、例えば、４－メチルヘキサヒドロフタル酸無水物、トリエチレンテトラミン、ジアミノジフェニルメタン、フェノールノボラック樹脂、トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルベンジルアミン、２－エチル－４－メチルイミダゾール、トリフェニルホスフィン、３－フェニル－１，１－ジメチルウレア等が挙げられる。 As a curing agent and a curing accelerator used to cure the thermosetting resin, any of known and commonly used ones which can be dissolved or dispersed in the above-mentioned organic solvent can be used, for example, 4-methylhexahydro Phthalic anhydride, triethylenetetramine, diaminodiphenylmethane, phenol novolak resin, tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, triphenylphosphine, 3-phenyl-1 , 1-dimethylurea and the like.
　なかでも、フェノールノボラック樹脂の様な高分子に比べれば、常温液状であるかまたは上記した有機溶剤への溶解性に優れ低粘度とすることができ、より低温かつより短時間での硬化が容易であり、硬化物の着色がより少ない、低分子の硬化剤及び硬化促進剤を用いることが好ましい。 Among them, compared to polymers such as phenol novolak resin, it is liquid at normal temperature or has excellent solubility in the above organic solvents and can be made low in viscosity, and curing at a lower temperature and in a shorter time is easier It is preferable to use a low molecular weight curing agent and a curing accelerator, which are less colored of the cured product.
　熱硬化性樹脂は、信頼性に優れるカラーフィルタ画素部が得られやすい観点から、アルカリ不溶性であってよい。熱硬化性樹脂がアルカリ不溶性であるとは、１質量％の水酸化カリウム水溶液に対する２５℃における熱硬化性樹脂の溶解量が、熱硬化性樹脂の全質量を基準として、３０質量％以下であることを意味する。熱硬化性樹脂の上記溶解量は、好ましくは、１０質量％以下であり、より好ましくは３質量％以下である。 The thermosetting resin may be alkali-insoluble from the viewpoint of easily obtaining a color filter pixel portion excellent in reliability. When the thermosetting resin is alkali insoluble, the amount of the thermosetting resin dissolved in a 1% by mass aqueous potassium hydroxide solution is 30% by mass or less based on the total mass of the thermosetting resin. It means that. The above-mentioned dissolution amount of the thermosetting resin is preferably 10% by mass or less, more preferably 3% by mass or less.
　熱硬化性樹脂の重量平均分子量は、インクジェットインクとして適正な粘度が得られやすい観点、インク組成物の硬化性が良好となる観点、並びに、画素部（インク組成物の硬化物）の耐溶剤性及び磨耗性が向上する観点から、７５０以上であってよく、１０００以上であってもよく、２０００以上であってよい。インクジェットインクとしての適正な粘度とする観点から、５０００００以下であってよく、３０００００以下であってもよく、２０００００以下であってもよい。ただし、架橋後の分子量に関してはこの限りでない。 The weight average molecular weight of the thermosetting resin is a viewpoint from which an appropriate viscosity is easily obtained as an inkjet ink, a viewpoint from which the curability of the ink composition becomes good, and a solvent resistance of the pixel portion (cured product of the ink composition) And from the viewpoint of improving the wear resistance, it may be 750 or more, 1000 or more, or 2000 or more. From the viewpoint of achieving an appropriate viscosity as an inkjet ink, it may be 500000 or less, 300000 or less, or 200000 or less. However, the molecular weight after crosslinking is not limited to this.
　熱硬化性樹脂の含有量は、インクジェットインクとして適正な粘度が得られやすい観点、インク組成物の硬化性が良好となる観点、並びに、画素部（インク組成物の硬化物）の耐溶剤性及び磨耗性が向上する観点から、インク組成物の不揮発分の質量を基準として、１０質量％以上であってよく、１５質量％以上であってもよく、２０質量％以上であってもよい。熱硬化性樹脂の含有量は、インクジェットインクの粘度が高くなりすぎず、画素部の厚さが光変換機能に対して厚くなりすぎない観点から、インク組成物の不揮発分の質量を基準として、９０質量％以下であってよく、８０質量％以下であってもよく、７０質量％以下であってもよく、６０質量％以下であってもよく、５０質量％以下であってもよい。 The content of the thermosetting resin is from the viewpoint that an appropriate viscosity as an inkjet ink can be easily obtained, from the viewpoint that the curability of the ink composition becomes good, and the solvent resistance of the pixel portion (cured product of the ink composition) From the viewpoint of improving the abrasion resistance, the content may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the mass of the nonvolatile component of the ink composition. The content of the thermosetting resin is based on the mass of the nonvolatile matter of the ink composition from the viewpoint that the viscosity of the inkjet ink does not become too high and the thickness of the pixel portion does not become too thick for the light conversion function. It may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
［有機溶剤］
　本発明における有機溶剤は、後記する特定ＬｏｇＰ値範囲の有機溶剤である。
　本発明においてインク組成物中に含有される有機溶剤としては、例えば、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールジブチルエーテル、アジピン酸ジエチル、シュウ酸ジブチル、マロン酸ジメチル、マロン酸ジエチル、コハク酸ジメチル、コハク酸ジエチル、１，４－ブタン時オールジアセテート、グリセリルトリアセテートなどが挙げられる。 [Organic solvent]
The organic solvent in the present invention is an organic solvent having a specific LogP value range described later.
Examples of the organic solvent contained in the ink composition in the present invention include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate and dimethyl malonate. And diethyl malonate, dimethyl succinate, diethyl succinate, 1,4-butanediol diacetate, glyceryl triacetate and the like.
　有機溶剤の沸点は、インクジェットインクの連続吐出安定性の観点から、１８０℃以上であることが好ましい。また、画素部の形成時には、インク組成物の硬化前にインク組成物から溶剤を除去する必要があるため、溶剤を除去しやすい観点から、溶剤の沸点は３００℃以下であることが好ましい。 The boiling point of the organic solvent is preferably 180 ° C. or more from the viewpoint of the continuous ejection stability of the inkjet ink. Moreover, since it is necessary to remove the solvent from the ink composition before curing the ink composition when forming the pixel portion, the boiling point of the solvent is preferably 300 ° C. or less from the viewpoint of easy removal of the solvent.
　本発明においては、インク組成物を均一となるように調製する観点、及び、インク組成物の流動性等を高めてムラの少ないカラーフィルタ画素部（光変換層）を形成する観点から、有機溶剤を用いることが好ましい。 In the present invention, from the viewpoint of preparing the ink composition to be uniform, and from the viewpoint of forming the color filter pixel portion (light conversion layer) with less unevenness by enhancing the fluidity of the ink composition, etc. It is preferable to use
〔ｌｏｇＰ値〕
　本発明にインク組成物は、特定のＬｏｇＰ値範囲の有機溶剤を用いることを最大の特徴としており、例えば、上記に例示した有機溶剤の中から当該特定のＬｏｇＰ値範囲にある有機溶剤を選択して必須成分として用いることができる。この様な特定のＬｏｇＰ値範囲の有機溶剤を用いることにより、本発明においては、インク組成物の硬化物を不具合を生じ難いものとすることができる。本発明においてｌｏｇＰ値とは、有機溶剤の、１－オクタノール／水の分配係数の対数値を表し、「Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈａｒｍａｃｅｕｔｉｃａｌ　Ｓｃｉｅｎｃｅｓ　、　８３ページ、８４巻，　Ｎｏ．　１，　１９９５年刊」（ＷＩＬＬＩＡＭ　Ｍ．　ＭＥＹＬＡＮ　、　ＰＨＩＬＩＰ　Ｈ．　ＨＯＷＡＲＤ著）に記載の方法で算出される。ｌｏｇＰ値は一般に有機化合物の親疎水性の相対的評価に用いられる数値である。 [LogP value]
The ink composition of the present invention is characterized most in using an organic solvent having a specific LogP value range, and for example, an organic solvent having a specific LogP value range is selected from the organic solvents exemplified above. Can be used as an essential ingredient. In the present invention, the cured product of the ink composition can be made less susceptible to problems by using the organic solvent having such a specific LogP value range. In the present invention, the log P value represents the logarithm value of the 1-octanol / water partition coefficient of the organic solvent, "Journal of Pharmaceutical Sciences, page 83, volume 84, No. 1, 1995" (WILLIAM M. MEYLAN Calculated by the method described in PHILIP H. HOWARD). The log P value is a numerical value generally used to evaluate the relative hydrophobicity of organic compounds.
　例えば、以下のように求められる。
１，４－ブタンジオールジアセテート　　　　　　　　１．３９
テトラリン　　　　　　　　　　　　　　　　　　　　３．２７
ＬＤＯ　　　　　　　　　　　　　　　　　　　　　　１．３５
ＯＸＴ－２２１　　　　　　　　　　　　　　　　　　２．０２
エチレングリコール　　　　　　　　　　　　　　　－１．６１
ｎ－ラウリルメタクリレート　　　　　　　　　　　　６．６８ For example, it is calculated as follows.
1,4-butanediol diacetate 1.39
Tetralin 3.27
LDO 1.35
OXT-221 2.02
Ethylene glycol -1.61
n-lauryl methacrylate 6.68
　尚、１－オクタノール／水の分配係数の対数値は、ＪＩＳ　Ｚ　７２６０－１１７に基づいて実測することも可能であるが、上記計算方法で求めた値が多数の実測結果を非常によい相関を示すことが上記文献に示されている。 The logarithmic value of the 1-octanol / water partition coefficient can also be measured based on JIS Z 7260-117, but the values obtained by the above calculation method have a very good correlation with many measured results. It is shown in the above-mentioned literature to show.
　本発明のインク組成物において、中でもインクジェット用インク組成物においては、有機溶剤のＬｏｇＰ値は－１．０以上～６．５以下であり、必要であれば、本発明の技術的効果を損なわない範囲において、ＬｏｇＰ値がこの範囲外の有機溶剤を含有していてもよい。
　有機溶剤のＬｏｇＰ値は、発光性ナノ結晶の水分による劣化を抑える点で、５．０以下であってよく、４．０以下であってよく、３．０以下であってよく、２．０以下であってよい。また、発光性ナノ結晶を含有するインク組成物の吸水性を抑える観点から、－０．５以上であってよく、０．０以上であってよく、１．０以上であってよい。
　ＬｏｇＰ値が上記範囲の－１．０以上～６．５以下の範囲外の有機溶剤を含有する場合、その有機溶剤は、発光性ナノ結晶の大気中の酸素や水分による劣化を抑える点で、インク中に３０質量％以下であってよく、２０質量％以下であってよく、１０質量％であってよく、５質量％以下であってよく、２質量％以下であってよい。 In the ink composition of the present invention, particularly in the ink composition for inkjet, the LogP value of the organic solvent is -1.0 or more and 6.5 or less, and the technical effect of the present invention is not impaired if necessary. In the range, the LogP value may contain an organic solvent outside this range.
The LogP value of the organic solvent may be 5.0 or less, 4.0 or less, or 3.0 or less, from the viewpoint of suppressing the deterioration of the luminescent nanocrystals due to moisture. It may be the following. Further, from the viewpoint of suppressing the water absorbency of the ink composition containing the light emitting nanocrystals, it may be −0.5 or more, 0.0 or more, or 1.0 or more.
If the LogP value contains an organic solvent outside the range of -1.0 or more to 6.5 or less in the above range, the organic solvent suppresses deterioration of the luminescent nanocrystal due to oxygen or moisture in the air, In the ink, it may be 30% by mass or less, 20% by mass or less, 10% by mass, 5% by mass or less, or 2% by mass or less.
　本発明のインク組成物は、熱硬化性樹脂を用いる熱硬化性インク組成物であることから、例えば、光硬化を行うことによる発光性ナノ結晶粒子の劣化を抑制することができる。 Since the ink composition of the present invention is a thermosetting ink composition using a thermosetting resin, it is possible to suppress, for example, the deterioration of light-emitting nanocrystal particles caused by photocuring.
　本実施形態のインク組成物は、公知慣用のカラーフィルタの製造方法に用いるインクとして適用が可能であるが、比較的高額である発光性ナノ結晶粒子、溶剤等の材料を無駄に消費せずに、必要な箇所に必要な量を用いるだけでカラーフィルタ画素部（光変換層）を形成できる点で、フォトリソグラフィ方式用よりも、インクジェット方式用に適合するよう、適切に調製して用いることが好ましい。 The ink composition of the present embodiment can be applied as an ink used in a well-known and commonly used method of manufacturing a color filter, but without consuming waste materials such as relatively expensive light-emitting nanocrystal particles and solvent. The color filter pixel portion (light conversion layer) can be formed only by using the necessary amount in the necessary places, so that it can be properly prepared and used so as to be compatible with the inkjet method rather than the photolithography method. preferable.
　インク組成物の粘度は、例えば、インクジェット印刷時の吐出安定性の観点から、２ｍＰａ・ｓ以上であってよく、５ｍＰａ・ｓ以上であってもよく、７ｍＰａ・ｓ以上であってもよい。インク組成物の粘度は、２０ｍＰａ・ｓ以下であってよく、１５ｍＰａ・ｓ以下であってもよく、１２ｍＰａ・ｓ以下であってもよい。インク組成物の粘度が２ｍＰａ・ｓ以上である場合、吐出ヘッドのインク吐出孔の先端におけるインク組成物のメニスカス形状が安定するため、インク組成物の吐出制御（例えば、吐出量及び吐出のタイミングの制御）が容易となる。一方、粘度が２０ｍＰａ・ｓ以下である場合、インク吐出孔からインク組成物を円滑に吐出させることができる。インク組成物の粘度は、２～２０ｍＰａ・ｓ、２～１５ｍＰａ・ｓ、２～１２ｍＰａ・ｓ、５～２０ｍＰａ・ｓ、５～１５ｍＰａ・２～２０ｍＰａ・ｓ、７～１５ｍＰａ・ｓ、７～１２ｍＰａ・ｓ、ｓ、又は７～１２ｍＰａ・ｓであってもよい。インク組成物の粘度は、例えば、Ｅ型粘度計によって測定される。 The viscosity of the ink composition may be, for example, 2 mPa · s or more, 5 mPa · s or more, or 7 mPa · s or more from the viewpoint of discharge stability during inkjet printing. The viscosity of the ink composition may be 20 mPa · s or less, 15 mPa · s or less, or 12 mPa · s or less. When the viscosity of the ink composition is 2 mPa · s or more, the meniscus shape of the ink composition at the tip of the ink discharge hole of the discharge head is stabilized, so discharge control of the ink composition (for example, discharge amount and discharge timing) Control) is easy. On the other hand, when the viscosity is 20 mPa · s or less, the ink composition can be smoothly discharged from the ink discharge hole. The viscosity of the ink composition is 2 to 20 mPa · s, 2 to 15 mPa · s, 2 to 12 mPa · s, 5 to 20 mPa · s, 5 to 15 mPa · 2 to 20 mPa · s, 7 to 15 mPa · s, 7 to 12 mPa S, s, or 7 to 12 mPa · s may be used. The viscosity of the ink composition is measured, for example, by an E-type viscometer.
　インク組成物の表面張力は、インクジェット方式に適した表面張力であることが好ましく、具体的には、２０～４０ｍＮ／ｍの範囲であることが好ましく、２５～３５ｍＮ／ｍであることがより好ましい。表面張力を該範囲とすることで飛行曲がりの発生を抑制することができる。なお、飛行曲がりとは、インク組成物をインク吐出孔から吐出させたとき、インク組成物の着弾位置が目標位置に対して３０μｍ以上のずれを生じることをいう。表面張力が４０ｍＮ／ｍ以下である場合、インク吐出孔の先端におけるメニスカス形状が安定するため、インク組成物の吐出制御（例えば、吐出量及び吐出のタイミングの制御）が容易となる。一方、表面張力が２０ｍＮ／ｍ以下である場合、飛行曲がりの発生を抑制できる。すなわち、着弾すべき画素部形成領域に正確に着弾されずにインク組成物の充填が不十分な画素部が生じたり、着弾すべき画素部形成領域に隣接する画素部形成領域（又は画素部）にインク組成物が着弾し、色再現性が低下したりすることがない。 The surface tension of the ink composition is preferably a surface tension suitable for the ink jet system, specifically, preferably in the range of 20 to 40 mN / m, and more preferably 25 to 35 mN / m. . By setting the surface tension in this range, it is possible to suppress the occurrence of flight bending. The term "flying" means that when the ink composition is discharged from the ink discharge hole, the landing position of the ink composition causes a shift of 30 μm or more with respect to the target position. When the surface tension is 40 mN / m or less, the meniscus shape at the tip of the ink discharge hole is stabilized, and the discharge control of the ink composition (for example, control of discharge amount and discharge timing) becomes easy. On the other hand, when the surface tension is 20 mN / m or less, the occurrence of flight deflection can be suppressed. That is, a pixel portion which is not sufficiently landed in the pixel portion formation region to be landed and insufficiently filled with the ink composition is generated, or a pixel portion formation region (or pixel portion) adjacent to the pixel portion formation region to be landed The ink composition does not land on the surface, and the color reproducibility does not decrease.
　インク組成物は、本発明の効果を阻害しない範囲で、発光性ナノ結晶粒子、光散乱性粒子、熱硬化性樹脂、高分子分散剤、及び有機リガンド以外の他の成分を更に含有していてもよい。他の成分としては、例えば、光重合性化合物、重合開始剤、増感剤等が挙げられる。 The ink composition further contains components other than the luminescent nanocrystal particles, the light scattering particles, the thermosetting resin, the polymer dispersant, and the organic ligand, as long as the effects of the present invention are not impaired. It is also good. As another component, a photopolymerizable compound, a polymerization initiator, a sensitizer etc. are mentioned, for example.
［水分含有率］
　本発明のインク組成物において、インク組成物の水分の含有率は、カールフィッシャー水分計（例えば、三菱化学（株）製、型番ＣＡ－０６、気化ユニットは同社製ＶＡ－０６）により測定できる。インク組成物中の水分は、発光性ナノ結晶の劣化を抑制する観点から、９０ｐｐｍ以下であってよく、５０ｐｐｍ以下であってよく、２０ｐｐｍ以下であってよく、９ｐｐｍ以下であってよく、４ｐｐｍ以下であってよく、２ｐｐｍ以下であってよく、１ｐｐｍ以下であってよい。 [Water content rate]
In the ink composition of the present invention, the water content of the ink composition can be measured by a Karl Fischer moisture meter (for example, Mitsubishi Chemical Co., Ltd., model number CA-06, vaporization unit is VA-06 manufactured by the same company). The water content in the ink composition may be 90 ppm or less, 50 ppm or less, 20 ppm or less, 9 ppm or less, or 4 ppm or less from the viewpoint of suppressing deterioration of the luminescent nanocrystals. It may be 2 ppm or less and 1 ppm or less.
　本発明のインク組成物においては、特定ＬｏｇＰ値範囲の有機溶剤を用いた上で、上記した水分含有率範囲とすることが、硬化物により不具合が発生し難い、発光性ナノ結晶の劣化をより効果的に抑制できる観点から、より好ましい。インクジェット用インク組成物の場合は、その吐出方式とも相俟って最良の技術的効果が期待できる。 In the ink composition of the present invention, using an organic solvent having a specific Log P value range and setting the above-described water content range further degrades the light-emitting nanocrystals, which hardly causes a problem due to a cured product. It is more preferable from the viewpoint of being able to be effectively suppressed. In the case of the ink composition for inkjet, the best technical effect can be expected together with the discharge method.
　本発明において、インク組成物や有機溶剤などインク組成物原料の水分含有率は、以下の方法で上記した特定含有率値範囲にコントロールすることができる。例えば、モレキュラーシーブスを加えて脱水した有機溶剤を用いてインク組成物を調製したり、熱硬化性樹脂と有機溶剤の混合物中にモレキュラーシーブスを加える、インク組成物にモレキュラーシーブスを加えて脱水後に濾過する方法である。必要ならば、左記の様な濾過を行わなくても良い。 In the present invention, the water content of the ink composition raw material such as the ink composition and the organic solvent can be controlled to the above-mentioned specific content value range by the following method. For example, molecular sieves are added to prepare an ink composition using a dehydrated organic solvent, or molecular sieves are added to a mixture of a thermosetting resin and an organic solvent, molecular sieves are added to the ink composition, and filtration is performed after dehydration. How to If necessary, the filtration as described in the left does not have to be performed.
　脱水処理時間は、特に制限されるものではないが、モレキュラーシーブスがインク組成物や有機溶剤などインク組成物原料に含有される水分子を吸着するのに時間を要するため、モレキュラーシーブスを加えてから１２時間以上脱水処理してよく、２４時間以上脱水してよく、４８時間以上脱水してよい。この際、大気雰囲気下であってもよいが、水分が実質的に存在しない不活性ガス雰囲気下で脱水処理することが好ましい。尚、用いるモレキュラーシーブスは、使用前に加熱処理などにより吸着した水分を除去して用いることが好ましく、加熱温度は２００℃以上であってよく、２５０℃以上であってよく、３００℃以上であってよく３５０℃以上であってよい。加熱の際に減圧することも吸着水分子を除く観点で好ましく、０．１ｍｍＨｇ以下であってよく、０．０１ｍｍＨｇであってよく、０．００１ｍｍＨｇ以下であってよい。
　光散乱性粒子など固体原料は、水分子を吸着しうるため、使用前に脱水してよく、大気中で、または不活性ガス雰囲気下、または減圧下で、過熱して水分を除去してよい。 The dehydration treatment time is not particularly limited, but since molecular sieves take time to adsorb water molecules contained in the ink composition raw material such as the ink composition and the organic solvent, it is necessary to add the molecular sieves after addition. It may be dehydrated for 12 hours or more, may be dehydrated for 24 hours or more, and may be dehydrated for 48 hours or more. Under the present circumstances, although it may be air | atmosphere atmosphere, it is preferable to dehydrate in the inert gas atmosphere which water substantially does not exist. In addition, it is preferable to use after removing the moisture adsorbed by heat processing etc. before use, and to use the molecular sieves to be used, a heating temperature may be 200 degreeC or more, 250 degreeC or more, and 300 degreeC or more. The temperature may be 350 ° C. or higher. Depressurizing at the time of heating is also preferable in view of removing adsorbed water molecules, and may be 0.1 mmHg or less, 0.01 mmHg, or 0.001 mmHg or less.
Since solid materials such as light scattering particles can adsorb water molecules, they may be dehydrated prior to use, and may be superheated to remove water in the atmosphere or in an inert gas atmosphere or under reduced pressure. .
　水分は大気下では液体に溶解することから、インク組成物原料をそれぞれ脱水してからインク組成物を調製してもよく、インク組成物原料を脱水することなくインク組成物を調製して、当該インク組成物を脱水してもよい。インク組成物原料をそれぞれ脱水してからインク組成物を調製した上で、当該インク組成物を更に脱水してもよい。より厳重に脱水操作を行うことで、硬化物により不具合が発生し難くなり、発光性ナノ結晶の劣化をより確実に抑制できる。 Since water dissolves in liquid in the atmosphere, the ink composition raw material may be dehydrated before preparing the ink composition, or the ink composition may be prepared without dewatering the ink composition raw material. The ink composition may be dewatered. The ink composition may be further dehydrated after each of the ink composition raw materials is dehydrated to prepare the ink composition. By performing the dehydration operation more rigorously, it becomes difficult for a problem to occur due to the cured product, and the deterioration of the luminescent nanocrystal can be more reliably suppressed.
［溶存酸素濃度］
　一実施態様において、インク組成物や有機溶剤などインク組成物原料の溶存酸素濃度は、インクや有機溶剤に窒素やアルゴンなどの不活性ガス気流に晒す、または不活性ガスを吹き込むことで低減できる。光散乱性粒子などの固体原料についても、容器内を窒素気流で満たし、窒素雰囲気下で保存することでインク組成物への酸素の混入を抑制できる。 [Dissolved oxygen concentration]
In one embodiment, the dissolved oxygen concentration of the ink composition raw material such as the ink composition and the organic solvent can be reduced by exposing the ink or the organic solvent to an inert gas flow such as nitrogen or argon or blowing an inert gas. With regard to solid raw materials such as light scattering particles, the inside of the container is filled with a nitrogen stream, and the mixture is stored under a nitrogen atmosphere, whereby the mixing of oxygen into the ink composition can be suppressed.
　溶存酸素濃度は、インク組成物の溶存酸素を光学式かつ耐溶剤性のある溶存酸素濃度計を用いて測定される値であり、具体的に例えば、Ｈａｍｉｌｔｏｎ社Ｖｉｓｉｆｅｒｍを使用し、インク組成物の溶存酸素濃度を測定できる。尚、溶存酸素濃度を測定する装置の測定可能な下限よりも、溶存酸素濃度を低減することは可能であり、その場合も本発明の一実施形態である。 The dissolved oxygen concentration is a value obtained by measuring the dissolved oxygen of the ink composition using an optical type and a solvent-resistant dissolved oxygen analyzer, and specifically, for example, using a Visiferm manufactured by Hamilton, an ink composition Dissolved oxygen concentration can be measured. In addition, it is possible to reduce a dissolved oxygen concentration rather than the measurable lower limit of the apparatus which measures a dissolved oxygen concentration, In that case, it is one Embodiment of this invention.
［脱酸素剤］
　一実施形態のインク組成物は、脱酸素剤を含有し脱酸素剤は、溶存酸素と反応し酸素濃度を低下させるものであればよく、例えば、Ｌ－アスコルビン酸、エリソルビン酸、没食子酸、及びこれらの塩、ピロガロール、ガラセトフェノン等が挙げられる。
　また、本発明において脱酸素剤の、インク組成物中の含有量は、発光性ナノ結晶の劣化を抑えられる点から、０．０１質量％以上であってよく、０．１質量％以上であってよく、０．５質量％以上であってよく、１質量％以上であってよく、インク硬化膜の着色を避ける点から、３０質量％以下であってよく、２０質量％以下であってよく、１０質量％以下であってよく、５質量％以下であってよい。 [Oxygen scavenger]
In the ink composition of one embodiment, the oxygen scavenger may be any agent as long as it reacts with dissolved oxygen to reduce the oxygen concentration, for example, L-ascorbic acid, erythorbic acid, gallic acid, and These salts, pyrogallol, galacetophenone and the like can be mentioned.
In the present invention, the content of the oxygen scavenger in the ink composition may be 0.01% by mass or more and 0.1% by mass or more from the viewpoint of suppressing deterioration of the light-emitting nanocrystals. May be 0.5% by mass or more, 1% by mass or more, and 30% by mass or less, or 20% by mass or less from the viewpoint of avoiding coloring of the cured ink film. And 10% by mass or less, and may be 5% by mass or less.
　溶存ガスをインク組成物から除去する方法としては、より簡便であることから、インク組成物に窒素ガスなどの不活性ガスを導入して、溶存酸素を含む溶存ガスを除去する方法、もしくはインク組成物を減圧する方法を採用することが好ましい。
　尚、上記したインク組成物中の溶存酸素を含む溶存ガスを除去する方法と、上記した当該インク組成物を脱水する方法を組み合わせて行うことにより、溶存ガス濃度も水分濃度も、いずれも低いインク組成物を調製でき、硬化物の不具合や発光性ナノ結晶の劣化をより効果的に抑制できる観点から、より好ましい。 As a method of removing the dissolved gas from the ink composition, it is simpler, a method of removing the dissolved gas containing dissolved oxygen by introducing an inert gas such as nitrogen gas into the ink composition, or an ink composition It is preferable to adopt a method of depressurizing the material.
In addition, both the dissolved gas concentration and the water concentration are low by performing the method of removing the dissolved gas containing dissolved oxygen in the ink composition described above and the method of dewatering the ink composition described above. It is more preferable from the viewpoint of being able to prepare the composition and more effectively suppressing the defects of the cured product and the deterioration of the luminescent nanocrystals.
　以上、カラーフィルタ用インク組成物の一実施形態について説明したが、上述した実施形態のインク組成物は、インクジェット方式の他に、例えば、フォトリソグラフィ方式で用いることもできる。この場合、インク組成物は、バインダーポリマーとしてアルカリ可溶性樹脂を含有する。 As mentioned above, although one Embodiment of the ink composition for color filters was described, the ink composition of embodiment mentioned above can also be used by a photolithographic system other than an inkjet system, for example. In this case, the ink composition contains an alkali soluble resin as a binder polymer.
　インク組成物をフォトグラフィー方式で用いる場合、まず、インク組成物を基材上に塗布し、インク組成物が溶剤を含有する場合には、さらにインク組成物を乾燥させて塗布膜を形成する。このようにして得られる塗布膜は、アルカリ現像液に可溶性であり、アルカリ現像液で処理されることでパターニングされる。この際、アルカリ現像液は、現像液の廃液処理の容易さ等の観点から、水溶液であることが大半を占めるため、インク組成物の塗布膜は水溶液で処理されることとなる。一方、発光性ナノ結晶粒子（量子ドット等）を用いたインク組成物の場合、発光性ナノ結晶粒子が水に対して不安定であり、発光性（例えば蛍光性）が水分により損なわれる。このため本実施形態においては、アルカリ現像液（水溶液）で処理する必要のない、インクジェット方式が好ましい。 When the ink composition is used in the photolithography method, first, the ink composition is applied on a substrate, and when the ink composition contains a solvent, the ink composition is further dried to form a coating film. The coating film thus obtained is soluble in an alkaline developer and is patterned by being treated with the alkaline developer. At this time, since the alkaline developing solution is mainly an aqueous solution from the viewpoint of easiness of waste liquid processing of the developing solution etc., the coating film of the ink composition is treated with the aqueous solution. On the other hand, in the case of the ink composition using light emitting nanocrystal particles (quantum dots etc.), the light emitting nanocrystal particles are unstable to water, and the light emitting property (for example, fluorescence) is impaired by water. For this reason, in the present embodiment, an inkjet method which does not require treatment with an alkaline developer (aqueous solution) is preferable.
　また、インク組成物の塗布膜に対してアルカリ現像液による処理を行わない場合でも、インク組成物がアルカリ可溶性である場合、インク組成物の塗布膜が大気中の水分を吸収しやすく、時間が経過するにつれて発光性ナノ結晶粒子（量子ドット等）の発光性（例えば蛍光性）が損なわれてゆく。この観点から、本実施形態においては、インク組成物の塗布膜はアルカリ不溶性であることが好ましい。すなわち、本実施形態のインク組成物は、アルカリ不溶性の塗布膜を形成可能なインク組成物であることが好ましい。このようなインク組成物は、熱硬化性樹脂として、アルカリ不溶性の熱硬化性樹脂を用いることにより得ることができる。インク組成物の塗布膜がアルカリ不溶性であるとは、１質量％の水酸化カリウム水溶液に対する２５℃におけるインク組成物の塗布膜の溶解量が、インク組成物の塗布膜の全質量を基準として、３０質量％以下であることを意味する。インク組成物の塗布膜の上記溶解量は、好ましくは、１０質量％以下であり、より好ましくは３質量％以下である。なお、インク組成物がアルカリ不溶性の塗布膜を形成可能なインク組成物であることは、インク組成物を基材上に塗布した後、溶剤を含む場合８０℃、３分の条件で乾燥して得られる厚さ１μｍの塗布膜の、上記溶解量を測定することにより確認できる。 In addition, even when the coating film of the ink composition is not treated with an alkaline developer, when the ink composition is alkali-soluble, the coating film of the ink composition tends to absorb moisture in the atmosphere, and the time As it progresses, the light emission (for example, fluorescence) of the light-emitting nanocrystal particles (such as quantum dots) is lost. From this point of view, in the present embodiment, the coating film of the ink composition is preferably alkali insoluble. That is, the ink composition of the present embodiment is preferably an ink composition capable of forming an alkali-insoluble coating film. Such an ink composition can be obtained by using an alkali-insoluble thermosetting resin as the thermosetting resin. The fact that the coating film of the ink composition is alkali insoluble means that the amount of dissolution of the coating film of the ink composition at 25 ° C. in a 1% by mass aqueous solution of potassium hydroxide is based on the total mass of the coating film of the ink composition. It means that it is 30 mass% or less. The dissolution amount of the coating film of the ink composition is preferably 10% by mass or less, more preferably 3% by mass or less. If the ink composition is an ink composition capable of forming an alkali-insoluble coating film, the ink composition is applied on a substrate and then dried under conditions of 80 ° C. for 3 minutes when it contains a solvent. It can confirm by measuring the said melt | dissolution amount of the coating film with a thickness of 1 micrometer obtained.
＜インク組成物の製造方法＞
　次に、上述した実施形態のインク組成物の製造方法について説明する。インク組成物の製造方法は、例えば、光散乱性粒子及び高分子分散剤を含有する、光散乱性粒子の分散体を用意する第１の工程と、光散乱性粒子の分散体及び発光性ナノ結晶粒子を混合する第２の工程と、を備える。この方法では、光散乱性粒子の分散体が熱硬化性樹脂、および上記した様な特定ＬｏｇＰ値範囲となる有機溶剤を必須成分として更に含有してよく、第２の工程において、熱硬化性樹脂を更に混合してもよい。この方法によれば、光散乱性粒子を充分に分散させることができる。そのため、画素部における漏れ光を低減することができるインク組成物を容易に得ることができる。 <Method of Producing Ink Composition>
Next, a method of manufacturing the ink composition of the above-described embodiment will be described. The method for producing an ink composition includes, for example, a first step of preparing a dispersion of light scattering particles containing light scattering particles and a polymer dispersant, a dispersion of light scattering particles, and a luminescent nano And d) mixing the crystal particles. In this method, the dispersion of the light scattering particles may further contain a thermosetting resin and an organic solvent having a specific Log P value range as described above as an essential component, and in the second step, the thermosetting resin May be further mixed. According to this method, the light scattering particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leaked light in the pixel portion can be easily obtained.
　光散乱性粒子の分散体を用意する工程では、光散乱性粒子と、高分子分散剤と、場合により、熱硬化性樹脂とを混合し、分散処理を行うことにより光散乱性粒子の分散体を調製してよい。混合及び分散処理は、ビーズミル、ペイントコンディショナー、遊星撹拌機等の分散装置を用いて行ってよい。光散乱性粒子の分散性が良好となり、光散乱性粒子の平均粒子径を所望の範囲に調整しやすい観点から、ビーズミル又はペイントコンディショナーを用いることが好ましい。 In the step of preparing a dispersion of light scattering particles, the dispersion of light scattering particles is carried out by mixing the light scattering particles, the polymer dispersant, and optionally, the thermosetting resin, and performing dispersion treatment. May be prepared. The mixing and dispersing process may be performed using a dispersing apparatus such as a bead mill, a paint conditioner, a planetary stirrer, or the like. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light scattering particles is good and the average particle diameter of the light scattering particles can be easily adjusted to a desired range.
　インク組成物の製造方法は、第２の工程の前に、発光性ナノ結晶粒子と、熱硬化性樹脂とを含有する、発光性ナノ結晶粒子の分散体を用意する工程を更に備えていてもよい。この場合、第２の工程では、光散乱性粒子の分散体と、発光性ナノ結晶粒子の分散体と、を混合する。この方法によれば、発光性ナノ結晶粒子を充分に分散させることができる。そのため、画素部における漏れ光を低減することができるインク組成物を容易に得ることができる。発光性ナノ結晶粒子の分散体を用意する工程では、光散乱性粒子の分散体を用意する工程と同様の分散装置を用いて、発光性ナノ結晶粒子と、熱硬化性樹脂との混合及び分散処理を行ってよい。 The method for producing an ink composition may further comprise, prior to the second step, a step of preparing a dispersion of light-emitting nanocrystal particles containing light-emitting nanocrystal particles and a thermosetting resin. Good. In this case, in the second step, the dispersion of light scattering particles and the dispersion of light emitting nanocrystal particles are mixed. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. Therefore, an ink composition capable of reducing leaked light in the pixel portion can be easily obtained. In the step of preparing the dispersion of light-emitting nanocrystal particles, mixing and dispersion of the light-emitting nanocrystal particles and the thermosetting resin using the same dispersion apparatus as the step of preparing the dispersion of light-scattering particles You may process it.
　こうして得られたインク組成物は、上記した様にして、特定水分含有率となる様に調製される。 The ink composition thus obtained is prepared to have a specific water content as described above.
　本実施形態のインク組成物を、インクジェット方式用のインク組成物として用いる場合には、圧電素子を用いた機械的吐出機構による、ピエゾジェット方式のインクジェット記録装置に適用することが好ましい。ピエゾジェット方式では、吐出に当たり、インク組成物が瞬間的に高温に晒されることがなく、発光性ナノ結晶粒子の変質が起こり難く、カラーフィルタ画素部（光変換層）も期待した通りの発光特性がより容易に得られやすい。 In the case where the ink composition of the present embodiment is used as an ink composition for an inkjet system, it is preferable to apply to an inkjet recording apparatus of a piezo jet system by a mechanical ejection mechanism using a piezoelectric element. In the piezo jet method, the ink composition is not instantaneously exposed to a high temperature upon discharge, so that the light-emitting nanocrystal particles are not easily degraded, and the light emission characteristics as expected for the color filter pixel portion (light conversion layer) Is easier to obtain.
＜光変換層及びカラーフィルタ＞
　次に、上述した実施形態のインク組成物を用いた、光変換層及びカラーフィルタの詳細について、図面を参照しつつ説明する。なお、以下の説明において、同一又は相当要素には同一符号を用い、重複する説明は省略する。 <Light conversion layer and color filter>
Next, details of the light conversion layer and the color filter using the ink composition of the embodiment described above will be described with reference to the drawings. In the following description, the same or corresponding elements will be denoted by the same reference symbols, without redundant description.
　図１は、一実施形態のカラーフィルタの模式断面図である。図１に示すように、カラーフィルタ１００は、基材４０と、基材４０上に設けられた光変換層３０と、を備える。光変換層３０は、複数の画素部１０と、遮光部２０と、を備えている。 FIG. 1 is a schematic cross-sectional view of a color filter according to one embodiment. As shown in FIG. 1, the color filter 100 includes a base 40 and a light conversion layer 30 provided on the base 40. The light conversion layer 30 includes a plurality of pixel units 10 and a light shielding unit 20.
　光変換層３０は、画素部１０として、第１の画素部１０ａと、第２の画素部１０ｂと、第３の画素部１０ｃとを有している。第１の画素部１０ａと、第２の画素部１０ｂと、第３の画素部１０ｃとは、この順に繰り返すように格子状に配列されている。遮光部２０は
、隣り合う画素部の間、すなわち、第１の画素部１０ａと第２の画素部１０ｂとの間、第２の画素部１０ｂと第３の画素部１０ｃとの間、第３の画素部１０ｃと第１の画素部１０ａとの間に設けられている。言い換えれば、これらの隣り合う画素部同士は、遮光部２０によって離間されている。 The light conversion layer 30 includes, as the pixel unit 10, a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c. The first pixel unit 10a, the second pixel unit 10b, and the third pixel unit 10c are arranged in a grid so as to be repeated in this order. The light shielding unit 20 is disposed between adjacent pixel units, that is, between the first pixel unit 10a and the second pixel unit 10b, between the second pixel unit 10b and the third pixel unit 10c, or the third. Are provided between the first pixel unit 10a and the second pixel unit 10c. In other words, these adjacent pixel portions are separated by the light shielding portion 20.
　第１の画素部１０ａ及び第２の画素部１０ｂは、それぞれ上述した実施形態のインク組成物の硬化物を含む。硬化物は、発光性ナノ結晶粒子と、光散乱性粒子と、硬化成分とを含有する。硬化成分は、熱硬化性樹脂の硬化物であり、具体的には、熱硬化性樹脂の架橋によって得られる硬化物である。すなわち、第１の画素部１０ａは、第１の硬化成分１３ａと、第１の硬化成分１３ａ中にそれぞれ分散された第１の発光性ナノ結晶粒子１１ａ及び第１の光散乱性粒子１２ａとを含む。同様に、第２の画素部１０ｂは、第２の硬化成分１３ｂと、第２の硬化成分１３ｂ中にそれぞれ分散された第２の発光性ナノ結晶粒子１１ｂ及び第２の光散乱性粒子１２ｂとを含む。第１の画素部１０ａ及び第２の画素部１０ｂにおいて、第１の硬化成分１３ａと第２の硬化成分１３ｂとは同一でもあっても異なっていてもよく、第１の光散乱性粒子１２ａと第２の光散乱性粒子１２ｂとは同一でもあっても異なっていてもよい。 The first pixel unit 10a and the second pixel unit 10b each include a cured product of the ink composition of the above-described embodiment. The cured product contains luminescent nanocrystal particles, light scattering particles, and a curing component. The curing component is a cured product of a thermosetting resin, and specifically, a cured product obtained by crosslinking of a thermosetting resin. That is, the first pixel portion 10a includes the first curing component 13a and the first light emitting nanocrystal particles 11a and the first light scattering particles 12a respectively dispersed in the first curing component 13a. Including. Similarly, the second pixel portion 10 b includes a second curing component 13 b and a second light emitting nanocrystal particle 11 b and a second light scattering particle 12 b respectively dispersed in the second curing component 13 b. including. In the first pixel unit 10a and the second pixel unit 10b, the first curing component 13a and the second curing component 13b may be the same or different, and the first light scattering particles 12a and The second light scattering particles 12 b may be the same as or different from each other.
　第１の発光性ナノ結晶粒子１１ａは、４２０～４８０ｎｍの範囲の波長の光を吸収し６０５～６６５ｎｍの範囲に発光ピーク波長を有する光を発する、赤色発光性のナノ結晶粒子である。すなわち、第１の画素部１０ａは、青色光を赤色光に変換するための赤色画素部と言い換えてよい。また、第２の発光性ナノ結晶粒子１１ｂは、４２０～４８０ｎｍの範囲の波長の光を吸収し５００～５６０ｎｍの範囲に発光ピーク波長を有する光を発する、緑色発光性のナノ結晶粒子である。すなわち、第２の画素部１０ｂは、青色光を緑色光に変換するための緑色画素部と言い換えてよい。 The first light-emitting nanocrystal particles 11a are red light-emitting nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel unit 10a may be rephrased as a red pixel unit for converting blue light into red light. The second light-emitting nanocrystal particles 11b are green light-emitting nanocrystal particles that absorb light having a wavelength of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel unit 10b may be reworded as a green pixel unit for converting blue light into green light.
　インク組成物の硬化物を含む画素部における発光性ナノ結晶粒子の含有量は、漏れ光の低減効果により優れる観点から、インク組成物の硬化物の全質量を基準として、５質量％以上であってよく、１０質量％以上であってもよく、１５質量％以上であってもよく、２０質量％以上であってもよく、３０質量％以上であってもよく、４０質量％以上であってもよい。発光性ナノ結晶粒子の含有量は、画素部の信頼性に優れる観点から、インク組成物の硬化物の全質量を基準として、７０質量％以下であってよく、６０質量％以下であってもよく、５５質量％以下であってもよく、５０質量％以下であってもよい。 The content of the light-emitting nanocrystal particles in the pixel portion containing the cured product of the ink composition is 5% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of being superior by the leakage light reduction effect. 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, It is also good. The content of the light-emitting nanocrystal particles may be 70% by mass or less and 60% by mass or less based on the total mass of the cured product of the ink composition, from the viewpoint of excellent reliability of the pixel portion. It may be 55% by mass or less, or 50% by mass or less.
　インク組成物の硬化物を含む画素部における光散乱性粒子の含有量は、漏れ光の低減効果により優れる観点から、インク組成物の硬化物の全質量を基準として、０．１質量％以上であってよく、１質量％以上であってもよく、５質量％以上であってもよく、７質量％以上であってもよく、１０質量％以上であってもよく、１２質量％以上であってもよい。光散乱性粒子の含有量は、漏れ光の低減効果により優れる観点及び画素部の信頼性に優れる観点から、インク組成物の硬化物の全質量を基準として、６０質量％以下であってよく、５０質量％以下であってもよく、４０質量％以下であってもよく、３０質量％以下であってもよく、２５質量％以下であってもよく、２０質量％以下であってもよく、１５質量％以下であってもよい。光散乱性粒子の含有量は、インク組成物の硬化物の全質量を基準として、０．１～６０質量％、０．１～５０質量％、０．１～４０質量％、０．１～３０質量％、０．１～２５質量％、０．１～２０質量％、０．１～１５質量％、１～６０質量％、１～５０質量％、１～４０質量％、１～３０質量％、１～２５質量％、１～２０質量％、１～１５質量％、５～６０質量％、５～５０質量％、５～４０質量％、５～３０質量％、５～２５質量％、５～２０質量％、５～１５質量％、７～６０質量％、７～５０質量
％、７～４０質量％、７～３０質量％、７～２５質量％、７～２０質量％、７～１５質量％、１０～６０質量％、１０～５０質量％、１０～４０質量％、１０～３０質量％、１０～２５質量％、１０～２０質量％、１０～１５質量％、１２～６０質量％、１２～５０質量％、１２～４０質量％、１２～３０質量％、１２～２５質量％、１２～２０質量％、又は１２～１５質量％であってもよい。 The content of the light scattering particles in the pixel portion containing the cured product of the ink composition is 0.1% by mass or more based on the total mass of the cured product of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light. It may be 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more. May be The content of the light scattering particles may be 60% by mass or less, based on the total mass of the cured product of the ink composition, from the viewpoint of being excellent by the reduction effect of leakage light and from the viewpoint of excellent reliability of the pixel portion. It may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. 15 mass% or less may be sufficient. The content of the light scattering particles is 0.1 to 60% by mass, 0.1 to 50% by mass, 0.1 to 40% by mass, or 0.1 to 60% by mass, based on the total mass of the cured product of the ink composition. 30% by mass, 0.1 to 25% by mass, 0.1 to 20% by mass, 0.1 to 15% by mass, 1 to 60% by mass, 1 to 50% by mass, 1 to 40% by mass, 1 to 30% by mass %, 1 to 25 mass%, 1 to 20 mass%, 1 to 15 mass%, 5 to 60 mass%, 5 to 50 mass%, 5 to 40 mass%, 5 to 30 mass%, 5 to 25 mass%, 5 to 20 mass%, 5 to 15 mass%, 7 to 60 mass%, 7 to 50 mass%, 7 to 40 mass%, 7 to 30 mass%, 7 to 25 mass%, 7 to 20 mass%, 7 to 15% by mass, 10 to 60% by mass, 10 to 50% by mass, 10 to 40% by mass, 10 to 30% by mass, 10 to 25% by mass, 10 to 20% by mass, 10 to 15% by mass 12 to 60 wt%, 12 to 50 mass%, 12 to 40 mass%, 12 to 30 wt%, 12 to 25 wt%, 12 to 20% by weight, or 12 to be a 15% by mass.
　第３の画素部１０ｃは、４２０～４８０ｎｍの範囲の波長の光に対し３０％以上の透過率を有する。そのため、第３の画素部１０ｃは、４２０～４８０ｎｍの範囲の波長の光を発する光源を用いる場合に、青色画素部として機能する。第３の画素部１０ｃは、例えば、上述の熱硬化性樹脂を含有する組成物の硬化物を含む。硬化物は、第３の硬化成分１３ｃを含有する。第３の硬化成分１３ｃは、熱硬化性樹脂の硬化物であり、具体的には、熱硬化性樹脂の架橋によって得られる硬化物である。すなわち、第３の画素部１０ｃは、第３の硬化成分１３ｃを含む。第３の画素部１０ｃが上述の硬化物を含む場合、熱硬化性樹脂を含有する組成物は、４２０～４８０ｎｍの範囲の波長の光に対する透過率が３０％以上となる限りにおいて、上述のインク組成物に含有される成分のうち、熱硬化性樹脂以外の成分を更に含有していてもよい。なお、第３の画素部１０ｃの透過率は、顕微分光装置により測定することができる。 The third pixel unit 10c has a transmittance of 30% or more to light of wavelengths in the range of 420 to 480 nm. Therefore, the third pixel unit 10c functions as a blue pixel unit when using a light source that emits light in the wavelength range of 420 to 480 nm. The third pixel portion 10c includes, for example, a cured product of a composition containing the above-mentioned thermosetting resin. The cured product contains the third cured component 13c. The third curing component 13c is a cured product of a thermosetting resin, and specifically, a cured product obtained by crosslinking of the thermosetting resin. That is, the third pixel unit 10c includes the third curing component 13c. When the third pixel portion 10c contains the above-described cured product, the composition containing a thermosetting resin can be used as the above-described ink as long as the transmittance to light in the wavelength range of 420 to 480 nm is 30% or more. Among the components contained in the composition, components other than the thermosetting resin may be further contained. The transmittance of the third pixel unit 10c can be measured by a microspectroscope.
　画素部（第１の画素部１０ａ、第２の画素部１０ｂ及び第３の画素部１０ｃ）の厚さは、例えば、１μｍ以上であってよく、２μｍ以上であってもよく、３μｍ以上であってもよい。画素部（第１の画素部１０ａ、第２の画素部１０ｂ及び第３の画素部１０ｃ）の厚さは、例えば、３０μｍ以下であってよく、２０μｍ以下であってもよく、１５μｍ以下であってもよい。 The thickness of the pixel portion (the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c) may be, for example, 1 μm or more, 2 μm or more, or 3 μm or more. May be The thickness of the pixel unit (the first pixel unit 10a, the second pixel unit 10b, and the third pixel unit 10c) may be, for example, 30 μm or less, 20 μm or less, or 15 μm or less. May be
　遮光部２０は、隣り合う画素部を離間して混色を防ぐ目的及び光源からの光漏れを防ぐ目的で設けられる、いわゆるブラックマトリックスである。遮光部２０を構成する材料は、特に限定されず、クロム等の金属の他、バインダーポリマーにカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂組成物の硬化物等を用いることができる。ここで用いられるバインダーポリマーとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種又は２種以上混合したもの、感光性樹脂、Ｏ／Ｗエマルジョン型の樹脂組成物（例えば、反応性シリコーンをエマルジョン化したもの）などを用いることができる。遮光部２０の厚さは、例えば、０．５μｍ以上であってよく、１０μｍ以下であってよい。 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 which comprises the light-shielding part 20 is not specifically limited, In addition to metals, such as chromium, hardening of the resin composition which made the binder polymer contain light-shielding particles, such as carbon particulates, a metal oxide, an inorganic pigment, and an organic pigment, A thing etc. can be used. As a binder polymer used here, what mixed 1 type, or 2 or more types of resin, such as a polyimide resin, an acrylic resin, an epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, a cellulose, photosensitive resin, O / W An emulsion type resin composition (for example, one obtained by emulsifying a reactive silicone) can be used. The thickness of the light shielding portion 20 may be, for example, 0.5 μm or more, and may be 10 μm or less.
　基材４０は、光透過性を有する透明基材であり、例えば、石英ガラス、パイレックス（登録商標）ガラス、合成石英板等の透明なガラス基板、透明樹脂フィルム、光学用樹脂フィルム等の透明なフレキシブル基材などを用いることができる。これらの中でも、ガラス中にアルカリ成分を含まない無アルカリガラスからなるガラス基板を用いることが好ましい。具体的には、コーニング社製の「７０５９ガラス」、「１７３７ガラス」、「イーグル２００」及び「イーグルＸＧ」、旭硝子社製の「ＡＮ１００」、日本電気硝子社製の「ＯＡ－１０Ｇ」及び「ＯＡ－１１」が好適である。これらは、熱膨脹率の小さい素材であり寸法安定性及び高温加熱処理における作業性に優れる。 The base material 40 is a transparent base material having light transmittance, and for example, transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, transparent resin films, optical resin films, etc. A flexible substrate or the like can be used. Among these, it is preferable to use a glass substrate made of non-alkali glass containing no alkali component in the glass. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" manufactured by Corning, "AN 100" manufactured by Asahi Glass, "OA-10G" manufactured by Nippon Electric Glass, and " OA-11 "is preferred. These are materials having a small thermal expansion coefficient, and are excellent in dimensional stability and workability in high-temperature heat treatment.
　以上の光変換層３０を備えるカラーフィルタ１００は、４２０～４８０ｎｍの範囲の波長の光を発する光源を用いる場合に好適に用いられる。 The color filter 100 including the light conversion layer 30 described above is suitably used in the case of using a light source that emits light in the wavelength range of 420 to 480 nm.
　カラーフィルタ１００は、例えば、基材４０上に遮光部２０をパターン状に形成した後、基材４０上の遮光部２０によって区画された画素部形成領域に、上述した実施形態のインク組成物（インクジェットインク）をインクジェット方式により選択的に付着させ、活性エネルギー線の照射又は加熱によりインク組成物を硬化させる方法により製造することができる。 In the color filter 100, for example, after the light shielding portion 20 is formed in a pattern on the base material 40, the ink composition of the above-described embodiment is formed in the pixel portion forming region partitioned by the light shielding portion 20 on the base material The ink composition can be manufactured by a method in which an ink-jet ink is selectively deposited by an ink-jet method, and the ink composition is cured by irradiation with an active energy ray or heating.
　遮光部２０を形成させる方法は、基材４０の一面側の複数の画素部間の境界となる領域に、クロム等の金属薄膜、又は、遮光性粒子を含有させた樹脂組成物の薄膜を形成し、この薄膜をパターニングする方法等が挙げられる。金属薄膜は、例えば、スパッタリング法、真空蒸着法等により形成することができ、遮光性粒子を含有させた樹脂組成物の薄膜は、例えば、塗布、印刷等の方法により形成することができる。パターニングを行う方法としては、フォトリソグラフィ法等が挙げられる。 In the method of forming the light shielding portion 20, a thin film of a metal thin film such as chromium or a thin film of a resin composition containing light shielding particles is formed in a region serving as a boundary between a plurality of pixel portions on one surface side of the substrate 40 And a method of patterning this thin film. The metal thin film can be formed, for example, by a sputtering method, a vacuum evaporation 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. A photolithography method etc. are mentioned as a method of patterning.
　インクジェット方式としては、エネルギー発生素子として電気熱変換体を用いたバブルジェット（登録商標）方式、或いは圧電素子を用いたピエゾジェット方式等が挙げられる。 Examples of the inkjet method include a bubble jet (registered trademark) method using an electrothermal transducer as an energy generating element, and a piezo jet method using a piezoelectric element.
　インク組成物の硬化を活性エネルギー線（例えば紫外線）の照射により行う場合、例えば、水銀ランプ、メタルハライドランプ、キセノンランプ、ＬＥＤ等を用いてよい。照射する光の波長は、例えば、２００ｎｍ以上であってよく、４４０ｎｍ以下であってよい。露光量は、例えば、１０ｍＪ／ｃｍ２以上であってよく、４０００ｍＪ／ｃｍ２以下であってよい。 When curing of the ink composition is performed by irradiation with active energy rays (for example, ultraviolet light), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like may be used. The wavelength of light to be irradiated may be, for example, 200 nm or more and 440 nm or less. The exposure dose may be, for example, 10 mJ / cm 2 or more, and may be 4000 mJ / cm 2 or less.
　インク組成物の硬化を加熱により行う場合、加熱温度は、例えば、１１０℃以上であってよく、２５０℃以下であってよい。加熱時間は、例えば、１０分以上であってよく、１２０分以下であってよい。 When the ink composition is cured by heating, the heating temperature may be, for example, 110 ° C. or more and 250 ° C. or less. The heating time may be, for example, 10 minutes or more and 120 minutes or less.
　以上、カラーフィルタ及び光変換層、並びにこれらの製造方法の一実施形態について説明したが、本発明は上記実施形態に限定されない。 As mentioned above, although one embodiment of a color filter, a light conversion layer, and these manufacturing methods was described, the present invention is not limited to the above-mentioned embodiment.
　例えば、光変換層は、第３の画素部１０ｃに代えて、又は、第３の画素部１０ｃに加えて、青色発光性のナノ結晶粒子を含有するインク組成物の硬化物を含む画素部（青色画素部）を備えていてもよい。また、光変換層は、赤、緑、青以外の他の色の光を発するナノ結晶粒子を含有するインク組成物の硬化物を含む画素部（例えば黄色画素部）を備えていてもよい。これらの場合、光変換層の各画素部に含有される発光性ナノ結晶粒子のそれぞれは、同一の波長域に吸収極大波長を有することが好ましい。 For example, the light conversion layer is a pixel portion including a cured product of an ink composition containing blue light-emitting nanocrystal particles in place of or in addition to the third pixel portion 10c. (Blue pixel portion) may be provided. In addition, the light conversion layer may be provided with a pixel portion (for example, a yellow pixel portion) including a cured product of an ink composition containing nanocrystal particles that emits light of colors other than red, green and blue. In these cases, each of the luminescent nanocrystal particles contained in each pixel portion of the light conversion layer preferably has an absorption maximum wavelength in the same wavelength range.
　また、光変換層の画素部の少なくとも一部は、発光性ナノ結晶粒子以外の顔料を含有する組成物の硬化物を含むものであってもよい。 In addition, 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 the luminescent nanocrystal particles.
　また、カラーフィルタは、遮光部のパターン上に、遮光部よりも幅の狭い撥インク性を持つ材料からなる撥インク層を備えていてもよい。また、撥インク層を設けるのではなく、画素部形成領域を含む領域に、濡れ性可変層としての光触媒含有層をベタ塗り状に形成した後、該光触媒含有層にフォトマスクを介して光を照射して露光を行い、画素部形成領域の親インク性を選択的に増大させてもよい。光触媒としては、酸化チタン等が挙げられる。 In addition, the color filter may be provided with an ink repellent layer made of a material having ink repellent property narrower than the light shielding portion on the pattern of the light shielding portion. In addition, the photocatalyst containing layer as the wettability variable layer is formed in a solid form in the area including the pixel portion forming area instead of providing the ink repellent layer, and then light is applied to the photocatalyst containing layer through the photomask. The exposure may be performed by irradiation to selectively increase the parent ink property of the pixel portion formation region. Examples of the photocatalyst include titanium oxide and the like.
　また、カラーフィルタは、基材と画素部との間に、ヒドロキシプロピルセルロース等を含むインク受容層を備えていてもよい。 In addition, the color filter may be provided with an ink receiving layer containing hydroxypropyl cellulose or the like between the base and the pixel portion.
　また、カラーフィルタは、画素部上に保護層を備えていてもよい。この保護層は、カラーフィルタを平坦化するとともに、画素部に含有される成分、又は、画素部に含有される成分及び光触媒含有層に含有される成分の液晶層への溶出を防止するために設けられるものである。保護層を構成する材料は、公知のカラーフィルタ用保護層として使用されているものを使用できる。 In addition, the color filter may include a protective layer on the pixel portion. The protective layer planarizes the color filter and prevents the components contained in the pixel section or the components contained in the pixel section and the components contained in the photocatalyst containing layer from eluting into the liquid crystal layer. It is provided. As materials constituting the protective layer, those used as known protective layers for color filters can be used.
　また、カラーフィルタ及び光変換層の製造では、インクジェット方式ではなく、フォトリソグラフィ方式で画素部を形成してもよい。この場合、まず、基材にインク組成物を層状に塗工し、インク組成物層を形成する。次いで、インク組成物層をパターン状に露光した後、現像液を用いて現像する。このようにして、インク組成物の硬化物からなる画素部が形成される。現像液は、通常アルカリ性であるため、バインダーポリマーとして、アルカリ可溶性のポリマーが用いられる。ただし、材料の使用効率の観点では、インクジェット方式がフォトリソグラフィ方式よりも優れている。これはフォトリソグラフィ方式では、その原理上、材料のほぼ２／３以上を除去することとなり、材料が無駄になるからである。このため、本実施形態では、インクジェットインクを用い、インクジェット方式により画素部を形成することが好ましい。 Further, in the manufacture of the color filter and the light conversion layer, the pixel portion may be formed not by the inkjet method but by the photolithography method. In this case, first, the ink composition is applied in layers to the substrate to form an ink composition layer. Next, the ink composition layer is exposed in a pattern, and then developed using a developer. Thus, a pixel portion made of the cured product of the ink composition is formed. Since the developing solution is usually alkaline, an alkali-soluble polymer is used as a binder polymer. However, in terms of material use efficiency, the inkjet method is superior to the photolithography method. This is because the photolithography method, in principle, removes about 2/3 or more of the material, and the material is wasted. Therefore, in the present embodiment, it is preferable to form the pixel portion by an inkjet method using an inkjet ink.
　また、本実施形態の光変換層の画素部には、上記した発光性ナノ結晶粒子に加えて、発光性ナノ結晶粒子の発光色と概ね同色の顔料を更に含有させてもよい。例えば、液晶表示素子の画素部として、青色光を吸収して発光する発光性ナノ結晶粒子を含有する画素部を採用する場合、光源からの光として青色光乃至は４５０ｎｍにピークを持つ準白色光を用いるが、画素部における発光性ナノ結晶粒子の濃度が十分でない場合には、液晶表示素子を駆動させた際に光源からの光が光変換層を透過してしまう。この光源からの透過光（青色光、漏れ光）と、発光性ナノ結晶粒子が発する光とが混色してしまう。このような混色の発生による色再現性の低下を防止する観点から、光変換層の画素部に顔料を含有させてもよい。顔料を画素部に含有させるため、インク組成物に顔料を含有させてもよい。 In addition to the luminescent nanocrystal particles described above, 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 nanocrystal particles. For example, in the case of employing a pixel portion containing light emitting nanocrystals that absorbs blue light and emits light as a pixel portion of a liquid crystal display element, blue light or quasi-white light having a peak at 450 nm as light from a light source However, when the concentration of the luminescent nanocrystal particles in the pixel portion is not sufficient, light from the light source is transmitted through the light conversion layer when the liquid crystal display element is driven. The transmitted light (blue light, leaked light) from this light source and the light emitted by the luminescent nanocrystal particles are mixed. A pigment may be contained in the pixel portion of the light conversion layer from the viewpoint of preventing the decrease in color reproducibility due to the occurrence of such color mixing. The pigment may be contained in the ink composition in order to contain the pigment in the pixel portion.
　また、本実施形態の光変換層中の赤色画素部（Ｒ）、緑色画素部（Ｇ）、及び青色画素部（Ｂ）のうち、一種又は二種を発光性ナノ結晶粒子を含有させずに色材を含有させた画素部としてもよい。ここで使用し得る色材としては、公知の色材を使用することができ、例えば、赤色画素部（Ｒ）に用いる色材としては、ジケトピロロピロール顔料及び／又はアニオン性赤色有機染料が挙げられる。緑色画素部（Ｇ）に用いる色材としては、ハロゲン化銅フタロシニアン顔料、フタロシアニン系緑色染料、フタロシアニン系青色染料とアゾ系黄色有機染料との混合物からなる群から選ばれる少なくとも一種が挙げられる。青色画素部（Ｂ）に用いる色材としては、ε型銅フタロシニアン顔料及び／又はカチオン性青色有機染料が挙げられる。これらの色材の使用量は、光変換層に含有させる場合には、透過率の低下を防止できる観点から、画素部（インク組成物の硬化物）の全質量を基準として、１～５質量％であることが好ましい。






















In addition, one or two or more of the red pixel portion (R), the green pixel portion (G), and the blue pixel portion (B) in the light conversion layer of the present embodiment do not contain the luminescent nanocrystal particles. It may be a pixel portion containing a coloring material. As a coloring material which can be used here, a well-known coloring material can be used, For example, as a coloring material used for a red pixel part (R), a diketopyrrolopyrrole pigment and / or anionic red organic dye are It can be mentioned. Examples of the color material used for the green pixel portion (G) include at least one selected from the group consisting of a halogenated copper phthalocyanine dye, a phthalocyanine green dye, and a mixture of a phthalocyanine blue dye and an azo yellow organic dye. As a coloring material used for a blue pixel part (B), (epsilon) type copper phthalocyanin pigment and / or a cationic blue organic dye are mentioned. The amount of the coloring material used is 1 to 5 mass based on the total mass of the pixel portion (cured product of ink composition) from the viewpoint of preventing a decrease in transmittance when it is contained in the light conversion layer. % Is preferred.






















　以下、実施例により本発明を具体的に説明する。ただし、本発明は下記の実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.
　下記の発光性ナノ結晶を製造する操作、及びインクを製造する操作は、窒素で満たしたグローブボックス内、または、大気を遮断し窒素気流下のフラスコ内で行った。
　また以下で例示するすべての原料は、その容器内の大気を、容器内に窒素ガスを導入して窒素ガスにあらかじめ置換しておき用いた。尚、液体材料に関しては、液体に窒素ガスを導入して溶存酸素を窒素ガスに置換し用いた。
　また、以下で用いる、クロロホルム、エタノール、ヘキサン、トルエン、１，４－ブタンジオールジアセテートは、あらかじめモレキュラーシーブス（基本的に３Ａを使用、ヘキサン、トルエン、ブタンジオールジアセテートは４Ａを使用）で４８時間以上脱水、乾燥させたものを用いた。
　酸化チタンについては使用前に、１ｍｍＨｇの減圧下、２時間、１２０℃で加熱し、窒素ガス雰囲気下で放冷した。 The following operations for producing luminescent nanocrystals and for producing inks were carried out in a nitrogen-filled glove box or in a flask under a nitrogen stream with the atmosphere shut off.
Moreover, as for all the raw materials illustrated below, the nitrogen gas was introduce | transduced in the container and the atmosphere in the container was previously substituted by nitrogen gas, and was used. As for the liquid material, nitrogen gas was introduced into the liquid to replace dissolved oxygen with nitrogen gas.
In addition, chloroform, ethanol, hexane, toluene, 1,4-butanediol diacetate used in the following are pre-made with molecular sieves (basically using 3A, hexane, toluene, butanediol diacetate using 4A). It was used after being dehydrated and dried over time.
Before use, titanium oxide was heated at 120 ° C. under a reduced pressure of 1 mmHg for 2 hours, and allowed to cool under a nitrogen gas atmosphere.
〔赤色発光性ナノ結晶の製造〕
　１０００ｍｌのフラスコに酢酸インジウム１７．４８ｇ、トリオクチルホスフィンオキサイド２５．０ｇ、ラウリン酸３５．９８ｇを仕込み、窒素ガスでバブリングしながら１６０℃で４０分撹拌した。更に２５０℃で２０分間撹拌した後、３００℃まで加熱して撹拌を続けた。グローブボックス内でトリス（トリメチルシリル）ホスフィン４．０ｇをトリオクチルホスフィン１５．０ｇに溶解させた後、ガラス注射器に充填した。これを３００℃に保たれたフラスコ中に注入し、２５０℃で１０分間反応させた。さらにグローブボックス内でトリス（トリメチルシリル）ホスフィン７．５ｇをトリオクチルホスフィン３０．０ｇに溶解させた混合液５ｍｌを上記反応溶液に１２分間で滴下し、その後、使い切るまで１５分間隔で５ｍｌずつ反応溶液に加えた。 [Production of red light emitting nanocrystals]
In a 1000 ml flask, 17.48 g of indium acetate, 25.0 g of trioctyl phosphine oxide and 35.98 g of lauric acid were charged and stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. After further stirring at 250 ° C. for 20 minutes, it was heated to 300 ° C. and stirring was continued. In a glove box, 4.0 g of tris (trimethylsilyl) phosphine was dissolved in 15.0 g of trioctyl phosphine and then filled in a glass syringe. This was poured into a flask kept at 300 ° C., and reacted at 250 ° C. for 10 minutes. Further, 5 ml of a mixed solution of 7.5 g of tris (trimethylsilyl) phosphine dissolved in 30.0 g of trioctylphosphine is added dropwise to the above reaction solution in 12 minutes in a glove box, and then 5 ml of the reaction solution is used at intervals of 15 minutes until used up. Added to.
　別の三口フラスコにて酢酸インジウム５．５９５ｇ、トリオクチルホスフィンオキシド１０．０ｇ、ラウリン酸１１．５１５ｇを仕込み、窒素ガスでバブリングしながら１６０℃で４０分撹拌した。更に２５０℃で２０分間撹拌、３００℃まで加熱した後、７０℃まで冷却した混合溶液を上記反応溶液に加えた。グローブボックス内でトリス（トリメチルシリル）ホスフィン４．０ｇをトリオクチルホスフィン１５．０ｇに溶解させた混合液５ｍｌを再度、上記反応溶液に１２分間で滴下し、その後、使い切るまで１５分間隔で５ｍｌずつ反応溶液に加えた。１時間攪拌を維持、室温まで冷却した後、トルエン１００ｍｌとエタノール４００ｍｌを加えて微粒子を凝集させた。遠心分離機を用いて微粒子を沈殿させた後、上澄み液を廃棄し、沈殿した微粒子をトリオクチルホスフィンに溶解させる事によりリン化インジウム（ＩｎＰ）赤色発光性ナノ結晶のトリオクチルホスフィン溶液を得た。 In a separate three-necked flask, 5.595 g of indium acetate, 10.0 g of trioctylphosphine oxide and 11.515 g of lauric acid were charged, and the mixture was stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. After further stirring at 250 ° C. for 20 minutes and heating to 300 ° C., the mixed solution cooled to 70 ° C. was added to the above reaction solution. In a glove box, 5 ml of a mixed solution of 4.0 g of tris (trimethylsilyl) phosphine dissolved in 15.0 g of trioctylphosphine is dropped again to the above reaction solution in 12 minutes, and then 5 ml of each is reacted at 15 minute intervals until used up. Added to the solution. Stirring was maintained for 1 hour, and after cooling to room temperature, 100 ml of toluene and 400 ml of ethanol were added to coagulate the fine particles. After precipitating fine particles using a centrifuge, the supernatant was discarded, and the precipitated fine particles were dissolved in trioctyl phosphine to obtain a trioctyl phosphine solution of indium phosphide (InP) red light emitting nanocrystals. .
〔緑色発光性ナノ結晶の製造〕
　１０００ｍｌのフラスコに酢酸インジウム２３．３ｇ、トリオクチルホスフィンオキサイド４０．０ｇ、ラウリン酸４８．０ｇを仕込み、窒素ガスでバブリングしながら１６０℃で４０分撹拌した。更に２５０℃で２０分間撹拌した後、３００℃まで加熱して撹拌を続けた。グローブボックス内でトリス（トリメチルシリル）ホスフィン１０．０ｇをトリオクチルホスフィン３０．０ｇに溶解させた後、ガラス注射器に充填した。これを３００℃に保たれたフラスコ中に注入し、２５０℃で５分間反応させた。フラスコを室温まで冷却し、トルエン１００ｍｌとエタノール４００ｍｌを加えて微粒子を凝集させた。遠心分離機を用いて微粒子を沈殿させた後、上澄み液を廃棄し、沈殿した微粒子をトリオクチルホスフィンに溶解させる事によりリン化インジウム（ＩｎＰ）緑色発光性ナノ結晶のトリオクチルホスフィン溶液を得た。 [Production of green light emitting nanocrystals]
In a 1000 ml flask, 23.3 g of indium acetate, 40.0 g of trioctyl phosphine oxide and 48.0 g of lauric acid were charged, and stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. After further stirring at 250 ° C. for 20 minutes, it was heated to 300 ° C. and stirring was continued. In a glove box, 10.0 g of tris (trimethylsilyl) phosphine was dissolved in 30.0 g of trioctyl phosphine and then filled in a glass syringe. This was poured into a flask kept at 300 ° C., and reacted at 250 ° C. for 5 minutes. The flask was cooled to room temperature, and 100 ml of toluene and 400 ml of ethanol were added to coagulate the fine particles. After the microparticles were precipitated using a centrifuge, the supernatant was discarded, and the precipitated microparticles were dissolved in trioctyl phosphine to obtain a trioctyl phosphine solution of indium phosphide (InP) green light emitting nanocrystals. .
〔ＩｎＰ／ＺｎＳコアシェルナノ結晶の製造〕
　上記にて合成したＩｎＰナノ結晶のトリオクチルホスフィン溶液においてＩｎＰ３．６ｇ、トリオクチルホスフィン９０ｇに調整した後、１０００ｍｌのフラスコに投入し、さらにトリオクチルホスフィンオキシド９０ｇ、ラウリン酸３０ｇを加える。一方、グローブボックス内でジエチル亜鉛の１Ｍヘキサン溶液４２．９ｍｌ、ビストリメチルシリルスルフィドのトリオクチルホスフィン９．０９重量％溶液９２．４９ｇをトリオクチルホスフィン１６２ｇ混合する事でストックソリューションを作製する。にフラスコ内を窒素雰囲気に置換した後、フラスコの温度を１８０℃に設定し、８０℃に達した時点で上記ストックソリューション１５ｍｌを添加し、その後１０分ごとに１５ｍｌを添加し続ける。（フラスコ温度は１８０℃に維持）。最後の添加が終了後、さらに１０分間温度を維持する事で反応を終了させた。反応終了後、溶液を常温まで冷却させ、トルエン５００ｍｌとエタノール２０００ｍｌを加えてナノ結晶を凝集させた。遠心分離機を用い、ナノ結晶を沈殿した後、上澄み液を廃棄し、溶液中のナノ結晶濃度が２０質量％となる様、沈殿物を再度クロロホルムに溶解させる事により、ＩｎＰ／ＺｎＳコアシェルナノ結晶のクロロホルム溶液を得た。 [Production of InP / ZnS core-shell nanocrystals]
The solution of InP nanocrystals synthesized above is adjusted to 3.6 g of InP and 90 g of trioctyl phosphine in a trioctyl phosphine solution, charged into a 1000 ml flask, and then 90 g of trioctyl phosphine oxide and 30 g of lauric acid are added. On the other hand, a stock solution is prepared by mixing 42.9 ml of a 1 M solution of diethyl zinc in hexane and 92.49 g of a 9.09% by weight solution of bistrimethylsilyl sulfide in 92 g of trioctylphosphine in a glove box. After the inside of the flask was replaced with a nitrogen atmosphere, the temperature of the flask was set to 180 ° C., and when reaching 80 ° C., 15 ml of the above stock solution was added, and thereafter 15 ml was added every 10 minutes. (Flask temperature maintained at 180 ° C.). After the final addition, the reaction was terminated by maintaining the temperature for an additional 10 minutes. After completion of the reaction, the solution was cooled to room temperature, and 500 ml of toluene and 2000 ml of ethanol were added to aggregate the nanocrystals. After precipitating the nanocrystals using a centrifuge, discard the supernatant and dissolve the precipitate again in chloroform so that the concentration of nanocrystals in the solution becomes 20% by mass, InP / ZnS core-shell nanocrystals Chloroform solution was obtained.
〔ＱＤのリガンド交換〕
　特開２００２―１２１５４９号公報を参考にして３－メルカプトプロパン酸のトリエチレングリコールモノメチルエーテルエステル（トリエチレングリコールモノメチルエーテルメルカプトプロピオネート）（ＴＥＧＭＥＭＰ）を合成した。
　窒素ガスで満たした容器内で、ＱＤ分散液１（上記のＩｎＰ／ＺｎＳコアシェルナノ結晶（赤色発光性））と、上記で合成したＴＥＧＭＥＭＰ８ｇを溶解したクロロホルム溶液８０ｇを混合して８０℃で２時間撹拌することでリガンド交換を行い、室温まで冷却した。
　その後、減圧下４０℃で撹拌しながらトルエン／クロロホルムを蒸発させ、液量が１００ｍｌになるまで濃縮した。この分散液に４倍重量のｎ－ヘキサンを加えてＱＤを凝集させ、遠心分離とデカンテーションによって上澄み液を除いた。沈殿物に５０ｇのトルエンを加えて超音波で再分散させた。この洗浄操作を計３回行い、液中に残存する遊離しているリガンド成分を除去した。デカンテーション後の沈殿物を室温で２時間真空乾燥してＴＥＧＭＥＭＰで修飾されたＱＤ（ＱＤ－ＴＥＧＭＥＭＰ）の粉体２ｇを得た。 [Ligand exchange of QD]
Triethylene glycol monomethyl ether ester (triethylene glycol monomethyl ether mercaptopropionate) (TEGMEMP) of 3-mercaptopropanoic acid was synthesized with reference to JP-A-2002-121549.
In a container filled with nitrogen gas, QD dispersion 1 (above InP / ZnS core-shell nanocrystal (red light emitting property)) and 80 g of a chloroform solution in which 8 g of TEGMEMP synthesized above was dissolved were mixed and heated at 80 ° C. for 2 hours The ligand exchange was carried out by stirring and cooled to room temperature.
Then, while stirring at 40 ° C. under reduced pressure, toluene / chloroform was evaporated and concentrated until the liquid volume reached 100 ml. Four-fold weight n-hexane was added to this dispersion to aggregate QD, and the supernatant was removed by centrifugation and decantation. The precipitate was added with 50 g of toluene and redispersed with ultrasound. This washing operation was performed a total of three times to remove free ligand components remaining in the solution. The precipitate after decantation was vacuum dried at room temperature for 2 hours to obtain 2 g of a powder of TEGMEMP modified QD (QD-TEGMEMP).
〔酸化チタン分散液の調製〕
　窒素ガスで満たした容器内で、酸化チタン６ｇと、高分子分散剤１．０１ｇと、１，４－ブタンジオールジアセテートとを不揮発分４０％となるように混合した。窒素ガスで満たした容器内の配合物にジルコニアビーズ（直径：１．２５ｍｍ）を加えた後、窒素ガスで満たした密閉容器をペイントコンディショナーを用いて２時間振とうさせることで配合物の分散処理を行った。これにより光散乱性粒子分散体１を得た。
上記の材料は全て、窒素ガスを導入して溶存酸素を窒素ガスに置換したものを用いた。 [Preparation of titanium oxide dispersion]
In a container filled with nitrogen gas, 6 g of titanium oxide, 1.01 g of a polymer dispersant, and 1,4-butanediol diacetate were mixed so as to have a nonvolatile content of 40%. After adding zirconia beads (diameter: 1.25 mm) to the compound in the container filled with nitrogen gas, the compound is dispersed by shaking the closed container filled with nitrogen gas for 2 hours using a paint conditioner Did. Thus, a light scattering particle dispersion 1 was obtained.
As the above-mentioned materials, those in which nitrogen gas was introduced to replace dissolved oxygen with nitrogen gas were used.
〔実施例１〕
〔インク組成物の調製〕
　窒素ガスで満たした容器内で、以下の（１）、（２）及び（３）を均一に混合した後、グローブボックス内で、混合物を孔径５μｍのフィルターでろ過、更に窒素ガスをインク内に導入し窒素ガスを飽和させた。
　次いで減圧して窒素ガスを除去することにより、インク組成物を得た。尚、使用した材料は以下である。 Example 1
[Preparation of Ink Composition]
After uniformly mixing the following (1), (2) and (3) in a container filled with nitrogen gas, the mixture is filtered with a filter with a pore size of 5 μm in a glove box and nitrogen gas is further added into the ink It was introduced to saturate nitrogen gas.
Then, the ink composition was obtained by reducing pressure and removing nitrogen gas. The following materials were used.
［光散乱性粒子］
・酸化チタン：ＭＰＴ１４１（石原産業（株）製）
［熱硬化系樹脂］
・グリシジル基含有固形アクリル樹脂：「ファインディックＡ－２５４」
　　　　　　　　　　　　　　　　　　（ＤＩＣ（株）製、エポキシ当量５００）
［高分子分散剤］
・高分子分散剤：ＢＹＫ－２１６４
　　　　　　　（ＢＹＫ社製の商品名、「ＤＩＳＰＥＲＢＹＫ」は登録商標）
［有機溶剤］
・１、４－ブタンジオールジアセテート　（（株）ダイセル製） [Light-scattering particles]
-Titanium oxide: MPT 141 (manufactured by Ishihara Sangyo Co., Ltd.)
[Thermosetting resin]
・ Glycidyl group-containing solid acrylic resin: "FINEDIC A-254"
(Manufactured by DIC Corporation, epoxy equivalent 500)
[Polymer dispersant]
・ Polymer dispersing agent: BYK-2164
(Brand name made by BYK, "DISPERBYK" is a registered trademark)
[Organic solvent]
・ 1, 4-butanediol diacetate (made by Daicel Co., Ltd.)
（１）上記で調製したＱＤ－ＴＥＧＭＥＭＰに、有機溶剤１，４－ブタンジオールジアセテートを混合し不揮発分３０％としたＱＤ分散液　２２．５ｇ
（２）熱硬化系樹脂：ＤＩＣ（株）製「ファインディックＡ－２５４」（６．２８ｇ）と、硬化剤：１－メチルシクロヘキサン－４，５－ジカルボン酸無水物　（１．０５ｇ）と硬化促進剤：ジメチルベンジルアミン　（０．０８ｇ）とを、有機溶剤：１、４－ブタンジオールジアセテートに不揮発分３０％となるように溶解した、熱硬化性樹脂溶液　１２．５ｇ
（３）前記光散乱性粒子分散体１　７．５ｇ (1) 22.5 g of a QD dispersion, in which the organic solvent 1,4-butanediol diacetate is mixed with the QD-TEGMEMP prepared above to make the nonvolatile content 30%
(2) Thermosetting resin: DIC Corporation "FINEDIC A-254" (6.28 g) and curing agent: 1-methylcyclohexane-4,5-dicarboxylic acid anhydride (1.05 g) and curing Accelerator: 12.5 g of a thermosetting resin solution in which dimethylbenzylamine (0.08 g) is dissolved in an organic solvent: 1,4-butanediol diacetate to a nonvolatile content of 30%.
(3) 7.5 g of the light scattering particle dispersion
〔実施例２〕
〔インク組成物の調製〕
　ＱＤ分散液１の代わりに、ＱＤ分散液２（上記のＩｎＰ／ＺｎＳコアシェルナノ結晶（緑色発光性））を用い、実施例１と同様にしてインク組成物を得た。 Example 2
[Preparation of Ink Composition]
In the same manner as in Example 1, an ink composition was obtained using QD dispersion 2 (the above-mentioned InP / ZnS core-shell nanocrystal (green light emitting property)) instead of QD dispersion 1.
〔比較例１〕
　有機溶剤として、デシルベンゼンを用いて実施例１と同様にして作成した、窒素ガス中に密閉されたインク組成物を大気中で攪拌しインク組成物を得た。溶存酸素濃度の上昇が認められた。 Comparative Example 1
An ink composition sealed in nitrogen gas and prepared in the same manner as in Example 1 using decylbenzene as an organic solvent was stirred in the air to obtain an ink composition. An increase in dissolved oxygen concentration was observed.
〔光変換フィルターの作製〕
　上記で得られたインク組成物を、ガラス基板上に、乾燥後の膜厚が３．５μｍとなるように、スピンコーターにて大気中で塗布した。塗布膜を１８０℃に窒素中で加熱して硬化させて、ガラス基板上にインク組成物の硬化物からなる層（光変換層）を形成した。以上の操作により光変換フィルターを得た。 [Preparation of light conversion filter]
The ink composition obtained above was applied on a glass substrate in the air with a spin coater so that the film thickness after drying was 3.5 μm. The coating film was heated at 180 ° C. in nitrogen for curing to form a layer (light conversion layer) comprising a cured product of the ink composition on a glass substrate. The light conversion filter was obtained by the above operation.
（３）評価
　上記で得られたインク組成物及び上記で得られた光変換フィルターを用いて、以下の手順で評価を行った。結果を表１に示す。 (3) Evaluation Using the ink composition obtained above and the light conversion filter obtained above, evaluation was performed according to the following procedure. The results are shown in Table 1.
〔外部量子効率（ＥＱＥ）〕
　前記の青色ＬＥＤ（ピーク発光波長：４５０ｎｍ）を用い、前記の大塚電子（株）製の放射分光光度計（商品名「ＭＣＰＤ－９８００」）に積分球を接続し、青色ＬＥＤの上側に積分球を設置した。青色ＬＥＤと積分球との間に光変換層を有する基材を挿入し、青色ＬＥＤを点灯させて観測されるスペクトル、各波長における照度を測定した。
　上記の測定装置で測定されるスペクトル、および照度より、以下のようにして外部量子効率を求めた。この値は、光変換層に入射した光（光子）のうち、どの程度の割合で蛍光として観測者側に放射されるかを示す値である。従って、この値が大きければ光変換層が優れていることを示しており、Ｓ（ＰＬ）とともに重要な評価指標である。
　赤色発光光変換層の外部量子効率＝Ｐ（Ｒｅｄ）／　Ｅ（Ｂｌｕｅ）×１００　　（％）
　緑色発光光変換層の外部量子効率＝Ｐ（Ｇｌｅｅｎ）／　Ｅ（Ｂｌｕｅ）×１００　（％） [External quantum efficiency (EQE)]
An integrating sphere is connected to the Otsuka Electronics Co., Ltd. radiation spectrophotometer (trade name "MCPD-9800") using the blue LED (peak emission wavelength: 450 nm), and the integrating sphere is on the upper side of the blue LED. Installed. A substrate having a light conversion layer was inserted between the blue LED and the integrating sphere, and the blue LED was turned on to measure the spectrum observed and the illuminance at each wavelength.
The external quantum efficiency was determined from the spectrum measured by the above-mentioned measuring apparatus and the illuminance as follows. This value is a value indicating how much of the light (photon) incident on the light conversion layer is emitted as fluorescence to the observer side. Therefore, a large value of this value indicates that the light conversion layer is excellent and is an important evaluation index together with S (PL).
External quantum efficiency of red light emitting light conversion layer = P (Red) / E (Blue) x 100 (%)
External quantum efficiency of green light emitting light conversion layer = P (Gleen) / E (Blue) x 100 (%)
　ここで、Ｅ（Ｂｌｕｅ）、Ｐ（Ｒｅｄ）、Ｐ（Ｇｌｅｅｎ）は、それぞれ以下を表す。
Ｅ（Ｂｌｕｅ）：
　３８０～４９０ｎｍの波長における「照度×波長÷ｈｃ」の、この波長域での合計値を表す。尚、ｈは、プランク定数、ｃは光速を表す。（これは観測した光子数に相当する値である。）
Ｐ（Ｒｅｄ）：
　４９０～５９０ｎｍの測定波長における「照度×波長÷ｈｃ」の、この波長域での合計値を表す。　（観測した光子数に相当する）
Ｐ（Ｇｌｅｅｎ）：
　５９０～７８０ｎｍの測定波長における「照度×波長÷ｈｃ」の、この波長域での合計値を表す。　（観測した光子数に相当する） Here, E (Blue), P (Red), and P (Gleen) respectively represent the following.
E (Blue):
It represents the total value in this wavelength range of "illuminance x wavelength 波長 hc" at a wavelength of 380 to 490 nm. Here, h represents Planck's constant and c represents the speed of light. (This is a value corresponding to the number of observed photons.)
P (Red):
It represents the total value in this wavelength range of "illuminance x wavelength ÷ hc" at the measurement wavelength of 490 to 590 nm. (Corresponding to the number of observed photons)
P (Gleen):
It represents the total value in this wavelength range of "illuminance x wavelength ÷ hc" at the measurement wavelength of 590 to 780 nm. (Corresponding to the number of observed photons)
　上記に基づいて、ＥＱＥを算出し、実施例２のＥＱＥを１０とし、測定したサンプルのＥＱＥを相対値で以下のように評価した。
＜評価基準＞
　１０未満：Ｄ
　１０：Ｃ
　１０を越え１００以下：Ｂ
　１００を越えるもの：Ａ Based on the above, EQE was calculated, EQE of Example 2 was set to 10, and EQE of the measured sample was evaluated as follows using relative values.
<Evaluation criteria>
Less than 10: D
10: C
More than 10 and less than 100: B
More than 100: A
［気泡評価］
　送液ポンプを用いて前記のインクを送液し、配管チューブ内の気泡の発生を目視観察した。
［水分含有率評価］
　水分含有率は、カールフィッシャー水分計（三菱化学（株）製、型番ＣＡ－０６、気化ユニットは同社製ＶＡ－０６）により測定した。 [Air bubble evaluation]
The ink was fed using a feed pump, and the generation of air bubbles in the piping tube was visually observed.
[Water content rate evaluation]
The water content rate was measured using a Karl-Fisher moisture meter (manufactured by Mitsubishi Chemical Co., Ltd., model number CA-06, and a vaporization unit manufactured by the company, VA-06).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔実施例３〕
　第１に、以下の手順でブラックマトリックス（ＢＭ）と呼ばれる遮光部を有する基板（ＢＭ基板）を作製した。すなわち、無アルカリガラスからなるガラス基板（日本電気硝子社製の「ＯＡ－１０Ｇ」）上にブラックレジスト（東京応化工業社製の「ＣＦＰＲ　ＢＫ」）を塗布した後、プリベーク、パターン露光、現像及びポストベークを行うことにより、パターン状の遮光部を形成した。露光は、ブラックレジストに対し、２５０ｍＪ／ｃｍ２の露光量で紫外線を照射することにより行った。遮光部のパターンは、２００μｍ×６００μｍのサブ画素に相当する、開口部分を有するパターンであり、線幅は２０μｍであり、厚さは２．６μｍであった。 [Example 3]
First, a substrate (BM substrate) having a light shielding portion called a black matrix (BM) was produced in the following procedure. That is, after a black resist ("CFPR BK" manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on a glass substrate ("OA-10G" manufactured by Nippon Electric Glass Co., Ltd.) made of alkali free glass, prebaking, pattern exposure, development and By performing post-baking, a patterned light shielding portion was formed. The exposure was performed by irradiating the black resist with ultraviolet light at an exposure amount of 250 mJ / cm 2 . The pattern of the light shielding portion was a pattern having an opening portion corresponding to a 200 μm × 600 μm sub-pixel, the line width was 20 μm, and the thickness was 2.6 μm.
　次いで、実施例１で得られた赤色発光インク組成物をインクジェット方式でＢＭ基板上の開口部分に印刷した後、紫外線を照射、次いで窒素雰囲気下１５０℃で３０分間加熱した。これにより、インク組成物を硬化させて、インク組成物の硬化物からなる画素部を形成した。得られた画素部は青色光を赤色光に変換する画素部である。画素部の厚さは２．１μｍであった。以上の操作により、パターン付き光変換フィルターを得た。 Subsequently, the red light emitting ink composition obtained in Example 1 was printed on the opening portion on the BM substrate by an inkjet method, then irradiated with ultraviolet light, and then heated at 150 ° C. for 30 minutes under a nitrogen atmosphere. Thus, the ink composition was cured to form a pixel portion made of a cured product of the ink composition. The obtained pixel part is a pixel part which converts blue light into red light. The thickness of the pixel portion was 2.1 μm. A patterned light conversion filter was obtained by the above operation.
〔実施例４〕
　実施例３と同様にして、ＢＭ基板を用意した。次いで、実施例１で得られた赤色発光インク組成物及び実施例２で得られた緑色発光インク組成物を、インクジェット方式でＢＭ基板上の開口部分に印刷した後、紫外線を照射し実施例３と同様にインク組成物を硬化させた。これにより、ＢＭ基板上に、青色光を赤色光に変換する画素部、及び、青色光を緑色光に変換する画素部を形成した。以上の操作により、複数種の画素部を備えるパターン付き光変換フィルターを得た。 Example 4
In the same manner as in Example 3, a BM substrate was prepared. Subsequently, the red light emitting ink composition obtained in Example 1 and the green light emitting ink composition obtained in Example 2 are printed on the opening portion on the BM substrate by an inkjet method, and then the ultraviolet ray is irradiated. The ink composition was cured in the same manner. Thus, on the BM substrate, a pixel portion that converts blue light to red light and a pixel portion that converts blue light to green light are formed. By the above-described operation, a patterned light conversion filter including a plurality of types of pixel units is obtained.
１０…画素部、１０ａ…第１の画素部、１０ｂ…第２の画素部、１０ｃ…第３の画素部、１１ａ…第１の発光性ナノ結晶粒子、１１ｂ…第２の発光性ナノ結晶粒子、１２ａ…第１の光散乱性粒子、１２ｂ…第２の光散乱性粒子、２０…遮光部、３０…光変換層、４０…基材、１００…カラーフィルタ。 DESCRIPTION OF SYMBOLS 10 ... Pixel part, 10a ... 1st pixel part, 10b ... 2nd pixel part 10c ... 3rd pixel part, 11a ... 1st luminescent nanocrystalline particle, 11b ... 2nd luminescent nanocrystalline particle 12a: first light scattering particle, 12b: second light scattering particle, 20: light shielding portion, 30: light conversion layer, 40: base material, 100: color filter.

Claims (17)

  1. 　発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
    前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であることを特徴とするインク組成物。     Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
    An ink composition wherein the LogP value of the organic solvent is -1.0 or more and 6.5 or less.
  2. 　発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
    前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であり、
    カールフィッシャー水分計に基づく水分（Ｈ２Ｏ）含有率が、９０ｐｐｍ以下であることを特徴とするインク組成物。     Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
    The LogP value of the organic solvent is -1.0 or more and 6.5 or less,
    An ink composition having a water (H 2 O) content based on a Karl Fischer moisture meter of 90 ppm or less.
  3. 　発光性ナノ結晶粒子と熱硬化性樹脂と有機溶剤を含有し、
    前記有機溶剤のＬｏｇＰ値が－１．０以上～６．５以下であり、
    カールフィッシャー水分計に基づく水分（Ｈ２Ｏ）含有率が、９０ｐｐｍ以下であることを特徴とするインクジェット用インク組成物。     Containing luminescent nanocrystal particles, thermosetting resin and organic solvent,
    The LogP value of the organic solvent is -1.0 or more and 6.5 or less,
    An ink composition for inkjet according to claim 1, wherein a water content (H 2 O) content based on a Karl Fischer moisture meter is 90 ppm or less.
  4. 　前記インク組成物の製造方法であって、前記インク組成物を減圧し溶存ガスを除去することを特徴とする、前記請求項３記載のインクジェット用インク組成物の製造方法。 The method for producing an ink composition according to claim 3, which is a method for producing the ink composition, wherein the pressure of the ink composition is reduced to remove the dissolved gas.
  5. 前記水分（Ｈ２Ｏ）含有率が、２０ｐｐｍ以下であることを前記請求項３記載のインクジェット用インク組成物。 The ink composition according to claim 3, wherein the water (H 2 O) content is 20 ppm or less.
  6. 　前記熱硬化性樹脂が、アルカリ不溶性である、前記請求項３または５のいずれか一項記載のインクジェット用インク組成物。 The ink composition for inkjet according to any one of claims 3 or 5, wherein the thermosetting resin is alkali insoluble.
  7. 　アルカリ不溶性の塗布膜を形成可能である、前記請求項３、５または６のいずれか一項記載のインクジェット用インク組成物。 The ink composition for inkjet according to any one of claims 3, 5 or 6, which can form an alkali insoluble coating film.
  8. 　表面張力が２０～４０ｍＮ／ｍである、前記請求項３、５、６または７のいずれか一項記載のインクジェット用インク組成物。 The ink composition for inkjet according to any one of claims 3, 5, 6 or 7, which has a surface tension of 20 to 40 mN / m.
  9. 　粘度が２～２０ｍＰａ・ｓである、前記請求項３、５、６、７または８のいずれか一項記載のインクジェット用インク組成物。 The inkjet ink composition according to any one of claims 3, 5, 6, 7, or 8, which has a viscosity of 2 to 20 mPa · s.
  10. 　沸点が１８０℃以上である溶剤を更に含有する、前記請求項３、５、６、７、８または９のいずれか一項記載のインクジェット用インク組成物。 The ink composition for inkjet according to any one of claims 3, 5, 6, 7, 8 or 9, further comprising a solvent having a boiling point of 180 ° C or higher.
  11. 　カラーフィルタ用である、前記請求項３、５、６、７、８、９または１０のいずれか一項記載のインクジェット用インク組成物。 The ink composition for inkjet according to any one of claims 3, 5, 6, 7, 8, 9 or 10, which is for color filters.
  12. 　前記請求項１～３のいずれか一項記載のインク組成物の硬化物からなる光変換層。 A light conversion layer comprising a cured product of the ink composition according to any one of claims 1 to 3.
  13. 　前期請求項１～３のいずれか一項記載のインク組成物の硬化物からなる光変換層がアルカリ不溶性である光変換層。 A light conversion layer, wherein the light conversion layer formed of the cured product of the ink composition according to any one of claims 1 to 3 is alkali insoluble.
  14. 　複数の画素部を備える光変換層であって、
    　前記複数の画素部は、前記請求項３、５、６、７、８、９または１０のいずれか一項記載のインクジェット用インク組成物の硬化物を含む画素部を有する、光変換層。     A light conversion layer comprising a plurality of pixel portions, wherein
    A light conversion layer having a pixel portion containing a cured product of the ink composition for ink jet recording according to any one of claims 3, 5, 6, 7, 8, 9, or 10.
  15. 　前記複数の画素部間に設けられた遮光部を更に備え、
    　前記複数の画素部は、
    　前記硬化物を含み、且つ、前記発光性ナノ結晶粒子として、４２０～４８０ｎｍの範囲
    の波長の光を吸収し６０５～６６５ｎｍの範囲に発光ピーク波長を有する光を発する発光
    性ナノ結晶粒子を含有する、第１の画素部と、
    　前記硬化物を含み、且つ、前記発光性ナノ結晶粒子として、４２０～４８０ｎｍの範囲
    の波長の光を吸収し５００～５６０ｎｍの範囲に発光ピーク波長を有する光を発する発光
    性ナノ結晶粒子を含有する、第２の画素部と、を有する、前記請求項１２～１４のいずれか一項記載の光変換層。     It further comprises a light shielding part provided between the plurality of pixel parts,
    The plurality of pixel units are
    It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 605 to 665 nm. , The first pixel portion,
    It contains the cured product, and as the luminescent nanocrystal particles, it contains luminescent nanocrystal particles that absorb light in the wavelength range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. The light conversion layer according to any one of claims 12 to 14, having a second pixel portion.
  16. 　前記複数の画素部は、４２０～４８０ｎｍの範囲の波長の光に対する透過率が３０％以
    上である第３の画素部を更に有する、前記請求項１２～１５のいずれか一項記載の光変換層。     The light conversion layer according to any one of claims 12 to 15, wherein the plurality of pixel parts further have a third pixel part having a transmittance of 30% or more to light of a wavelength in the range of 420 to 480 nm. .
  17. 　前記請求項１２～１６のいずれか一項記載の光変換層を備える、カラーフィルタ。 A color filter comprising the light conversion layer according to any one of claims 12 to 16.
PCT/JP2018/027064 2017-07-21 2018-07-19 Ink composition, method for producing same, light conversion layer and color filter WO2019017423A1 (en)

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