JP2019086745A - Ink composition, light conversion layer, and color filter - Google Patents

Abstract

To provide an ink composition that features good injectability and superior coated film curability.SOLUTION: An ink composition contains luminescent nanocrystal particles and one or more compound selected from a group comprised of a photopolymerizable compound, photo acid generator, photosensitizing compound, and diol compound. The photopolymerizable compound contains an aliphatic epoxy compound and an oxetane compound, at least one of which being monofunctional.SELECTED DRAWING: None

Description

  The present invention relates to an ink composition, a light conversion layer and a color filter.

  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.

  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

  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 inkjet method (Patent Document 1).

International Publication No. 2008/001693

  In order to efficiently form a color filter pixel portion (hereinafter, also simply referred to as “pixel portion”) by an ink jet method using an ink composition containing luminescent nanocrystal particles, the ink composition has good dischargeability. It is required to be excellent in curability when forming a coating film.

  Then, an object of this invention is to provide with the ink composition which has favorable discharge property and is excellent in the hardenability of a coating film. Another object of the present invention is to provide a light conversion layer and a color filter formed using the ink composition.

  One aspect of the present invention contains light-emitting nanocrystal particles, a photopolymerizable compound, a photoacid generator, and one or more compounds selected from the group consisting of a photosensitizing compound and a diol compound. The present invention relates to an ink composition, wherein the photopolymerizable compound contains an alicyclic epoxy compound and an oxetane compound, and at least one of the alicyclic epoxy compound and the oxetane compound is monofunctional. Such an ink composition is excellent in dischargeability when used in an ink jet system, and also excellent in curability when forming a coating film.

  The photosensitizing compound may have a maximum absorption wavelength in a wavelength range of 380 nm or more.

  The diol compound may contain a diol compound having 4 or more carbon atoms.

  The ink composition may further contain light scattering particles. The average particle diameter of the light scattering particles may be 0.05 to 1.0 μm, and may be 0.3 to 0.6 μm. Such an ink composition is excellent in the reduction effect of leak light.

  The light scattering particles may contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate and silica.

  The ink composition may further contain a polymeric dispersant. The weight average molecular weight of the polymer dispersant may be 1,000 or more.

  The photopolymerizable compound may be alkali insoluble.

  The ink composition may be an ink composition capable of forming an alkali-insoluble coating film.

  The surface tension of the ink composition may be 20 to 40 mN / m.

  The viscosity at 40 ° C. of the ink composition may be 2 to 20 mPa · s.

  The ink composition may be for a color filter.

  The ink composition may be an ink composition (inkjet ink) used in an inkjet method.

  One aspect of the present invention relates to a light conversion layer including a plurality of pixel units, wherein the plurality of pixel units includes a pixel unit including a cured product of the above-described ink composition.

  The light conversion layer may further include a light shielding portion provided between a plurality of pixel portions, the plurality of pixel portions include the cured product, and have a range of 420 to 480 nm as light emitting nanocrystal particles. A light-emitting nanocrystal particle comprising: a first pixel portion containing a light-emitting nanocrystal particle that absorbs light of a wavelength and emits light having a light emission peak wavelength in the range of 605 to 665 nm; And a second pixel portion containing luminescent 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. According to this light conversion layer, leaked light in the pixel portion can be further reduced.

  The plurality of pixel units may further include a third pixel unit having a transmittance of 30% or more to light in the wavelength range of 420 to 480 nm.

  One aspect of the present invention relates to a color filter provided with the light conversion layer described above.

  According to the present invention, it is possible to provide an ink composition which has good dischargeability and is excellent in the curability of a coating film. According to the present invention, it is also possible to provide a light conversion layer and a color filter formed using the ink composition.

FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail.

<Ink composition>
The ink composition according to one embodiment includes: light emitting nanocrystal particles; a photopolymerizable compound; a photoacid generator; and one or more compounds selected from the group consisting of a photosensitizing compound and a diol compound And preferably further comprises light scattering particles, and more preferably further comprises a polymeric dispersant. Here, the photopolymerizable compound contains an alicyclic epoxy compound and an oxetane compound, and at least one of the alicyclic epoxy compound and the oxetane compound is monofunctional. The ink composition according to one embodiment is, for example, a color filter ink composition used to form a pixel portion of a color filter by an inkjet method. The ink composition having the above-described structure contains at least one of the photosensitizing compound and the diol compound, so that excellent dischargeability is obtained in the ink jet method, and curability when forming a coating film is also excellent. . The ink composition is suitably used for forming a color filter pixel portion by an inkjet method.

  In the following, at least one compound selected from the group consisting of light emitting nanocrystal particles, a photoacid generator, a photopolymerizable compound, a photosensitizing compound and a diol compound, a light scattering particle, and The ink composition for color filters (ink jet ink for color filters) used for the ink jet system which contains a molecular dispersing agent will be described as an example.

[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.

  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 that emits (green light), and may be a blue light-emitting nanocrystal particle that emits light (blue light) having an emission peak wavelength in the range of 420 to 480 nm . In the present embodiment, the ink composition preferably contains at least one of these light emitting nanocrystal particles. The light absorbed by the luminescent 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 particles can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using a spectrofluorimeter.

  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. 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.

  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.

  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, 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, Ga Sb, AlNP, AlNAs, AlPAs, AlPAs, AlPSb, InPS, InNAs, InNSb, InNAbs, InPAs, InPSb, InPSb, GaAlNP, GaAlNAs, GaAlNs, GaAlPAs, GaAlPSb, GaAlPSb, GaInNPs, GaInNSb, GaInNSb, GaInPSb, InAlNP, InAlNAs, InAlAls, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe 2, CuGaSe _2, CuInS _2, CuG _{S 2, CuInSe 2, AgInS 2} , AgGaSe 2, AgGaS 2, C, include Si and Ge. 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 .

  Examples of red light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe and nanocrystalline particles having a core / shell structure, wherein the shell portion is CdS and the inner core portion is CdSe. Particles, nanocrystal particles having a core / shell structure, wherein the shell part is CdS and the inner core part is ZnSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, InP nano particles Crystalline particles, nanocrystalline particles having a core / shell structure, wherein the shell part is ZnS and the inner core part is InP: nanocrystalline particles, a nanocrystalline particle having a core / shell structure, The shell portion is a mixed crystal of ZnS and ZnSe, and the inner core portion is a nanocrystal particle having InP, a nanocrystal particle having a core / shell structure, and the shell portion is Z Nanocrystal particle of mixed crystal of S and ZnSeS, inner core part is InP, nanocrystalline particle of mixed crystal of CdSe and CdS, nanocrystalline particle of mixed crystal of ZnSe and CdS, core / shell / shell A nanocrystalline particle having a structure, wherein the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP, a core / shell / shell structure It is a nanocrystalline particle provided, wherein the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the inner core portion is InP, etc. .

  Examples of green light emitting semiconductor nanocrystal particles include nanocrystalline particles of CdSe, nanocrystalline particles of mixed crystals of CdSe and ZnS, and nanocrystalline particles having a core / shell structure, and the shell portion is ZnS. A nano-crystal particle having an inner core part of InP, a nano-crystal particle having a core / shell structure, the shell part being a mixed crystal of ZnS and ZnSe, and an inner core part being an InP nano A nanocrystalline particle having a crystal particle and a core / shell / shell structure, wherein the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP A nanocrystalline particle having a core / shell / shell structure, wherein the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the inner core portion is I; Nanocrystalline particles or the like is P and the like.

  Blue light emitting semiconductor nanocrystal particles include, for example, nanocrystalline particles of ZnSe, nanocrystalline particles of ZnS, nanocrystalline particles having a core / shell structure, wherein the shell portion is ZnSe, and the inner core portion A nanocrystalline particle of ZnS, a nanocrystalline particle of CdS, a nanocrystalline particle having a core / shell structure, wherein the shell portion is ZnS and the inner core portion is InP, the core / shell structure Nanocrystalline particles having a structure, wherein the shell part is a mixed crystal of ZnS and ZnSe, and the inner core part is an InP nanocrystalline particle, a nanocrystalline particle having a core / shell / shell structure A nano-crystal particle in which the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP, a core / shell / shell structure. A crystal grain, the first shell portion is a mixed crystal of ZnS and ZnSe, a second shell portion is ZnS, include nanocrystalline like core portion of the inner is InP. 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 particle itself, one that has the least adverse effect on the human body and the like. 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.

  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.

  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. In other words, the surface of the luminescent nanocrystal particle may be passivated by the organic ligand. When the ink composition further contains a polymer dispersant described later, the light-emitting nanocrystal particles may have a polymer dispersant on the surface thereof. In this embodiment, for example, the organic ligand is removed from the luminescent nanocrystal particle having the above-mentioned organic ligand, and the polymer ligand is dispersed on the surface of the luminescent nanocrystal particle by exchanging the organic ligand and the polymer dispersant. 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.

  As the organic ligand, a functional group (hereinafter, also simply referred to as “affinity group”) for securing the affinity to the resin and the solvent, and a functional group for securing the adsorptivity to the luminescent nanocrystal ( Hereinafter, it is preferable that it is a compound which only has "an adsorption group." As the affinity group, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be linear or may have a branched structure. The aliphatic hydrocarbon group may have an unsaturated bond or may not have an unsaturated bond. Examples of the adsorptive group include a hydrogen group, an amino group, a carboxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphine group, a phosphine oxide group, and alkoxyxylsilyl. 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).

［式（１）中、ｐは０〜５０の整数を示し、ｑは０〜５０の整数を示す。］ The organic ligand preferably has an aliphatic hydrocarbon having an ethylene oxide chain and / or a propylene oxide chain as an affinity group, from the viewpoint that the dispersibility and emission intensity of the luminescent nanocrystal particle are further improved. . The organic ligand may be, for example, an organic ligand represented by the following general formula (1).

[In formula (1), p shows the integer of 0-50, q shows the integer of 0-50. ]

  In the organic ligand represented by the above general formula (1), at least one of p and q is preferably 1 or more, and it is more preferable that both p and q are 1 or more.

  As the light-emitting nanocrystal particles, those dispersed in the form of colloid in an organic solvent or the like 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.

  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 is 5% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of further improving the light emission characteristics of the ink composition by improving the light emission characteristics of the ink composition. 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more Good. 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. When the luminescent nanocrystal particle is modified with an organic ligand, the total amount of the luminescent nanocrystal particle and the organic ligand that modifies the luminescent nanocrystal particle may be in the above range. In the present specification, the “mass of nonvolatile content of ink composition” refers to the mass obtained by removing the mass of the solvent from the total mass of the ink composition when the ink composition contains the solvent, and the ink composition When not containing a solvent, it refers to the total mass of the ink composition.

[Photopolymerizable compound]
The photopolymerizable compound of the present embodiment contains an alicyclic epoxy compound, an oxetane compound, and preferably two kinds of an alicyclic epoxy compound and an oxetane compound. At least one of the alicyclic epoxy compound and the oxetane compound is monofunctional. That is, the photopolymerizable compound of the present embodiment includes an alicyclic epoxy compound having one alicyclic epoxy group as a polymerizable group and / or an oxetane compound having one oxetane group as a polymerizable group. The ink composition becomes excellent in dischargeability by containing such a photopolymerizable compound.

  When the alicyclic epoxy compound is monofunctional, the oxetane compound may be monofunctional or bifunctional or more (having two or more oxetane groups), preferably monofunctional or bifunctional . When the oxetane compound is monofunctional, the alicyclic epoxy compound may be monofunctional or bifunctional or more, preferably monofunctional or bifunctional. The difunctional or higher alicyclic epoxy compound has two or more epoxy groups as a polymerizable group, and at least one of the two or more epoxy groups may be an alicyclic epoxy group. That is, for example, a difunctional alicyclic epoxy compound may have two alicyclic epoxy groups, and has one alicyclic epoxy group and an epoxy group other than one alicyclic epoxy group. It may be done. From the viewpoint of further improving the curability of the coating film, the photopolymerizable compound preferably contains a combination in which one of the alicyclic epoxy compound and the oxetane compound is monofunctional and the other is bifunctional.

  As monofunctional alicyclic epoxy compounds, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, cyclohexene oxide, 3-methacryloyloxymethyl cyclohexene oxide, 3-acryloyloxymethyl cyclohexene Oxide, 3-vinyl cyclohexene oxide, etc. are mentioned. As these monofunctional alicyclic epoxy compounds, commercially available products such as "Celoxide 2000" and "Cyclomer M100" manufactured by Daicel Corporation can be used.

  Examples of difunctional alicyclic epoxy compounds include limonene diepoxide, 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane, 3 ', 4'-epoxy Examples include cyclohexylmethyl 3,4-epoxycyclohexane carboxylate, ε-caprolactone modified 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate and the like. It is also possible to use a commercial item as these bifunctional epoxy compounds. As a commercial item of the epoxy compound, for example, “CELLOXIDE 2021P” made by Daicel, “Syracure UVR-6105” made by Dow Chemical Japan Ltd., “Syracure UVR-6107”, “Syracure UVR-6110”, And "CYRA CURE UVR-6128", "ERL 4299" manufactured by Union Carbide, and the like can be used.

  Examples of trifunctional or higher cycloaliphatic epoxy compounds include compounds such as butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone. As these trifunctional or more alicyclic epoxy compounds, "Epolide GT300" and "Epolide GT301" by Daicel Chemical Industries Ltd., and "Epolide GT302" (more than three functions), "Epolide GT400", "Epolide GT401" And “Epolide GT403” (above, tetrafunctional), “ERL 4289” (trifunctional) manufactured by Union Carbide, and the like can be used.

  Examples of monofunctional oxetane compounds include 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyl oxetane, 3-hydroxymethyl-3-ethyl oxetane, 3-hydroxymethyl-3-propyl oxetane, 3-hydroxymethyl-3-3 Normal butyl oxetane, 3-hydroxymethyl-3-phenyl oxetane, 3-hydroxymethyl-3-benzyl oxetane, 3-hydroxyethyl-3-methyl oxetane, 3-hydroxyethyl-3-ethyl oxetane, 3-hydroxyethyl-3 -Propyl oxetane, 3-hydroxyethyl-3-phenyl oxetane, 3-hydroxypropyl-3-methyl oxetane, 3-hydroxypropyl-3-ethyl oxetane, 3-hydroxypropyl-3-propyl oxetane, 3- Droxypropyl-3-phenyloxetane, 3-hydroxybutyl-3-methyloxetane, (3-methyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-methyl-3-oxetanyl) Examples include oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and the like. As these monofunctional oxetane compounds, commercially available products such as "OXMA" from Ube Industries, Ltd., "OXT-101", "OXT-211", "OXT-212" and "OXT-213" from Toa Gosei Co., Ltd. It is possible to use

  Examples of difunctional oxetane compounds include xylylene bis oxetane, bis [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4 And -bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4,4'-bis [(3-ethyl-3-oxetanylmethoxy) methyl] biphenyl and the like. As these bifunctional oxetane compounds, commercially available products such as "OXT-121" and "OXT-221" manufactured by Toagosei Co., Ltd. can be used.

  Examples of trifunctional or higher functional oxetane compounds include compounds such as 1,3,3-tris (4- (2- (3-oxetanyl) butoxyphenyl) butane.

  In addition, known alicyclic epoxy compounds and oxetane compounds (for example, alicyclic epoxy compounds described in JP-A No. 2009-40830 and the like, oxetane compounds, and the like) can also be used.

  The photopolymerizable compound may include other photocationic polymerizable compounds such as vinyl ether and cyclic ether. Examples of vinyl ether compounds include 2-hydroxyethyl vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether and the like. As cyclic ethers, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2 -Epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide and the like can be mentioned.

  The content of the alicyclic epoxy compound may be 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the mass of the nonvolatile component of the ink composition. The content of the alicyclic epoxy compound may be 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the mass of the nonvolatile component of the ink composition.

  The content of the oxetane compound may be 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the mass of the nonvolatile component of the ink composition. The content of the oxetane compound may be 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the mass of the nonvolatile component of the ink composition.

  The ratio of the content of the oxetane compound to the content of the alicyclic epoxy compound (oxetane compound / alicyclic epoxy compound) may be 20/80 or more, 40/60 or more, 60/40 or more It may be The ratio may be 80/20 or less, 60/40 or less, or 40/60 or less.

  The total content of the alicyclic epoxy compound and the oxetane compound may be 60% by mass or more, 70% by mass or more, 80% by mass or more based on the total amount of the photopolymerizable compound And 100% by mass.

  With respect to the content of the photopolymerizable compound, it is easy to obtain an appropriate viscosity as an inkjet ink, and from the viewpoint of being excellent in dischargeability, and from the viewpoint of being excellent in curability of the ink composition, and From the viewpoint of improving the solvent resistance and 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. May be With regard to the content of the photopolymerizable compound, it is easy to obtain an appropriate viscosity as an inkjet ink, and from the viewpoint of being excellent in dischargeability and from the viewpoint of obtaining more excellent optical characteristics (leakage light) 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, based on the mass. May be

[Photo acid generator]
Examples of the photoacid generator (hereinafter, also referred to as “photocationic polymerization initiator”) include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate and the like; Examples include polyaryl iodonium salts such as fluoroantimonate and P-nonylphenyl iodonium hexafluoroantimonate.

  A commercial item can also be used as a photo-acid generator. As commercially available products, sulfonium salts such as "CPI-100P", "CPI-101A", "CPI-200K" manufactured by San-Apro, "Irgacure PAG103", "Irgacure PAG121", "Irgacure PAG203" manufactured by BASF, etc. Photoacid generators, sulfonium salt photocationic polymerization initiators such as "Irgacure 270" and "Irgacure PAG 290" manufactured by BASF, and iodonium salt photocationic polymerization initiators such as "Irgacure 250" can be mentioned.

  The content of the photoacid generator may be 0.1 parts by mass or more and 0.5 parts by mass or more with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of the curability of the ink composition. It may be 1 part by mass or more. The content of the photopolymerization initiator may be 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the photopolymerizable compound from the viewpoint of the temporal stability of the pixel portion (cured product of the ink composition). The amount may be less than or equal to 20 parts by mass.

[Photosensitizing compound]
As the photosensitizing compound, those used as photosensitizers can be used. The photosensitizer preferably has a maximum value of the absorption wavelength on the longer wavelength side than the absorption wavelength band in the ultraviolet wavelength range of light emitting nanocrystal particles, light scattering particles and the like. By using such a photosensitizer, irradiation for curing a photopolymerizable compound in a coating film formed using an ink composition containing light emitting nanocrystal particles, light scattering particles and the like Light can be absorbed more efficiently, which can contribute to the improvement of the acid generation efficiency of the photoacid generator.

  The photosensitizing compound is a compound having a maximum absorption wavelength in a wavelength range of preferably 380 nm or more, more preferably 400 nm or more, still more preferably 410 nm or more. The photosensitizing compound has a maximum absorption wavelength, for example, in a wavelength range of 500 nm or less. The maximum absorption wavelength means a wavelength at which the absorbance reaches a maximum value when the UV-visible absorption spectrum of the photosensitizing compound is measured. When there are a plurality of wavelengths at which the absorbance has a maximum value in the UV-visible absorption spectrum of the photosensitizing compound, at least one of the wavelengths may be in the above wavelength range.

  Examples of the photosensitizing compound include 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and the like.

[Diol compound]
The diol compound may be, for example, an aliphatic diol compound. The aliphatic diol compound is a compound in which two hydrogen atoms of aliphatic hydrocarbon are respectively substituted by a hydroxyl group. The aliphatic diol compound may be linear or cyclic, and is preferably linear. The diol compound is preferably a diol compound having 4 or more carbon atoms. By using such a diol compound, intramolecular condensation that occurs when the oxetane compound undergoes cationic polymerization can be suppressed, and curing of the ink composition can be made more sufficient. The number of carbon atoms constituting the diol compound is more preferably 4 or more carbon atoms, and it is easy to obtain an appropriate viscosity as an inkjet ink, and from the viewpoint of excellent dischargeability, preferably 8 or less, more preferably Is 5 or less.

  As a diol compound, for example, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1-methyl-1 , 4-butanediol and the like.

  The ink composition according to the present embodiment contains one or more compounds selected from the group consisting of a photosensitizing compound and a diol compound. The photosensitizing compound and the diol compound may be used alone or in combination. From the viewpoint of enhancing the light emission properties of the ink composition or the cured product thereof by increasing the content of light emitting nanocrystal particles and light scattering particles in the ink composition, the ink composition is preferably a photosensitizing compound and Only one of the diol compounds is included.

  The content of the photosensitizing compound is preferably 0.1% by mass or more based on the total amount of the ink composition, from the viewpoint of further improving the dischargeability of the ink composition and the curability of the coating film, and more preferably It is 0.5 mass% or more, More preferably, it is 1 mass% or more. The content of the photosensitizing compound is preferably 10% by mass or less based on the total amount of the ink composition, and more preferably 5% by mass, based on the total amount of the ink composition, from the viewpoint of obtaining appropriate viscosity as an inkjet ink Or less, more preferably 3% by mass or less.

  The content of the diol compound is preferably 0.3% by mass or more based on the total amount of the ink composition from the viewpoint of further improving the dischargeability of the ink composition and the curability of the coating film, and more preferably 0. It is 5% by mass or more, more preferably 1% by mass or more. The content of the diol compound is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass, based on the total amount of the ink composition, from the viewpoint of the decrease in the curability of the coating film. It is below.

  The total content of the photosensitizing compound and the diol compound is preferably 0.4% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more, based on the total amount of the ink composition. It is. When the total content of the photosensitizing compound and the diol compound is 0.4% by mass or more, the dischargeability of the ink composition and the curability of the coating film can be further improved. The total content of the photosensitizing compound and the diol compound is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less based on the total amount of the ink composition. .

[Light-scattering particles]
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, magnesium oxide, barium oxide, aluminum oxide, aluminum oxide, bismuth oxide, zirconium oxide, metal oxides such as zinc oxide; magnesium carbonate, barium carbonate, Metal carbonates such as bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, bismuth subnitrate Etc metal And the like. The light scattering particles contain at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate and silica, from the viewpoint of being superior in the reduction effect of leakage light. It is preferable to include at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium titanate.

  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.

  The average particle diameter (volume average diameter) of the light scattering particles in the ink composition is preferably 0.05 μm or more from the viewpoint of improving the light emission characteristics of the ink composition by the effect of reducing leakage light. It may be 0.1 μm or more, may be 0.2 μm or more, and 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, 0.1 to 1 .0 μm, 0.1 to 0.6 μm, 0.1 to 0.4 μm, 0.2 to 1.0 μm, 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 in the ink composition can be 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 is 0.1% by mass or more based on the mass of the non-volatile component of the ink composition, from the viewpoint of improving the light emission characteristics of the ink composition by improving the light emission characteristics of the ink composition. 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 It may also be 15% by mass or more. The content of the light scattering particles is 60 based on the mass of the non-volatile component of the ink composition, from the viewpoint of further improving the light emission characteristics of the ink composition and the viewpoint of improving the ejection stability. The content 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. It may be% or less. In the present embodiment, since the ink composition contains the polymer dispersant, the light scattering particles can be favorably dispersed even when the content of the light scattering particles is in the above range.

  The mass ratio of the content of light scattering particles to the content of light emitting nanocrystal particles (light scattering particles / light emitting nanocrystal particles) is superior due to the reduction effect of leakage light, and the light emission characteristics of the ink composition are further improved. From the point of view of being made to be, it may be 0.1 or more, may be 0.2 or more, and may be 0.5 or more. The mass ratio (light scattering particles / luminescent nanocrystal particles) is more excellent because of the reduction effect of leakage light, further improving the light emission characteristics of the ink composition, and also excellent in the continuous discharge property at the time of ink jet printing. It may be 0 or less, 2.0 or less, or 1.5 or less. 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 if the same backlight is used, it is considered that the light absorption amount in the pixel portion is increased, and the emission intensity of the luminescent nanocrystal particle is further improved. As a result, it is considered that such mechanism can prevent light leakage and further improve the light emission characteristics of the ink composition.

[Polymer dispersant]
In the present invention, the polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity to the light scattering particles, and has a function of dispersing the light scattering particles. Have. The polymer dispersant is adsorbed to the light scattering particles through the functional group having affinity to the light scattering particles, and the light scattering particles are obtained by electrostatic repulsion and / or steric repulsion between the polymer dispersants. 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.

  By the way, aggregation of light-emitting nanocrystal particles and light-scattering particles can be considered as one of the causes of deterioration in discharge stability when forming a color filter pixel portion by an inkjet method using a conventional ink composition. . Therefore, it is conceivable to improve the ejection stability by miniaturizing the light-emitting nanocrystal particles and the light-scattering particles, reducing the content of the light-emitting nanocrystal particles and the light-scattering particles, etc. In this case, the reduction effect of the leaked light is likely to be reduced, and it is difficult to achieve both the discharge stability and the reduction of the leaked light in high dimensions. On the other hand, according to the ink composition further containing the polymer dispersant, it is possible to achieve both the excellent ejection stability and the reduction of the leaked light at a high level. The reason why such an effect is obtained is not clear, but the aggregation of the light-emitting nanocrystal particles and the light-scattering particles (particularly, light-scattering particles) is significantly suppressed by the polymer dispersant. It is guessed.

  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) may 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.

As a 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.

  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.

  The polymeric dispersant having an acidic functional group has an acid value. The acid value of the polymeric dispersant having an acidic functional group is preferably 1 to 150 mg KOH / g. When the acid value is 1 mg KOH / g or more, sufficient dispersibility of the light scattering particles is easily obtained, and when the acid value is 150 mg KOH / g or less, the storage stability of the pixel portion (cured product of the ink composition) Is hard to lower.

The acid value of the polymeric dispersant can be measured as follows. Prepare a sample solution in which 50 mL of a mixed solution of a polymer dispersant pg and 1 mL of phenolphthalein TS mixed with toluene and ethanol at a volume ratio of 1: 1 and prepare 0.1 mol / L ethanolic potassium hydroxide solution Titration was performed with (7.0 g of potassium hydroxide was dissolved in 5.0 ml of distilled water and adjusted to 1000 ml by adding 95 vol% ethanol) until the sample solution exhibited a pink color, and the acid value was calculated by the following equation It can be calculated.
Acid value = q × r × 5.611 / p
In the formula, q represents the titration amount (ml) of 0.1 mol / L ethanolic potassium hydroxide solution required for titration, r represents the titer of 0.1 mol / L ethanolic potassium hydroxide solution required for titration And p represents the mass (g) of the polymeric dispersant.

  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. When the amine value is 1 mg KOH / g or more, sufficient dispersibility of the light scattering particles can be easily obtained, and when the amine value is 200 mg KOH / g or less, the storage stability of the pixel portion (cured product of ink composition) Is hard to lower.

The amine value of the polymeric dispersant can be measured as follows. Prepare a sample solution prepared by dissolving xg of polymer dispersant and 1 mL of bromophenol blue test solution in 50 mL of mixed solution of toluene and ethanol mixed at a volume ratio of 1: 1, and use 0.5 mol / L hydrochloric acid to make the sample solution The titration is performed until it exhibits a green color, and the amine value can be calculated by the following equation.
Amine value = y / x × 28.05
In the formula, y represents the titration amount (mL) of 0.5 mol / L hydrochloric acid required for titration, and x represents the mass (g) of the polymeric dispersant.

  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.

  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.

  Examples of commercially available products include “DISPERBYK-130”, “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-164”, “DISPERBYK-166”, “DISPERBYK-166”, “DISPERBYK-166”, “DISPERBYK-163”, manufactured by BIC Chemie 167 "," DISPERBYK-168 "," DISPERBYK-170 "," DISPERBYK-171 "," DISPERBYK-174 "," DISPERBYK-180 "," DISPERBYK-182 "," DISPERBYK-183 "," DISPERBYK-184 "," 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 ";" EFKA 4010 "," EFKA 4015 "," EFKA 4046 "," EFKA 4047 "," EFKA 4051 "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"; "TEGO disperss 650" manufactured by Evonik, "TEGO disperss 660 C", "TEGO “Dispers 662 C”, “TEGO Disperss 670”, “TEGO Disperss 685”, “TEGO Disperss 700”, “TEGO Disperss 710” and “TEGO Disperss 760 W”; “Disperon DA-703-50”, “DA-705” and “DA-” manufactured by Kushimoto Chemical Co., Ltd. 725 "can be used.

  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. About the detail of a cationic monomer, an anionic monomer, the monomer which has a hydrophobic group, and another monomer, the monomer as described in stage 0034-0036 of Unexamined-Japanese-Patent No. 2004-250502 can be mentioned.

  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 the side chain amino group is modified with polyester, graft polymer having polyester type macromonomer as described in JP-A-9-171253 as copolymer component, added polyester polyol described in JP-A-60-166318 A polyurethane etc. are mentioned suitably.

  The weight average molecular weight of the polymer dispersant may be 750 or more, or 1000 or more from the viewpoint of being able to disperse the light scattering particles well and improving the effect of reducing 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 improve the reduction effect of the leak light, and can discharge the viscosity of the ink jet ink and is a viscosity suitable for stable discharge. From the viewpoint of making it, it may be 100,000 or less, 50,000 or less, or 30,000 or less.

  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.

  The ink composition is a light-emitting nanocrystal particle, a photopolymerizable compound, a photoacid generator, a photosensitizing compound, a diol compound, a light scattering particle, a polymer dispersant, and a range in which the effects of the present invention are not impaired. It may further contain other components other than the organic ligand. As another component, surfactant, a polymerization inhibitor, etc. are mentioned, for example.

  When the ink composition is alkali-soluble, the coating film of the ink composition tends to absorb moisture in the air, and the light-emitting property (e.g., fluorescence) of light-emitting nanocrystal particles (such as quantum dots) increases over time. It will be 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 photopolymerizable compound as the photopolymerizable compound. 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 1% by mass potassium hydroxide aqueous solution 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. The ink composition is an ink composition capable of forming an alkali-insoluble coating film by measuring the amount of dissolution of the 1 μm-thick coating film obtained after the ink composition is coated on a substrate. It can confirm by doing.

  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 is preferable to use appropriately prepared so as to be suitable for the ink jet system.

  The viscosity of the ink composition at 40 ° C. 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 ink jet printing. Good. The viscosity at 40 ° C. 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 at 40 ° C. 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 the discharge control of the ink composition (for example, discharge amount and discharge) Timing control) is easy. On the other hand, when the viscosity at 40 ° C. of the ink composition is 20 mPa · s or less, the ink composition can be smoothly ejected from the ink ejection hole. The viscosity of the ink composition at 40 ° C. 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 · s, 5 to 20 mPa · s, 7 to 20 mPa · s. It may be 7 to 15 mPa · s, or 7 to 12 mPa · s. The viscosity of the ink composition is measured, for example, by an E-type viscometer. The viscosity of the ink composition can be adjusted to a desired range by changing, for example, the type and content of the photopolymerizable compound.

  The surface tension of the ink composition is preferably a surface tension suitable for the ink jet system, and specifically, it is 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 more, 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 surface tension of the ink composition can be adjusted to a desired range by using, for example, a silicon surfactant, a fluorine surfactant, an acetylene surfactant and the like in combination.

<Method of Producing Ink Composition>
Next, a method of manufacturing the ink composition of the above-described embodiment will be described. The ink composition can be obtained, for example, by mixing the components of the ink composition described above and performing dispersion processing. In the following, as an example of a method for producing an ink composition, light emitting nanocrystal particles, a photopolymerizable compound, a photoacid generator, a photosensitizing compound, a light scattering particle, and a polymer dispersant The method for producing the ink composition to be contained is 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 light scattering particles may further contain a photopolymerizable compound, a photoacid generator and a photosensitizing compound, and in the second step, the photopolymerizable compound, the photoacid generator and The photosensitizing compounds may be further mixed. In the second step, the photopolymerizable compound and a solution containing the photoacid generator and the photosensitizing compound, which has been prepared in advance, may be mixed. According to this method, the light scattering particles can be sufficiently dispersed. Therefore, the leaked light in the pixel portion can be reduced, and the light emission intensity can be further improved, and an ink composition having excellent ejection stability can be easily obtained.

  In the step of preparing the dispersion of the light scattering particles, for example, the light scattering particles, the polymer dispersant, and the photopolymerizable compound are mixed, and the dispersion treatment is performed to obtain the dispersion of the light scattering particles. It 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 luminescent nanocrystal particles containing luminescent nanocrystal particles and a photopolymerizable compound. Good. In this case, in the second step, a solution containing a photoacid generator and a photosensitizing compound prepared in advance by mixing a dispersion of light scattering particles and a dispersion of light emitting nanocrystal particles and further preparing in advance. Mix. According to this method, the luminescent nanocrystal particles can be sufficiently dispersed. Therefore, the leaked light in the pixel portion can be reduced, and the light emission intensity can be further improved, and an ink composition having excellent ejection stability 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 photopolymerizable compound using the same dispersion apparatus as the step of preparing the dispersion of light-scattering particles You may process it.

  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.

<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.

  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.

  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 the photopolymerizable compound, and specifically, a cured product obtained by crosslinking of the photopolymerizable compound. 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.

  The first light-emitting nanocrystalline particles 11a are red light-emitting nanocrystalline 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 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 11 b are green light-emitting nanocrystal particles that absorb light in the wavelength range of 420 to 480 nm and emit light having a light 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 mass based on the total mass of the cured product of the ink composition, from the viewpoint of being more excellent in the reduction effect of leakage light and light emission characteristics. % Or more, 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass It may be more than. The content of the light scattering particles is 60% by mass or less based on the total mass of the cured product of the ink composition, from the viewpoint of being more excellent in the reduction effect of leakage light and the light emission characteristics and the reliability of the pixel portion. May be 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, and 20% by mass or less It may also be 15% by mass or less.

  The third pixel unit 10c has a transmittance of 30% or more to light of a wavelength 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 having a wavelength of 420 to 480 nm. The third pixel portion 10c includes, for example, a cured product of a composition containing the above-described photopolymerizable compound. The cured product contains the third cured component 13c. The third curing component 13c is a cured product of a photopolymerizable compound, and specifically, a cured product obtained by crosslinking of the photopolymerizable compound. That is, the third pixel unit 10c includes the third curing component 13c. When the third pixel portion 10c contains the above-mentioned cured product, the composition containing the photopolymerizable compound has the above-described ink as long as the transmittance to light having a wavelength of 420 to 480 nm is 30% or more. Among the components contained in the composition, components other than the photopolymerizable compound 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 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

  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.

  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.

  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.

  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.

  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.

  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.

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.

  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.

  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 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.

  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.

  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.

  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.

  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.

  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.

  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 the ink composition) from the viewpoint of preventing a decrease in transmittance when it is contained in the light conversion layer. % Is preferred.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In addition, all the materials used in the Example used what introduce | transduced argon gas and removed dissolved oxygen. The titanium oxide was heated at 120 ° C. for 2 hours under a reduced pressure of 1 mmHg and allowed to cool under an argon gas atmosphere prior to mixing. The liquid materials used in the examples were previously dehydrated with molecular sieves 3A for 48 hours or longer before mixing.

Preparation of InP / ZnSeS / ZnS Nanocrystalline Particle Dispersion 1 (Nonvolatile Content: 47.5% by Mass)>
[Synthesis of red light emitting nanocrystalline particle core (InP core)]
5 g of trioctyl phosphine oxide (TOPO), 1.46 g (5 mmol) of indium acetate, and 3.16 g (15.8 mmol) of lauric acid were added to the reaction flask to obtain a mixture. The mixture was heated at 160 ° C. for 40 minutes under a nitrogen environment and then heated at 250 ° C. for 20 minutes under vacuum. The reaction temperature (the temperature of the mixture) was then raised to 300 ° C. under a nitrogen (N ₂ ) environment. At this temperature, a mixture of 3 g of 1-octadecene (ODE) and 0.25 g (1 mmol) of tris (trimethylsilyl) phosphine was rapidly introduced into the reaction flask and the reaction temperature was maintained at 260 ° C. After 5 minutes, the reaction was quenched by removal of the heater and the resulting reaction solution was cooled to room temperature. Then, 8 mL of toluene and 20 mL of ethanol were added to the reaction solution in the glove box. Subsequently, the resultant was centrifuged to precipitate InP nanocrystal particles, and the supernatant was decanted to obtain InP nanocrystal particles. Next, the obtained InP nanocrystal particles were dispersed in hexane to obtain a hexane dispersion of InP nanocrystal particles (InP nanocrystal particle content: 5% by mass).

[Preparation of indium laurate solution]
10 g of 1-octadecene (ODE), 146 mg (0.5 mmol) of indium acetate and 300 mg (1.5 mmol) of lauric acid were added to the reaction flask to obtain a mixture. The mixture was heated at 140 ° C. for 2 hours under vacuum to obtain a clear solution (indium laurate precursor solution). The precursor solution was maintained in the glove box at room temperature until needed. Since indium laurate has low solubility at room temperature and tends to precipitate, when using the precursor solution, the precipitated indium laurate in the precursor solution (ODE mixture) is heated to about 90 ° C. to be transparent. After forming a solution, the desired amount was weighed and used.

[Growth of red light emitting nanocrystalline particles]
A hexane dispersion of InP nanocrystal particles (InP core) and an indium laurate solution were charged into a reaction flask to obtain a mixture. The amounts of the hexane dispersion of the InP core and the indium laurate solution were 0.5 g (InP core content: 25 mg) and 5 g, respectively. The mixture was allowed to stand at room temperature under vacuum for 10 minutes, then the inside of the flask was returned to normal pressure with nitrogen gas, the temperature of the mixture was raised to 230 ° C., and the temperature was maintained for 2 hours to remove hexane from the inside of the flask . Next, the temperature in the flask is raised to 250 ° C., a mixture of 3 g of 1-octadecene (ODE) and 0.03 g (0.125 mmol) of tris (trimethylsilyl) phosphine is rapidly introduced into the reaction flask, and the reaction temperature is 230 Maintained at ° C. After 5 minutes, the reaction was quenched by removal of the heater and the resulting reaction solution was cooled to room temperature. Then, 8 mL of toluene and 20 mL of ethanol were added to the reaction solution in the glove box. Subsequently, the resultant was centrifuged to precipitate InP nanocrystal particles, and the supernatant was decanted to obtain InP nanocrystal particles. Next, the obtained InP nanocrystal particles were dispersed in hexane to obtain a dispersion of InP nanocrystal particles (InP nanocrystal particle content: 5% by mass).

[Synthesis of red light emitting nanocrystalline particle shell (ZnSeS / ZnS shell)]
Next, 2.5 g of the hexane dispersion obtained above was charged into a reaction flask, 0.7 g of oleic acid was added to the reaction flask, the temperature was raised to 80 ° C., and held for 2 hours. Then, 14 mg of diethylzinc dissolved in 1 mL of ODE, 8 mg of bis (trimethylsilyl) selenide and 7 mg of hexamethyldisilathiane (ZnSeS precursor solution) are added dropwise to this reaction mixture, and the temperature is raised to 200 ° C. and maintained for 10 minutes. Thus, a 0.5 monolayer thick ZnSe S shell was formed.

  The temperature was then raised to 140 ° C. and held for 30 minutes. Next, 69 mg of diethylzinc dissolved in 2 mL of ODE and 66 mg of hexamethyldisilatian (ZnS precursor solution) dissolved in 2 mL of ODE were added dropwise to the reaction mixture, and the temperature was raised to 200 ° C. and held for 30 minutes. Formed a ZnS shell. Ten minutes after the dropwise addition of the ZnS precursor solution, the reaction was stopped by removing the heater. Then, the reaction mixture is cooled to room temperature, and the obtained white precipitate is removed by centrifugation to obtain a transparent nanocrystal particle dispersion (ODE dispersion) in which InP / ZnSeS / ZnS nanocrystal particles are dispersed. The

[Synthesis of Ligands for Luminescent Nano-Crystal Particles]
After charging JEFAMINE M-1000 (manufactured by Huntsman) into a flask, while stirring in a nitrogen gas environment, succinic acid anhydride (manufactured by Sigma-Aldrich) equivalent to JEFAMINE M-1000 was added thereto. The internal temperature of the flask was raised to 80 ° C., and the mixture was stirred for 8 hours to obtain a ligand represented by the following formula (1A) as a pale yellow viscous oil.

[Preparation of InP / ZnSeS / ZnS nanocrystal particle dispersion 1 by ligand exchange]
30 mg of the ligand obtained above was added to 1 mL of the ODE solution of the nanocrystal particle obtained above. Subsequently, ligand exchange was performed by heating at 90 ° C. for 5 hours. Aggregation of nanocrystal particles was observed as the ligand exchange progressed. After completion of ligand exchange, the supernatant was decanted, and 3 mL of ethanol was added to the nanocrystal particles, and redispersed by sonication. 10 mL of n-hexane was added to 3 mL of the nanocrystal particle solution after ligand exchange. Subsequently, centrifugation is performed to precipitate nanocrystal particles, and then the supernatant is decanted and dried under a vacuum to obtain nanocrystal particles (InP / ZnSeS / ZnS nano modified with a ligand represented by the above formula (1A)). Crystal particles were obtained. The obtained nanocrystalline particles were dispersed in a photopolymerizable compound to obtain a luminescent nanocrystalline particle dispersion 1 (nonvolatile content: 47.5% by mass).

<Preparation of Photoacid Generator>
A 50% propylene carbonate solution of Triarylsulfonium · (Rf) _n PF _6-n salt (trade name “CPI-200K” manufactured by San-Apro Co., Ltd.) was prepared as a photoacid generator.

<Preparation of Photopolymerizable Compound>
The following materials were prepared as photopolymerizable compounds.
(Alicyclic epoxy compound)
Monofunctional: 1,2-epoxy-4-vinylcyclohexane (Daicel Corporation, trade name: Celoxide 2000)
Difunctional: 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (Axillary Industrial Co., Ltd., trade name: LDO)
(Oxetane compound)
-Monofunctional: (3-methyl-3-oxetanyl) methyl methacrylate (Ube Industries, Ltd., trade name: ETERNACOLL OXMA)
-Bifunctional: bis [1-ethyl (3-oxetanyl)] methyl ether (Toa Gosei Co., Ltd., trade name: OXT-221)

Preparation of Photosensitizing Compound
As a photosensitizing compound, 9,10-dibutoxyanthracene (Kawasaki Kasei Co., Ltd., trade name "UVS-1331", maximum absorption wavelengths 365 nm, 382 nm, and 405 nm, maximum absorption wavelength 382 nm) was prepared.

<Preparation of Diol Compound>
As a diol compound, 1,4-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared.

Preparation of Light-Scattering Particles
As light scattering particles, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name "CR-60-2", average particle diameter (volume average diameter): 210 nm) was prepared.

Preparation of Polymer Dispersant
As a polymer dispersant, AZISPAR PB-821 (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name “AZISPAR” registered trademark) was prepared.

<Preparation of Light-Scattering Particle Dispersion>
In a container filled with argon gas, 30.0 g of titanium oxide, 0.9 g of a polymer dispersant, and 49.5 g of an oxetane compound are mixed, and then zirconia beads (diameter: 1.25 mm) are obtained in the obtained mixture The mixture was dispersed by shaking for 2 hours using a paint conditioner, and zirconia beads were removed with a polyester mesh filter to obtain a light scattering particle dispersion 1.

Example 1
(1) Preparation of Ink Composition (Inkjet Ink) 4.21 g of Light Emitting Nano-Crystal Particle Dispersion 1, 5.23 g of Light-Scattering Particle Dispersion 1, 0.47 g of a photoacid generator, and photosensitization After mixing 0.09 g of the agent, the mixture was filtered through a filter with a pore size of 5 μm to obtain an ink composition. The average particle diameter (volume average diameter MV) of the light scattering particles in the ink composition was 0.22 μm. In the present embodiment, the average particle diameter (volume average diameter MV) of the light scattering particles in the ink composition is determined by using a dynamic light scattering nanotrack particle size distribution meter (trade name “Nanotrac, manufactured by Nikkiso Co., Ltd. It measured using ").

(2) Evaluation [Dischargeability of Ink Composition]
The ink composition was subjected to a discharge test using an inkjet printer (manufactured by Fujifilm Dimatix, trade name "DMP-2850"). In the ejection test, the ink composition was continuously ejected for 10 minutes (the temperature of the inkjet head of the inkjet printer: 40 ° C.). In addition, 16 nozzles were formed in the head part which discharges the ink of this inkjet printer, and the usage-amount of the ink composition per discharge was set to 10 pL per nozzle. Discharge stability was evaluated based on the following criteria. The results are shown in Table 1.
A: Continuous discharge possible (out of 16 nozzles, continuous discharge possible with 10 or more nozzles)
B: Continuous discharge not possible (of 16 nozzles, the number of nozzles that can be continuously discharged is 9 or less)

[Curability of coating film]
Subsequently, using the ink composition obtained in the above (1), the following curability was evaluated. That is, a coating film (film thickness 6 μm) of the ink composition was formed on a glass substrate by a spin coater. The formed coating was irradiated with UV. The coating film surface after UV irradiation was rubbed with a cotton swab, and the curability was evaluated according to the following criteria. The results are shown in Table 1.
A: Cured (the ink composition does not adhere to the tip of the swab)
B: Not cured (the ink composition adheres to the tip of the swab)

Examples 2 to 4 and Comparative Examples 1 to 7
Ink compositions of Examples 2 to 4 and Comparative Examples 1 to 7 were obtained in the same manner as Example 1 except that the composition of the ink composition was changed to the composition described in Table 1. The average particle diameter (volume average diameter MV) of the light scattering particles in each ink composition is 0.22 μm (Example 2), 0.23 μm (Example 3), and 0.23 μm (Example 4), respectively. ), 0.22 μm (comparative example 1), 0.23 μm (comparative example 2), 0.23 μm (comparative example 3), 0.23 μm (comparative example 4), 0.22 μm (comparative example 5), 0.22 μm Comparative Example 6 and 0.23 μm (Comparative Example 7). Using the ink compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 7, evaluations of dischargeability and curability of the coating were performed in the same manner as in Example 1. The results are shown in Table 1.

  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 (19)

A luminescent nanocrystal particle, a photopolymerizable compound, a photoacid generator, and at least one compound selected from the group consisting of a photosensitizing compound and a diol compound,
The photopolymerizable compound includes an alicyclic epoxy compound and an oxetane compound,
An ink composition, wherein at least one of the alicyclic epoxy compound and the oxetane compound is monofunctional.   The ink composition according to claim 1, wherein the photosensitizing compound has a maximum absorption wavelength in a wavelength range of 380 nm or more.   The ink composition according to claim 1, wherein the diol compound comprises a diol compound having 4 or more carbon atoms.   The ink composition according to any one of claims 1 to 3, further comprising light scattering particles.   The ink composition according to claim 4, wherein the light scattering particles have an average particle size of 0.05 to 1.0 μm.   The light scattering particles have an average particle size of 0.3 to 0.6 μm. The ink composition according to claim 4 or 5.   The light scattering particle according to any one of claims 4 to 6, wherein the light scattering particle comprises at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate and silica. The ink composition according to one item.   The ink composition according to any one of claims 4 to 7, further comprising a polymeric dispersant.   The ink composition according to claim 8, wherein the weight average molecular weight of the polymer dispersant is 1,000 or more.   The ink composition according to any one of claims 1 to 9, wherein the photopolymerizable compound is alkali insoluble.   The ink composition according to any one of claims 1 to 10, which can form an alkali insoluble coating film.   The ink composition according to any one of claims 1 to 11, wherein the surface tension is 20 to 40 mN / m.   The ink composition according to any one of claims 1 to 12, which has a viscosity of 2 to 20 mPa · s at 40 ° C.   The ink composition according to any one of claims 1 to 13, which is for color filters.   The ink composition according to any one of claims 1 to 14, which is used in an inkjet method. 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 as described in any one of Claims 1-15. 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 contains, as the luminescent nanocrystal particles, 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 605 to 665 nm. , The first pixel portion,
It contains the cured product and, as the light emitting nanocrystal particles, contains light emitting 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 second pixel portion,
The light conversion layer according to claim 16, comprising:   The light conversion layer according to claim 17, wherein the plurality of pixel units further includes a third pixel unit having a transmittance of 30% or more to light in a wavelength range of 420 to 480 nm.   A color filter comprising the light conversion layer according to any one of claims 16 to 18.

Images