TW202233807A - Inkjet ink composition, light-converting layer, and color filter - Google Patents

Abstract

The present invention addresses the problem of providing: an inkjet ink composition which contains semiconductor nanocrystals composed of a metal halide and from which a cured film having excellent light resistance at a high temperature can be formed; and a light-converting layer and a color filter which use said ink composition. The problem can be solved by an inkjet ink composition according to the present invention, the ink composition comprising: light-emitting particles including semiconductor nanocrystal particles composed of a metal halide; a photopolymerizable compound; a photopolymerization initiator; and an NOR-type hindered amine compound having a structure represented by formula (1). [In formula (1), R1-R5 each independently represent a hydrocarbon group, and * represents a dangling bond.].

Description

Ink composition for inkjet, light conversion layer and color filter

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

In recent years, with the demand for low power consumption of displays, the use of luminescent nanoparticles such as quantum dots, quantum rods, and other inorganic phosphor particles has replaced red organic pigment particles or green organic pigment particles. Research on color filters for pixel parts such as pixels and green pixels is increasingly active. Under the premise that the color filter has an ideal fine pattern, in the photo-etching method, since the luminescent nanocrystalline particles will be wasted and consumed, so the ink-jet method ( inkjet method) to form the light conversion layer. For example, Patent Document 1 discloses an inkjet ink composition containing luminescent nanocrystal particles formed of core/shell type semiconductor nanocrystals, and a wavelength conversion member composed of a cured film of the composition.

Luminescent nanocrystal particles such as semiconductor nanocrystals are easily degraded by light irradiation in the presence of water vapor, oxygen, or the like. In particular, there is a problem in that the light conversion layer is heated by the strong light from the backlight, and thus irradiated with light at high temperature, the luminescent nanocrystal particles are degraded, and the luminous intensity is lowered. For this problem, for example, a technique has been proposed for improving the light resistance of the obtained cured film in a high temperature environment by adding a curable composition containing core/shell semiconductor nanocrystals to a hindered amine compound (See Patent Document 2).

On the other hand, when the core/shell type semiconductor nanocrystal is used as the light conversion material, in order to adjust the emission wavelength region, it is necessary to strictly control the particle size of the core part and the shell part, and it is difficult to produce an ink with stable industrial quality. high degree. Therefore, in recent years, semiconductor crystals composed of metal halides, especially compounds represented by CsPbX ₃ (X represents Cl, Br, or I), have been found as inorganic luminescent particles whose particle size can be adjusted relatively easily. A semiconductor nanocrystal with a representative perovskite-type crystal structure has attracted attention (for example, Patent Document 3). Semiconductor nanocrystals with perovskite-type crystalline structure not only control the particle size relatively easily, but also have the following advantages, namely, the emission wavelength can be arbitrarily changed even by the type of halogen element, and the peak width of the emission spectrum is half as large. The peak width is small. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-76976 [Patent Document 2] International Publication No. 2019/186734 [Patent Document 3] Japanese Patent Publication No. 2018-506625

[The problem to be solved by the invention]

However, only by applying perovskite-type semiconductor nanocrystals to inkjet ink compositions and adding the hindered amine compound disclosed in Patent Document 2, a cured film (light conversion layer) can be obtained at high temperature. The bad situation of insufficient light fastness.

The problem to be solved by the present invention is to provide an ink composition for inkjet containing semiconductor nanocrystals composed of metal halides, a light conversion layer and a color filter using the ink composition, the inkjet With the ink composition, a cured film with excellent light resistance at high temperature can be formed. [Technical means to solve the problem]

As a result of diligent research conducted by the present inventors, it has been found that in an inkjet ink composition containing semiconductor nanocrystals composed of metal halides, when the hindered amine compound has a specific structure, a cured film having excellent light resistance at high temperature can be formed , thus considering the present invention.

[式（1）中，R ¹～R ⁵分別獨立地表示烴基，*表示鍵結鍵]。 That is, the ink composition for inkjet of the present invention is characterized by comprising: luminescent particles including semiconductor nanocrystalline particles composed of metal halides, a photopolymerizable compound, a photopolymerization initiator, and a compound having the following formula (1) NOR type hindered amine compound of the indicated structure;

[In formula (1), R ¹ to R ⁵ each independently represent a hydrocarbon group, and * represents a bonding bond].

The melting point of the NOR-type hindered amine compound is preferably 70°C or higher. The molecular weight of the NOR type hindered amine compound is preferably 1000 or more.

The luminescent particle is a particle having a surface layer formed on the surface of the semiconductor nanocrystal particle, and the surface layer preferably contains a bonding group capable of bonding with the surface of the semiconductor nanocrystal particle and a hydrolyzable silicon group polymers of silane compounds.

The light-emitting particle may be "a hollow particle further comprising an inner space capable of accommodating the semiconductor nanocrystal particle, and a hollow particle having pores communicating with the inner space, and the semiconductor nanocrystal particle is accommodated in the inner space." .

The SP value of the photopolymerizable compound is preferably 10.0 or less. The photopolymerizable compound preferably has a cyclic structure.

The ink composition preferably further contains light-scattering particles. The ink composition preferably further contains a polymer dispersant.

The viscosity of the ink composition at 30°C is preferably 7-12mPa･s.

Another aspect of the present invention relates to a light conversion layer including a plurality of pixel portions and a light shielding portion provided between the plurality of pixel portions, the plurality of pixel portions having: a cured ink composition comprising the above-mentioned inkjet ink composition The light-emitting pixel portion of the object. Another aspect of the present invention relates to a color filter including the above-mentioned light conversion layer. [Effect of invention]

According to an aspect of this invention, the ink composition for inkjet which can form the cured film excellent in the light resistance at high temperature can be provided. According to another aspect of the present invention, a light conversion layer and a color filter using the ink composition for inkjet described above can be provided.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

<Ink composition> One embodiment of the present invention is an inkjet ink composition (hereinafter, also simply referred to as an "ink composition"). The ink composition of one embodiment contains: luminescent particles including semiconductor nanocrystalline particles composed of a metal halide (hereinafter, also simply referred to as "nanocrystalline particles"), a photopolymerizable compound, and a photopolymerization initiator , and the NOR-type hindered amine compound represented by the following formula (1).

The ink composition may be, for example, an ink composition for forming a light conversion layer (for example, for forming a pixel portion of a color filter) for forming a light conversion layer (pixel portion of the light conversion layer) included in a color filter or the like. . The above-mentioned ink composition is a composition (inkjet ink) used in an ultraviolet curable inkjet method.

＜＜Luminescent particles＞＞ The luminescent particles include nanocrystalline particles. Nanocrystalline particle system: composed of metal halide, absorbs excitation light, emits fluorescent or phosphorescent nano-sized crystals (nanocrystalline particles). As a light-emitting nanocrystal composed of a metal halide, for example, quantum dots having a perovskite-type crystal structure to be described later are widely known. The nanocrystalline particles are, for example, crystals with a maximum particle diameter of 100 nm or less measured by a transmission electron microscope or a scanning electron microscope. For example, the nanocrystalline particles can be excited by light energy or electrical energy of a specific wavelength to emit fluorescence or phosphorescence.

Nanocrystalline particles composed of metal halides are compounds represented by the general formula: A _a M _b X _c . In the formula, A is at least one of organic cations and metal cations. Examples of organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea, and the like, and examples of metal cations include Cs, Rb, K, Na, Li, and the like cation. M is at least one metal cation. Examples of the metal cations include Groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, and 15. of metal cations. More preferably, Ag, Au, Bi, Ca, Ce, Co, Cr, Cu, Eu, Fe, Ga, Ge, Hf, In, Ir, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os, Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, Zr and other cations. X is at least one kind of anion. As anion, chloride ion, bromide ion, iodide ion, cyanide ion, etc. are mentioned, and at least 1 type of halogen is contained. a is 1-7, b is 1-4, and c is 3-16. The nanocrystalline particles can control the emission wavelength (emission color) by adjusting the particle size, the type and the existing ratio of anions constituting the X lattice site.

Specifically, the compound represented by the general formula A _a M _b X _c is preferably AMX, A ₄ MX, AMX ₂ , AMX ₃ , A ₂ MX ₃ , AM ₂ X ₃ , A ₂ MX ₄ , A ₂ MX _{5 , A3MX5 , A3M2X5 , A3MX6 , A4MX6 , AM2X6 , A2MX6 , A4M2X6 , A3MX8 , A3M2X _ _ 9} . A compound represented by A ₃ M ₃ X ₉ , A ₂ M ₂ X ₁₀ , and A ₇ M ₃ X ₁₆ . In the formula, A is at least one of organic cations and metal cations. Examples of organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea, and the like, and examples of metal cations include ions such as Cs, Rb, K, Na, and Li. In the formula, M is at least one metal cation. Specifically, one metal cation (M ¹ ), two metal cations (M ¹ _α M ² _β ), three metal cations (M ¹ _α M ² _β M ³ _γ ), four metal cations ( M ¹ _α M ² _β M ³ _γ M ⁴ _δ ) and so on. Among them, α, β, γ, and δ represent real numbers from 0 to 1, respectively, and represent α+β+γ+δ=1. Examples of the metal cations include Groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, and 15. of metal cations. More preferably, Ag, Au, Bi, Ca, Ce, Co, Cr, Cu, Eu, Fe, Ga, Ge, Hf, In, Ir, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os, Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, Zr and other cations. In the formula, X is an anion containing at least one halogen. Specifically, one type of halide anion (X ¹ ), two types of halide anion (X ¹ _α X ² _β ), and the like are exemplified. Examples of the anion include chloride ion, bromide ion, iodide ion, cyanide ion, and the like, and at least one type of halide ion is included.

The compound composed of metal halide represented by the above general formula A _a M _b X _c may also be added (doped) with Bi, Mn, Ca, Eu, Sb different from the metal cation used in the above M lattice site , Yb and other metal ions, in order to make the luminous properties better.

Regarding the compound having a perovskite crystal structure among the compounds consisting of metal halides represented by the general formula A _a M _b X _c , the particle size, the type of the metal cation constituting the M lattice site, and the In terms of the existence ratio, the type and the existence ratio of the anions constituting the X lattice site can be adjusted, and the emission wavelength (emission color) can be controlled, and it is particularly preferably used in the form of a luminescent nanocrystal. Since this adjustment operation can be easily performed, the perovskite-type semiconductor nanocrystal has the characteristics of easier control of the emission wavelength compared with the conventional core-shell type semiconductor nanocrystal, and thus has the characteristics of higher productivity. Specifically, compounds represented by AMX ₃ , A ₃ MX ₅ , A ₃ MX ₆ , A ₄ MX ₆ , and A ₂ MX ₆ are preferred. A, M and X in the formula are as described above. In addition, the compound having a perovskite crystal structure may be added (doped) with metal ions such as Bi, Mn, Ca, Eu, Sb, Yb, etc., which are different from the metal cations used in the above-mentioned M lattice sites as described above. .

In the compound having a perovskite crystal structure, in order to exhibit further good light-emitting properties, it is preferred that A is Cs, Rb, K, Na, Li, and M is one metal cation (M ¹ ), or two metal cations (M ¹ _α M ² _β ), X is a chloride ion, a bromide ion, or an iodide ion. Among them, α and β represent real numbers from 0 to 1, respectively, and represent α+β=1. Specifically, M is preferably selected from Ag, Au, Bi, Cu, Eu, Fe, Ge, K, In, Na, Mn, Pb, Pd, Sb, Si, Sn, Yb, Zn, and Zr.

As a specific composition of luminescent nanocrystalline particles having a perovskite-type crystal structure and composed of metal halides, nanocrystals using Pb as M, such as CsPbBr ₃ , CH ₃ NH ₃ PbBr ₃ , CHN ₂ H ₄ PbBr ₃ , etc. Particles are preferred because they are excellent in both light intensity and quantum efficiency. In addition, nanocrystalline particles using metal cations other than Pb as M, such as CsSnBr ₃ , CsEuBr ₃ , and CsYbI ₃ , are preferable because they have low toxicity and less impact on the environment.

Regarding the nanocrystalline particles, it may be a red luminescent crystal that emits light with a luminescence peak in the wavelength range of 605 to 665 nm (red light), and may be light with a luminescence peak in the wavelength range of 500 to 560 nm (green light) The green luminescent crystal can also be a blue luminescent crystal that emits light with a luminescence peak (blue light) in the wavelength range of 420 to 480 nm. In addition, in one embodiment, a combination of these nanocrystalline particles may also be used. In addition, the wavelength of the emission peak of the nanocrystalline particles can be confirmed by, for example, a fluorescence spectrum or a phosphorescence spectrum measured using an absolute PL quantum yield measurement device.

The red luminescent nanocrystalline particles are preferably 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less The wavelength ranges below 643 nm, below 640 nm, below 637 nm, below 635 nm, below 632 nm or below 630 nm have emission peaks, and preferably above 628 nm, above 625 nm, above 623 nm, above 620 nm The wavelength ranges above 615 nm, above 610 nm, above 607 nm, or above 605 nm have emission peaks. These upper limit values and lower limit values can be arbitrarily combined. In addition, in the following similar descriptions, the upper limit value and the lower limit value of the individual descriptions can be combined arbitrarily.

The green luminescent nanocrystalline particles are preferably 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less The wavelength range below 532 nm or below 530 nm has a luminescence peak, and preferably above 528 nm, above 525 nm, above 523 nm, above 520 nm, above 515 nm, above 510 nm, above 507 nm, 505 nm or above The wavelength range above nm, above 503 nm, or above 500 nm has a luminescence peak.

The blue luminescent nanocrystalline particles are preferably 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less. The wavelength range below 452 nm or below 450 nm has a luminescence peak, and preferably above 450 nm, above 445 nm, above 440 nm, above 435 nm, above 430 nm, above 428 nm, above 425 nm, The wavelength range above 422 nm or above 420 nm has a luminescence peak.

The shape of the nanocrystalline particles is not particularly limited, and may be any geometric shape or any irregular shape. Examples of the shape of the nanocrystalline particles include rectangular parallelepiped, cubic, spherical, tetrahedral, ellipsoidal, pyramidal, disc, branch, mesh, and rod shapes. Furthermore, as the shape of the nanocrystalline particles, a rectangular parallelepiped shape, a cubic shape or a spherical shape is preferable.

The average particle diameter (volume average diameter) of the nanocrystalline particles is preferably 40 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less. In addition, the average particle diameter of the nanocrystalline particles is preferably 1 nm or more, more preferably 1.5 nm or more, and still more preferably 2 nm or more. Nanocrystalline particles having the above-mentioned average particle diameter are preferred because they easily emit light of a desired wavelength. In addition, the average particle diameter of the nanocrystalline particles is obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.

[surface layer] The luminescent particle is preferably a particle further provided with a surface layer formed on the surface of the nanocrystalline particle. The surface layer preferably contains a polymer of a silane compound having a bonding group capable of bonding with the surface of the semiconductor nanocrystal particles and a hydrolyzable silicon group.

The binding group that can be bound to the surface of the nanocrystalline particles may be a binding group that can be bound (coordinated) to cations contained in the nanocrystalline particles. Examples of the binding group include a carboxyl group, an amino group, an ammonium group, a mercapto group, a phosphine group, a phosphine oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group, and a boronic acid group. Wait. Among them, as the binding group, at least one of a carboxyl group, a mercapto group, and an amine group is preferred. The binding groups have higher affinity for cations contained in the nanocrystalline particles than the hydrolyzable silicon groups. Therefore, the silane compound can coordinate the bonding group on the side of the nanocrystalline particles, so that the nanocrystalline particles having the surface layer can be more easily and surely formed.

The silane compound is formed by the reaction of precursor compounds having a bonding group and a hydrolyzable silicon group with each other. Hydrolyzable silicon groups can easily form siloxane bonds. The hydrolyzable silicon group is preferably a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms.

As the precursor compound, one type of silane compound having a binding group and a hydrolyzable silicon group may be used alone, or two or more types may be used in combination.

The precursor compound may contain one or more compounds selected from the group consisting of a carboxyl group-containing silicon compound, an amine group-containing silicon compound, and a mercapto group-containing silicon compound.

Specific examples of the carboxyl group-containing silicon compound include, for example, 3-(trimethoxysilyl)propionic acid, 3-(triethoxysilyl)propionic acid, 2-, carboxyethylphenylbis(2) -Methoxyethoxy)silane, N-[3-(trimethoxysilyl)propyl]-N'-carboxymethylethylenediamine, N-[3-(trimethoxysilyl)propyl] ] phthalamide, N-[3-(trimethoxysilyl)propyl]ethylenediamine-N,N',N'-triacetic acid, etc.

Specific examples of the amino group-containing silicon compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3 -Aminopropylmethyldipropoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiisopropoxysilane, N-(2-aminoethyl)- 3-Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl Tripropoxysilane, N-(2-aminoethyl)-3-aminopropyltriisopropoxysilane, N-(2-aminoethyl)-3-aminoisobutyldi Methylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyl Trimethoxysilane, N-(2-aminoethyl)-3-aminopropylsilanetriol, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propane N-phenyl-3-aminopropyltrimethoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl) ) phenyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, (aminoethylaminoethyl)phenyltripropoxysilane, (aminoethylamine) (aminoethyl)phenyltriisopropoxysilane, (aminoethylaminomethyl)phenyltrimethoxysilane, (aminoethylaminomethyl)phenyltriethoxysilane, (amine (aminoethylaminomethyl)phenyltripropoxysilane, (aminoethylaminomethyl)phenyltriisopropoxysilane, N-(vinylbenzyl)-2-aminoethyl -3-Aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-β-(N-ethylene Benzylaminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxysilane, N-β-(N-bis(vinylbenzyl)aminoethyl) base)-γ-aminopropyltrimethoxysilane, N-β-(N-bis(vinylbenzyl)aminoethyl)-N-γ-(N-vinylbenzyl)-γ-amine propyltrimethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, dimethylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylamine propyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane Silane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylamino) Ethyl)phenethyltriethoxysilane, (aminoethylaminoethyl)phenethyltripropoxysilane, (aminoethylaminoethyl)phenethyltriisopropoxysilane , (aminoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl) Methyl)phenethyltriethoxysilane, (aminoethylaminomethyl)phenethyltripropoxysilane, (aminoethylaminomethyl)phenethyltriisopropoxysilane , N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(triethoxysilyl)propylamino]ethyl Ethyl]ethylenediamine, N-[2-[3-(tripropoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(triisopropoxysilyl) ) propylamino]ethyl]ethylenediamine, etc.

Specific examples of the mercapto group-containing silicon compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyl Methyldiethoxysilane, 3-[ethoxybis(3,6,9,12,15-pentoxaoctacos-1-yloxy)silyl]-1-propanethiol ( 3-[ethoxy bis(3,6,9,12,15-pentaoxaoctacosane-1-yloxy)silyl]-1-propanethiol) etc.

The thickness of the surface layer is preferably 0.5-50 nm, more preferably 1.0-30 nm. If it is a light-emitting particle having a surface layer of this thickness, the thermal stability of the nanocrystalline particle can be sufficiently improved. Furthermore, the thickness of the surface layer can be changed by adjusting the number of atoms (chain length) of the connecting structure connecting the binding group of the precursor compound and the hydrolyzable silicon group.

The surface layer can be formed by the following method, that is, after mixing the solution containing the raw material compound of the nanocrystalline particles and the solution containing the precursor compound, and then coordinating the hydrolysis of the surface of the precipitated nanocrystalline particles Sexual silicon condensation.

[Hollow Particles] The luminescent particle may further include a hollow particle having an inner space for accommodating the nanocrystal particles and pores communicating with the inner space. By accommodating nanocrystalline particles in the hollow particles, the stability of the luminescent particles to oxygen and moisture can be further improved.

The hollow particles may also be spherical (true spherical), elongated spherical (elliptical spherical) or cubic (including cuboid and cube). Hollow particles can also be referred to as particles with a balloon structure.

There may be one nanocrystalline particle or a plurality of nanocrystalline particles in the inner space. In addition, the inner space may be entirely occupied by one or a plurality of nanocrystal particles, or only a part thereof may be occupied.

As the hollow particles, any material may be used as long as the nanocrystal particles can be protected. From the viewpoints of ease of synthesis, penetration rate, cost, etc., the hollow particles are preferably hollow silica particles, hollow alumina particles, hollow titanium oxide particles or hollow polymer particles, and more preferably hollow dioxide particles Silicon particles or hollow alumina particles, more preferably hollow silica particles.

The average outer diameter of the hollow particles is not particularly limited, but is preferably 5 to 300 nm, more preferably 6 to 100 nm, further preferably 8 to 50 nm, particularly preferably 10 to 25 nm. In addition, the average inner diameter of the hollow silica particles is not particularly limited, but is preferably 1-250 nm, more preferably 2-100 nm, further preferably 3-50 nm, particularly preferably 5-15 nm. If it is a hollow particle of this size, the thermal stability of the nanocrystalline particle can be sufficiently improved.

The size of the pores is not particularly limited, but is preferably 0.5 to 10 nm, more preferably 1 to 5 nm. In this case, the solution of the raw material compound containing the nanocrystalline particles can be smoothly and surely filled into the inner space.

Commercially available products may also be used for the hollow silica particles. As this commercial item, "SiliNax (registered trademark) SP-PN (b)" etc. are mentioned by Nittetsu Mining Co., Ltd. product, for example. The hollow particles are preferably hollow silica particles in terms of not only the stabilization of the semiconductor nanocrystal particles, but also the luminescence properties and the dispersibility to inks and the like.

For example, by impregnating the hollow particles with a solution of the raw material compound containing the nanocrystalline particles and drying them, the nanocrystalline particles are precipitated in the inner space of the hollow particles, whereby the nanocrystalline particles are accommodated inside the hollow particles. space. [polymer layer] The luminescent particles may further include a polymer layer containing a hydrophobic polymer. The polymer layer may be provided on the outermost layer of the luminescent particles including the nanocrystalline particles. For example, when the luminescent particle has a surface layer, the polymer layer may be a layer covering at least a part of the surface layer. When the luminescent particles include hollow silica, the polymer layer may be a layer covering at least a portion of the hollow silica. When the nanocrystalline particles have a polymer layer, high stability to oxygen and moisture can be imparted to the luminescent particles. Moreover, when preparing an ink composition using the luminescent particle which has a polymer layer, the dispersion stability of a luminescent particle can also be improved. When the polymer layer is provided, the luminescent particles tend to be less likely to agglomerate when the ink composition is prepared, and the reduction of the light-emitting properties due to the agglomeration tends to be less likely to occur.

The polymer layer can be formed by coating the surface of the particle to be coated (hereinafter, also referred to as "mother particle") with a hydrophobic polymer. The polymer layer is formed by polymerizing the monomer (M) in the presence of the mother particle, the non-aqueous solvent, and the polymer (P).

[Non-aqueous solvent] The non-aqueous solvent is preferably an organic solvent capable of dissolving the hydrophobic polymer, and it is more preferable if the base particles can be uniformly dispersed. By using such a non-aqueous solvent, the hydrophobic polymer can be adsorbed to the mother particle very simply to coat the polymer layer. Furthermore, a non-aqueous solvent-based low-dielectric-constant solvent is preferable. By using a low-dielectric-constant solvent, the hydrophobic polymer can be firmly adsorbed on the surface of the mother particle to coat the polymer layer by mixing the hydrophobic polymer and the mother particle in the non-aqueous solvent. Even when the luminescent particles are washed with a solvent as described below, the polymer layer obtained as described above is difficult to remove from the mother particles. Furthermore, the lower the dielectric constant of the non-aqueous solvent, the better. Specifically, the dielectric constant of the non-aqueous solvent is preferably 10 or less, more preferably 6 or less, and particularly preferably 5 or less. Preferable non-aqueous solvents are aliphatic hydrocarbon-based solvents and alicyclic hydrocarbon-based solvents, and preferably organic solvents containing at least one of them.

Examples of the aliphatic hydrocarbon-based solvent or the alicyclic hydrocarbon-based solvent include n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, and ethylcyclohexane. In addition, a mixed solvent obtained by mixing another organic solvent with at least one of the aliphatic hydrocarbon-based solvent and the alicyclic hydrocarbon-based solvent may be used as the non-aqueous solvent within a range that does not impair the effects of the present invention. Examples of the above-mentioned other organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, and amyl acetate; acetone, methyl acetate, etc. Ethyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and other ketone solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol-based solvents, etc. . When used as a mixed solvent, the usage-amount of at least one of the aliphatic hydrocarbon-based solvent and the alicyclic hydrocarbon-based solvent can be 50% by mass or more, and more preferably 60% by mass or more.

[Polymer (P)] The polymer (P) is a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent. As the polymer (P), a fluorine-containing compound (B, C) containing an alkyl (meth)acrylate (A) having an alkyl group having 4 or more carbon atoms or a polymerizable unsaturated group can be used. A polymer obtained by introducing a polymerizable unsaturated group into a copolymer of a polymerizable unsaturated monomer as the main component, or an alkyl (meth)acrylate (A) having an alkyl group having 4 or more carbon atoms, or A macromonomer, etc. composed of a copolymer of a polymerizable unsaturated monomer having a fluorine-containing compound (B, C) having a polymerizable unsaturated group as the main component.

As alkyl (meth)acrylate (A), for example, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 3-butyl (meth)acrylate, and (meth)acrylic acid are mentioned. 2-ethylhexyl, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate ester, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate. Here, in this specification, "(meth)acrylate" means both methacrylate and acrylate. The same is true for the expression "(meth)acryloyl".

Examples of the fluorine-containing compound (B) having a polymerizable unsaturated group include methacrylates represented by the following formulae (B1-1) to (B1-7), and the following (B1-8) to (B1- 15) Acrylates, etc. indicated. In addition, these compounds may be used individually by 1 type, and may use 2 or more types together.

Moreover, as a fluorine-containing compound (C) which has a polymerizable unsaturated group, the compound which has a poly (perfluoroalkylene ether) chain and the polymerizable unsaturated group at both terminals is mentioned, for example. Specific examples of the fluorine-containing compound (C) include compounds represented by the following formulae (C-1) to (C-13). Furthermore, "-PFPE-" in the following formulae (C-1) to (C-13) is a poly(perfluoroalkylene ether) chain.

Among them, the fluorine-containing compound (C) is preferably represented by the above formula (C-1), (C-2), (C-5) or (C-6) in terms of easy industrial production The compound is more preferably both ends of the poly(perfluoroalkylene ether) chain represented by the above formula (C-1) in terms of being able to synthesize the polymer (P) that is easily entangled on the surface of the mother particle A compound having an acryl group, or a compound having a methacryloyl group at both ends of the poly(perfluoroalkylene ether) chain represented by the above formula (C-2).

Moreover, as for the polymer (P), as a compound other than the above-mentioned alkyl (meth)acrylate (A) and fluorine-containing compounds (B, C), for example, styrene, α-methylstyrene, Aromatic vinyl compounds such as p-tertiary styrene and vinyltoluene; benzyl (meth)acrylate, dimethylamino (meth)acrylate, diethylamino (meth)acrylate, dibromo (Meth)acrylate-based compounds such as propyl (meth)acrylate and phenyl tribromo(meth)acrylate; unsaturated diacids such as maleic acid, fumaric acid, and itaconic acid Diester-based compounds of carboxylic acids and monohydric alcohols; vinyl benzoate, vinyl ester-based compounds such as "Veova (registered trademark)" (vinyl ester manufactured by Shell, Netherlands), and the like. These compounds are preferably used as random copolymers with alkyl (meth)acrylates (A) or fluorine-containing compounds (B, C). Thereby, the solubility in the nonaqueous solvent of the obtained polymer (P) can be fully improved.

The compound which can be used as the said polymer (P) may be used individually by 1 type, and may use 2 or more types together. Among them, it is preferable to use n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl methacrylate and the like, which have linear or branched carbon atoms of 4 to 12 Alkyl (meth)acrylate (A).

After polymerizing these compounds by a general method to obtain a copolymer of the compound, a polymerizable unsaturated group is introduced into the copolymer, whereby a polymer (P) can be obtained.

As a method of introducing a polymerizable unsaturated group, for example, the following methods are mentioned: a carboxylic acid group-containing polymerizable monomer such as acrylic acid and methacrylic acid as a copolymerization component; a methacrylic acid dimethylamino group Ethyl ester, dimethylaminopropyl acrylamide and other amine group-containing polymerizable monomers are copolymerized to obtain a copolymer having a carboxylic acid group or an amine group, and the carboxylic acid group or the amine group is obtained. The amine group reacts with a monomer having a glycidyl group and a polymerizable unsaturated group such as glycidyl methacrylate.

[Single (M)] The monomer (M) is a polymerizable unsaturated monomer which is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble in a non-aqueous solvent after polymerization. Examples of the monomer (M) include vinyl-based monomers without reactive polar groups (functional groups), vinyl-based monomers containing amide bonds, and (meth)acryloyloxyalkylphosphoric acid. Esters, (meth)acryloyloxyalkyl phosphites, phosphorus atom-containing vinyl monomers, hydroxyl-containing polymerizable unsaturated monomers, (meth)acrylic acid dialkylamino alkanes base esters, epoxy group-containing polymerizable unsaturated monomers, isocyanate group-containing α,β-ethylenically unsaturated monomers, alkoxysilyl group-containing polymerizable unsaturated monomers, Carboxyl-containing α,β-ethylenically unsaturated monomers, etc.

Specific examples of vinyl monomers having no reactive polar group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylate. (Meth)acrylates such as isopropyl acrylate; olefins such as (meth)acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride. Specific examples of amide bond-containing vinyl monomers include (meth)acrylamide, dimethyl(meth)acrylamide, and N-tert-butyl(meth)acrylamide, for example. Amine, N-octyl (meth)acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide, alkoxylated N-methylol (meth)acrylamide, etc. .

Specific examples of (meth)acryloyloxyalkyl phosphates include, for example, dialkyl[(meth)acrylooxyalkyl]phosphates, (meth)acryloyloxyalkanes base acid phosphates, etc. Specific examples of (meth)acryloyloxyalkyl phosphites include dialkyl[(meth)acrylooxyalkyl]phosphites, (meth)acryloyloxy Alkyl acid phosphites, etc. Specific examples of the phosphorus atom-containing vinyl monomers include the above-mentioned (meth)acryloyloxyalkyl acid phosphates and (meth)acryloyloxyalkyl acid phosphites, for example. Such alkylene oxide adducts; (meth) glycidyl acrylate, (meth) glycidyl methyl acrylate and other epoxy-containing vinyl monomers and phosphoric acid, phosphorous acid or their acid esters Class of ester compounds; (meth)acrylic acid 3-chloro-2-acid phosphinoyloxypropyl ester, etc.

Specific examples of hydroxyl-containing polymerizable unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate, for example. ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, Di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl fumarate, monobutyl fumarate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate Such as hydroxyalkyl esters of polymerizable unsaturated carboxylic acids or their adducts with ε-caprolactone; (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, Polymerizable unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as itaconic acid and methyl maleic acid, and monoesters of dicarboxylic acids and monohydric alcohols; hydroxyalkanes of the above-mentioned polymerizable unsaturated carboxylic acids Anhydrides of base esters and polycarboxylic acids (maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "bicyclic Monoglycidyl esters of various unsaturated carboxylic acids and monocarboxylic acids such as adducts of heptenedicarboxylic acid (himic acid), tetrachlorophthalic acid, dodecynylsuccinic acid, etc. glycerol ester, caprylic acid glycidyl ester, etc.), butyl glycidyl ether, ethylene oxide, propylene oxide and other monoepoxy compound adducts or their adducts with ε-caprolactone; hydroxyvinyl ether etc.

Specific examples of (meth)acrylic acid dialkylaminoalkyl esters include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and the like. Specific examples of epoxy group-containing polymerizable unsaturated monomers include molar adducts such as polymerizable unsaturated carboxylic acids, hydroxyl group-containing vinyl monomers, and acid anhydrides of the above-mentioned polycarboxylic acids. Various unsaturated carboxylic acids such as (mono-2-(meth)acryloyloxymonoethyl phthalate, etc.) and various polyepoxy compounds having at least 2 epoxy groups in one molecule are equimolar. Epoxy group-containing polymerizable compound obtained by addition reaction of ear ratio, glycidyl (meth)acrylate, (β-methyl)glycidyl (meth)acrylate, (meth)allyl glycidyl Glyceryl ether, etc.

Specific examples of isocyanate group-containing α,β-ethylenically unsaturated monomers include molar adducts such as 2-hydroxyethyl (meth)acrylate and hexamethylene diisocyanate, for example. , (meth)acrylic acid ethyl isocyanate and other monomers with isocyanate groups and vinyl groups. Specific examples of the alkoxysilyl group-containing polymerizable unsaturated monomers include vinylethoxysilane, α-methacryloyloxypropyltrimethoxysilane, (meth)acrylic acid Polysiloxane-based monomers such as trimethylsiloxyethyl ester, etc.

Specific examples of carboxyl group-containing α,β-ethylenically unsaturated monomers include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itonic acid, methyl α,β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as maleic acid, and monoesters of dicarboxylic acids and monohydric alcohols; 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Hydroxybutyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, poly α, β-Unsaturated carboxylic acid hydrogen alkyl esters such as ethylene glycol mono(meth)acrylate and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid Adducts of acid anhydrides of polycarboxylic acids such as phthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "bicycloheptenedicarboxylic acid", tetrachlorophthalic acid, and dodecynylsuccinic acid, etc. .

Among them, the monomer (M) is preferably an alkyl (meth)acrylate having an alkyl group having 3 or less carbon atoms, such as methyl (meth)acrylate and ethyl (meth)acrylate.

The polymer layer is formed by polymerizing the monomer (M) in the presence of the mother particle, the non-aqueous solvent and the polymer (P). The mother particles and the polymer (P) are preferably mixed before the polymerization is carried out. For mixing, for example, a homogenizer, a disperser, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill, or the like can be used. The form of the mother particles used in forming the polymer layer is not particularly limited, and forms such as slurry, wet cake, and powder may be used. After the mother particles and the polymer (P) are mixed, the monomer (M) and the following polymerization initiator are mixed to carry out the polymerization, thereby forming a polymer composed of the polymer (P) and the monomer (M) composed of polymer layers. Thereby, luminescent particles can be obtained.

In this case, the number average molecular weight of the polymer (P) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000, and still more preferably 3,000 to 100,000. By using a polymer (P) having a molecular weight in such a range, the surface of the mother particle can be favorably coated with a polymer layer. Moreover, the usage-amount of the polymer (P) is appropriately set depending on the purpose, and is not particularly limited, but is usually preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the mother particles, and further Preferably it is 2-35 mass parts. Moreover, the usage-amount of the monomer (M) is also appropriately set according to the purpose, and is not particularly limited, but is usually preferably 0.5 to 40 parts by mass, more preferably 1 to 35 parts by mass with respect to 100 parts by mass of the mother particles, and further Preferably it is 2-30 mass parts.

The amount of the hydrophobic polymer finally covering the surface of the mother particles is preferably 1-60 parts by mass, more preferably 2-50 parts by mass, and still more preferably 3-40 parts by mass, relative to 100 parts by mass of the mother particles. In this case, the amount of the monomer (M) is usually preferably 10 to 100 parts by mass, more preferably 30 to 90 parts by mass, and still more preferably 50 to 80 parts by mass relative to 100 parts by mass of the polymer (P). parts by mass. The thickness of the polymer layer is preferably 0.5-100 nm, more preferably 0.7-50 nm, and still more preferably 1-30 nm. If the thickness of the polymer layer is less than 0.5 nm, dispersion stability cannot be obtained in many cases. When the thickness of the polymer layer exceeds 100 nm, it is difficult to contain the mother particles at a high concentration in many cases. By coating the mother particles with the polymer layer having the above-mentioned thickness, the stability of the luminescent particles to oxygen and moisture can be further improved.

The polymerization of the monomer (M) in the presence of the mother particles, the non-aqueous solvent and the polymer (P) can be carried out by a known polymerization method, preferably in the presence of a polymerization initiator. As the above-mentioned polymerization initiator, for example, 2,2-azobis(2-methylpropionic acid) dimethyl ester, azobisisobutyronitrile (AIBN), 2,2-azobis(2- methyl butyronitrile), benzyl peroxide, tert-butyl peroxybenzoate, tert-butyl 2-ethylhexanoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, Cumene hydroperoxide, etc. These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator which is hardly soluble in the non-aqueous solvent is preferably added to the mixed liquid containing the mother particles and the polymer (P) in a state of being dissolved in the monomer (M).

In addition, the monomer (M) or the monomer (M) in which the polymerization initiator is dissolved can also be added to the mixed solution at the polymerization temperature by dropwise addition for polymerization, but it is more stable to add it at room temperature before the temperature rises. It is preferable that the temperature is raised in the mixed liquid and sufficiently mixed to carry out the polymerization. The polymerization temperature is preferably in the range of 60 to 130°C, more preferably in the range of 70 to 100°C. If the polymerization of the monomer (M) is carried out at the above-mentioned polymerization temperature, morphological changes (eg, deterioration, crystal growth, etc.) of the nanocrystalline particles can be well prevented. After the polymerization of the monomer (M), the polymer that is not adsorbed on the surface of the mother particle is removed to obtain luminescent particles. As a method for removing the unadsorbed polymer, centrifugal sedimentation and ultrafiltration are exemplified. In the centrifugal sedimentation, the dispersion liquid containing the parent particles and the unadsorbed polymer is rotated at a high speed, so that the parent particles in the dispersion liquid are settled, and the unadsorbed polymer is separated. In ultrafiltration, a dispersion containing parent particles and unadsorbed polymer is diluted with an appropriate solvent, and the dilution is passed through a filter membrane with an appropriate pore size to separate the unadsorbed polymer from the parent particles. In this way, light-emitting particles having a polymer layer can be obtained. The luminescent particles can be stored in a state of being dispersed in a dispersion medium or a photopolymerizable compound (that is, in the form of a dispersion liquid), or can be stored as a powder (aggregate of luminescent particle monomers) by removing the dispersion medium.

[Content of luminescent particles] The content of the luminescent particles in the ink composition is preferably 0.1 mass % or more, 0.5 mass % or more, or 1 mass % or more, and 20 mass % or less, 15 mass % or less, or 10 mass % or less. By setting the content of the luminescent particles within the above range, when the ink composition containing the luminescent particles is discharged by the ink jet printing method, the discharge stability of the ink composition can be further improved. In addition, it is difficult for the light-emitting particles to agglomerate with each other, and the external quantum efficiency of the obtained light-emitting layer (light conversion layer) can also be improved.

The ink composition may contain two or more of red light-emitting particles, green light-emitting particles, and blue light-emitting particles as light-emitting particles, and more preferably only one of these particles. When the ink composition contains red luminescent particles, the content of the green luminescent particles and the content of the blue luminescent particles are based on the total mass of the luminescent particles, preferably 5 mass % or less, more preferably 0 mass % %. When the ink composition contains green luminescent particles, the content of the red luminescent particles and the content of the blue luminescent particles is based on the total mass of the luminescent particles, preferably 5 mass % or less, more preferably 0 mass % %.

[式（1）中，R ¹～R ⁵分別獨立地表示烴基，*表示鍵結鍵]。 <<NOR-type hindered amine compound>> The ink composition contains a NOR-type hindered amine compound represented by the following formula (1). The hindered amine compound is a compound having an imine group (NOR type hindered amine group) in which a hydrocarbon group (R) is bonded via an oxygen atom (O) as a hindered amine group. The NOR-type hindered amine compound may be a compound having one NOR-type hindered amine group, or may be a compound having a plurality of (eg, two or more) NOR-type hindered amine groups. Furthermore, only one type of NOR-type hindered amine compound may be used for the ink composition, or two or more types may be used.

[In formula (1), R ¹ to R ⁵ each independently represent a hydrocarbon group, and * represents a bonding bond].

The carbon number of the hydrocarbon group of R ¹ and R ⁴ is, for example, 1 or more or 2 or more, preferably 8 or less or 7 or less. R ¹ is preferably, for example, an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The alkyl group may be straight or branched. Cycloalkyl can be, for example, cyclohexyl.

As the hydrocarbon group of R ² to R ⁵ and R ⁶ to R ¹⁰ , for example, an alkyl group may be used. The number of carbon atoms in the hydrocarbon group of R ² to R ⁵ may be, for example, 1 or more or 8 or less. R ² to R ⁵ may be, for example, methyl groups.

* represents a bond, and may be a bond site with a carbon atom, a nitrogen atom, or an oxygen atom, for example.

Since the ink composition of the present embodiment contains the NOR-type hindered amine compound represented by the above formula (1), the solubility of the photopolymerizable compound in the ink composition is compared with the case where the NR-type hindered amine compound is contained Excellent, and can form a cured film having excellent light resistance at high temperature. As the photopolymerizable compound used as the ink composition, in terms of compatibility with the light-emitting particles, a compound with low polarity is preferable, and a NOR-type hindered amine compound is more preferable. In addition, the NOR type hindered amine compound is presumably more difficult to coordinate with the surface of the semiconductor nanocrystal than the NR type hindered amine compound, so that the photostabilization effect of the hindered amine compound is not hindered, so it has excellent light resistance. Furthermore, the NR type hindered amine compound refers to one having a structure represented by "-N-R" in place of the structure represented by "-N-O-R" of the NOR type hindered amine compound, and R is hydrogen or an alkyl group.

環之化合物。例如，式（1）所表示之結構亦可直接或經由其他原子（例如氮原子）而與1,3,5-三

環鍵結。NOR type hindered amine compound can be 1,3,5-tris

ring compound. For example, the structure represented by formula (1) can also be directly or via other atoms (such as nitrogen atoms) and 1,3,5-tri

Ring bond.

The NOR-type hindered amine compound can also be used, for example, in a liquid state at 20°C, or in a solid state at 20°C. However, if it is considered that the cured product of the ink composition may be heated to, for example, about 50°C with light irradiation, the NOR type hindered amine compound with a higher melting point is preferable, preferably 70°C or higher, 80°C or higher or above 85°C. If a NOR type hindered amine compound with a melting point of 70°C or higher is used, the liquefaction of the hindered amine compound will not occur even when the hardened product of the ink composition is heated to a high temperature of about 50°C, thus preventing the occurrence of A phenomenon in which hindered amine compounds bleed out from a cured product to the surface of a cured product (bleed-out phenomenon) (bleed-out resistance). On the other hand, in consideration of solubility in the ink composition, the melting point of the NOR-type hindered amine compound is preferably 180° C. or lower.

The molecular weight (or molar mass) or mass average molecular weight of the NOR type hindered amine compound may be 1000 or more. In this specification, the "mass average molecular weight" can be a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. When the molecular weight or the mass average molecular weight is within the above-mentioned range, the melting point becomes high, so that the bleed-out resistance in a high-temperature environment can be surely obtained, and the light resistance is more excellent.

The NOR-type hindered amine compound is preferably a compound represented by, for example, the following formula (1a), the following formula (1b), the following formula (1c), the following formula (1d), or the following formula (1e). The NOR-type hindered amine compound is more preferably a compound represented by the following formula (1a) or the following formula (1b) from the viewpoint of more excellent curability and more excellent light resistance at high temperature.

[式（1a）中，n表示1～15之整數]。

[In formula (1a), n represents an integer of 1 to 15].

[式（1b）中，R表示下述式（1b-R）所表示之基。

式（1b-R）中，*表示與氮原子之鍵結部位]。

[In the formula (1b), R represents a group represented by the following formula (1b-R).

In formula (1b-R), * represents a bonding site with a nitrogen atom].

Examples of commercially available NOR-type hindered amine compounds include TINUVIN (registered trademark) NOR371 (melting point: 91 to 104°C, mass average molecular weight: 2800 to 4000, BASF JAPAN Co., Ltd.) having a structure represented by the above formula (1a). Co., Ltd.), Flamestab NOR116FF (melting point: 108-123°C, molecular weight: 2261, manufactured by BASF JAPAN Co., Ltd.) having the structure represented by the above formula (1b), TINUVIN having the structure represented by the above formula (1c) (registered trademark) 123 (melting point < 20°C (liquid), molecular weight: 737, manufactured by BASF JAPAN Co., Ltd.), LA-81 (melting point < 20°C (liquid) having the structure represented by the above formula (1d) , molecular weight 681, manufactured by ADEKA Co., Ltd.), TINUVIN (registered trademark) 152 (melting point 83-90°C, molecular weight 757, manufactured by BASF JAPAN Co., Ltd.) having a structure represented by the above formula (1e).

The content of the NOR-type hindered amine compound may be 0.1 mass % or more, 0.2 mass % or more, or 0.3 mass % based on the total mass of the ink composition from the viewpoint of achieving better light resistance at high temperature above. The content of the NOR-type hindered amine compound may be, for example, 5.0 mass % or less, 3.0 mass % or less, or 2.0 mass % or less.

＜＜Photopolymerizable compound＞＞ The ink composition contains a photopolymerizable compound. The photopolymerizable compound is preferably a photoradical polymerizable compound polymerized by irradiating light, and may be a photopolymerizable monomer or oligomer. These are used together with photopolymerization initiators. One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.

The photopolymerizable compound preferably contains a monofunctional monomer having one photopolymerizable group and a polyfunctional monomer having two or more photopolymerizable groups. The mass ratio of the monofunctional monomer to the polyfunctional monomer in the photopolymerizable compound may be 1.0, 5.0 or 10.0. If the mass ratio of the monofunctional monomer to the polyfunctional monomer is within this range, the ink viscosity will be suitable for inkjet compatibility, and the cured film will have excellent curability, so it will be the light emission characteristic of the cured film (light conversion layer). more excellent.

As a photopolymerizable compound (photoradical polymerizable compound), a (meth)acrylate compound is mentioned. The (meth)acrylate compound includes a methacrylate compound having a methacryloyl group and an acrylate compound having an acryl group.

The (meth)acrylate compound may be a monofunctional (meth)acrylate having one (meth)acryloyl group, or may be a polyfunctional (meth)acrylic acid having a plurality of (meth)acryloyl groups ester. From the viewpoints of excellent fluidity during preparation of the ink composition, more excellent ejection stability, and suppression of the reduction in smoothness due to curing shrinkage during the production of cured films, a combination of monofunctional ( Meth)acrylates and polyfunctional (meth)acrylates are used.

Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Amyl acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, Octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate , Nonylphenoxyethyl (meth)acrylate, Glycidyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, ( Isobornyl meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2- (meth)acrylate Hydroxy-3-phenoxypropyl, tetrahydrofuran methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, succinic acid Mono(2-acryloyloxyethyl) ester, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrakis Hydrogen phthalimide, etc.

The multifunctional (meth)acrylate can be 2-functional (meth)acrylate, 3-functional (meth)acrylate, 4-functional (meth)acrylate, 5-functional (meth)acrylate, 6-functional (meth)acrylate base) acrylates, etc., for example, di(meth)acrylates in which 2 hydroxyl groups of diol compounds are substituted by (meth)acryloyloxy groups, and 2 or 3 hydroxyl groups of triol compounds are replaced by (methyl) Acryloyloxy substituted two or three (meth)acrylates, etc.

Specific examples of the bifunctional (meth)acrylate include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-butanediol di(meth)acrylate, -Pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyldiol Alcohol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate Acrylates, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate base) acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxytrimethylacetate diacrylate, 2 hydroxyl groups of isocyanurate (2-hydroxyethyl) ester are (methyl) base) acryloxy-substituted di(meth)acrylate, the two hydroxyl groups of the diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol are (Meth) acryloxy-substituted di(meth)acrylate, two hydroxyl groups of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A are ( Meth) acryloxy-substituted di(meth)acrylate, 2 triols obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Di(meth)acrylates in which hydroxyl groups are substituted with (meth)acryloyloxy groups, and 2 of diols obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A A di(meth)acrylate in which one hydroxyl group is substituted by a (meth)acryloyloxy group, etc.

Specific examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, glycerol triacrylate, neotaerythritol tri(meth)acrylate, Tris(meth)acrylates in which 3 hydroxyl groups of triols obtained by adding more than 3 moles of ethylene oxide or propylene oxide to trimethylolpropane are substituted with (meth)acryloyloxy groups Wait. As a specific example of a tetrafunctional (meth)acrylate, neopentaerythritol tetra (meth)acrylate etc. are mentioned, for example. As a specific example of a pentafunctional (meth)acrylate, dipeotaerythritol penta(meth)acrylate etc. are mentioned, for example. As a specific example of a hexafunctional (meth)acrylate, dipeotaerythritol hexa(meth)acrylate etc. are mentioned, for example.

The polyfunctional (meth)acrylate may also be a poly(methyl) group in which a plurality of hydroxyl groups of dipeoerythritol are substituted with (meth)acryloyloxy groups, such as dipeptaerythritol hexa(meth)acrylate and the like. Acrylate. The (meth)acrylate compound may be an ethylene oxide-modified phosphoric acid (meth)acrylate having a phosphoric acid group, an ethylene oxide-modified phosphoric acid (meth)acrylate, or the like.

In the ink composition, when the curable component is composed of only a photopolymerizable compound or the curable component is composed of a photopolymerizable compound as the main component, the durability (strength, heat resistance, etc.) of the cured product can be further improved. As the photopolymerizable compound described above, it is more preferable to use, as an essential component, a bifunctional or more multifunctional photopolymerizable compound having two or more polymerizable functional groups in one molecule.

In addition, from the viewpoints of excellent viscosity stability when the ink composition is prepared, from the viewpoints of more excellent ejection stability, and from the viewpoints of suppressing the reduction in the smoothness of the cured film due to curing shrinkage during the manufacture of the cured film, it is preferable to use A monofunctional (meth)acrylate and a polyfunctional (meth)acrylate are used in combination.

The molecular weight of the photopolymerizable compound may be, for example, 50 or more, 100 or more, or 150 or more. The molecular weight of the photopolymerizable compound is, for example, 500 or less, and may be 400 or less or 300 or less. From the viewpoint of easily achieving both the viscosity as an inkjet ink and the volatility of the ink after ejection, it is preferably 50 to 500, more preferably 100 to 400.

When a monofunctional (meth)acrylate and a polyfunctional (meth)acrylate are combined as the photopolymerizable compound, the viscosity of the monofunctional (meth)acrylate is, for example, 2 mPa･s or more, or 3 mPa･s. s or more or 5mPa･s or more. The viscosity of the monofunctional (meth)acrylate may be, for example, 50 or less, 20 or less, or 10 or less. From the viewpoint of being easily compatible with viscosity, dischargeability, and viscosity stability as an inkjet ink, it is preferably 2 to 50 mPa･s, more preferably 3 to 20 mPa･s, and still more preferably 5 to 10 mPa･s.

烷-5-基丙烯酸甲酯（黏度10.0mPa･s）、2-乙基己基丙烯酸酯（黏度2mPa･s、）、2-[2-（乙氧基）乙氧基]丙烯酸乙酯（黏度4～5mPa･s）、甲氧基三甘醇丙烯酸酯（黏度5～6mPa･s）、2-乙基己基卡必醇丙烯酸酯（黏度4～5mPa･s）、甲氧基聚乙二醇#400丙烯酸酯（黏度25～30mPa･s）、甲氧基二丙二醇丙烯酸酯（黏度2～3mPa･s）、甲基丙烯酸月桂酯（黏度5mPa･s）、甲基丙烯酸第三丁酯（黏度2mPa･s）、甲基丙烯酸2-乙基己酯（黏度3mPa･s）、甲基丙烯酸異癸酯（黏度5mPa･s）、甲基丙烯酸異莰酯（黏度6mPa･s）、甲基丙烯酸環己酯（黏度2～4mPa･s）、甲基丙烯酸芐酯（黏度2～4mPa･s）、甲基丙烯酸苯氧乙酯（黏度7mPa･s）、甲基丙烯酸二環戊烯氧基乙酯（黏度15～20mPa･s）、甲基丙烯酸二環戊酯（黏度7～17mPa･s）等。Examples of monofunctional (meth)acrylate compounds having a viscosity of 2 to 50 mPa･s at room temperature include lauryl acrylate (viscosity 4 to 5 mPa･s), isostearyl acrylate (viscosity 17 mPa･s, viscosity 4～5mPa･s), isodecyl acrylate (viscosity 2.7mPa･s), isobornyl acrylate (viscosity 7.7mPa･s), cyclohexyl acrylate (viscosity 2.5mPa･s), benzyl acrylate (viscosity 2.2mPa ･s), phenoxyethyl acrylate (viscosity 9mPa･s), dicyclopentenyl acrylate (viscosity 8～18mPa･s), dicyclopentenyloxyethyl acrylate (viscosity 15～25mPa･s), acrylic acid Dicyclopentyl ester (viscosity 7～17mPa･s), methyl (2-methyl-2-ethyl-1,3-dioxolan-4-yl)acrylate (viscosity 5.1mPa･s), tetrahydrofuran acrylate Methyl ester (viscosity 2.8mPa･s), 5-ethyl-1,3-di

Methyl alk-5-yl acrylate (viscosity 10.0mPa･s), 2-ethylhexyl acrylate (viscosity 2mPa･s,), 2-[2-(ethoxy)ethoxy]ethyl acrylate (viscosity 2mPa･s) 4～5mPa･s), Methoxytriethylene glycol acrylate (viscosity 5～6mPa･s), 2-ethylhexylcarbitol acrylate (viscosity 4～5mPa･s), methoxypolyethylene glycol #400 Acrylate (viscosity 25～30mPa･s), Methoxydipropylene glycol acrylate (viscosity 2～3mPa･s), lauryl methacrylate (viscosity 5mPa･s), tert-butyl methacrylate (viscosity 5mPa･s) 2mPa･s), 2-ethylhexyl methacrylate (viscosity 3mPa･s), isodecyl methacrylate (viscosity 5mPa･s), isobornyl methacrylate (viscosity 6mPa･s), methacrylic acid Cyclohexyl ester (viscosity 2～4mPa･s), benzyl methacrylate (viscosity 2～4mPa･s), phenoxyethyl methacrylate (viscosity 7mPa･s), dicyclopentenyloxyethyl methacrylate Ester (viscosity 15～20mPa･s), dicyclopentyl methacrylate (viscosity 7～17mPa･s), etc.

From the viewpoint of reducing the tackiness (stickiness) of the surface of the cured product of the ink composition, it is preferable to use a radically polymerizable compound having a cyclic structure as the photopolymerizable compound. The ring structure may be an aromatic ring structure or a non-aromatic ring structure. The number of cyclic structures (the sum of the numbers of aromatic rings and non-aromatic rings) is 1 or 2 or more, preferably 3 or less. The number of carbon atoms constituting the cyclic structure is, for example, 4 or more, preferably 5 or more or 6 or more. The number of carbon atoms is, for example, 20 or less, or preferably 18 or less.

The aromatic ring structure is preferably a structure having an aromatic ring having 6 to 18 carbon atoms. A benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring etc. are mentioned as a C6-C18 aromatic ring. The aromatic ring structure may also be a structure having an aromatic heterocyclic ring. As an aromatic heterocyclic ring, a furan ring, a pyrrole ring, a piperane ring, a pyridine ring, etc. are mentioned, for example. The number of aromatic rings may be 1, or may be 2 or more, and preferably 3 or less. The organic group may have a structure in which two or more aromatic rings are bonded by a single bond (for example, a biphenyl structure).

The non-aromatic ring structure is preferably, for example, a structure having an alicyclic ring having 5 to 20 carbon atoms. Examples of the alicyclic ring having 5 to 20 carbon atoms include cycloalkane rings such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring , cyclooctene rings and other cycloalkene rings, etc. The alicyclic ring may also be a condensed ring such as a bicycloundecane ring, a decahydronaphthalene ring, a norbornene ring, a norbornadiene ring, and an isobornyl ring. The non-aromatic ring structure may also be a structure having a non-aromatic heterocyclic ring. As a non-aromatic heterocyclic ring, a tetrahydrofuran ring, a pyrrolidine ring, a tetrahydropyranyl ring, a piperidine ring, etc. are mentioned, for example.

The radically polymerizable compound having a cyclic structure is preferably a monofunctional or polyfunctional (meth)acrylate having a cyclic structure, and more preferably a monofunctional (meth)acrylate having a cyclic structure. Specifically, phenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, biphenyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate can be preferably used. Meth) tetrahydrofuran methyl acrylate, (meth) acrylate dicyclopentenyloxyethyl, etc.

Regarding the content of the radically polymerizable compound having a cyclic structure, it is easy to suppress the surface stickiness (tackiness) of the ink composition, and from the viewpoint of easy to obtain a viscosity suitable for inkjet ink and easy to obtain excellent ejectability In terms of the total mass of the photopolymerizable compounds in the ink composition, it is preferably 3 to 85 mass %, more preferably 10 to 80 mass %, further preferably 20 to 75 mass %, particularly preferably 30 to 70 mass %.

From the viewpoint of easily obtaining excellent jetting properties, it is preferable to use a radical polymerizable compound having a linear structure with a carbon number of 3 or more, more preferably a linear structure with a carbon number of 4 or more, as the ink composition. free radical polymerizable compounds. The straight-chain structure represents a hydrocarbon chain having 3 or more carbon atoms. In the radically polymerizable compound having a linear structure, the hydrogen atom directly bonded to the carbon atom constituting the linear structure may be substituted with a methyl group or an ethyl group, and the number of substitutions is preferably 3 or less. Among the radically polymerizable compounds having a straight-chain structure having 4 or more carbon atoms, the straight-chain structure is preferably a structure in which atoms other than hydrogen atoms are connected unbranched, and may have oxygen atoms in addition to carbon atoms and hydrogen atoms equal heteroatoms. That is, the straight-chain structure is not limited to a structure in which three or more carbon atoms are connected in a straight-chain form, and a straight-chain structure in which three or more carbon atoms are connected via a heteroatom such as an oxygen atom may be used. The straight-chain structure may have an unsaturated bond, but it is preferably composed of only a saturated bond. The number of carbon atoms constituting the linear structure is preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more. The number of carbon atoms constituting the linear structure is preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. Furthermore, from the viewpoint of ejectability, it has a linear structure with a total number of carbon atoms of 3 or more (a carbon atom of a methyl group or an ethyl group in which a hydrogen atom directly bonded to a carbon atom forming the linear structure is substituted and the The radically polymerizable compound not included) preferably does not have a cyclic structure.

The linear structure is preferably a structure having a linear alkyl group having 4 or more carbon atoms, for example. Examples of straight-chain alkyl groups having 4 or more carbon atoms include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, deca Tetraalkyl, pentadecyl, etc. As the radically polymerizable compound having such a structure, an alkyl (meth)acrylate obtained by directly bonding the above-mentioned straight-chain alkyl group to a (meth)acryloyloxy group can be preferably used.

The linear structure is preferably a structure having a linear alkyl group having 4 or more carbon atoms, for example. Examples of linear alkylene groups having 4 or more carbon atoms include butylene, pentyl, hexyl, heptyl, octyl, nononyl, decyl, undecyl, and dodecyl base, thirteen bases, fourteen bases, fifteen bases, etc. As the radically polymerizable compound having such a structure, an alkylene glycol di(meth)acrylic acid in which two (meth)acryloyloxy groups are bonded via the above-mentioned linear alkyl group can be preferably used ester.

The straight-chain structure is preferably, for example, a structure in which a straight-chain alkyl group and one or more straight-chain alkylene groups are bonded via an oxygen atom (a structure having an alkyl(poly)oxyalkylene group). The number of linear alkyl groups is preferably 2 or more and 6 or less. When the number of straight-chain alkyl groups is two or more, the two or more alkyl groups may be the same or different. The carbon number of the straight-chain alkyl group and the straight-chain extended alkyl group may be 1 or more, and may be 2 or more or 3 or more, but preferably 4 or less. As a linear alkyl group, a methyl group, an ethyl group, and a propyl group are mentioned other than the said C4 or more linear alkyl group. As the straight-chain alkylene group, in addition to the above-mentioned straight-chain alkylene group having 4 or more carbon atoms, a methylene group, an ethylidene group, and a propylidene group can be mentioned. As a radically polymerizable compound having such a structure, a (meth)acrylic acid alkyl group (meth)acrylic acid alkyl group (meth)acrylic acid alkyl group (meth)acrylic acid alkyl group (meth)acrylic acid alkyl group (meth)acrylic acid alkyl group (meth)acryloyloxy group obtained by directly bonding the above-mentioned alkyl (poly)oxyalkylene group with a (meth)acryloyloxy group can be preferably used. Poly)oxyalkylene esters.

Regarding the content of the radically polymerizable compound having a linear structure with a carbon number of 3 or more, it is easy to obtain a viscosity suitable for an inkjet ink, and it is easy to obtain an excellent discharge property, and a viewpoint that the curability of the ink composition is excellent, From the viewpoint of easily suppressing the surface stickiness (tackiness) of the ink composition, it is preferably 10 to 90% by mass, more preferably 15 to 80% by mass based on the total mass of the photopolymerizable compounds in the ink composition. The mass % is particularly preferably 20 to 70 mass %.

As the photopolymerizable compound, from the viewpoint of excellent surface uniformity of the pixel portion, it is preferable to use two or more types of radically polymerizable compounds, and it is more preferable to use a combination of the above-mentioned radically polymerizable compound having a cyclic structure, and The above-mentioned radically polymerizable compound having a linear structure with 3 or more carbon atoms is used. In the case where the amount of nanocrystal particles including luminescent nanocrystals is increased in order to improve the external quantum efficiency, the surface uniformity of the pixel portion may decrease, but according to the combination of the above-mentioned photopolymerizable compounds, even here In such a case, there is a tendency to obtain a pixel portion with excellent surface uniformity.

The SP value of the photopolymerizable compound is preferably 10.0 or less. The SP value of the photopolymerizable compound may be, for example, 9.75 or less, or 9.50 or less, and may be 8.50 or more or 8.70 or more. When the SP value is within the above range, the solubility of the NOR-type hindered amine compound, the storage stability of the ink, and the optical properties (eg, external quantum efficiency) are more excellent.

When the ink composition of the present invention contains the above-mentioned photopolymerizable compound having an SP value of 10.0 or less, the content of the photopolymerizable compound is from the viewpoint of obtaining excellent storage stability of the ink, and from the viewpoint of obtaining excellent ink. From the viewpoint of optical properties (such as external quantum efficiency), based on the total mass of the photopolymerizable compounds in the ink composition, it is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, and more preferably 0 to 5 mass %.

Furthermore, the SP value (solubility parameter/unit: ((cal/cm ³ ) ^0.5 ) in the present invention refers to the solubility parameter calculated by the so-called Fedors method described in RFFedors, Polymer Engineering Science, 14, p147 (1974). In the Fedors method, it is considered that the cohesion energy density and the molar molecular volume depend on the type and quantity of the substituents, and the solubility parameter is expressed by the following formula (1). The solubility parameter is the inherent value of each compound.

[Formula 1]

In the above formula (1), ΣEcoh represents the cohesion energy, and ΣV represents the molar molecular volume.

The SI unit of the SP value is (J/cm ³ ) ^0.5 or (MPa) ^0.5 , and in this specification, the conventionally used (cal/cm ³ ) ^0.5 is used. The unit of SP value can be converted by the following formula: 1 (cal/cm ³ ) ^0.5 ≒ 2.05 (J/cm ³ ) ^0.5 ≒ 2.05 (MPa) ^0.5 .

烷-5-基丙烯酸甲酯（SP値：9.35）、2-乙基己基丙烯酸酯（SP値：8.62）、2-[2-（乙氧基）乙氧基]丙烯酸乙酯（SP値：9.08）、甲氧基三甘醇丙烯酸酯（SP値：9.18）、2-乙基己基卡必醇丙烯酸酯（SP値：8.82）、甲氧基聚乙二醇#400丙烯酸酯（SP値：9.28）、甲氧基二丙二醇丙烯酸酯（SP値：9.29）、甲基丙烯酸丙烯酯（SP値：8.99）、甲基丙烯酸月桂酯（SP値：9.02）、甲基丙烯酸第三丁酯（SP値：8.48）、甲基丙烯酸2-乙基己酯（SP値：8.63）、甲基丙烯酸異癸酯（SP値：8.42）、甲基丙烯酸異莰酯（SP値：8.70）、甲基丙烯酸環己酯（SP値：9.22）、甲基丙烯酸芐酯（SP値：9.64）、甲基丙烯酸苯氧乙酯（SP値：9.68）、甲基丙烯酸二環戊烯氧基乙酯（SP値：9.60）、甲基丙烯酸二環戊酯（SP値：9.60）、1,4-丁二醇二丙烯酸酯（SP値：9.73）、1,6-己二醇二丙烯酸酯（SP値：9.56）、1,9-壬二醇二丙烯酸酯（SP値：9.39）、1,10-癸二醇二丙烯酸酯（SP値：9.34）、二丙二醇二丙烯酸酯（SP値：9.60）、新戊二醇二丙烯酸酯（SP値：9.40）、三環癸烷二甲醇二丙烯酸酯（SP値：9.68）、三甘醇二丙烯酸酯（SP値：9.77）、聚乙二醇#200二丙烯酸酯（SP値：9.72）、聚乙二醇#400二丙烯酸酯（SP値：9.58）、聚乙二醇#600二丙烯酸酯（SP値：9.52）、新戊四醇三丙烯酸酯（SP値：8.78）、三羥甲基丙烷三丙烯酸酯（SP値：9.88）、雙三羥甲基丙烷四丙烯酸酯（SP値：9.81）、1,4-丁二醇二甲基丙烯酸酯（SP値：9.61）、1,6己二醇二甲基丙烯酸酯（SP値：9.48）、1,9-壬二醇二甲基丙烯酸酯（SP値：9.33）、乙二醇二甲基丙烯酸酯（SP値：9.78）、二甘醇二甲基丙烯酸酯（SP値：9.71）、三甘醇二甲基丙烯酸酯（SP値：9.66）、聚乙二醇#200二甲基丙烯酸酯（SP値：9.63）、聚乙二醇#400二甲基丙烯酸酯（SP値：9.53）、聚乙二醇#600二甲基丙烯酸酯（SP値：9.49）等。Examples of the (meth)acrylate compound having an SP value of 10.0 or less include lauryl acrylate (SP value: 8.70), isostearyl acrylate (SP value: 8.59), and isodecyl acrylate (SP value: 8.39) ), n-butyl acrylate (SP value: 8.82), isobornyl acrylate (SP value: 8.70), cyclohexyl acrylate (SP value: 9.26), benzyl acrylate (SP value: 9.71), phenoxyethyl acrylate (SP value: 9.74), Dicyclopentenyl acrylate (SP value: 9.71), Dicyclopentenyloxyethyl acrylate (SP value: 9.65), Dicyclopentenyl acrylate (SP value: 9.66), (2 -Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (SP value: 9.21), tetrahydrofuran methyl acrylate (SP value: 9.51), 5-ethyl-1, 3-two

Methyl alk-5-yl acrylate (SP value: 9.35), 2-ethylhexyl acrylate (SP value: 8.62), 2-[2-(ethoxy)ethoxy]ethyl acrylate (SP value: 8.62) 9.08), methoxytriethylene glycol acrylate (SP value: 9.18), 2-ethylhexyl carbitol acrylate (SP value: 8.82), methoxypolyethylene glycol #400 acrylate (SP value: 9.28), methoxydipropylene glycol acrylate (SP value: 9.29), propylene methacrylate (SP value: 8.99), lauryl methacrylate (SP value: 9.02), tertiary butyl methacrylate (SP value: 9.02) value: 8.48), 2-ethylhexyl methacrylate (SP value: 8.63), isodecyl methacrylate (SP value: 8.42), isobornyl methacrylate (SP value: 8.70), methacrylic acid Cyclohexyl ester (SP value: 9.22), benzyl methacrylate (SP value: 9.64), phenoxyethyl methacrylate (SP value: 9.68), dicyclopentenyloxyethyl methacrylate (SP value: 9.68) : 9.60), dicyclopentyl methacrylate (SP value: 9.60), 1,4-butanediol diacrylate (SP value: 9.73), 1,6-hexanediol diacrylate (SP value: 9.56) ), 1,9-nonanediol diacrylate (SP value: 9.39), 1,10-decanediol diacrylate (SP value: 9.34), dipropylene glycol diacrylate (SP value: 9.60), neopentyl Glycol diacrylate (SP value: 9.40), tricyclodecane dimethanol diacrylate (SP value: 9.68), triethylene glycol diacrylate (SP value: 9.77), polyethylene glycol #200 diacrylate (SP value: 9.72), polyethylene glycol #400 diacrylate (SP value: 9.58), polyethylene glycol #600 diacrylate (SP value: 9.52), neopentaerythritol triacrylate (SP value: 8.78), trimethylolpropane triacrylate (SP value: 9.88), bis-trimethylolpropane tetraacrylate (SP value: 9.81), 1,4-butanediol dimethacrylate (SP value: 9.61), 1,6-hexanediol dimethacrylate (SP value: 9.48), 1,9-nonanediol dimethacrylate (SP value: 9.33), ethylene glycol dimethacrylate (SP value: 9.33) value: 9.78), diethylene glycol dimethacrylate (SP value: 9.71), triethylene glycol dimethacrylate (SP value: 9.66), polyethylene glycol #200 dimethacrylate (SP value: 9.66) 9.63), polyethylene glycol #400 dimethacrylate (SP value: 9.53), polyethylene glycol #600 dimethacrylate (SP value: 9.49), etc.

In the ink composition, when the curable component is composed of only a photopolymerizable compound, or the curable component is composed of a photopolymerizable compound as the main component, as the above-mentioned photopolymerizable compound, one having 2 or more in one molecule is used. A polyfunctional photopolymerizable compound having a difunctional or more functional polymerizable functional group as an essential component is more preferable because it can further improve the durability (strength, heat resistance, etc.) of the cured product.

（式中，R ^1a表示選自下述式（R ^1a-1）～式（R ^1a-6）之基，R ^2a、R ^2b及R ^2c分別獨立，表示選自下述式（R ²-1）～式（R ²-7）之基） Regarding the content of the photopolymerizable compound contained in the ink composition, it is easy to obtain a viscosity suitable for an inkjet ink, a viewpoint that the curability of the ink composition becomes good, and the pixel portion (hardened product of the ink composition) ) from the viewpoint of improving solvent resistance and abrasion resistance, and from the viewpoint of obtaining more excellent optical properties (such as external quantum efficiency), preferably 70 to 95% by mass based on the total mass of the ink composition , more preferably 75 to 94 mass %, still more preferably 80 to 93 mass %. <<Photopolymerization initiator>> The photopolymerization initiator is preferably at least one selected from the group consisting of alkylphenone-based compounds, acylphosphine oxide-based compounds, and oxime ester-based compounds. As an alkylphenone type photopolymerization initiator, the compound represented by Formula (b-1) is mentioned, for example.

(In the formula, R ^1a represents a group selected from the following formulae (R ^1a -1) to (R ^1a -6), and R ^2a , R ^2b and R ^2c are each independently and represent a group selected from the following formula (R ² - 1)～Base of formula (R ² -7))

As a specific example of the compound represented by the above formula (b-1), the compounds represented by the following formulae (b-1-1) to (b-1-6) are preferable, and the following formula (b-1-6) are more preferable. b-1-1), a compound represented by formula (b-1-5), or formula (b-1-6).

（式中，R ²⁴表示烷基、芳基或雜環基，R ²⁵及R ²⁶分別獨立，表示烷基、芳基、雜環基或烷醯基，該等基可被烷基、羥基、羧基、碸基、芳基、烷氧基、芳硫基取代）。 Examples of the acylphosphine oxide-based photopolymerization initiator include compounds represented by formula (b-2).

(In the formula, R ²⁴ represents an alkyl group, an aryl group or a heterocyclic group, and R ²⁵ and R ²⁶ are each independently and represent an alkyl group, an aryl group, a heterocyclic group or an alkanoyl group, and these groups may be replaced by an alkyl group, a hydroxyl group, a Carboxyl, sulfonyl, aryl, alkoxy, arylthio substituted).

As a specific example of the compound represented by the above formula (b-2), the compounds represented by the following formulae (b-2-1) to (b-2-5) are preferred, and the following formula (b-2-5) are more preferred. b-2-1) or a compound represented by formula (b-2-5).

（式中，R ²⁷～R ³¹分別獨立，表示氫原子、碳原子數1～12之環狀、直鏈狀或支鏈狀之烷基、或者苯基，各烷基及苯基亦可被選自由鹵素原子、碳原子數1～6之烷氧基及苯基所組成之群中取代基取代，X ¹表示氧原子或氮原子，X ²表示氧原子或NR，R表示碳原子數1～6之烷基）。 Examples of the oxime ester-based photopolymerization initiator include compounds represented by the following formula (b-3-1) or formula (b-3-2).

(In the formula, R ²⁷ to R ³¹ are each independently and represent a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may also be Substituents selected from the group consisting of halogen atoms, alkoxy groups with 1 to 6 carbon atoms and phenyl groups, X ¹ represents oxygen atom or nitrogen atom, X ² represents oxygen atom or NR, R represents carbon number 1 ~6 alkyl).

As specific examples of the compounds represented by the above formula (b-3-1) and formula (b-3-2), the following formulae (b-3-1-1) to (b-3-1) are preferred -2) and compounds represented by the following formulae (b-3-2-1) to (b-3-2-2), more preferably the following formulae (b-3-1-1) and (b) -3-2-1) or a compound represented by formula (b-3-2-2).

The content of the photopolymerization initiator is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, with respect to the total amount of the photopolymerizable compound contained in the ink composition. In addition, one type of photopolymerization initiator may be used alone, or two or more types may be mixed and used. The ink composition containing the photopolymerization initiator in this amount can sufficiently maintain the sensitivity during photocuring, and it is difficult to precipitate the crystals of the photopolymerization initiator when the cured film is dried, so that the deterioration of the physical properties of the cured film can be suppressed.

When the photopolymerization initiator is dissolved in the ink composition, it is preferably used after being dissolved in the photopolymerizable compound in advance. When dissolving in the photopolymerizable compound, it is preferable to dissolve the photopolymerizable compound uniformly while stirring the photopolymerizable compound so as not to initiate the reaction due to heat. The dissolution temperature of the photopolymerization initiator may be appropriately adjusted in consideration of the solubility of the photopolymerization initiator to be used in the photopolymerizable compound and the polymerizability of the photopolymerizable compound by heat. However, from the viewpoint of not starting the polymerization of the photopolymerizable compound, it is preferably 10 to 50°C, more preferably 10 to 40°C, and even more preferably 10 to 30°C.

＜＜Light scattering particles＞＞ The ink composition may further contain light-scattering particles. The light-scattering particles are preferably, for example, optically inactive inorganic fine particles. The light-scattering particles can scatter the light from the light source part irradiated to the light-emitting layer (light conversion layer). Examples of materials constituting the light-scattering particles include elemental metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, crude platinum, and gold; silica, barium sulfate , barium carbonate, calcium carbonate, talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide metal oxides such as magnesium carbonate, barium carbonate, bismuth subcarbonate, calcium carbonate, etc.; metal hydroxides such as aluminum hydroxide; barium zirconate, calcium zirconate, calcium titanate, titanate Composite oxides such as barium and strontium titanate, metal salts such as bismuth subnitrite, and the like. Among them, as the material constituting the light-scattering particles, it is preferable to contain a material selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silicon dioxide from the viewpoint that the effect of reducing light leakage is more excellent. At least one of the group consisting of, more preferably at least one selected from the group consisting of titanium oxide, barium sulfate, and calcium carbonate, and particularly preferably titanium oxide.

In the case of using titanium oxide, from the viewpoint of dispersibility, surface-treated titanium oxide is preferred. As a surface treatment method of titanium oxide, a well-known method is known, and a surface treatment containing at least alumina is more preferable.

The so-called surface-treated titanium oxide containing aluminum oxide refers to a treatment in which at least aluminum oxide is precipitated on the surface of titanium oxide particles, and in addition to aluminum oxide, silicon dioxide and the like can also be used. In addition, alumina or silica also includes hydrates thereof.

In this way, by subjecting the titanium oxide particles to the surface treatment containing aluminum oxide, the surfaces of the titanium oxide particles are uniformly surface-coated, and the dispersibility of the titanium oxide particles becomes good when the titanium oxide particles at least surface-treated with aluminum oxide are used. .

In addition, when the titanium oxide particles are subjected to the treatment with silica and the treatment with alumina, the alumina treatment and the silica treatment can be carried out at the same time, and in particular, the alumina treatment can be carried out first, and then the silica treatment can be carried out. deal with. In addition, when the alumina treatment and the silica treatment are respectively performed, the treatment amount of alumina and silica is preferably more silica than alumina.

The surface treatment of the above-mentioned titanium oxide with metal oxides such as aluminum oxide and silicon dioxide can be performed by a wet method. For example, titanium oxide particles subjected to surface treatment of aluminum oxide or silicon dioxide can be produced in the following manner.

Aqueous slurry is prepared by dispersing titanium oxide particles (number average primary particle size: 200-400 nm) in water at a concentration of 50-350 g/L, and adding water-soluble silicate or water-soluble aluminum compound to it . Then, an alkali or an acid is added for neutralization, and silica or alumina is deposited on the surface of the titanium oxide particles. Next, filtration, washing, and drying are performed to obtain the target surface-treated titanium oxide. In the case of using sodium silicate as the above water-soluble silicate, it can be neutralized with acids such as sulfuric acid, nitric acid, and hydrochloric acid. On the other hand, when aluminum sulfate is used as the water-soluble aluminum compound, it can be neutralized with a base such as sodium hydroxide or potassium hydroxide.

The content of the light-scattering particles may be 0.5 mass % or more, 1 mass % or more, or 2 mass % or more, or 10 mass % or less, 9 mass % or less, or 8 mass % based on the total mass of the ink composition. %the following.

＜＜Polymer dispersant＞＞ The ink composition may further contain a polymer dispersant. The polymer dispersant is a compound with a weight-average molecular weight (Mw) exceeding 5,000, which can improve the dispersion stability of the light-scattering particles in the ink composition. The polymer dispersant can also impart dispersion stability to the luminescent particles.

The "weight average molecular weight (Mw)" can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

Examples of polymer dispersants include acrylic resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, polyether-based resins, phenol-based resins, polysiloxane-based resins, and polyurea-based resins. Resins, ammonia-based resins, polyamine-based resins (polyethyleneimine, polyallylamine, etc.), epoxy-based resins, polyimide-based resins; wood rosin, gum rosin, tall oil rosin, etc. Natural rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alcohol Acid adducts, rosin derivatives such as rosin-modified phenol, etc. Furthermore, as a commercial product of a polymer dispersant, for example, DISPERBYK (registered trademark) series manufactured by BYK-Chemie, TEGO (registered trademark) Dispers series manufactured by Evonik, and EFKA (registered trademark) manufactured by BASF can be used. ) series, SOLSPERSE (registered trademark) series manufactured by Lubrizol Corporation of Japan, Ajisper (registered trademark) series manufactured by Ajinomoto Fine-Techno Corporation, DISPARLON (registered trademark) series manufactured by Kusumoto Chemical Co., Ltd., Flowlen manufactured by Kyoeisha Chemical Co., Ltd. series, etc.

Moreover, as this polymer dispersing agent, a block copolymer is especially preferable. The use of the block copolymer in the polymer dispersant will bring the following effects: by making the block copolymer composed of a hydrophilic region and a pigment adsorption region, higher dispersibility can be obtained, and a more random copolymer or More excellent dispersibility of cross copolymer

Specifically, in a random copolymer or the like, the probability that the monomer constituting the copolymer is sterically or electrically stably arranged in the copolymer at the time of polymer formation increases. Since the part (molecule) in which the monomer is stably arranged is sterically or electrically stable, it is often a hindrance when it is adsorbed on the surface of the pigment. On the other hand, in the block copolymer type polymer dispersant in which the molecular arrangement is controlled, the part that prevents the dispersant from being adsorbed to the pigment can be arranged at a position away from the adsorption part of the pigment and the dispersant. That is, it is presumed that the most suitable part for adsorption is arranged by the adsorption part of the pigment and the dispersant, and the suitable part is arranged in the part that requires solvent affinity, especially in the inkjet ink of the system containing the pigment with a small crystal size. In dispersion, good dispersibility can be achieved by the molecular arrangement composed of the block copolymer.

The polymer dispersant of the present invention is not limited as long as it has the above-mentioned properties, and block copolymers synthesized by using known ethylenically unsaturated monomers can be applied. As the ethylenically unsaturated monomers, for example, Take the following.

Styrene and styrene derivatives, such as alpha-methylstyrene or vinyltoluene; vinyl esters of carboxylic acids, such as vinyl acetate, vinyl propionate; vinyl halides; ethylenically unsaturated mono- and dicarboxylic acids , such as acrylic acid, methacrylic acid, itonic acid, maleic acid or fumaric acid, and monoalkyl esters of the aforementioned dicarboxylic acids and alkanols (preferably those having 1 to 4 carbon atoms) , and derivatives of the above-mentioned monoalkyl esters, and N-substituted derivatives thereof, aryl esters, and derivatives thereof; amides of unsaturated carboxylic acids, such as acrylamide, methacrylamide, N - methylol acrylamide or methacrylamide, N-alkyl acrylamide; vinylic monomers containing sulfonic acid groups and their ammonium or alkali metal salts, such as vinylsulfonic acid, vinylbenzenesulfonic acid, Alpha-acrylamidomethylpropanesulfonic acid, 2-sulfonated ethylidene methacrylate; vinylamine amides, such as vinylformamide, vinylacetamide; including secondary, tertiary or tetrakis Unsaturated ethylenic monomers with amine group or nitrogen-containing heterocyclic group, such as vinylpyridine, vinylimidazole, aminoalkyl (meth)acrylate, aminoalkyl(meth)acrylamide, acrylic acid or dimethylaminoethyl methacrylate, acrylic acid or di-tert-butylaminoethyl methacrylate, or dimethylaminomethacrylamide or methacrylamide; bipolar ionicity Monomers such as sulfopropyl(dimethyl)aminopropyl acrylate; dienes such as butadiene, isoprene, chloroprene; (meth)acrylates; vinyl nitriles; Vinylphosphonic acid and its derivatives.

The block copolymer can be synthesized using such an ethylenically unsaturated monomer according to a known method, for example, a synthesis method such as JP 2005-60669 A or JP 2007-314617 A.

Among them, it is preferable to use a (meth)acrylic block copolymer. For example, it can be synthesized by referring to the following well-known methods. These well-known methods are described in Japanese Patent Application Laid-Open No. 60-89452; Japanese Patent Application Laid-Open No. 9-62002 Bulletin No. 1; P. Lutz, P. Massonetal, Polym. Bull. 12, 79 (1984); B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, etal, Polym. J . 17, 977 (1985); K. Hatada, K. Ute, etal, Polym. J. 18, 1037 (1986); Right Hand Koichi, Hatada Koichi, Polymer Processing, 36, 366 (1987); Mitsuo Sawamoto, Proceedings on Polymers, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43,300 ( 1985); D. Y. Sogoh, W. R. Hertleretal, Macromolecules, 20, 1473 (1987); K. Matyaszewskietal, Chem. Rev. 2001, 101, 2921 - 2990, etc.

、咪唑、三氮唑之含氮雜環基等。該高分子分散劑之胺值較佳為6～90 mgKOH/g，更佳為7～70 mgKOH/g，進而較佳為8～50 mgKOH/g。若該高分子分散劑之胺值小於6 mgKOH/g，則高分子分散劑對於光擴散粒子之吸附性較低，又，若胺值大於90 mgKOH/g，則極性變高而容易導致凝聚、保存性變差，且發光性粒子之分散性亦會因此影響而變差。The polymer dispersant used in the present invention has basic polar groups, and as basic functional groups, there can be exemplified: primary, secondary and tertiary amine groups, ammonium groups, imino groups, and pyridine, pyrimidine, pyridine

, nitrogen-containing heterocyclic groups of imidazole and triazole, etc. The amine value of the polymer dispersant is preferably 6-90 mgKOH/g, more preferably 7-70 mgKOH/g, and still more preferably 8-50 mgKOH/g. If the amine value of the polymer dispersant is less than 6 mgKOH/g, the adsorption of the polymer dispersant to the light-diffusing particles will be low, and if the amine value is greater than 90 mgKOH/g, the polarity will become high, and it is easy to cause aggregation, The storage property is deteriorated, and the dispersibility of the luminescent particles is also deteriorated due to this influence.

The amine value of the polymer dispersant can be measured as follows. Dissolve xg of polymer dispersant and 1 mL of bromophenol blue reagent in 50 mL of a mixed solution of toluene and ethanol in a volume ratio of 1:1, prepare a sample solution, and titrate with 0.5 mol/L hydrochloric acid until The sample solution is green, and the amine value can be calculated from the following formula. Amine value=y/x×28.05 In the formula, y represents the titration (mL) of 0.5 mol/L hydrochloric acid required for the titration, and x represents the mass (g) of the polymer dispersant.

About content of a polymer dispersing agent, 0.5-50 mass % is preferable with respect to 100 mass % of light-scattering particles, 2-30 mass % is more preferable, 3-20 mass parts is especially preferable.

The ink composition may contain components other than luminescent particles, photopolymerizable compounds, photopolymerization initiators, light-scattering particles, and polymer dispersants within the range that does not inhibit the effects of the present invention. As other components, a polymerization inhibitor, an antioxidant, a leveling agent, a chain transfer agent, a dispersing aid, a thermoplastic resin, a sensitizer, etc. are mentioned.

＜＜Polymerization inhibitor＞＞ Examples of the polymerization inhibitor include p-methoxyphenol, cresol, tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylene Bis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3 -Methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol and other phenols Compounds; hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone , 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and other quinone compounds; p-phenylenediamine , 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-diiso Amine-based compounds such as propylphenyl-diphenylamine and 4,4'-dioctyl-diphenylamine; thioether-based compounds such as diphenhydramine and distearyl thiodipropionate; 2,2, 6,6-Tetramethylpiperidine-1-oxyl radical, 2,2,6,6-Tetramethylpiperidine, 4-Hydroxy-2,2,6,6-Tetramethylpiperidine-1 -N-oxyl compounds such as oxygen radicals; Benzene, p-nitroso diphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitroso diphenylamine, p-nitrosodimethylamine, p-nitroso Ketone-N,N-diethylamine, N-nitrosoethanolamine, N-nitroso-di-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso Ethyl-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso Nitro-N-phenylhydroxylamine ammonium salt (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "Q-1300"), nitrosobenzene, 2,4,6-tri-tert-butylnitronebenzene, N -Nitroso-N-methyl-p-toluamide, N-nitroso-N-ethylamine ester, N-nitroso-N-n-propylamine ester, 1-nitroso-2 -Naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate , 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) class of nitroso compounds, etc. The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0 mass %, more preferably 0.02 to 0.5 mass %, with respect to the total amount of the photopolymerizable compound contained in the ink composition.

[Antioxidants] Examples of antioxidants include neopentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name "IRGANOX (registered trademark) 1010"), Thiodieneethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name "IRGANOX (registered trademark) 1035"), 3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate octadecyl (product name "IRGANOX (registered trademark) 1076"), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Isooctyl acid (product name "IRGANOX (registered trademark) 1135"), 2,4,6-paraben (3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene (product name " IRGANOX1330"), 4,6-bis(octylthiomethyl)-o-cresol (product name "IRGANOX (registered trademark) 1520L"), 2,4-bis[(dodecylthio)methyl]-6 -Cresol (product name "IRGANOX (registered trademark) 1726"), bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene) ] (product name "IRGANOX (registered trademark) 245"), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (product name " IRGANOX (registered trademark) 259"), 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate (product name "IRGANOX (registered trademark) 3114"), 1,3,5-para[[ 4-(1,1-Dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-tris𠯤-2,4,6(1H,3H ,5H)-triketone (product name "IRGANOX (registered trademark) 3790"), bis[4-(1,1,3,3-tetramethylbutyl)phenyl]amine (product name "IRGANOX (registered trademark) 3790") ) 5057”), 4-[[4,6-bis(octylthio)-1,3,5-tris-2-yl]amino]-2,6-di-tert-butylphenol (product name "IRGANOX (registered trademark) 565") (above, manufactured by BASF Co., Ltd.); ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate (product name "ADK STAB (registered trademark) AO- 20”), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl] -2,4,8,10-Tetraoxaspiro[5.5]undecane (product name "ADK STAB (registered trademark) AO-30"), 4,4'-butylenebis(3-methyl-6 -Tertiarybutyl)phenol (product name "ADK STAB (registered trademark) AO-40"), n-octadecyl-3 (3',5'-di-tert-butyl-4'-hydroxyphenyl) Propionate (product name "ADK STAB (registered trademark) ) AO-50"), product name "ADK STAB (registered trademark) AO-60", 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) ) propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (product name "ADK STAB (registered trademark) AO-80" ), ginseng (4-nonylphenyl) phosphite (product name "ADK STAB (registered trademark) 1178"), ginseng phosphite (2,4-di-tert-butylphenyl) (product name "ADK STAB ( registered trademark) 2112”), 2,4,8,10-di(1,1-dimethylethyl)-6-[(2-ethylhexyl)oxy]-12H-dibenzo[d, g][1,3,2]dioxaphosphacyclo (product name "ADK STAB (registered trademark) HP-10", 3,9-bis(octadecyloxy)-2,4,8, 10-Tetraoxa-3,9-diphosphaspiro[5.5]undecane (product name "ADK STAB (registered trademark) PEP-8"), 3,9-bis(2,4-di-tertiary Butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (product name "ADK STAB (registered trademark) PEP-24", 3, 9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (product name "ADK STAB (registered trademark) PEP-36", triphenyl phosphite (product name "ADK STAB (registered trademark) TPP"), tetraalkyl (C12-15)-4,4'-idene Isopropyl diphenyl diphosphite (product name "ADK STAB (registered trademark) 1500") (above, manufactured by ADEKA Co., Ltd.); sannonylphenyl phosphite (product name "JP-351") , Tricresyl phosphite" (product name "JP-3CP"), triethyl phosphite (product name "JP-302"), ginseng (2-ethylhexyl) phosphite (product name "JP-308E" ”), tridecyl phosphite (product name “JP-310”), trilauryl phosphite (product name “JP-312L”), ﾄ tridecyl phosphite (product name “JP- 333"), trioleyl phosphite (product name "JP-318-O"), diphenyl mono(2-ethylhexyl) phosphite (product name "JPM-308"), diphenyl phosphite Monodecyl ester (product name "JPM-311")", diphenyl mono(tridecyl) phosphite (product name "JPM-313"), bis(decyl) neopentaerythritol diphosphite Esters (product name "JPE-10"), stearyl phosphite (product name "JP-318E") (above, manufactured by Seonghoku Chemical Industry Co., Ltd.); butylhydroxytoluene ("product name "Sumilizer (registered) trademark) BH T"), 4,4'-butylenebis(3-methyl-6-tert-butylphenol) (product name "Sumilizer (registered trademark) BBM-S"), 3,9-bis[1,1 -Dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro [5,5] Undecane (product name "Sumilizer (registered trademark) GA-80") (above, manufactured by Sumitomo Chemical Co., Ltd.), tetra (2,4-di-tert-butylphenyl-4,4 '-biphenylene diphosphite) (product name "Hostanox (registered trademark) P-EPQ") (above, manufactured by Clariant Chemical Co., Ltd.), tetra (2,4-di-tert-butyl- 5-methylphenyl)-4,4'-biphenylene diphosphite" (product name "GSY-P100") (above, manufactured by Sakai Chemical Industry Co., Ltd.) and the like. The addition amount of the antioxidant is preferably 0.01 to 2.0 mass %, more preferably 0.02 to 1.0 mass %, with respect to the total amount of the photopolymerizable compound contained in the ink composition.

＜＜Leveler＞＞ Although it does not specifically limit as a leveling agent, When forming the thin film of a luminescent particle, the compound which can reduce film thickness unevenness is preferable. Examples of the leveling agent include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene Derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, etc. The amount of the leveling agent added is preferably 0.005 to 2 mass %, more preferably 0.01 to 0.5 mass %, with respect to the total amount of the photopolymerizable compound contained in the ink composition.

系化合物、二苯甲酮系化合物、醌系化合物、胺類等。作為該敏化劑，例如可列舉2-異丙基9-氧硫

、2,4-二乙基9-氧硫

、二苯甲酮、4,4’-雙（二乙基胺基）二苯甲酮、2-乙基蒽醌、三甲胺、甲基二甲醇胺、三乙醇胺、對二乙基胺基苯乙酮、對二甲基胺基苯甲酸乙酯、對二甲基胺基苯甲酸異戊酯、N,N-二甲基苄胺等。 <<Chain Transfer Agent>> The chain transfer agent is a component used for the purpose of further improving the adhesion between the ink composition and the substrate. Examples of the chain transfer agent include aromatic hydrocarbons, halogenated hydrocarbons, mercaptan compounds, thiol compounds, sulfides, and the like. The addition amount of the chain transfer agent is preferably 0.1 to 10% by mass, more preferably 1.0 to 5% by mass, with respect to the total amount of the photopolymerizable compound contained in the ink composition. <<Thermoplastic resin>> Examples of thermoplastic resins include urethane-based resins, acrylic resins, polyamide-based resins, polyimide-based resins, styrene maleic acid-based resins, and styrene maleic anhydride-based resins. resin, polyester acrylate resin, etc. <<Sensitizer>> As the sensitizer, 9-oxosulfur can be used

series compounds, benzophenone series compounds, quinone series compounds, amines, etc. As the sensitizer, for example, 2-isopropyl 9-oxosulfur can be mentioned

, 2,4-diethyl 9-oxothio

, benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-ethylanthraquinone, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminobenzene Ethyl ketone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, etc.

＜＜Viscosity of ink composition＞＞ The viscosity of the ink composition at 30°C is preferably in the range of 2 to 20 mPa･s, more preferably in the range of 5 to 15 mPa･s, and still more preferably 7～12mPa･s range. At this time, the meniscus shape of the ink composition in the ink ejection holes of the nozzle is stable, so that the ejection control of the ink composition (such as the control of the ejection amount and the ejection timing) becomes easy. In addition, the ink composition can be smoothly ejected from the ink ejection holes. In addition, the viscosity of an ink composition can be measured with an E-type viscometer, for example.

The viscosity increase rate of the ink composition may be 5% or less, 1% or less, or 0.5% or less, and may be 0.01% or more. The viscosity increase rate of the ink composition is a value calculated by the following formula. Formula: (η ₁ -η ₀ )/η ₀ ×100 Here, η ₁ represents the viscosity of the ink composition after being left at 40°C for 1 week measured at 30°C, and η ₀ represents the ink of the ink composition before being left to stand The viscosity of the composition.

＜＜Surface tension of ink composition＞＞ The surface tension of the ink composition is preferably a surface tension suitable for ink jet printing. The specific value of the surface tension is preferably in the range of 20 to 40 mN/m, more preferably in the range of 25 to 35 mN/m. By setting the surface tension to the above-mentioned range, the occurrence of flying deviation of the droplets of the ink composition can be suppressed. In addition, the so-called flying deviation means that when the ink composition is ejected from the ink ejection hole, the ejection position of the ink composition is shifted by 30 μm or more from the target position.

The above-mentioned ink composition can be prepared by, for example, dispersing luminescent particles in a solution containing a NOR-type hindered amine compound and, if necessary, a photopolymerizable compound, a photopolymerization initiator, and the like. Dispersion of the luminescent particles can be performed by using, for example, a disperser such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion mixer, and an ultrasonic wave.

＜Ink composition set＞ Another embodiment of the present invention is an ink composition kit. The ink composition set of one embodiment includes the ink composition of the above-described embodiment. The ink composition set may include an ink composition (non-luminescent ink composition) that does not contain luminescent particles in addition to the ink composition (luminescent ink composition) of the above-described embodiment. The non-luminescent ink composition is, for example, a curable ink composition. The non-luminescent ink composition may be a conventionally known ink composition, or may have the same composition as the ink composition (luminescent ink composition) of the above-described embodiment except that luminescent particles are not contained.

Since the non-luminescent ink composition does not contain luminescent particles, when light is incident on the pixel portion formed by the non-luminescent ink composition (the pixel portion containing the cured product of the non-luminescent ink composition), light is emitted from the pixel portion. The emitted light has approximately the same wavelength as the incident light. Therefore, the non-luminescent ink composition can be suitably used for forming a pixel portion of the same color as the light from the light source. For example, when the light from the light source is light (blue light) having a wavelength in the range of 420 to 480 nm, the pixel portion formed by the non-luminescent ink composition may be a blue pixel portion.

The non-luminescent ink composition preferably contains light-scattering particles. When the non-luminescent ink composition contains light-scattering particles, the light incident on the pixel portion can be scattered by the pixel portion formed using the non-luminescent ink composition, thereby reducing the emission from the pixel portion. The light intensity difference of the incident light under the viewing angle.

<Light Conversion Layer and Color Filter> Another embodiment of the present invention is a light conversion layer and a color filter. Hereinafter, the details of the light conversion layer and the color filter obtained by using the ink composition or ink composition set of the above-described embodiment will be described with reference to the drawings. However, the following embodiments are embodiments when the ink composition contains light-scattering particles. In addition, in the following description, the same code|symbol is used for the same or equivalent element, and the repeated description is abbreviate|omitted.

FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment. As shown in FIG. 1 , the color filter 100 includes a base material 40 and a light conversion layer 30 provided on the base material 40 . The light conversion layer 30 includes a plurality of pixel portions 10 and a light shielding portion 20 .

The light conversion layer 30 includes, as the pixel portion 10, a first pixel portion 10a, a second pixel portion 10b, and a third pixel portion 10c. The 1st pixel part 10a, the 2nd pixel part 10b, and the 3rd pixel part 10c are arrange|positioned in a lattice shape so that it may repeat in order. The light shielding portion 20 is provided between adjacent pixel portions, that is, provided between the first pixel portion 10a and the second pixel portion 10b, between the second pixel portion 10b and the third pixel portion 10c, and between the third pixel portion 10c between the first pixel portion 10a. In other words, the adjacent pixel portions are separated from each other by the light shielding portion 20 .

The 1st pixel part 10a and the 2nd pixel part 10b each contain the luminescent pixel part (luminescent pixel part) of the hardened|cured material of the ink composition of the said embodiment. The cured product shown in FIG. 1 contains luminescent particles, a curing component, and light-scattering particles. The 1st pixel part 10a contains the 1st hardening component 13a, and the 1st luminescent particle 11a and the 1st light-scattering particle 12a which were each dispersed in the 1st hardening component 13a. Similarly, the 2nd pixel part 10b contains the 2nd hardening component 13b, and the 2nd luminescent particle 11b and the 2nd light-scattering particle 12b which were each dispersed in the 2nd hardening component 13b. The hardening component is a component obtained by polymerization of a photopolymerizable compound, and includes a polymer of a photopolymerizable compound. In addition to the above-mentioned polymer, components other than the organic solvent contained in the ink composition may be contained in the hardening component. In the first pixel portion 10a and the second pixel portion 10b, the first hardening component 13a and the second hardening component 13b may be the same or different, and the first light-scattering particles 12a and the second light-scattering particles 12b may be the same or the same. different.

The first luminescent particle 11a is a red luminescent nanocrystalline particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having an emission peak wavelength in the range of 605 to 665 nm. That is, the 1st pixel part 10a can be renamed as a red pixel part for converting blue light into red light. In addition, the second luminescent particles 11b are green luminescent nanocrystalline particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having an emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 10b can be renamed as a green pixel portion for converting blue light into green light.

The content of the luminescent particles in the luminescent pixel portion is based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of a more excellent effect of improving the external quantum efficiency and from the viewpoint of obtaining an excellent luminous intensity. Preferably it is 1 mass % or more, 2 mass % or more, or 3 mass % or more. The content of the luminescent particles is preferably 15% by mass or less based on the total mass of the cured product of the luminescent ink composition from the viewpoint of excellent reliability of the pixel portion and the viewpoint of obtaining excellent luminous intensity, 10 mass % or less, or 7 mass % or less.

The content of the light-scattering particles in the light-emitting pixel portion may be 0.1% by mass or more based on the total mass of the cured product of the light-emitting ink composition from the viewpoint of more excellent effect of improving the external quantum efficiency. , 1 mass % or more or 3 mass % or more. The content of the light-scattering particles may be 30 based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of a more excellent effect of improving the external quantum efficiency and the viewpoint of excellent reliability of the pixel portion. mass % or less, 25 mass % or less, 20 mass parts or less, 15 mass parts or less, or 10 mass % or less.

The third pixel portion 10 is a non-luminescent pixel portion (non-luminescent pixel portion) containing the cured product of the non-luminescent ink composition. The cured product does not contain light-emitting particles, but contains light-scattering particles and curing components. That is, the 3rd pixel part 10c contains the 3rd hardening component 13c, and the 3rd light-scattering particle 12c dispersed in the 3rd hardening component 13c. The 3rd hardening component 13c is a component obtained by superposing|polymerizing a polymerizable compound, for example, and contains the polymer of a polymerizable compound. The 3rd light-scattering particle 12c may be the same as the 1st light-scattering particle 12a and the 2nd light-scattering particle 12b, and may be different.

The third pixel portion 10c has, for example, a transmittance of 30% or more for light having a wavelength in the range of 420 to 480 nm. Therefore, the third pixel portion 10c functions as a blue pixel portion when a light source that emits light having a wavelength in the range of 420 to 480 nm is used. In addition, the transmittance of the 3rd pixel part 10c can be measured by the microspectroscopy apparatus.

The content of the light-scattering particles in the non-luminescent pixel portion may be 1 based on the total mass of the cured product of the non-luminescent ink composition from the viewpoint of further reducing the light intensity difference in the viewing angle. The mass % or more may be 5 mass % or more, or 10 mass % or more. The content of the light-scattering particles may be 80% by mass or less, or 75% by mass or less, based on the total mass of the cured product of the non-luminescent ink composition, from the viewpoint of further reducing light reflection. 70 mass % or less may be sufficient.

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. 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, 30 μm or less, 20 μm or less, or 15 μm or less.

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 preventing light leakage from the light source. The material constituting the light-shielding portion 20 is not particularly limited, and in addition to metals such as chromium, it can be used as a cured product of a resin composition containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the binder polymer, etc. . As the binder polymer used here, one or two or more kinds of polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, etc. can be used Resin mixture, photosensitive resin, O/W emulsion type resin composition (for example, one obtained by emulsifying reactive polysiloxane), etc. The thickness of the light shielding portion 20 may be, for example, 0.5 μm or more, or 10 μm or less.

The base material 40 is a transparent base material with light transmittance, for example, transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate, etc., transparent flexible base materials such as transparent resin films and optical resin films, etc. can be used. . Among these, it is preferable to use the glass substrate which consists of alkali-free glass which does not contain an alkali component in glass. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" manufactured by Corning Corporation, "AN100" manufactured by Asahi Glass Co., Ltd., "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. and "OA-11". These materials have a low coefficient of thermal expansion, and are excellent in dimensional stability and workability during high-temperature heat treatment.

The color filter 100 provided with the above light conversion layer 30 can be suitably used in the case of using a light source that emits light having a wavelength in the range of 420 to 480 nm.

The color filter 100 can be manufactured, for example, by a method of forming the light shielding portion 20 on the base material 40 in a pattern, and then forming the pixel portion 10 on the base material 40 in a pixel portion forming region divided by the light shielding portion 20 . . The pixel portion 10 can be formed by a method including the following steps: a step of selectively attaching an ink composition (inkjet ink) to the pixel portion forming region on the substrate 40 by an inkjet method; The composition is irradiated with active energy rays (such as ultraviolet rays) to harden the ink composition to obtain a light-emitting pixel portion. By using the above-mentioned luminescent ink composition as the ink composition, a luminescent pixel portion can be obtained, and by using a non-luminescent ink composition, a non-luminescent pixel portion can be obtained.

The method of forming the light-shielding portion 20 includes forming a thin film of a metal such as chromium, or a thin film of a resin composition containing light-shielding particles in a region on one surface side of the substrate 40 that serves as a boundary between a plurality of pixel portions, and applying the light-shielding particles to the thin film. Methods of thin film patterning, etc. The metal thin film can be formed by, for example, a sputtering method, a vacuum deposition method, or the like, and a thin film of a resin composition containing light-shielding particles can be formed by, for example, a method such as coating or printing. As a method of patterning, a photolithography method and the like are mentioned.

Examples of the inkjet method include a bubble inkjet (registered trademark) method using an electrothermal transducer as an energy generating element, a piezoelectric inkjet method using a piezoelectric element, and the like.

Curing of the ink composition can be performed using, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like. From the viewpoints of reducing the thermal load on the coating film and reducing power consumption, LEDs are preferred.

The wavelength of the irradiated light is preferably 250 nm to 440 nm, more preferably 300 nm to 400 nm. In the case of using an LED, from the viewpoint of sufficiently curing a film thickness of 10 μm or more, for example, it is preferably 350 to 400 nm or less. Furthermore, the intensity of light is preferably 0.2 to 2 kW/cm ² , more preferably 0.4 to 1 kW/cm ² . If the light intensity is less than 0.2 kW/cm ² , the coating film cannot be hardened sufficiently, and if the light intensity is 2 kW/cm ² or more, the hardening degree of the coating film surface and the interior will be uneven, and the coating film surface will be smooth. Sex becomes worse, so it is not good. The irradiation amount (exposure amount) of light is preferably 10 mJ/cm ² or more, and more preferably 4000 mJ/cm ² or less.

The hardening of the coating film can be carried out in the air or in an inert gas, but it is preferably carried out in an inert gas in order to suppress oxygen inhibition on the surface of the coating film and oxidation of the coating film. As an inert gas, nitrogen, argon, carbon dioxide, etc. are mentioned. By curing the coating film under such conditions, the coating film can be completely cured, so that the external quantum efficiency of the obtained light conversion layer can be further improved.

For example, the light conversion layer may further include a pixel portion (blue pixel portion) including a cured product of a luminescent ink composition containing blue luminescent nanocrystalline particles in place of the third pixel portion 10c, or in addition to the third pixel portion 10c. In addition to the pixel portion 10c, a pixel portion (blue pixel portion) including a cured product of an ink composition containing blue luminescent nanocrystalline particles is further provided. In addition, the light conversion layer may include a pixel portion (eg, a yellow pixel portion) including a cured product of a luminescent ink composition containing nanocrystalline particles that emit light other than red, green, and blue. In such cases, each luminescent particle contained in each pixel portion of the light conversion layer preferably has a maximum absorption wavelength in the same wavelength region.

Moreover, at least a part of the pixel part of a light conversion layer may be the hardened|cured material of the composition containing the pigment other than luminescent particle.

In addition, the color filter may include an ink repellent layer made of a material having ink repellency and having a width narrower than that of the light shielding portion on the pattern of the light shielding portion. In addition, the ink repellent layer may not be provided, and after the photocatalyst-containing layer as the wettability variable layer is formed in a fully coated state in the region including the pixel portion forming region, the photocatalyst-containing layer is exposed to light through a photomask, The ink affinity of the pixel portion formation region is selectively increased. As a photocatalyst, titanium oxide, zinc oxide, etc. are mentioned.

In addition, the color filter may include an ink-receiving layer containing hydroxypropyl cellulose, polyvinyl alcohol, gelatin, or the like between the substrate and the pixel portion.

In addition, the color filter may include a protective layer on the pixel portion. This protective layer is provided in order to flatten the color filter and prevent the components contained in the pixel portion, or the components contained in the pixel portion and the components contained in the photocatalyst-containing layer from being eluted into the liquid crystal layer. As the material constituting the protective layer, a known protective layer for color filters can be used.

Moreover, in the pixel part of the light conversion layer of this embodiment, in addition to the said luminescent particle, you may further contain the pigment whose color is substantially the same as the luminescent color of luminescent particle. In order to contain a pigment in a pixel part, you may contain a pigment in an ink composition.

In addition, one or both 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 may be set to not include light-emitting pixel portions. The pixel portion of the color material is contained as a property particle. As a color material which can be used here, a well-known color material can be used, For example, as a color material used for a red pixel part (R), a diketopyrrolopyrrole pigment and/or an anionic red organic dye can be mentioned. As the color material used in the green pixel portion (G), at least one selected from the group consisting of a copper halide phthalocyanine pigment, a phthalocyanine-based green dye, a mixture of a phthalocyanine-based blue dye, and an azo-based yellow organic dye can be used. A sort of. As a color material used for a blue pixel part (B), an ε-type copper phthalocyanine pigment and/or a cationic blue organic dye can be mentioned. The amount of these color materials used in the light conversion layer is preferably based on the total mass of the pixel portion (hardened product of the ink composition) from the viewpoint of preventing a decrease in transmittance. It is 1-5 mass %. [Example]

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.

The compound shown below was prepared as the hindered amine compound (A). (A-1) Flamestab NOR116FF (NOR type, melting point 108～123℃, molecular weight 2261) (A-2) TINUVIN (registered trademark) NOR371 (NOR type, melting point 91～104℃, molecular weight 2800～4000) (A-3) TINUVIN (registered trademark) 123 (NOR type, melting point <20°C (liquid), molecular weight 737) (A-4) TINUVIN (registered trademark) 144 (NR type, melting point 147-149°C, molecular weight 685) (A-5) ADK STAB (registered trademark) LA-72 (NR type, melting point <20°C (liquid state), molecular weight 509) Furthermore, (A-4) and (A-5) are not NOR-type hindered amine compounds, but NR-type hindered amine compounds, and have a structure in which a methyl group is bonded to a nitrogen atom.

(B-1) EFKA (registered trademark) PX-4701 was prepared as a polymer dispersant (B).

As antioxidants (C), (C-1) IRGANOX (registered trademark) 1010 (phenolic type) and (C-2) Hostanox (registered trademark) P-EPQ (phosphorus type) were prepared.

The compound shown below was prepared as a photopolymerizable compound (D). (D-1) Isobornyl methacrylate (LIGHT ESTER IB-X, monofunctional, cyclic, viscosity: 6mPa･s/25℃) (D-2) Lauryl methacrylate (LIGHT ESTER L, monofunctional, linear, viscosity: 3～8mPa･s/25℃) (D-3) Phenoxyethyl methacrylate (LIGHT ESTER PO, monofunctional, cyclic, viscosity: 7mPa･s/25℃) (D-4) 1,6-Hexanediol dimethacrylate (LIGHT ESTER 1,6-HX, bifunctional, linear, viscosity: 5～6mPa･s/25℃) (D-1) to (D-4) are all manufactured by Kyoeisha Chemical Co., Ltd.

The compounds shown below were prepared as the photopolymerization initiator (E). (E-1) Omnirad TPO-H (TPO-H) (E-2) Omnirad 819 (O-819) Both (E-1) and (E-2) are manufactured by IGM RESINS.

(F-1) Titanium oxide (CR60-2) was prepared as light-scattering particles (F).

<Preparation of Luminescent Particle (X) Dispersion> (Preparation of Luminescent Particle Dispersion) First, 0.81 g of cesium carbonate, 40 mL of 1-octadecene, and 2.5 mL of oleic acid were mixed to obtain a mixed solution. Next, this mixed liquid was dried under reduced pressure at 120° C. for 10 minutes, and then heated at 150° C. under an argon atmosphere. Thereby, a cesium-oleic acid solution was obtained. On the other hand, 138.0 mg of lead(II) bromide and 10 mL of 1-octadecene were mixed to obtain a mixed solution. Next, after drying the mixed solution under reduced pressure at 120° C. for 10 minutes, 1 mL of 3-aminopropyltriethoxysilane was added to the mixed solution under an argon atmosphere. Then, 1.3 mL of cesium-oleic acid solution was added to the said liquid mixture at 140 degreeC, and it reacted by heating and stirring for 5 seconds, and it cooled with an ice bath.

Next, after stirring the reaction liquid for 60 minutes in the atmosphere (23° C., humidity 45%), 20 mL of ethanol was added. After the obtained suspension was centrifuged (3,000 rpm, 5 minutes), the solid matter was collected to obtain luminescent particles X-1. This luminescent particle X-1 is a perovskite-type lead cesium tribromide crystal with a surface layer, and the average particle size is 10 nm as observed by a transmission electron microscope. In addition, the surface layer is a layer composed of 3-aminopropyltriethoxysilane, and its thickness is about 1 nm. That is, the luminescent particle X-1 is a particle|grains which were covered with silica. Furthermore, the luminescent particle dispersion liquid 1 in which the luminescent particle X-1 was dispersed was obtained by dispersing the luminescent particle X-1 in isobornyl methacrylate so that the solid content concentration might be 2.9 mass %.

<Preparation of Luminescent Particle Dispersion> The luminescent particle and the photopolymerizable compound were mixed to have the composition shown in Table 1, and were stirred with a rotary evaporator to obtain a luminescent sub-dispersion dispersion.

<Preparation of Light Scattering Particle Dispersion> In a container filled with nitrogen, 10.0 parts by mass of titanium oxide ("CR60-2" manufactured by Ishihara Sangyo Co., Ltd.), a polymer dispersant "EFKA PX4701" (amine value: 40.0 mgKOH/g, BASF Japan Co., Ltd. Production) 1.0 parts by mass and 14.0 parts by mass of phenoxyethyl methacrylate (LIGHT ESTER PO; manufactured by Kyōeisha Chemical Co., Ltd.) were mixed. Further, zirconia beads (diameter: 1.25 mm) were added to the obtained admixture, the container was sealed, and the admixture was shaken for 2 hours using a paint conditioner to disperse the admixture, thereby obtaining dispersion of light diffusing particles. body 1. The average particle diameter of the light-diffusing particles after the dispersion treatment was measured using NANOTRAC WAVE II, and found to be 0.245 μm.

<Preparation of ink composition> (Preparation of ink composition (1)) As the ink composition of Example 1, 5.15 parts by mass of luminescent particle dispersion 1 (luminous particle concentration: 2.9% by mass), 0.75 parts by mass of light-scattering particle dispersion 1 (40.0% by mass of titanium oxide content) were used as light 1.60 parts by mass of "lauryl methacrylate" (product name: LIGHT ESTER LM, manufactured by Kyōeisha Chemical Co., Ltd.) and "1,6-hexanediol dimethacrylate" (product name: LIGHT ESTER 1,6-HX, manufactured by Kyōeisha Chemical Co., Ltd.) 2.0 parts by mass, "diphenyl (2,4,6-trimethylbenzyl)phosphine oxide" as a photopolymerization initiator (Product name: Omnirad TPO-H, manufactured by BASF Japan Co., Ltd.) 0.3 parts by mass and "bis(2,4,6-trimethylbenzyl)phenylphosphine oxide" (Product name: Omnirad 819, BASF Japan Co., Ltd.) 0.15 parts by mass, as an antioxidant "neopentaerythritol [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]" (product name: Irganox (registered trademark) 1010, manufactured by BASF JAPAN Co., Ltd.) 0.05 parts by mass and "4 (2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4'-diyl Diphosphite" (product name: Hostanox (registered trademark) P-EPQ, manufactured by Clariant Chemicals Co., Ltd.) 0.05 parts by mass was mixed in a container filled with argon gas, and after uniformly dissolving, the dissolved material was used in a glove box. Filter through a filter with a pore size of 5 μm. Furthermore, argon gas was introduced into the container containing the obtained filtrate, and the container was saturated with argon gas. Next, the pressure was reduced to remove the argon gas, whereby an ink composition (1) was obtained. The content of the luminescent particles is 1.5% by mass, the content of IB-X is 50.0% by mass, the content of LM is 16.0% by mass, the content of PO is 4.2% by mass, the content of 1,6-HX is 20.0% by mass, and the content of TPO- The content of H was 3.0% by mass, the content of O-819 was 1.5% by mass, the content of Irganox 1010 was 0.5% by mass, the content of P-EPQ was 0.5% by mass, the content of light scattering particles was 3.0% by mass, and the polymer dispersed The content of the agent was 0.3% by mass. Furthermore, the above-mentioned content is the content based on the total mass of the ink composition.

(Preparation of Ink Compositions (2) to (9) and (C1) to (C3)) Light-emitting particle dispersion, light-scattering particle dispersion, photopolymerizable compounds D-2 and D-3, photopolymerization initiators E-1 and E-2, light stabilizers A-1 to A-5, Except that the addition amounts of antioxidants C-1 and C-2 were changed to the addition amounts shown in Table 1 below, Example 2 was obtained under the same conditions as in the preparation of the ink composition (1). Ink compositions (2) to (9) of ~9 and ink compositions (C1) to (C3) of Comparative Examples 1 to 3.

<Preparation of light conversion layer> The obtained ink composition was apply|coated on a glass substrate (Corning company make, "EagleXG") so that the film thickness after drying might become 15 micrometers by a spin coater. The obtained film was irradiated with ultraviolet light with a wavelength of 395 nm of an LED lamp at an exposure amount of 10 J/cm ² in a nitrogen environment. Thereby, the ink composition is cured, and a layer composed of the cured product of the ink composition is formed on the glass substrate, and this is used as a light conversion layer.

<Evaluation of ink composition and light conversion layer> (Example 1) <Viscosity of ink composition> Use an E-type viscometer to measure the viscosity (initial viscosity) of the ink composition at 30°C. <Coating film hardening> The surface of the obtained light conversion layer 1 was evaluated based on the following criteria by palpation using a cotton swab, and as a result, the surface was not damaged or sticky. [Evaluation Criteria] ⊚: No damage to the surface of the light conversion layer 1, and no stickiness. ○: The surface of the light conversion layer 1 is not damaged, and there is a little stickiness, but there is no practical problem. Δ: The surface of the light conversion layer 1 is slightly damaged and has a sticky feeling. ×: The surface of the light conversion layer 1 was damaged, and a part of the cured film adhered to the cotton swab.

<Exudation test> After the obtained light conversion layer 1 was allowed to stand at 60° C. for 30 days, it was further left to stand at 25° C. for 1 day, and then the surface of the light conversion layer 1 was visually inspected to confirm the presence or absence of exudation (components eluted from the light conversion layer 1 ). Whether there is exudation to the surface) and whether there is whitening (whether the surface of the light conversion layer 1 is whitened due to eluted components). ○: No bleeding and no whitening. △: There is bleeding, but no whitening. ×: Bleeding and whitening were present.

<Evaluation of light resistance at high temperature> (Lightfastness Test at High Temperature: Evaluation of External Quantum Efficiency (EQE)) An integrating sphere was placed above a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd. as a surface-emitting light source, and an emission spectrophotometer (trade name "MCPD-9800") manufactured by Otsuka Electronics Co., Ltd. connected to the integrating sphere. Next, the above-mentioned sample 1 for evaluation was inserted between the blue LED and the integrating sphere, the blue LED was lit, and the observed spectrum and the illuminance at each wavelength were measured with a radiation spectrophotometer. From the obtained spectrum and illuminance, the external quantum efficiency (EQE) was calculated as follows.

The external quantum efficiency is a value indicating the ratio of the degree to which light (photons) incident on the light conversion layer is emitted to the observer side in the form of fluorescence. Therefore, the larger the value, the more excellent the light-emitting properties of the light conversion layer, which is an important evaluation index. The external quantum efficiency (EQE) is calculated by the following formula (a). EQE[%]=P2/E(Blue)×100…(a) In the formula, E(Blue) represents the total value of “illuminance×wavelength÷hc” in the wavelength region of 380～490 nm, and P2 represents 500～650 The total value of "illuminance × wavelength÷hc" in the wavelength region of nm is equivalent to the number of photons observed. Furthermore, h represents Planck's constant, and c represents the speed of light. Here, the larger the numerical value of EQE, the smaller the deterioration of semiconductor nanocrystals caused by ultraviolet rays in the curing step of the coating film, that is, the more excellent the stability to ultraviolet rays. For use as a light conversion layer, the EQE is preferably 20% or more, more preferably 25% or more, meaning excellent. The EQE measured immediately after the production of the above-mentioned light conversion layer was taken as the initial external quantum efficiency EQE ₀ , and the EQE ₀ was measured and found to be 32%.

(Evaluation of External Quantum Efficiency Retention Rate) Next, the obtained light conversion layer was irradiated with LED light at 50° C. for 2 weeks. Taking the external quantum efficiency after irradiation as EQE _h , the external quantum retention [%] of the light conversion layer was calculated by the following formula (b), and the result was 81%. External quantum retention rate [%] = EQE _h /EQE ₀ ×100...(b) The light conversion layer is preferably other than EQE ₀ and EQE _h is also high. The higher the external quantum efficiency retention rate of the light conversion layer, the better the light resistance at high temperature.

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 1 2 3 Luminescent particle dispersion Luminous Particles (X) X-1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Photopolymerizable compound (D) D-1 50 50 50 50 50 50 50 50 50 50 50 50 Hindered amine solution D-2 16 15.5 16 15.5 16 15.5 15.5 15.5 15.5 16.5 15.5 15.5 D-4 20 20 20 20 20 20 20 20 20 20 20 20 Photopolymerization Initiator (E) E-1 3 3 3 3 3 3 3 3 3 3 3 3 E-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Hindered amine compound (A) A-1 NOR type 0.5 1 - - - - 0.5 - - - - - A-2 NOR type - - 0.5 1 - - - 0.5 - - - - A-3 NOR type - - - - 0.5 1 - - - - - - A-4 NR type - - - - - - - - - - 1 - A-5 NR type - - - - - - - - - - - 1 Antioxidant (C) C-1 - - - - - - 0.5 0.5 0.5 - - - C-2 - - - - - - 0.5 0.5 0.5 - - - Light Scattering Particle Dispersion Light Scattering Particles (F) F-1 3 3 3 3 3 3 3 3 3 3 3 3 Photopolymerizable compound (D) D-3 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 Polymer Dispersant (B) B-1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Evaluation Ink viscosity (mPa･s@30℃) 9.80 10.50 10.20 10.90 8.50 8.70 10.10 10.40 8.90 8.50 10.40 8.80 Hardness: 15μ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ○ ◎ ○ △ Exudation test ○ ○ ○ ○ △ △ ○ ○ △ ○ ○ △ High temperature light resistance test Coating film EQE% Retention % 81 85 83 87 79 81 84 84 81 39 58 56 initial 32 31 32 31 31 31 32 32 31 31 26 25 50℃ LED/2 weeks 26 26.5 26.5 27 24.5 25 27 27 25 12 15 14

As shown in Table 1, the ink compositions of Examples 1 to 9 containing the NOR-type hindered amine compound have the above-mentioned ink viscosity and excellent curability, so they are suitable as ink compositions for inkjet. Then, since the cured products of the ink compositions of Examples 1 to 9 are excellent in light resistance at high temperature, the ink compositions are suitable for the use of light conversion layers. Then, the ink compositions of Examples 1-4 and 7-8 containing NOR-type hindered amine compounds with a melting point exceeding 90° C. do not bleed and whiten on the surface of the light conversion layer 1 , which is particularly preferable.

On the other hand, the ink compositions of Comparative Example 1 containing no hindered amine compound at all and Comparative Examples 2 to 3 containing an NR-type hindered amine compound had insufficient light resistance at high temperatures.

10: Pixel part 10a: 1st pixel part 10b: 2nd pixel part 10c: 3rd pixel part 11a: The first luminescent particle 11b: Second luminescent particle 12a: The first light-scattering particle 12b: Second light-scattering particle 12c: Third light-scattering particle 20: Shading part 30: light conversion layer 40: Substrate 100: color filter

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

Claims (12)

An ink composition for inkjet, comprising: luminescent particles comprising semiconductor nanocrystalline particles composed of metal halides, a photopolymerizable compound, a photopolymerization initiator, and a compound having the following formula (1) Structure of NOR type hindered amine compound;

[In formula (1), R ¹ to R ⁵ each independently represent a hydrocarbon group, and * represents a bonding bond]. The ink composition for inkjet according to claim 1, wherein the melting point of the NOR-type hindered amine compound is 70°C or higher. The inkjet ink composition according to claim 1 or 2, wherein the mass average molecular weight of the NOR-type hindered amine compound is 1,000 or more. The ink composition for inkjet according to claim 1 or 2, wherein the luminescent particles are particles having a surface layer formed on the surfaces of the semiconductor nanocrystal particles, The surface layer contains a polymer of a silane compound having a bonding group capable of bonding with the surface of the semiconductor nanocrystal particles and a hydrolyzable silicon group. The ink composition for inkjet according to claim 1 or 2, wherein the luminescent particles further include an inner space capable of accommodating the semiconductor nanocrystal particles, and hollow particles having pores communicating with the inner space, and the above The semiconductor nanocrystal particles are accommodated in the inner space. The ink composition for inkjet according to claim 1 or 2, wherein the SP value of the photopolymerizable compound is 10.0 or less. The ink composition for inkjet according to claim 1 or 2, wherein the photopolymerizable compound has a cyclic structure. The ink-jet ink composition according to claim 1 or 2, which further contains light-scattering particles. The ink composition for inkjet according to claim 1 or 2, which further contains a polymer dispersant. As claimed in claim 1 or 2, the inkjet ink composition has a viscosity of 7-12 mPa･s at 30°C. A light conversion layer comprising a plurality of pixel portions and a light shielding portion disposed between the plurality of pixel portions, The above-mentioned plural pixel portions have light-emitting pixel portions including the cured product of the inkjet ink composition according to any one of claims 1 to 10. A color filter having the light conversion layer of claim 11.

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