JP7151914B2 - Nanocrystal-containing composition, ink composition, light conversion layer, and light-emitting device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a nanocrystal-containing composition, an ink composition using the composition, a light conversion layer containing a cured product of the ink composition, and a light emitting device having the light conversion layer.

BT2020, which is required as a next-generation display device, is an extremely ambitious standard, which is difficult to meet even with current color filters using pigments and organic EL. Quantum dots, on the other hand, are materials that emit red, green, blue, or other fluorescence with narrow half-value widths of emission wavelengths, and are attracting attention as light-emitting materials that can clear BT2020. In early quantum dots, core-shell nanoparticles using CdSe or the like were used, but InP or the like is recently used in order to avoid its harmfulness. However, since the emission wavelength of core-shell quantum dots is determined by the particle size, it is necessary to precisely control the dispersion of the particle size in order to obtain emission with a narrow half-width. There are many issues.

In recent years, luminescent nanocrystals made of metal halides, especially quantum dots having a perovskite crystal structure, have been discovered and are attracting attention. Common perovskite quantum dots (hereinafter sometimes referred to as “PeQDs”) are nano-sized crystal particles having a structure represented by CsPbX ₃ (X=Cl, Br, I). PeQDs are advantageous in terms of productivity compared to conventional quantum dots because the emission wavelength can be controlled by adjusting the proportion of halogen elements, and the particle size can be easily controlled compared to InP quantum dots. be.

Non-Patent Document 1 reports an ink composition containing PeQDs and poly(methyl methacrylate) (hereinafter sometimes referred to as "PMMA"). On the other hand, Patent Literature 1 points out that an ink composition containing PeQD and PMMA has a problem that the solvent resistance of the coating film is not always sufficient. Patent Document 1 discloses an ink composition containing PeQD and a photopolymerizable monomer, which may further contain a solvent, and in which the proportions of carbon, oxygen, and nitrogen contained in the photopolymerizable monomer and the solvent are specified. there is Furthermore, as a technique similar to Patent Document 1, Patent Document 2 discloses a curable composition containing fluorescent particles containing a perovskite compound, a photopolymerizable monomer, and a photopolymerization initiator, and defining the LogP value of the photopolymerizable monomer. A nanocrystal-containing composition as an article is disclosed. The technical point of Patent Documents 1 and 2 is considered to be that attention is focused on the polarity of the photopolymerizable monomer, and that the polarity is preferably low. However, as in the ink compositions or nanocrystal-containing compositions disclosed in these known documents, focusing only on the polarity of the photopolymerizable monomer is not sufficient to achieve both the dispersibility and emission properties of PeQDs. I had an inconvenience.

Patent No. 6506488 JP 2020-70443

Nano Lett. 2015, 15, 3692-3696

Accordingly, the problems to be solved by the present invention are a nanocrystal-containing composition excellent in dispersion stability and luminescence properties, an ink composition containing the composition, a light conversion layer containing a cured product of the ink composition, and An object of the present invention is to provide a light-emitting device having the light conversion layer.

As a result of intensive studies to solve the above problems, the present inventors have found that a ligand is provided on the surface of a luminescent nanocrystal made of a metal halide, and that the ligand and the photopolymerizable monomer satisfy specific conditions. The inventors have found that a nanocrystal-containing composition excellent in dispersion stability and luminescence properties can be provided by using a compound, and have completed the present invention.

で表され、式（Ｃ）中、ｎは屈折率を表し、Ｍは分子量を表し、ｄは密度を表す。）That is, the present invention contains one or more monomers and luminescent fine particles having one or more ligands on the surface of luminescent nanocrystals made of metal halides, and any photopolymerization When the absolute value |ΔMR| of the difference between the steric parameter MR of the steric monomer and the arbitrary steric parameter MR is calculated, there are at least one combination of a photopolymerizable monomer and a ligand that satisfies the following formula (A), and , for all combinations of each said photopolymerizable monomer and each said ligand contained in said nanocrystal-containing composition, the content of each said photopolymerizable monomer and each said ligand is equal to said luminescent nanocrystal A weighted average value |ΔMR| of |ΔMR| calculated in consideration of the coordination ratio on the surface of the nanocrystal-containing composition is provided, wherein the weighted average |ΔMR| _{weighted average} satisfies the following formula (B).
|ΔMR|=|(monomer steric parameter MR)−(ligand steric parameter MR)|≧12 (A)
|ΔMR| _{weighted average} ≧12 (B)
(However, the steric parameter MR is the following formula (C)

In formula (C), n represents the refractive index, M represents the molecular weight, and d represents the density. )

The present invention provides ink compositions comprising the nanocrystal-containing compositions described above.

The present invention provides a light conversion layer comprising a cured product of the ink composition described above.

The present invention provides a light-emitting device comprising the light conversion layer described above.

1 is a cross-sectional view showing an embodiment of luminescent fine particles contained in a luminescent nanocrystal-containing composition according to the present invention. FIG. FIG. 4 is a cross-sectional view showing another embodiment of luminescent fine particles contained in a luminescent nanocrystal-containing composition according to the present invention. 1 is a cross-sectional view showing an embodiment of a light emitting device according to the present invention; FIG. 1 is a schematic diagram showing the configuration of an active matrix circuit; FIG. 1 is a schematic diagram showing the configuration of an active matrix circuit; FIG.

Hereinafter, embodiments of the nanocrystal-containing composition, ink composition, light conversion layer and light-emitting device of the present invention and methods for producing them will be described in detail.

1. Nanocrystal-Containing Composition The nanocrystal-containing composition of the embodiment of the present invention comprises one or more photopolymerizable monomers and one or more coordination molecules on the surface of luminescent nanocrystals composed of metal halides. and luminescent particles with particles. A specific configuration of the light-emitting fine particles will be described later.

1-1. Conditions Concerning Steric Parameter The nanocrystal-containing composition of the present invention satisfies the following formula ( For all combinations of each of the photopolymerizable monomers and the ligands contained in the nanocrystal-containing composition, including at least one combination of the photopolymerizable monomers and the ligands that satisfies A) , the _weighted average value |ΔMR| (B) is satisfied.
|ΔMR|=|(monomer steric parameter MR)−(ligand steric parameter MR)|≧12 (A)
|ΔMR| _{weighted average} ≧12 (B)

The steric parameter MR of each photopolymerizable monomer or each ligand is represented by the following formula (C). In formula (C), n represents refractive index, M represents molecular weight, and d represents density.

The steric parameter MR is an index representing the three-dimensional size of the entire compound, which is used, for example, to investigate the correlation between molecular structure and pharmacological activity. -401, July issue, 1982” and “Journal of the Pesticide Science Society of Japan Experimental Technique Course Vol.38, No. 2, 195-203 (2013)”. Since the steric parameter MR is an index representing the overall size of a molecule, it is considered suitable as an index representing differences in the steric structures of compounds.

In the present invention, this steric parameter MR is applied as an index representing the difference in the steric structure of the compound that constitutes the photopolymerizable monomer or ligand. When the compound constituting the photopolymerizable monomer and the compound constituting the ligand contained in the nanocrystal-containing composition have structures similar to each other, |ΔMR| is a small value (for example, 10 or less). Become. In that case, in the nanocrystal-containing composition, the compound that constitutes the photopolymerizable monomer and the compound that constitutes the ligand have structures similar to each other, so that the ligand coordinated to the luminescent nanocrystal can emit light. As a result of being easily exchangeable with the polymerizable monomer, the energy level of the nanocrystals held by the ligands changes, resulting in changes in the luminescence properties and also in the dispersion stability, resulting in excellent luminescence properties. becomes difficult to maintain.

On the other hand, when |ΔMR| satisfies the formula (A), it means that the compound constituting the photopolymerizable monomer and the compound constituting the ligand have structures that are significantly different from each other. In that case, in the nanocrystal-containing composition, it is possible to suppress the exchange between the ligands that coordinate to the luminescent nanocrystals and the photopolymerizable monomer.

|ΔMR| is preferably 12 or more, more preferably 15 or more, and particularly preferably 20 or more. There is no particular upper limit for |ΔMR|. It is preferably 50 or less because the compatibility between the light-emitting fine particles having a ligand in and the photopolymerizable monomer is low.

When the nanocrystal-containing composition of the present invention contains two or more photopolymerizable monomers and two or more ligands, |ΔMR | satisfies the above formula (A), and the use of photopolymerizable monomers and ligands in which |ΔMR| does not satisfy the above formula (A) is not limited. For example, the nanocrystal-containing composition uses two photopolymerizable monomers P and Q and two ligands Y and Z, and |ΔMR| _PY in the combination of photopolymerizable monomer P and ligand Y is When the formula (A) is satisfied, |ΔMR| _PZ in the combination of the photopolymerizable monomer P and the ligand Z, | _ΔMR | |ΔMR| _QZ in the combination of monomer Q and ligand Z may or may not satisfy formula (A).

The nanocrystal-containing composition of the present invention satisfies |ΔMR| in at least one combination of a photopolymerizable monomer and a ligand and satisfies the above formula (A). A weighted average |ΔMR| _{weighted average} of |ΔMR| for all combinations of ligators satisfies the following equation (B). However, the |ΔMR| _{weighted average} is calculated in consideration of the content of each photopolymerizable monomer contained in the nanocrystal-containing composition and the proportion of each ligand coordinated to the surface of the nanocrystal.
|ΔMR| _{weighted average} ≧12 (B)

The weighted average |ΔMR| _weighted average |ΔMR| It means that the compound that constitutes the monomer and the compound that constitutes the ligand have structures that are significantly different from each other. In the nanocrystal-containing composition, since the above effect of suppressing the exchange of the ligands coordinating to the luminescent nanocrystals and the photopolymerizable monomer can be reliably obtained, excellent dispersion stability and excellent It is possible to achieve both the light emission characteristics and the light emission characteristics.

On the other hand, in the nanocrystal-containing composition, when the weighted average |ΔMR| _weighted average |ΔMR| of |ΔMR| Therefore, good dispersion stability and light emission properties cannot be ensured.

The |ΔMR| _{weighted average} is calculated by considering the content of each photopolymerizable monomer contained in the nanocrystal-containing composition and the proportion of each ligand coordinated to the surface of the nanocrystal. For example, the nanocrystal-containing composition contains m _P parts by weight of photopolymerizable monomer P (steric parameter MR _P ) and m _Q parts by weight of photopolymerizable monomer Q (steric parameter MR _Q ), When two types of ligands, a cationic ligand Y (steric parameter MR _Y ) and an anionic ligand Z (steric parameter MR _Z ), are coordinated to the surface of the luminescent nanocrystal, the following can be calculated by The |ΔMR| _{weighted average} is the same regardless of whether the nanocrystal-containing composition contains one or three or more photopolymerizable monomers or one or three or more ligands. can be calculated to

First, the absolute value |ΔMR| of the difference in the steric parameter for each combination of the photopolymerizable monomer and the ligand is calculated.
|ΔMR| _PY = |MR _P −MR _Y |
|ΔMR| _PZ =|MR _P -MR _Z |
|ΔMR| _QY =|MR _Q -MR _Y |
|ΔMR| _QZ = |MR _Q - MR _Z |

Next, _{| ΔMR |} calculate. If the ratio of coordination between the cationic ligand and the anionic ligand is known, it is preferable to calculate according to that ratio. For example, when the ligand Y and the ligand Z are coordinated to the surface of the luminescent nanocrystal at a ratio of r _Y :r _Z , the calculation is as follows.
|ΔMR| _{weighted average} ={(|ΔMR| _PY × _rY +|ΔMR| _PZ × _rZ )×mP ₊ (|ΔMR| _QY × _rY +|ΔMR| _QZ × _rZ )× _mQ }/ (mP _{+ mQ} )

However, if the coordination ratio between the ligand Y and the ligand Z is unknown, assuming that they are coordinated to the surface of the luminescent nanocrystal at a ratio of 0.5:0.5, Calculate as follows.
|ΔMR| _{weighted average} = {(|ΔMR| _PY × 0.5 + |ΔMR| _PZ × 0.5) × m _P + (|ΔMR| _QY × 0.5 + |ΔMR| _QZ × 0.5) × m _Q }/(m _P +m _Q )

In the combination of the photopolymerizable monomer and the ligand that satisfy the formula (A), at least one of the photopolymerizable monomer and the ligand is preferably a compound containing a cyclic structure. In particular, linear compounds such as oleylamine and oleic acid are often used as ligands on the surfaces of luminescent nanocrystals made of metal halides. When the ligand is a compound having such a linear molecular structure, it is particularly preferable to use a photopolymerizable monomer containing a cyclic structure. A photopolymerizable monomer containing a cyclic structure with a large steric hindrance is difficult to penetrate into a surface covered with a ligand having a linear molecular structure. It becomes difficult to exchange with On the other hand, when a compound containing a cyclic structure is used as a ligand, it is energetically disadvantageous for a linear photopolymerizable monomer having a shape different from that of the ligand to enter the luminescent nanocrystal. Exchange between the photopolymerizable monomer and the ligand becomes difficult to occur. Thus, by using a compound containing a cyclic structure for at least one of the photopolymerizable monomer and the ligand, exchange between the photopolymerizable monomer and the ligand can be suppressed. As a result, the surface of the luminescent nanocrystal made of metal halide can be stably covered with ligands, and an energy level trapped in the luminescent nanocrystal does not occur, resulting in a favorable Emission characteristics can be maintained.

In order to obtain a combination of a photopolymerizable monomer and a ligand that satisfies the formula (A), the photopolymerizable monomer is a compound containing a cyclic structure, or the ligand is a compound containing a compound having a cyclic structure. In the case of , it is preferable that the range of each preferred steric parameter is the range shown below.

(1) When a compound containing a cyclic structure is used as the photopolymerizable monomer, the steric parameter of the photopolymerizable monomer is in the range of 40 to 90, and the steric parameter of the ligand having a linear molecular structure is in the range of 60 to 110. is preferable in terms of maintaining a state in which the surface of the luminescent nanocrystal is stably covered with ligands. Furthermore, the steric parameter of the photopolymerizable monomer is in the range of 50 to 70, and the steric parameter of the ligand having a linear molecular structure is in the range of 80 to 90. It is particularly preferable for exhibiting the dispersion stability and luminescence properties of the polycrystalline nanocrystals.

(2) When a compound containing a cyclic structure is used as a ligand, the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 60 to 100, and the steric parameter of the ligand is in the range of 40 to 80. is preferable in order to keep the ligands stably covering the surface of the luminescent nanocrystal. Furthermore, the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 75-85, and the steric parameter of the ligand is in the range of 55-65. It is particularly preferable for exhibiting the dispersion stability and luminescence properties of the polycrystalline nanocrystals.

Specifically, the cyclic structure of the compound containing a cyclic structure can be represented by the following formulas (1-2) to (1-24). Each cyclic structure represented by formulas (1-2) to (1-24) can be bonded to other structural sites at any carbon atom in the cyclic structure.

Any —CH ₂ — in formulas (1-2) to (1-24) may be substituted with —O—, —S—, —N=, or —NH—. At least one of the photopolymerizable monomer or ligand is represented by formulas (1-3), (1-4), (1-6), (1-8), (1-10), (1-15) and A compound containing a cyclic structure represented by (1-19) to (1-24) is preferable because it is excellent in compatibility with the luminescent fine particles and can improve dispersibility. Furthermore, at least one of the photopolymerizable monomer or ligand is a compound containing a cyclic structure represented by formulas (1-3), (1-4) and (1-19) to (1-24) In this case, a high quantum yield can be ensured in addition to the dispersibility with the light-emitting fine particles, which is more preferable. In particular, compounds containing cyclic structures represented by formulas (1-3), (1-19) and (1-21) are more preferable because they can be used as both photopolymerizable monomers and ligands.

Any hydrogen atom in formulas (1-2) to (1-24) can be substituted with R ₁ . When R ₁ is a functional group, R ₁ may be a carboxyl group, a carboxylic anhydride 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, Mention may be made of sulfonic acid groups, boronic acid groups, amide groups, and thioamide groups. In particular, when the ligand is a compound containing a cyclic structure in which R ₁ is a carboxyl group, amino group, mercapto group, amide group, or thioamide group, it is possible to enhance the ability to coordinate to the light-emitting fine particles. preferable.

When R ₁ is an alkyl group, it represents a branched or linear alkyl group having 1 to 20 carbon atoms, and —CH ₃ at the end of the alkyl group is —NH ₂ , —OH, —SH, —COOH, — CONH ₂ , -CSNH ₂ , -CH ₂ - in the alkyl group may be substituted with -Si-, -NH- or -O-, and -(CH ₂ ) ₂ - may be substituted with -(CH=CH)-. The number of carbon atoms in R ₁ is preferably 1 to 10 in order to enhance the dispersibility with the luminescent fine particles, and the number of carbon atoms in R ₁ is preferably 1 to 5 in order to enhance the dispersibility with the luminescent fine particles and also increase the quantum yield. Especially preferred. In order to increase the quantum yield retention rate of the light-emitting fine particles, it is preferable to contain a polyalkoxysilane, polysilanol, or polysilazane structure capable of forming an inorganic coating layer containing Si.

When R ₁ is an alkoxy group, it represents a branched or linear alkoxyl group having 1 to 20 carbon atoms. —CH ₃ at the end of the alkoxy group may be substituted with —NH ₂ , —OH, —SH, —COOH, —CONH ₂ , —CSNH ₂ , and —CH ₂ — in the alkoxy group may be —Si It may be substituted with -, -NH- or -O-, and -(CH ₂ ) ₂ - in the alkoxy group may be substituted with -(CH=CH)-. The number of carbon atoms in R ₁ is preferably 1 to 10 in order to enhance the dispersibility with the luminescent fine particles, and the number of carbon atoms in R ₁ is preferably 1 to 5 in order to enhance the dispersibility with the luminescent fine particles and also increase the quantum yield. Especially preferred. In order to increase the quantum yield retention rate of the light-emitting fine particles, it is preferable to contain a polyalkoxysilane, polysilanol, or polysilazane structure capable of forming an inorganic coating layer containing Si.

Arbitrary hydrogen atoms in the above formulas (1-2) to (1-24) can be substituted with P. Each P is independently represented by the following general formulas (P-1) to (P-16). A black point in the formula represents a bond. When two or more P are present, they may be the same or different.

More preferably, (P-1), (P-2), and (P-3) are preferable, and (P-2) and (P-3) are preferable in that they can suppress the decrease in the quantum yield of the luminescent fine particles, (P-2) is particularly preferred.

When using a compound containing a cyclic structure represented by (1-2) to (1-24) as the photopolymerizable monomer, more specifically the following formulas (1-3-1) to (1-3- 8), (1-4-1) ~ (1-4-8), (1-19-1) ~ (1-19-16), (1-21-1) ~ (1-21-8) , (1-22-1) ~ (1-22-4), (1-23-1) ~ (1-23-8) and (1-24-1) ~ (1-24-4) can be preferably used. In the following formula, x and z are each independently preferably 0 to 18, and y and zz are each independently preferably 1 to 18. Furthermore, in order for the steric parameter of the photopolymerizable monomer comprising the compound containing these cyclic structures to be 40 to 90, x and z in the following formula are each independently preferably 0 to 5, and y and zz are preferably 1 to 5 independently. In order for the steric parameter to be 60 to 70 while maintaining the dispersibility with the light emitting fine particles, the following formulas (1-3-1) to (1-3-6), (1-4-1) to ( 1-4-8), (1-19-1) ~ (1-19-8), (1-21-1) ~ (1-21-4), (1-22-1) ~ (1- 22-4), compounds represented by (1-23-5) to (1-23-8) are preferred, and x and z in the following formula are each independently preferably 0 to 5, and y and zz are preferably 1 to 5 independently. Furthermore, when it is desired to increase the steric parameter above 65 as a cyclic structure, (1-19-1) to (1-19-8) having an adamantyl structure, or 1,2,2,6,6-pentamethyl-4 - (1-23-5) ~ (1-23-8) having a piperidyl structure are particularly preferred, x and z in the following formula are each independently preferably 0 to 5, and y and zz are each independently 1 to 5 is particularly preferred.

As described above, when using a compound in which the steric parameter of the photopolymerizable monomer having a cyclic molecular structure is 40 to 90, a suitable combination of ligands is a ligand having a linear molecular structure. The steric parameter of is preferably in the range of 60 to 110, more preferably the steric parameter of the photopolymerizable monomer having a cyclic molecular structure is 50 to 70, and the ligand having a linear molecular structure More preferably, the steric parameter will be in the range of 80-90. As a ligand compound that satisfies such conditions, a ligand having a terminal functional group of carboxylic acid or amine is preferable. Moreover, it is preferable to use these ligands whose terminal functional groups are carboxylic acids or amines at a ratio of 1:1.

As the ligand having a linear molecular structure with a terminal functional group of carboxylic acid, specifically, the following compounds are preferable, and (1) tridecanoic acid, 2-tridecenoic acid, myristic acid, pentadecanoic acid, cis-9-hexadecenoic acid, palmitic acid, 2-hexadecenoic acid, heptadecanoic acid, petroselinic acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, cis-5,8, 11,14,17-eicosapentaenoic acid, cis-8,11,14-eicosatrienoic acid, arachidonic acid, nonadecanic acid, arachidic acid, heneicosanoic acid, cis-4,7,10,13,16,19-docosahexaene Acid, erucic acid, behenic acid, lignoceric acid, and tricosanoic acid are preferred as coordinations in which the steric parameter of the ligand is 60 to 110, and (2) more preferred are pentadecanoic acid, cis-9-hexadecenoic acid, and palmitic acid. acid, 2-hexadecenoic acid, heptadecanoic acid, petroselinic acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, cis-5,8,11,14,17-eicosapentaene Acids, cis-8,11,14-eicosatrienoic acid, arachidonic acid, nonadecanic acid, arachidic acid, and heneicosanoic acid are preferred as coordinations in which the steric parameter of the ligand is 70 to 100, and (3) is particularly preferred. Heptadecanoic acid, petroselinic acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid and oleic acid are particularly preferred as ligands having a steric parameter of 80-90.

As the ligand having a linear molecular structure with an amine terminal functional group, specifically, the following compounds are preferable, and (1) dodecylamine, tetradecylamine, 1-aminotridecane, 1- Aminopentadecane, hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecane-9-amine, oleylamine, 1-aminononadecane, 2-n-octyl-1-dodecylamine have ligand steric parameters of 60 ~110 coordination, more preferably (2) 1-aminopentadecane, hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecane-9-amine, oleylamine, 1-aminononadecane, 2- n-octyl-1-dodecylamine is preferred as a coordination with a steric parameter of the ligand of 70 to 100, and (3) hexadecylamine, 1-aminoheptadecane, stearylamine and heptadecane-9 are particularly preferred. -Amine and oleylamine are particularly preferred as ligands with a steric parameter of 80-90.

On the other hand, when a compound containing a cyclic structure represented by (1-2) to (1-24) is used as a ligand to be coordinated to the surface of a luminescent nanocrystal made of a metal halide, the compound containing a cyclic structure In order for the steric parameter of the ligand to be in the range of 40 to 80, compounds represented by the following (1-19-A) to (1-19-H) can be preferably used, (1 -19-A) to (1-19-F) are particularly preferred. xx and yy in the following formula are each independently preferably 1 to 18, and in order for the steric parameter of the ligand to be in the range of 55 to 65, xx and yy in the following formula are each independently 1 to 5 are more preferable.

When using a compound having a steric parameter of a ligand having a cyclic molecular structure of 40 to 80, a photopolymerizable monomer having a linear molecular structure, which is a suitable combination, has a linear molecular structure. The steric parameter of the photopolymerizable monomer is preferably in the range of 50 to 100, more preferably the steric parameter of the ligand having a cyclic molecular structure is 55 to 65, and the light has a linear molecular structure. More preferably, the steric parameter of the polymerizable monomer is in the range of 75-85. Specifically, it is preferable to use the compounds shown below.

(1) Examples of methacrylate compounds include nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, and hexadecyl methacrylate. Decyl, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, and heptadecyl acrylate have a linear molecular structure with a steric parameter ranging from 60 to 100. Preferred as the polymerizable monomer, more preferably (2), the methacrylate compounds are dodecyl methacrylate and tridecyl methacrylate, and the acrylate compounds are decyl acrylate, undecyl acrylate, dodecyl acrylate, and tetradecyl acrylate. It is particularly preferred as a photopolymerizable monomer having a linear molecular structure with a parameter in the range of 75-85.

More specifically, preferred combinations of photopolymerizable monomers and ligands that satisfy the above formula (A) are the following combinations.

When a compound containing a cyclic structure is used as the photopolymerizable monomer, the steric parameter of the photopolymerizable monomer is in the range of 40 to 90, and the steric parameter of the ligand having a linear molecular structure is in the range of 60 to 110. is preferable for maintaining a state in which the surface of the luminescent nanocrystal is stably covered with a ligand. -1) ~ (1-3-8), (1-4-1) ~ (1-4-8), (1-19-1) ~ (1-19-16), (1-21-1 ) ~ (1-21-8), (1-22-1) ~ (1-22-4), (1-23-1) ~ (1-23-8) and (1-24-1) ~ A compound represented by (1-24-4), wherein x and z are each independently 0 to 5, and y and zz are each independently 1 to 5, a photopolymerizable monomer and a ligand having a linear molecular structure with a terminal functional group of carboxylic acid having a steric parameter of 60 to 110, tridecanoic acid, 2-tridecenoic acid, myristic acid, pentadecanoic acid, cis-9 - hexadecenoic acid, palmitic acid, 2-hexadecenoic acid, heptadecanoic acid, petroselinic acid, linoleic acid, gamma-linolenic acid, stearic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, cis-5,8,11,14 , 17-eicosapentaenoic acid, cis-8,11,14-eicosatrienoic acid, arachidonic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, cis-4,7,10,13,16,19-docosahexaenoic acid, eruca Acid, behenic acid, lignoceric acid, and tricosanoic acid have a steric parameter of 60 to 110. Ligands having a linear molecular structure with amine terminal functional groups include dodecylamine, tetradecylamine, 1 - selected from aminotridecane, 1-aminopentadecane, hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecane-9-amine, oleylamine, 1-aminononadecane, 2-n-octyl-1-dodecylamine, It is preferred to combine ligands that are

More preferably, the steric parameter of the photopolymerizable monomer is in the range of 50 to 70, and the steric parameter of the ligand having a linear molecular structure is in the range of 80 to 90. Particularly preferable for exhibiting dispersion stability and luminescence properties of the luminescent nanocrystals, specifically, as a photopolymerizable monomer having a steric parameter of 50 to 70, -3-6), (1-4-1) ~ (1-4-8), (1-19-1) ~ (1-19-8), (1-21-1) ~ (1-21 -4), (1-22-1) ~ (1-22-4), (1-23-5) ~ (1-23-8), (1-24-1) ~ (1-24-4) (1-3-5), (1-3-6), (1-3-5), (1-3-6), (1- 4-5) ~ (1-4-8), (1-19-3) ~ (1-19-8), (1-21-3), (1-21-4), (1-22- 3), (1-22-4), (1-23-3), (1-23-4), (1-23-7), (1-23-8), (1-24-3) , (1-24-4) is preferred, and among (1-24-3) and (1-24-4), while maintaining the dispersion stability of the QD dispersion or QD ink, the QD (1-24-4) is preferable in order to increase the PLQY retention rate of the dispersion and the light conversion layer. 1-19-1) ~ (1-19-8), or (1-23-5) ~ (1-23-8) having a 1,2,2,6,6-pentamethyl-4-piperidyl structure Particularly preferably, in the formula, x and z are each independently 0 to 5, y and zz are each independently 1 to 5, and a terminal functional having a steric parameter of 80 to 90 Ligands having a linear molecular structure in which the group is a carboxylic acid include heptadecanoic acid, petroselinic acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid, oleic acid, and steric parameters of 80 to 90. Ligands having a linear molecular structure with terminal functional groups of amines include ligands selected from hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecane-9-amine, and oleylamine. are preferably combined, especially as ligands in the alkyl chain Petroceric acid, linoleic acid, γ-linolenic acid, linolenic acid, oleic acid, and oleylamine with double bonds at the nuclei exhibit ligand coating stability, luminescent nanocrystal dispersion stability, and luminescent properties. Especially preferred above.

(2) When a compound containing a cyclic structure is used as a ligand, the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 60 to 100, and the steric parameter of the ligand is in the range of 40 to 80. In order to maintain a state in which the surface of the luminescent nanocrystal is stably covered with a ligand, specifically, light having a linear molecular structure with a steric parameter of 60 to 100 As the polymerizable monomer, an acrylate compound or a methacrylate compound having 6 to 17 carbon atoms is preferable, and as a ligand containing a cyclic structure having a steric parameter of 40 to 80, Compounds represented by -H) are preferred.

More preferably, the photopolymerizable monomer having a linear molecular structure with a steric parameter of 75 to 85 is preferably an acrylate compound or a methacrylate compound having 11 to 13 carbon atoms, which enhances the luminescent properties of the luminescent nanocrystal. Methacrylate compounds are preferable to acrylate compounds for enhancement, and the steric parameter is in the range of 55-65. compounds are particularly preferred for exhibiting coating stability of ligands, dispersion stability of luminescent nanocrystals, and luminescent properties.

1-2. Light-Emitting Fine Particles Light-emitting fine particles contained in the nanocrystal-containing composition described above will be described. Luminescent fine particles 910 shown in FIG. 1 have one or more ligands on the surface of luminescent nanocrystals 911 . A ligand layer 912 is formed by a large number of ligands coordinated to the surface of the luminescent nanocrystal 911 .

1-2-1. Luminescent Nanocrystal First, the luminescent nanocrystal 911 (hereinafter sometimes simply referred to as “nanocrystal 911”) will be described. Luminescent nanocrystals are nano-sized semiconductor nanocrystals (nanocrystal particles) that are made of metal halides and absorb excitation light to emit fluorescence or phosphorescence.

Quantum dots having a perovskite crystal structure, which will be described later, are widely known as luminescent nanocrystals made of metal halides. The luminescent nanocrystal is, for example, a crystal having a maximum particle size (or an average particle size) of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope. The luminescent nanocrystals can be excited, for example, by light energy of a predetermined wavelength or electrical energy to emit fluorescence or phosphorescence.

Luminescent nanocrystals made of metal _halides are made of compounds represented _by the general formula: _AaMmXx .
wherein A is at least one of an organic cation and a metal cation. Organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea and the like, and metal cations include cations such as Cs, Rb, K, Na and Li.
M is at least one metal cation. Metal cations selected from groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14 and 15 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, Cations such as Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, and Zr are included.
X is at least one anion. Anions include chloride ion, bromide ion, iodide ion, cyanide ion, etc., and contain at least one halogen.
a is an integer of 1-7, m is an integer of 1-4, and x is an integer of 3-16.

Specifically, the compound represented by the general _{formula AaMmXx} is _{AMX , A4MX} , _AMX2 , _AMX3 , _{A2MX3 , AM2X3} , _{A2MX4 , A2MX 5 , A3MX5 , A3M2X5 , A3MX6 , A4MX6 , AM2X6 , A2MX6 , A4M2X6 , A3MX8 , A3M2 _ _} Compounds represented by X ₉ , A ₃ M ₃ X ₉ , A ₂ M ₂ X ₁₀ and A ₇ M ₃ X ₁₆ are preferred.
wherein A is at least one of an organic cation and a metal cation. Organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, protonated thiourea and the like, and metal cations include cations such as Cs, Rb, K, Na and Li.
wherein 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 cations (M ¹ _α M ² _β M ³ _γ M ⁴ _δ ) and the like. However, α, β, γ, and δ each represent a real number between 0 and 1, and α+β+γ+δ=1. Metal cations selected from groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14 and 15 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, Cations such as Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, and Zr are included.
In the formula, X is an anion containing at least one halogen. Specifically, one type of halogen anion (X ¹ ), two types of halogen anions (X ¹ _α X ² _β ), and the like are included. Anions include chloride ion, bromide ion, iodide ion, cyanide ion, etc., and contain at least one halogen.

The compound composed of the metal halide represented _by the _above general formula _AaMmXx is doped with metal ions such as Bi, Mn, Ca, Eu, Sb, and Yb in order to improve the light emission characteristics. may be

Among the compounds composed of metal _halides represented by the general formula _AaMmXx , the compound having a perovskite-type crystal structure is adjusted by adjusting the particle size, the type and abundance of metal cations constituting the _M site, Furthermore, it is particularly preferable for use as a luminescent nanocrystal in that the emission wavelength (emission color) can be controlled by adjusting the type and abundance of the anion that constitutes the X site. 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. Also, the compound having the perovskite crystal structure may be doped with metal ions such as Bi, Mn, Ca, Eu, Sb, and Yb, as described above.

Among compounds exhibiting a perovskite crystal structure, A is Cs, Rb, K, Na, or Li, and M is one kind of metal cation (M ¹ ), or two kinds of It is preferably a metal cation (M ¹ _α M ² _β ) and X is chloride, bromide or iodide. However, α and β each represent a real number between 0 and 1, and α+β=1. Specifically, M may be selected from Ag, Au, Bi, Cu, Eu, Fe, Ge, K, In, Na, Mn, Pb, Pd, Sb, Si, Sn, Yb, Zn, Zr. preferable.

As specific compositions of luminescent nanocrystals made of metal halides exhibiting a perovskite crystal structure, luminescent nanocrystals using Pb as M such as CsPbBr ₃ , CH ₃ NH ₃ PbBr ₃ , CHN ₂ H ₄ PbBr ₃ are It is preferable because it is excellent in light intensity and excellent in quantum efficiency. Luminescent nanocrystals using metal cations other than Pb as M, such as CsSnBr ₃ , CsEuBr ₃ CsYbI ₃ , etc., are preferable because they have low toxicity and little impact on the environment.

Luminescent nanocrystals may be red-emitting crystals that emit light with an emission peak in the wavelength range of 605-665 nm (red light), and light with an emission peak in the wavelength range of 500-560 nm (green light). It may be a green light-emitting crystal that emits , or a blue light-emitting crystal that emits light (blue light) having an emission peak in the wavelength range of 420 to 480 nm. Also, in one embodiment, a combination of different types of luminescent nanocrystals may be used. The wavelength of the emission peak of the luminescent nanocrystal can be confirmed, for example, in the fluorescence spectrum or phosphorescence spectrum measured using an absolute PL quantum yield spectrometer.

Red-emitting luminescent nanocrystals are 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less, 640 nm or less, 637 nm or less, 635 nm. Hereinafter, it is preferable to have an emission peak in a wavelength range of 632 nm or less or 630 nm or less, and has an emission peak in a wavelength range of 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more, 610 nm or more, 607 nm or more, or 605 nm or more is preferred. These upper and lower limits can be combined arbitrarily. In addition, in the following similar description, the upper limit value and the lower limit value described individually can be combined arbitrarily.

Green-emitting luminescent nanocrystals emit in a wavelength range of 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less, or 530 nm or less. It preferably has an emission peak in a wavelength range of 528 nm or longer, 525 nm or longer, 523 nm or longer, 520 nm or longer, 515 nm or longer, 510 nm or longer, 507 nm or longer, 505 nm or longer, 503 nm or longer, or 500 nm or longer.

Blue-emitting luminescent nanocrystals emit in a wavelength range of 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm or less, or 450 nm or less. It preferably has an emission peak in a wavelength range of 450 nm or more, 445 nm or more, 440 nm or more, 435 nm or more, 430 nm or more, 428 nm or more, 425 nm or more, 422 nm or more, or 420 nm or more.

The shape of the luminescent nanocrystals is not particularly limited and may be any geometric shape or any irregular shape. Examples of the shape of the luminescent nanocrystal include cuboid, cubic, spherical, tetrahedral, ellipsoidal, pyramidal, disk-like, branch-like, net-like, and rod-like. The shape of the luminescent nanocrystals is preferably rectangular parallelepiped, cubic or spherical.

The average particle size (volume average size) of the luminescent nanocrystals is preferably 40 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less. The average particle size of the luminescent nanocrystals is preferably 1 nm or more, more preferably 1.5 nm or more, and even more preferably 2 nm or more. Luminescent nanocrystals having such an average particle size are preferable because light of a desired wavelength can be obtained easily. The average particle size of the luminescent nanocrystals is obtained by measuring with a transmission electron microscope or scanning electron microscope and calculating the volume average size.
preferable.

1-2-2. Ligands When synthesizing luminescent nanocrystals made of metal halides, ligands coordinate to the surface of the formed luminescent nanocrystals to suppress crystal growth and obtain nano-sized crystals. is required for In addition, since the ligand can stably cover the surface of the luminescent nanocrystal made of metal halide, the ligand can prevent the generation of a trap level on the surface of the luminescent nanocrystal, resulting in good light emission. characteristics can be maintained. Furthermore, the ligand has the function of enhancing the compatibility with the photopolymerizable monomer and ensuring the dispersibility of the luminescent nanocrystals by coordinating to the surface of the luminescent nanocrystals made of inorganic materials. . Therefore, the loss of ligands from the surface of luminescent nanocrystals leads to aggregation of luminescent nanocrystals and deterioration of luminescent properties and dispersibility. Therefore, it is important to stably coordinate to the surface of the luminescent nanocrystal. As the ligand that coordinates to the surface of the luminescent nanocrystal, there is one ligand that satisfies the above formula (A) when combined with any photopolymerizable monomer contained in the nanocrystal-containing composition. In addition to the essential use of the above, ligands that do not satisfy the above formula (A) may also be used. Further, as the ligand, in addition to the compound containing the cyclic structure, a compound containing a linear structure without a cyclic structure can also be used.

As a ligand having such a linear structure, a compound having a binding group that binds to the cation or anion contained in the luminescent nanocrystal is preferable. Examples of binding groups include carboxyl group, carboxylic anhydride group, amino group, ammonium group, mercapto group, phosphine group, phosphine oxide group, phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfonic acid group, amide It is preferably at least one of a group, a thioamide group and a boronic acid group, more preferably at least one of a carboxyl group and an amino group. Examples of such ligands include carboxyl group- or amino group-containing compounds and the like, and these ligands may be used singly or in combination of two or more.

Carboxyl group-containing compounds include, for example, linear or branched aliphatic carboxylic acids having 1 to 30 carbon atoms. Specific examples of such carboxyl group-containing compounds include arachidonic acid, crotonic acid, trans-2-decenoic acid, erucic acid, 3-decenoic acid, cis-4,7,10,13,16,19-docosahexaenoic acid. , 4-decenoic acid, all cis-5,8,11,14,17-eicosapentaenoic acid, all cis-8,11,14-eicosatrienoic acid, cis-9-hexadecenoic acid, trans-3-hexenoic acid , trans-2-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 2-hexadecenoic acid, linolenic acid, linoleic acid, γ-linolenic acid, 3-nonenoic acid, 2-nonenoic acid, trans-2-octenoic acid , petroselinic acid, elaidic acid, oleic acid, 3-octenoic acid, trans-2-pentenoic acid, trans-3-pentenoic acid, ricinoleic acid, sorbic acid, 2-tridecenoic acid, cis-15-tetracosenoic acid, 10-undecene acid, 2-undecenoic acid, acetic acid, butyric acid, behenic acid, cerotic acid, decanoic acid, arachidic acid, heneicosanoic acid, heptadecanoic acid, heptanoic acid, hexanoic acid, heptacosanoic acid, lauric acid, myristic acid, melisic acid, octacosanoic acid, nonadecanic acid, nonacosanoic acid, n-octanoic acid, palmitic acid, pentadecanoic acid, propionic acid, pentacosanoic acid, nonanoic acid, stearic acid, lignoceric acid, tricosanoic acid, tridecanoic acid, undecanoic acid, valeric acid and the like.

Examples of amino group-containing compounds include linear or branched aliphatic amines having 1 to 30 carbon atoms. Specific examples of such amino group-containing compounds include 1-aminoheptadecane, 1-aminononadecane, heptadecane-9-amine, stearylamine, oleylamine, 2-n-octyl-1-dodecylamine, allylamine, and amylamine. , 2-ethoxyethylamine, 3-ethoxypropylamine, isobutylamine, isoamylamine, 3-methoxypropylamine, 2-methoxyethylamine, 2-methylbutylamine, neopentylamine, propylamine, methylamine, ethylamine, butylamine, hexylamine , heptylamine, n-octylamine, 1-aminodecane, nonylamine, 1-aminoundecane, dodecylamine, 1-aminopentadecane, 1-aminotridecane, hexadecylamine, tetradecylamine and the like.

1-2-3. Method for Preparing Light-Emitting Fine Particle Next, a method for preparing the light-emitting fine particle 910 shown in FIG. 1 will be described. Luminous fine particles 910 are provided with one or more of the above-described ligands on the surface of luminescent nanocrystals 911 , and by a large number of ligands coordinated on the surface of luminescent nanocrystals 911 , A ligand layer 912 is provided. As a method for manufacturing such light-emitting fine particles 910, there are a method with heating and a method without heating.

First, an example of a method of manufacturing the light-emitting fine particles 910 by heating will be described. _First , two solutions containing raw material compounds capable of synthesizing the compound represented by the general formula _{AaMbXc (} hereinafter sometimes referred to as "semiconductor raw material-containing solutions") are prepared. Of the two semiconductor raw material-containing solutions, one is a solution containing a compound containing A or a compound containing A and X, and the other is a solution containing a compound containing M and X. At this time, a compound capable of forming a ligand that satisfies the above formula (A) is added to at least one of the semiconductor raw material-containing solutions.

Next, these two semiconductor raw material-containing solutions are mixed in an inert gas atmosphere and reacted at a temperature of 140 to 260.degree. Next, the nanocrystals are precipitated by cooling to -20 to 30°C and stirring. The deposited nanocrystal 911 has a ligand layer 912 formed of ligands coordinated on its surface. By recovering the nanocrystals 911 by a standard method such as centrifugation, the luminescent fine particles 910 can be obtained.

Specifically, for example, a solution containing cesium carbonate as a semiconductor raw material, oleic acid as a ligand, and an organic solvent is prepared. As an organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. At this time, it is preferable to adjust the respective amounts to be added so that 0.2 to 2 g of cesium carbonate and 0.1 to 10 mL of oleic acid are added to 40 mL of the organic solvent. The obtained solution is dried under reduced pressure at 90 to 150° C. for 10 to 180 minutes, and then heated to 100 to 200° C. in an inert gas atmosphere such as argon or nitrogen to obtain a cesium-oleic acid solution.

On the other hand, a solution containing lead (II) bromide, which is a semiconductor raw material, and the same organic solvent as described above is prepared. At this time, 20 to 100 mg of lead (II) bromide and 0.1 to 10 mL of oleylamine are added to 5 mL of the organic solvent. The resulting solution is dried under reduced pressure at 90-150° C. for 10-180 minutes.

Then, while the solution containing lead (II) bromide is heated to 140 to 260° C., the above-described cesium-oleic acid solution is added, and the mixture is reacted by heating and stirring for 1 to 10 seconds to obtain the reaction. Cool the liquid in an ice bath. At this time, it is preferable to add 0.1 to 1 mL of the cesium-oleic acid solution to 5 mL of the solution containing lead (II) bromide. During stirring at −20 to 30° C., nanocrystals 911 made of lead cesium tribromide are precipitated, and oleic acid and oleylamine are coordinated to the surfaces of the nanocrystals 911 .

The obtained suspension is centrifuged to recover the solid, and the solid is added to toluene to form a ligand layer of oleic acid and oleylamine on the surface of the nanocrystals 911 to which oleic acid is coordinated. A luminescent fine particle dispersion liquid in which the luminescent fine particles 910 having 912 are dispersed in toluene can be obtained.

Next, an example of a method for manufacturing the light-emitting fine particles 910 without heating will be described. First, a solution containing raw material compounds capable of synthesizing semiconductor nanocrystals by reaction is prepared. At this time, a compound capable of forming a ligand that satisfies the above formula (A) is added to the raw material compound-containing solution. Then, the resulting solution is added to a large amount of an organic solvent which is a poor solvent for nanocrystals, thereby precipitating nanocrystals with ligands coordinated to their surfaces. At this time, the amount of the organic solvent used is preferably 10 to 1000 times the mass of the semiconductor nanocrystals.

Specifically, as the semiconductor raw material-containing solution, for example, a solution containing lead (II) bromide, cesium bromide, a compound forming a ligand satisfying the above formula (A), and an organic solvent is used. Prepare. The organic solvent may be any good solvent for nanocrystals, but dimethylsulfoxide, N,N-dimethylformamide, N-methylformamide, and mixed solvents thereof are preferred from the viewpoint of compatibility. At this time, it is preferable to adjust the amounts of lead (II) bromide and cesium bromide to be 50 to 200 mg and 10 to 100 mg, respectively, relative to 10 mL of the organic solvent.

Then, 0.1 to 5 mL of the above solution containing lead (II) bromide and cesium bromide is added to a large amount of negative solvent, stirred in the atmosphere for 5 to 180 seconds, and then centrifuged to obtain a solid. recover. When the mixture is added to a large amount of negative solvent, nanocrystals 911 are precipitated, and a compound that forms a ligand that satisfies the above formula (A) is coordinated to the surface of the nanocrystals 911 .

By adding this recovered solid matter to toluene, coated light-emitting fine particles 910 having a ligand layer 912 of a compound that forms a ligand that satisfies the above formula (A) on the surface of the nanocrystals 911 are obtained. A luminescent fine particle dispersion liquid dispersed in toluene can be obtained.

1-3. Photopolymerizable monomer As the photopolymerizable monomer used in the present invention, in addition to the photopolymerizable monomer containing the cyclic structure, a general photoradical polymerizable monomer that polymerizes by irradiation with light can be used. It may be a polymerizable monomer or oligomer. These are used together with a photoinitiator. A photopolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

A (meth)acrylate compound is mentioned as such a radically photopolymerizable monomer. The (meth)acrylate compound may be a monofunctional (meth)acrylate having one (meth)acryloyl group, or may be a polyfunctional (meth)acrylate having multiple (meth)acryloyl groups.

From the viewpoint of excellent fluidity when using the nanocrystal-containing composition as an ink composition, the viewpoint of more excellent ejection stability, and the viewpoint of being able to suppress the decrease in smoothness due to curing shrinkage during the production of the luminescent fine particle coating film, It is preferable to use a combination of a functional (meth)acrylate and a polyfunctional (meth)acrylate.

Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)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, phenoxy ethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (Meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, etc. is mentioned.

Polyfunctional (meth)acrylates may be bifunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, pentafunctional (meth)acrylates, hexafunctional (meth)acrylates, etc. For example, Di(meth)acrylate in which two hydroxyl groups of a diol compound are substituted by (meth)acryloyloxy groups, di or tri(meth)acrylate in which two or three hydroxyl groups of a triol compound are substituted by (meth)acryloyloxy groups etc.

Specific examples of bifunctional (meth)acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate Two hydroxyl groups of (meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate diacrylate, and tris(2-hydroxyethyl)isocyanurate are (meth)acryloyl Di(meth)acrylate substituted with oxy group, two hydroxyl groups of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, substituted with (meth)acryloyloxy group Di(meth)acrylate, 1 mol of di(meth)acrylate obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, in which two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups di(meth)acrylate in which two hydroxyl groups of the triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to trimethylolpropane are substituted by (meth)acryloyloxy groups, 4 mol per 1 mol of bisphenol A Examples include di(meth)acrylates obtained by adding ethylene oxide or propylene oxide, and two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups.

Specific examples of trifunctional (meth)acrylates include, for example, trimethylolpropane tri(meth)acrylate, glycerin triacrylate, pentaerythritol tri(meth)acrylate, 1 mol of trimethylolpropane and 3 mol or more of ethylene oxide or propylene. A tri(meth)acrylate obtained by adding an oxide to a triol in which three hydroxyl groups are substituted with a (meth)acryloyloxy group.
Specific examples of tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate.
Specific examples of pentafunctional (meth)acrylates include, for example, dipentaerythritol penta(meth)acrylate.
Specific examples of hexafunctional (meth)acrylates include, for example, dipentaerythritol hexa(meth)acrylate.

Polyfunctional (meth)acrylates may be poly(meth)acrylates in which multiple hydroxyl groups of dipentaerythritol, such as dipentaerythritol hexa(meth)acrylate, are substituted with (meth)acryloyloxy groups.
The (meth)acrylate compound may be an ethylene oxide-modified phosphoric acid (meth)acrylate, an ethylene oxide-modified alkyl phosphoric acid (meth)acrylate, or the like having a phosphoric acid group.

In the nanocrystal-containing composition of the present invention, when the curable component is composed of only a photopolymerizable monomer or it as a main component, the photopolymerizable monomer as described above has one polymerizable functional group. It is more preferable to use a bifunctional or higher polyfunctional photopolymerizable monomer having two or more in the molecule as an essential component because the durability (strength, heat resistance, etc.) of the cured product can be further enhanced.

The amount of photopolymerizable monomer contained in the nanocrystal-containing composition is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, even more preferably 70 to 99% by mass. . By setting the amount of the photopolymerizable monomer contained in the nanocrystal-containing composition within the above range, the luminous efficiency of the luminescent nanoparticles can be increased. Furthermore, in the light-emitting layer (light conversion layer) obtained by curing the ink composition containing the nanocrystal-containing composition, the state of dispersion of the light-emitting fine particles is improved, so that the external quantum efficiency can be further increased.

1-4. Other Configuration Examples of Light-Emitting Fine Particles The nanocrystal-containing composition containing the light-emitting fine particles 910 having one or more ligands on the surfaces of the light-emitting nanocrystals 911 has been described above. is not limited to that shown in FIG. For example, on the surface of the luminescent nanocrystal 911, in addition to the ligand that satisfies the above formula (A), a ligand having a reactive group capable of forming a siloxane bond is coordinated to form a siloxane bond. Luminescent microparticles with an inorganic coating layer comprising Si formed by ligands with possible reactive groups can be used. Next, the light-emitting fine particles provided with this inorganic coating layer will be described. A luminescent fine particle provided with an inorganic coating layer may be referred to as an "inorganic coated luminescent fine particle", and a luminescent fine particle not provided with an inorganic coating layer may be referred to as an "uncoated luminescent fine particle".

The luminescent fine particles 90 (inorganic-coated luminescent fine particles) shown in FIG. is coordinated with the ligand having, at least the molecular length of the ligand that satisfies the above formula (A) is longer than the ligand having a reactive group capable of forming a siloxane bond, In this case, the ligand having a reactive group capable of forming a siloxane bond forms a siloxane bond in the vicinity of the luminescent nanocrystal 911, thereby forming a network structure composed of many siloxane bonds and containing Si. An inorganic coating layer 91 is formed. The ligands that satisfy at least the above formula (A) coordinated to the surfaces of the luminescent nanocrystals 911 form the ligand layer 912 exposed from the network structure of the inorganic coating layer 91 .

Since the inorganic coated light-emitting fine particles 90 have ligands exposed from the inorganic coating layer 91, dispersibility can be ensured when mixed with the photopolymerizable monomer. At this time, since at least one of the ligands is a ligand that satisfies the above formula (A), ligand exchange with the photopolymerizable monomer can be made difficult to occur. In addition, the inorganic coated luminescent fine particles 90 can protect the luminescent nanocrystals 911 from light, heat, moisture, etc. by providing the inorganic coating layer 91 containing Si. , the quantum yield retention and the external quantum efficiency retention can be further improved.

The thickness of the inorganic coating layer 91 is preferably 0.5 to 50 nm, more preferably 1.0 to 30 nm. The light-emitting fine particles 90 having the inorganic coating layer 91 with such a thickness can sufficiently improve the stability of the nanocrystals 911 against light, heat, moisture, and the like. Note that the thickness of the inorganic coating layer 91 can be changed by adjusting the number of atoms (chain length) of the connecting structure that connects the bonding group and the reactive group of the ligand.

In the ligand having a reactive group capable of forming a siloxane bond, the reactive group may be a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms, since a siloxane bond is easily formed. hydrolyzable silyl groups are preferred.

Further, the ligand having a reactive group capable of forming a siloxane bond preferably has a binding group that binds to the cation or anion contained in the luminescent nanocrystal 911 made of metal halide.

Examples of binding groups include carboxyl group, carboxylic anhydride group, amino group, ammonium group, mercapto group, phosphine group, phosphine oxide group, phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfonic acid group, boron An acid group and the like can be mentioned. Among them, the binding group is preferably at least one of a carboxyl group and an amino group. These binding groups have a higher affinity (reactivity) for the cations or anions contained in the luminescent nanocrystals having the perovskite crystal structure than the reactive groups. Therefore, the binding group in the ligand is coordinated to the luminescent nanocrystals 911 constituting the inorganic coated luminescent fine particles 90, and the inorganic coating layer 91 formed by the siloxane bond can be formed more easily and reliably. can be done.

From these facts, the ligand having a reactive group capable of forming the siloxane bond includes a carboxyl group- or amino group-containing silicon compound, and the like, and one of these may be used alone, or two or more of them may be used. can be used together.

Specific examples of carboxyl group-containing silicon compounds include trimethoxysilylpropyl acid, triethoxysilylpropyl acid, N-[3-(trimethoxysilyl)propyl]-N'-carboxymethylethylenediamine, N-[3- (trimethoxysilyl)propyl]phthalamide, N-[3-(trimethoxysilyl)propyl]ethylenediamine-N,N',N'-triacetic acid and the like.

On the other hand, specific examples of amino group-containing silicon compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropylmethylethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldipropoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiisopropoxysilane Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltri Propoxysilane, N-(2-aminoethyl)-3-aminopropyltriisopropoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-amino isobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylsilanetriol, 3-triethoxysilyl-N-(1, 3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl)phenyltrimethoxysilane, ( aminoethylaminoethyl)phenyltriethoxysilane, (aminoethylaminoethyl)phenyltripropoxysilane, (aminoethylaminoethyl)phenyltriisopropoxysilane, (aminoethylaminomethyl)phenyltrimethoxysilane, (aminoethylaminomethyl) Phenyltriethoxysilane, (aminoethylaminomethyl)phenyltripropoxysilane, (aminoethylaminomethyl)phenyltriisopropoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxysilane, N-β-(N-di(vinylbenzyl)aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(N-di(vinylbenzyl) ) aminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, dimethylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltrimethoxysilane methoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminoethyl)phenethyltriethoxysilane, (aminoethylaminoethyl)phenethyltripropoxysilane, (aminoethylaminoethyl)phenethyltriisopropoxysilane, (aminoethylaminomethyl) ) phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxysilane, (aminoethylaminomethyl)phenethyltripropoxysilane, (aminoethylaminomethyl)phenethyltriisopropoxysilane, N-[2-[3-(tri methoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(triethoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(tripropoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(triisopropoxysilyl)propylamino]ethyl]ethylenediamine and the like.

Specific examples of mercapto group-containing silicon compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 2-mercaptoethyl. trimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-[ethoxybis(3,6,9,12,15-pentoxaoctacosane-1 -yloxy)silyl]-1-propanethiol and the like.

The inorganic coated light-emitting fine particles 90 described above are composed of a solution containing a semiconductor raw material-containing solution, a ligand having a reactive group capable of forming an inorganic coating layer containing Si, and a coordination satisfying the above formula (A). a ligand having a reactive group capable of precipitating a semiconductor nanocrystal made of a metal halide having luminescent properties and forming an inorganic coating layer on the surface of the semiconductor nanocrystal by mixing with a compound that forms a ligand; and a ligand that satisfies the above formula (A), and then forming the inorganic coating layer 91 having the reactive group. Methods for manufacturing the inorganic coated light-emitting fine particles 90 include a method involving heating and a method involving no heating.

First, a method of manufacturing the inorganic coated light-emitting fine particles 91 by heating will be described. Two starting compound-containing solutions are prepared respectively. At this time, a compound that forms a ligand that satisfies the above formula (A) and a reactive group that contains Si and is capable of forming a siloxane bond is added to either or both of the two raw material compound-containing solutions. Add the compound that has These are then mixed under an inert gas atmosphere and reacted at a temperature of 140 to 260°C. Next, a method of precipitating nanocrystals by cooling to −20 to 30° C. and stirring may be used. In the precipitated nanocrystals, ligands are coordinated to the surface of the nanocrystals 911, and an inorganic coating layer 91 having siloxane bonds is formed. Thereafter, the silica-coated luminescent fine particles 91 can be obtained by collecting the obtained particles by a standard method such as centrifugation.

Specifically, for example, a solution containing cesium carbonate, oleic acid, and an organic solvent is prepared. As an organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. At this time, it is preferable to adjust the respective amounts to be added so that 0.2 to 2 g of cesium carbonate and 0.1 to 10 mL of oleic acid are added to 40 mL of the organic solvent. The obtained solution is dried under reduced pressure at 90 to 150° C. for 10 to 180 minutes, and then heated to 100 to 200° C. in an inert gas atmosphere such as argon or nitrogen to obtain a cesium-oleic acid solution.

Meanwhile, a solution containing lead (II) bromide and the same organic solvent as described above is prepared. At this time, 20 to 100 mg of lead (II) bromide is added to 5 mL of the organic solvent. After drying the resulting solution at 90 to 150° C. for 10 to 180 minutes under reduced pressure, 0.1 to 2 mL of 3-aminopropyltriethoxysilane is added under an inert gas atmosphere such as argon or nitrogen.

Then, while the solution containing lead (II) bromide and 3-aminopropyltriethoxysilane is heated to 140 to 260° C., the above-mentioned cesium-oleic acid solution is added, and the mixture is heated and stirred for 1 to 10 seconds to react. After allowing to react, the resulting reaction solution is cooled in an ice bath. At this time, it is preferable to add 0.1 to 1 mL of the cesium-oleic acid solution to 5 mL of the solution containing lead (II) bromide and 3-aminopropyltriethoxysilane. During stirring at −20 to 30° C., nanocrystals 911 are precipitated, and 3-aminopropyltriethoxysilane and oleic acid are coordinated to the surface of the nanocrystals 911 .

After that, the obtained reaction solution is stirred for 5 to 300 minutes at room temperature (10 to 30° C., humidity 5 to 60%) in the atmosphere, and then 0.1 to 50 mL of ethanol is added to form a suspension. obtain. The alkoxysilyl groups of 3-aminopropyltriethoxysilane are condensed during stirring at room temperature in the air, forming inorganic coating layers 91 having siloxane bonds on the surfaces of nanocrystals 911 to which oleic acid is coordinated.

The resulting suspension is centrifuged to collect the solids, and the solids are added to toluene to provide an inorganic coating layer 91 having a siloxane bond on the surface of the nanocrystals 911, and the nanocrystals 911. A luminescent fine particle dispersion liquid can be obtained in which silica-coated luminescent fine particles 90 are dispersed in toluene, and oleic acid is also coordinated to the surface and the ligand layer 912 is exposed from between the inorganic coated particles.

Next, a method for manufacturing silica-coated luminescent fine particles 90 without heating will be described. A solution containing a raw material compound for semiconductor nanocrystals and a solution containing a compound containing Si and having a reactive group capable of forming a siloxane bond are mixed in the air, and then the resulting mixture is applied to the nanocrystals. A method of precipitating nanocrystals by adding a large amount of an organic solvent, which is a poor solvent, can be mentioned. The amount of the organic solvent used is preferably 10 to 1000 times the mass of the semiconductor nanocrystals. In addition, the deposited nanocrystals are nanocrystals 911 on which the inorganic coating layer 91 having siloxane bonds is formed. Silica-coated luminescent fine particles 90 can be obtained by collecting the obtained particles by a standard method such as centrifugation.

Specifically, for example, a solution containing lead (II) bromide and methylamine hydrobromide in an organic solvent is prepared as a solution containing raw material compounds for semiconductor nanocrystals. The organic solvent may be any good solvent for nanocrystals, but dimethylsulfoxide, N,N-dimethylformamide, N-methylformamide, and mixed solvents thereof are preferred from the viewpoint of compatibility. At this time, it is preferable to adjust the amounts of lead (II) bromide and methylamine hydrobromide to be 50 to 200 mg and 10 to 100 mg, respectively, relative to 10 mL of the organic solvent.

On the other hand, as a solution containing a compound containing Si and having a reactive group capable of forming a siloxane bond, for example, 3-aminopropyltriethoxysilane, oleic acid, and a poor solvent are prepared. As a poor solvent, isopropyl alcohol, toluene, hexane, or the like can be used. At this time, it is possible to adjust the respective amounts to be added so that 0.01 to 0.5 mL of 3-aminopropyltriethoxysilane and 0.01 to 0.5 mL of oleic acid are added to 5 mL of the poor solvent. preferable.

Then, with respect to 0.1 to 5 mL of the solution containing lead (II) bromide and methylamine hydrobromide described above, 5 mL of the above solution containing 3-aminopropyltriethoxysilane was added to 0 to 0 in the atmosphere. Add at 60° C. to obtain a mixture. Immediately thereafter, the resulting mixture is added to a large volume of negative solvent and stirred under air for 5-180 seconds before collecting the solid by centrifugation. When the mixture is added to a large amount of negative solvent, nanocrystals 911 precipitate and 3-aminopropyltriethoxysilane and oleic acid are coordinated to the surface of nanocrystals 911 . Then, the alkoxysilyl groups of 3-aminopropyltriethoxysilane are condensed during stirring in the air, and a surface layer 91 having siloxane bonds is formed on the surface of the nanocrystals 911 .

By adding this recovered solid matter to toluene, silica-coated luminescent fine particles 90 having a surface layer 91 having a siloxane bond on the surface of nanocrystals 911 made of methylammonium lead tribromide crystals are dispersed in toluene. A fine particle dispersion can be obtained.

1-5. Photopolymerization Initiator The nanocrystal-containing composition of the present invention preferably further contains a polymerization initiator. The photopolymerization initiator is preferably at least one selected from the group consisting of alkylphenone compounds, acylphosphine oxide compounds and oxime ester compounds.

Examples of alkylphenone-based photopolymerization initiators include compounds represented by formula (b-1).

In formula ( ^b -1), R1a represents a group selected from the following formulas (R1a- ¹ ) to (R1a-6), and ^R2a , ^R2b and ^R2c each independently represent the following represents a group selected from formulas (R ² -1) to (R ² -7).

Specific examples of the compound represented by the above formula (b-1) are preferably compounds represented by the following formulas (b-1-1) to (b-1-6), and the following formula (b-1 -1), compounds represented by formula (b-1-5) or formula (b-1-6) are more preferred.

Examples of acylphosphine oxide-based photopolymerization initiators include compounds represented by formula (b-2).

In formula (b-2), R ²⁴ represents an alkyl group, an aryl group or a heterocyclic group, and R ²⁵ and R ²⁶ each independently represents an alkyl group, an aryl group, a heterocyclic group or an alkanoyl group. , these groups may be substituted with alkyl groups, hydroxyl groups, carboxyl groups, sulfone groups, aryl groups, alkoxy groups, arylthio groups.

Specific examples of the compound represented by the formula (b-2) are preferably compounds represented by the following formulas (b-2-1) to (b-2-5), and the following formula (b-2 -1) or compounds represented by formula (b-2-5) are more preferred.

Examples of the oxime ester photopolymerization initiator include compounds represented by the following formula (b-3-1) or (b-3-2).

In the above formula, R ²⁷ to R ³¹ each independently represent a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and a phenyl group, X ¹ represents an oxygen atom or a nitrogen atom, X ² represents an oxygen represents an atom or NR, where R represents an alkyl group having 1 to 6 carbon atoms.

Specific examples of the compounds represented by the above formulas (b-3-1) and (b-3-2) include the following formulas (b-3-1-1) to (b-3-1-2 ) and compounds represented by the following formulas (b-3-2-1) to (b-3-2-2) are preferable, and the following formulas (b-3-1-1) and (b-3-2 -1) or compounds represented by formula (b-3-2-2) are more preferred.

The amount of the photopolymerization initiator is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, relative to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. is more preferred, and 1 to 6% by mass is even more preferred. In addition, a photoinitiator can also be used individually by 1 type, and can also be used in mixture of 2 or more types. A nanocrystal-containing composition containing a photopolymerization initiator in such an amount sufficiently maintains photosensitivity during photocuring, and crystals of the photopolymerization initiator are less likely to precipitate when the coating film is dried, thus improving the physical properties of the coating film. Deterioration can be suppressed.

When dissolving the photopolymerization initiator in the nanocrystal-containing composition, it is preferable to dissolve it in the photopolymerizable monomer in advance before use.
When dissolving in the photopolymerizable monomer, it is preferable to uniformly dissolve the photopolymerizable monomer by adding the photopolymerization initiator while stirring the photopolymerizable monomer 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 in the photopolymerizable monomer and the thermal polymerizability of the photopolymerizable monomer. is preferably 10 to 60.degree. C., more preferably 10 to 40.degree.

1-6. Light Scattering Agent The nanocrystal-containing composition of the present invention preferably further contains a light scattering agent. Since the light-scattering agent is generally particulate, it is hereinafter referred to as "light-scattering particles". Light-scattering particles are, for example, optically inactive inorganic fine particles. The light-scattering particles can scatter light emitted from the light source unit in a light-emitting layer (light conversion layer) formed by curing a nanocrystal-containing composition or an ink composition containing the composition. can.

Materials constituting the light-scattering particles include single metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; silica, barium sulfate, barium carbonate, and 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 carbonates such as magnesium, barium carbonate, bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate and the like; Composite oxides, metal salts such as bismuth subnitrate, and the like are included. Among them, the material constituting the light-scattering particles is at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silica, from the viewpoint of being more effective in reducing leakage light. It preferably contains seeds, more preferably at least one selected from the group consisting of titanium oxide, barium sulfate and calcium carbonate.

The shape of the light-scattering particles may be spherical, filamentous, amorphous, or the like. However, as the light-scattering particles, the use of particles with less directionality (e.g., spherical, regular tetrahedral particles, etc.) as the particle shape improves the uniformity, fluidity, and light scattering properties of the nanocrystal-containing composition. is preferable in that the

The average particle diameter (volume average diameter) of the light-scattering particles in the nanocrystal-containing composition may be 0.05 μm or more, or even 0.2 μm or more, from the viewpoint of an excellent effect of reducing leakage light. It may be 0.3 μm or more. The average particle diameter (volume average diameter) of the light-scattering particles in the nanocrystal-containing composition may be 1.0 μm or less, or 0.6 μm or less, from the viewpoint of excellent ejection stability. , 0.4 μm or less. The average particle diameter (volume average diameter) of the light scattering particles in the nanocrystal-containing composition is 0.05 to 1.0 μm, 0.05 to 0.6 μm, 0.05 to 0.4 μm, 0.2 may be ~1.0 μm, 0.2-0.6 μm, 0.2-0.4 μm, 0.3-1.0 μm, 0.3-0.6 μm, or 0.3-0.4 μm . From the viewpoint of easily obtaining such an average particle diameter (volume average diameter), the average particle diameter (volume average diameter) of the light-scattering particles used may be 50 nm or more and 1000 nm or less. The average particle diameter (volume average diameter) of the light scattering particles in the nanocrystal-containing composition is obtained by measuring with a dynamic light scattering Nanotrac particle size distribution meter and calculating the volume average diameter. The average particle size (volume average size) of the light-scattering particles to be used can be obtained by measuring the particle size of each particle with, for example, a transmission electron microscope or scanning electron microscope and calculating the volume average size.

The content of the light-scattering particles may be 0.1% by mass or more, and may be 1% by mass or more, based on the mass of the nonvolatile matter in the nanocrystal-containing composition, from the viewpoint of achieving an excellent effect of reducing leaked light. may be 5% by mass or more, 7% by mass or more, 10% by mass or more, or 12% by mass or more. The content of the light-scattering particles may be 60% by mass or less based on the mass of the non-volatile matter in the nanocrystal-containing composition, from the standpoint of excellent leakage light reduction effect and excellent ejection stability. % by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less, 15 % by mass or less. In the present embodiment, since the nanocrystal-containing composition contains a polymer dispersant, the light-scattering particles can be satisfactorily dispersed even when the content of the light-scattering particles is within the above range.
The mass ratio of the content of the light-scattering particles to the content of the light-emitting fine particles (light-scattering particles/luminescent nanocrystals) may be 0.1 or more, and may be 0.1 or more, from the viewpoint of being more effective in reducing leakage light. It may be 2 or more, or 0.5 or more. The mass ratio (light-scattering particles/luminescent nanocrystals) may be 5.0 or less, and may be 2.0 or less, from the viewpoint of being excellent in the effect of reducing leaked light and being excellent in continuous discharge properties during inkjet printing. may be less than or equal to 1.5. In addition, it is considered that the leakage light reduction by the light scattering particles is based on the following mechanism. In other words, in the absence of the light-scattering particles, the light from the backlight passes almost straight through the pixel portion, and is less likely to be absorbed by the light-emitting fine particles. On the other hand, if the light-scattering particles are present in the same pixel portion as the light-emitting fine particles, the light from the backlight is scattered in all directions in the pixel portion, and the light-emitting fine particles can receive the light. Even if it is used, it is considered that the amount of light absorption in the pixel portion increases. As a result, it is considered that such a mechanism has made it possible to prevent leakage light.

1-7. Dispersant The nanocrystal-containing composition of the present invention preferably further contains a dispersant. The dispersant is not particularly limited as long as it is a compound capable of further improving the dispersion stability of the luminescent fine particles in the nanocrystal-containing composition. Dispersants are classified into low molecular weight dispersants and polymeric dispersants. As used herein, "low molecular weight" means molecules with a weight average molecular weight (Mw) of 5,000 or less, and "high molecular weight" means molecules with a weight average molecular weight (Mw) of greater than 5,000. means As used herein, the "weight average molecular weight (Mw)" can be a value measured using gel permeation chromatography (GPC) using polystyrene as a standard substance.

Low-molecular-weight dispersants include, for example, oleic acid; triethyl phosphate, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), octylphosphine phosphorus atom-containing compounds such as acid (OPA); nitrogen atom-containing compounds such as oleylamine, octylamine, trioctylamine, hexadecylamine; sulfur atoms such as 1-decanethiol, octanethiol, dodecanethiol, amyl sulfide containing compounds and the like.

On the other hand, polymer dispersants include, for example, acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyether resins, phenol resins, silicone resins, polyurea resins, amino resins, and polyamine resins. Resins (polyethyleneimine, polyallylamine, etc.), epoxy resins, polyimide resins, natural rosins such as wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, and maleated rosin modified rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, and rosin derivative such as rosin-modified phenol.

Commercially available polymeric dispersants include, for example, DISPERBYK series manufactured by BYK-Chemie, TEGO Dispers series manufactured by Evonik, EFKA series manufactured by BASF, SOLSPERSE series manufactured by Lubrizol Japan, and Ajinomoto Fine-Techno Co., Ltd. The Spar series, the DISPARLON series manufactured by Kusumoto Kasei, the Floren series manufactured by Kyoeisha Chemical Co., Ltd., and the like can be used.

The blending amount of the dispersant is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the light-emitting fine particles 910 and 90 .

By the way, when a color filter pixel portion is formed by an inkjet method using a conventional ink composition, the ejection stability from an inkjet nozzle may be deteriorated due to aggregation of light-emitting fine particles and light-scattering particles. In addition, it is conceivable to improve the ejection stability by miniaturizing the luminescent fine particles and the light-scattering particles, reducing the content of the luminescent fine particles and the light-scattering particles, and the like. The effect tends to decrease, and it has been difficult to achieve both sufficient ejection stability and the effect of reducing leaked light. On the other hand, according to the nanocrystal-containing composition of the present invention, which further contains a dispersant, it is possible to further reduce leakage light while ensuring sufficient ejection stability. Although the reason why such an effect is obtained is not clear, it is presumed that the dispersant significantly suppresses the aggregation of the light-emitting fine particles and the light-scattering particles (particularly, the light-scattering particles).

Functional groups that have an affinity for light scattering particles include acidic functional groups, basic functional groups and nonionic functional groups. Acidic functional groups have dissociative protons and may be neutralized with bases such as amines and hydroxide ions, while basic functional groups are neutralized with acids such as organic acids and inorganic acids. may

Examples of acidic functional groups include a carboxyl group (--COOH), a sulfo group (--SO3H), a sulfate group (--OSO3H), a phosphonic acid group (--PO(OH)3), and a phosphoric acid group (--OPO(OH)3). , a phosphinic acid group (--PO(OH)--) and a mercapto group (--SH).

Basic functional groups include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.

Nonionic functional groups include hydroxy group, ether group, thioether group, sulfinyl group (-SO-), sulfonyl group (-SO2-), carbonyl group, formyl group, ester group, carbonate group, amide group, carbamoyl group, ureido group, thioamide group, thioureido group, sulfamoyl group, cyano group, alkenyl group, alkynyl group, phosphine oxide group and phosphine sulfide group.

From the viewpoint of the dispersion stability of the light-scattering particles, the side effect of sedimentation of the light-emitting fine particles, the ease of synthesizing the polymer dispersant, and the stability of the functional group, the acidic functional group is , a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group are preferably used, and an amino group is preferably used as the basic functional group. Among these, carboxyl group, phosphonic acid group and amino group are more preferably used, and amino group is most preferably used.

Dispersants with acidic functional groups have an acid number. The acid value of the polymeric dispersant having an acidic functional group is preferably 1 to 150 mgKOH/g in terms of solid content. When the acid value is 1 or more, sufficient dispersibility of the light-scattering particles is likely to be obtained, and when the acid value is 150 or less, the storage stability of the pixel portion (cured product of the ink composition) is less likely to decrease. .
Also, dispersants with basic functional groups have an amine value. The amine value of the dispersant having a basic functional group is preferably 1-200 mgKOH/g in terms of solid content. When the amine value is 1 or more, sufficient dispersibility of the light-scattering particles is likely to be obtained, and when the amine value is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) is less likely to decrease. .
The weight-average molecular weight of the dispersant may be 750 or more, or 1000 or more, from the viewpoint of being able to satisfactorily disperse the light scattering particles and further improving the effect of reducing leaked light. It may be 2000 or more, or 3000 or more. In addition, the weight-average molecular weight of the dispersant is such that the light-scattering particles can be well dispersed, the effect of reducing leaked light can be further improved, and the viscosity of the inkjet ink can be adjusted so that it is suitable for stable ejection. From the viewpoint of viscosity, it may be 100,000 or less, 50,000 or less, or 30,000 or less.

From the viewpoint of the dispersibility of the light-scattering particles, the content of the dispersant may be 0.5 parts by mass or more, or 2 parts by mass or more, with respect to 100 parts by mass of the light-scattering particles. It may be 5 parts by mass or more. The content of the polymer dispersion may be 50 parts by mass or less, and 30 parts by mass or less with respect to 100 parts by mass of the light-scattering particles, from the viewpoint of wet heat stability of the pixel portion (cured product of the ink composition). or 10 parts by mass or less.

1-8. Other Components The nanocrystal-containing composition used in the present invention contains other components other than the light-emitting fine particles 910 and 90, the photopolymerizable monomer, the photopolymerization initiator, and the light-scattering particles within a range that does not impede the effects of the present invention. may contain. Such other components include polymerization inhibitors, antioxidants, leveling agents, chain transfer agents, dispersing aids, thermoplastic resins, sensitizers and the like.

1-8-1. Polymerization inhibitor Examples of polymerization inhibitors include p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylenebis(4-methyl-6 -t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, Phenolic compounds such as 4,4'-dialkoxy-2,2'-bi-1-naphthol; hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p -quinone compounds such as benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone and diphenoquinone; phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-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'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine amine compounds such as; phenothiazine, thioether compounds such as distearyl thiodipropionate; 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 2,2,6,6-tetramethyl N-oxyl compounds such as piperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p- Nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrondimethylamine, p-nitron-N,N-diethylamine , N-nitrosoethanolamine, N-nitroso-di-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso Troso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "Q-1300 ”), nitrosobenzene, 2,4,6-tri-tert-butylnitrobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn - propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, Nitroso compounds such as 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, and Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
The amount of polymerization inhibitor to be added is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.5% by mass, relative to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. is more preferable.

1-8-2. Antioxidant Antioxidants include, for example, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (“IRGANOX1010”), thiodiethylenebis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate (“IRGANOX1035”), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (“IRGANOX1076”), “IRGANOX1135”, "IRGANOX1330", 4,6-bis(octylthiomethyl)-o-cresol ("IRGANOX1520L"), "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" ” (manufactured by BASF Corporation); ” (manufactured by ADEKA Co., Ltd.); “JP-360”, “JP-308E”, “JPE-10” (manufactured by Johoku Chemical Industry Co., Ltd.); “Sumilizer BHT”, “Sumilizer BBM-S”, "Sumilizer GA-80" (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

The amount of the antioxidant added is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 1.0% by mass, relative to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. is more preferable.

1-8-3. Leveling Agent The leveling agent is not particularly limited, but is preferably a compound capable of reducing film thickness unevenness when forming a thin film of the light-emitting fine particles 90 .
Such leveling agents include, for example, alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives , polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like.

Specific examples of leveling agents include "Megafac F-114", "Megafac F-251", "Megafac F-281", "Megafac F-410", "Megafac F-430", "Megafuck F-444", "Megafuck F-472SF", "Megafuck F-477", "Megafuck F-510", "Megafuck F-511", "Megafuck F-552", "Megafuck F-552" Fuck F-553", "Megafuck F-554", "Megafuck F-555", "Megafuck F-556", "Megafuck F-557", "Megafuck F-558", "Megafuck F -559", "Megafuck F-560", "Megafuck F-561", "Megafuck F-562", "Megafuck F-563", "Megafuck F-565", "Megafuck F-567" ”, “Megafuck F-568”, “Megafuck F-569”, “Megafuck F-570”, “Megafuck F-571”, “Megafuck R-40”, “Megafuck R-41”, "Megafuck R-43", "Megafuck R-94", "Megafuck RS-72-K", "Megafuck RS-75", "Megafuck RS-76-E", "Megafuck RS-76" -NS”, “Megafuck RS-90”, “Megafuck EXP.TF-1367”, “Megafuck EXP.TF1437”, “Megafuck EXP.TF1537”, “Megafuck EXP.TF-2066” (above, DIC Corporation) and the like.

Other specific examples of the leveling agent include "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", "Ftergent 150CH", "Ftergent 100A-K", “Ftergent 300”, “Ftergent 310”, “Ftergent 320”, “Ftergent 400SW”, “Ftergent 251”, “Ftergent 215M”, “Ftergent 212M”, “Ftergent 215M”, “Ftergent Ftergent 250”, “Ftergent 222F”, “Ftergent 212D”, “FTX-218”, “Ftergent 209F”, “Ftergent 245F”, “Ftergent 208G”, “Ftergent 240G”, “Ftergent 212P” ”, “Futergent 220P”, “Futergent 228P”, “DFX-18”, “Futergent 601AD”, “Futergent 602A”, “Futergent 650A”, “Futergent 750FM”, “FTX-730FM”, "Futergent 730FL", "Futergent 710FS", "Futergent 710FM", "Futergent 710FL", "Futergent 750LL", "FTX-730LS", "Futergent 730LM" (manufactured by Neos Co., Ltd.) etc.

Other specific examples of the leveling agent include "BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK -320", "BYK-322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-340" ”, “BYK-344”, “BYK-370”, “BYK-375”, “BYK-377”, “BYK-350”, “BYK-352”, “BYK-354”, “BYK-355”, "BYK-356", "BYK-358N", "BYK-361N", "BYK-357", "BYK-390", "BYK-392", "BYK-UV3500", "BYK-UV3510", "BYK -UV3570” and “BYK-Silclean3700” (manufactured by BYK Corporation).

Other specific examples of leveling agents include "TEGO Rad2100", "TEGO Rad2011", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2600", and "TEGO Rad2650." ”, “TEGO Rad2700”, “TEGO Flow300”, “TEGO Flow370”, “TEGO Flow425”, “TEGO Flow ATF2”, “TEGO Flow ZFS460”, “TEGO Glide100”, “TEGO Glide110”, “TEGO Glide130”, “ TEGO Glide410", "TEGO Glide411", "TEGO Glide415", "TEGO Glide432", "TEGO Glide440", "TEGO Glide450", "TEGO Glide482", "TEGO Glide A115", "TEGO Glide4, TEGO Glide4 G08 G0Z" B14 , TEGO Twin4000, TEGO Twin4100, TEGO Twin4200, TEGO Wet240, TEGO Wet250, TEGO Wet260, TEGO Wet265, TEGO Wet270, TEGO Wet280, TEGO Wet500 ", "TEGO Wet505", "TEGO Wet510", "TEGO Wet520", and "TEGO Wet KL245" (manufactured by Evonik Industries Ltd.).

Other specific examples of leveling agents include "FC-4430", "FC-4432" (manufactured by 3M Japan Ltd.), "Unidyne NS" (manufactured by Daikin Industries, Ltd.); -241", "Surfron S-242", "Surfron S-243", "Surfron S-420", "Surfron S-611", "Surfron S-651", "Surfron S-386" (AGC Seimi Chemical Co., Ltd.) and the like.

Other specific examples of leveling agents include "DISPARLON OX-880EF", "DISPARLON OX-881", "DISPARLON OX-883", "DISPARLON OX-77EF", "DISPARLON OX-710", and "DISPARLON 1922". ”, “DISPARLON 1927”, “DISPARLON 1958”, “DISPARLON P-410EF”, “DISPARLON P-420”, “DISPARLON P-425”, “DISPARLON PD-7”, “DISPARLON 1970”, “DISPARLON 230”, "DISPARLON LF-1980", "DISPARLON LF-1982", "DISPARLON LF-1983", "DISPARLON LF-1084", "DISPARLON LF-1985", "DISPARLON LHP-90", "DISPARLON LHP-91", " DISPARLON LHP-95, DISPARLON LHP-96, DISPARLON OX-715, DISPARLON 1930N, DISPARLON 1931, DISPARLON 1933, DISPARLON 1934, DISPARLON 1711EF, DISPARLON 1751N, "DISPARLON 1761", "DISPARLON LS-009", "DISPARLON LS-001", "DISPARLON LS-050" (manufactured by Kusumoto Kasei Co., Ltd.) and the like.

Other specific examples of leveling agents include "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-652-NF", "PF-3320" (manufactured by OMNOVA SOLUTIONS); "Polyflow No.7", "Polyflow No.50E", "Polyflow No.50EHF", "Polyflow No.54N", "Polyflow No.75", " Polyflow No. 77", "Polyflow No. 85", "Polyflow No. 85HF", "Polyflow No. 90", "Polyflow No. 90D-50", "Polyflow No. 95", "Polyflow No. 99C", "Polyflow KL-400K", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-100", " Polyflow LE-604", "Polyflow KL-700", "Floren AC-300", "Floren AC-303", "Floren AC-324", "Floren AC-326F", "Floren AC-530", "Floren AC-903”, “Floren AC-903HF”, “Floren AC-1160”, “Floren AC-1190”, “Floren AC-2000”, “Floren AC-2300C”, “Floren AO-82”, “Floren AO -98”, “Floren AO-108” (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Further, other specific examples of the leveling agent include "L-7001", "L-7002", "8032ADDITIVE", "57ADDTIVE", "L-7064", "FZ-2110", "FZ-2105 ”, “67ADDTIVE”, and “8616ADDTIVE” (manufactured by Dow Toray Silicone Co., Ltd.).
The amount of the leveling agent added is preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, relative to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. is more preferred.

1-8-4. Chain Transfer Agent The chain transfer agent is a component used for the purpose of further improving the adhesion of the ink composition to the substrate when the nanocrystal-containing composition is used as the ink composition.
Examples of chain transfer agents include aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane; octylmercaptan, n-butylmercaptan, n-pentylmercaptan, Mercaptan compounds such as n-hexadecylmercaptan, n-tetradecylmer, n-dodecylmercaptan, t-tetradecylmercaptan, t-dodecylmercaptan; hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate , 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3 -mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) trimercaptopropionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-tri Thiol compounds such as mercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine; dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropyl xanthogen disulfide, tetramethylthiuram disulfide, tetraethyl Thiuram disulfide, sulfide compounds such as tetrabutylthiuram disulfide; N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ- Tervinene, dipentene and the like can be mentioned, but 2,4-diphenyl-4-methyl-1-pentene and thiol compounds are preferred.

Specific examples of chain transfer agents are preferably compounds represented by the following general formulas (9-1) to (9-12).

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms. and sulfur atoms may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO- or -CH=CH- without directly bonding to each other.
R ⁹⁶ represents an alkylene group having 2 to 18 carbon atoms, and one or more methylene groups in the alkylene group are an oxygen atom, a sulfur atom, —CO— , -OCO-, -COO- or -CH=CH-.
The amount of the chain transfer agent added is preferably 0.1 to 10% by mass, more preferably 1.0 to 5% by mass, relative to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. more preferred.

1-8-5. Dispersing aid Dispersing aids include organic pigment derivatives such as phthalimidomethyl derivatives, phthalimidosulfonic acid derivatives, phthalimido N-(dialkylamino)methyl derivatives, and phthalimido N-(dialkylaminoalkyl)sulfonic acid amide derivatives. mentioned. These dispersing aids may be used alone or in combination of two or more.
1-8-6. Thermoplastic Resin Examples of thermoplastic resins include urethane-based resins, acrylic-based resins, polyamide-based resins, polyimide-based resins, styrene-maleic acid-based resins, styrene-maleic anhydride-based resins, and polyester acrylate-based resins.
1-8-7. Sensitizer As the sensitizer, amines that do not cause an addition reaction with the photopolymerizable monomer can be used. Examples of such sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, 4 , 4′-bis(diethylamino)benzophenone and the like.

1-9. Method for Preparing Nanocrystal-Containing Composition The nanocrystal-containing composition as described above is prepared by dispersing the above-described light-emitting fine particles 910 and 90 in a solution containing a mixture of a photopolymerizable monomer, a photopolymerization initiator, and the like. can be done. The luminescent fine particles 910, 90 can be dispersed by using, for example, a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, an ultrasonic disperser, or the like.

The content of the luminescent fine particles 910 and 91 in the nanocrystal-containing composition is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, and further preferably 1 to 40% by mass. preferable. By setting the content of the light-emitting fine particles 910, 90 in the nanocrystal-containing composition to the above range, when the ink composition composed of the nanocrystal-containing monomer is ejected by an inkjet printing method, the ejection is stabilized. It is possible to further improve the performance. In addition, the uncoated light-emitting fine particles 910 or the inorganic-coated light-emitting fine particles 91 are less likely to agglomerate, and the external quantum efficiency of the resulting light-emitting layer (light conversion layer) can be increased.

A cured product of the nanocrystal-containing composition of the present invention can be obtained by forming a film on a substrate by various methods such as inkjet printer, photolithography, spin coater, etc., and heating and curing the film. Among others, the nanocrystal-containing composition of the present invention is particularly suitable as an ink composition for use in inkjet printers.

The viscosity of the nanocrystal-containing composition as the ink composition is preferably in the range of 2 to 20 mPa s, more preferably in the range of 5 to 15 mPa s, from the viewpoint of ejection stability during inkjet printing. It is preferably in the range of 7 to 12 mPa·s, more preferably. In this case, since the meniscus shape of the nanocrystal-containing composition in the ink ejection holes of the ejection head is stabilized, ink ejection control (for example, ejection amount and ejection timing control) becomes easy. In addition, ink can be smoothly discharged from the ink discharge holes. The viscosity of the nanocrystal-containing composition can be measured, for example, with an E-type viscometer.

Moreover, the surface tension of the nanocrystal-containing composition as the ink composition is preferably a surface tension suitable for the inkjet printing method. A 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 within the above range, it is possible to suppress the deflection of ink droplets. Note that flight deflection means that the ink landing position deviates from the target position by 30 μm or more when the ink is ejected from the ink ejection holes.

2. Light-Emitting Device Formed Using Nanocrystal-Containing Composition The above-described nanocrystal-containing composition can be obtained by forming a film on a substrate by various methods such as an inkjet printer, photolithography, or spin coater, and then heating the film. A cured product can be obtained by curing with Hereinafter, a case of forming a color filter pixel portion of a light-emitting element having a blue organic LED backlight using a nanocrystal-containing composition as an ink composition will be described as an example.

FIG. 3 is a cross-sectional view showing an embodiment of the light-emitting device of the present invention, and FIGS. 4 and 5 are schematic diagrams showing the configuration of active matrix circuits, respectively. In addition, in FIG. 3, the dimensions of each part and their ratios are exaggerated for the sake of convenience, and may differ from the actual dimensions. Also, the materials, dimensions, and the like shown below are examples, and the present invention is not limited to them, and can be changed as appropriate without changing the gist of the invention. For convenience of explanation, the upper side of FIG. 3 is hereinafter referred to as "upper side" or "upper side", and the upper side is referred to as "lower side" or "lower side". In addition, in FIG. 3, hatching indicating a cross section is omitted in order to avoid complication of the drawing.

As shown in FIG. 3, the light-emitting element 100 includes a lower substrate 1, an EL light source section 200, a filling layer 10, a protective layer 11, and a light conversion layer 12 containing the above-described light-emitting fine particles and acting as a light-emitting layer. , and the upper substrate 13 are laminated in this order. The light-emitting fine particles contained in the light conversion layer 12 may be uncoated light-emitting fine particles 910 having neither an inorganic coating layer nor a resin coating layer, or may be inorganic-coated light-emitting fine particles 90 . The EL light source section 200 includes an anode 2, an EL layer 14 composed of a plurality of layers, a cathode 8, a polarizing plate (not shown), and a sealing layer 9 in this order. The EL layer 14 includes a hole injection layer 3 , a hole transport layer 4 , a light emitting layer 5 , an electron transport layer 6 and an electron injection layer 7 which are sequentially stacked from the anode 2 side.

The light-emitting element 100 is a photoluminescence element in which the light emitted from the EL light source section 200 (EL layer 14) is absorbed and re-emitted by the light conversion layer 12, or is transmitted therethrough, and extracted to the outside from the upper substrate 13 side. . At this time, the luminous fine particles 910 or 90 contained in the light conversion layer 12 convert the light into light of a predetermined color. Each layer will be described below in order.

2-1. lower substrate 1 and upper substrate 13
The lower substrate 1 and the upper substrate 13 each have a function of supporting and/or protecting each layer constituting the light emitting device 100 . When the light emitting device 100 is of the top emission type, the upper substrate 13 is composed of a transparent substrate. On the other hand, when the light emitting device 100 is of the bottom emission type, the lower substrate 1 is composed of a transparent substrate. Here, the transparent substrate means a substrate capable of transmitting light having a wavelength in the visible light region, and transparent includes colorless transparent, colored transparent, and translucent.

Examples of transparent substrates include transparent glass substrates such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plates, quartz substrates, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), A plastic substrate (resin substrate) made of polyimide (PI), polycarbonate (PC) or the like, a metal substrate made of iron, stainless steel, aluminum, copper or the like, a silicon substrate, a gallium arsenide substrate, or the like can be used. Among these, it is preferable to use a glass substrate made of alkali-free glass that does not contain an alkali component. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" manufactured by Corning, "AN100" manufactured by Asahi Glass Co., Ltd., "OA-10G" manufactured by Nippon Electric Glass Co., Ltd. and " OA-11” is preferred. These materials have a small coefficient of thermal expansion and are excellent in dimensional stability and workability in high-temperature heat treatment. In addition, in the case of imparting flexibility to the light emitting element 100, the lower substrate 1 and the upper substrate 13 may be plastic substrates (substrates mainly composed of a polymer material) and relatively thin substrates. A metal substrate is selected.

The thicknesses of the lower substrate 1 and the upper substrate 13 are not particularly limited, but are preferably in the range of 100 to 1,000 μm, more preferably in the range of 300 to 800 μm.
One or both of the lower substrate 1 and the upper substrate 13 may be omitted depending on the usage of the light emitting device 100 .

As shown in FIG. 4, on the lower substrate 1, a signal line driving circuit C1 and a scanning line driving circuit C2 for controlling current supply to the anodes 2 constituting the pixel electrodes PE indicated by R, G, and B are provided. , a control circuit C3 for controlling the operation of these circuits, a plurality of signal lines 706 connected to the signal line driving circuit C1, and a plurality of scanning lines 707 connected to the scanning line driving circuit C2. 5, a capacitor 701, a driving transistor 702, and a switching transistor 708 are provided in the vicinity of intersections of the signal lines 706 and the scanning lines 707. As shown in FIG.

The capacitor 701 has one electrode connected to the gate electrode of the drive transistor 702 and the other electrode connected to the source electrode of the drive transistor 702 . The drive transistor 702 has a gate electrode connected to one electrode of the capacitor 701 , a source electrode connected to the other electrode of the capacitor 701 and a power supply line 703 for supplying a drive current, and a drain electrode connected to the anode 4 of the EL light source section 200 . It is connected to the.

The switching transistor 708 has a gate electrode connected to the scanning line 707 , a source electrode connected to the signal line 706 , and a drain electrode connected to the gate electrode of the drive transistor 702 . Further, in this embodiment, the common electrode 705 constitutes the cathode 8 of the EL light source section 200 . Note that the driving transistor 702 and the switching transistor 708 can be configured by thin film transistors or the like, for example.

The scanning line driving circuit C2 supplies or cuts off a scanning voltage corresponding to a scanning signal to the gate electrode of the switching transistor 708 through the scanning line 707 to turn the switching transistor 708 on or off. Thereby, the scanning line driving circuit C2 adjusts the timing at which the signal line driving circuit C1 writes the signal voltage. On the other hand, the signal line driving circuit C1 supplies or cuts off a signal voltage corresponding to the video signal to the gate electrode of the driving transistor 702 via the signal line 706 and the switching transistor 708, and reduces the signal current supplied to the EL light source section 200. Adjust quantity.

Therefore, when the scanning voltage is supplied to the gate electrode of the switching transistor 708 from the scanning line driving circuit C2 and the switching transistor 708 is turned on, the signal voltage is supplied to the gate electrode of the switching transistor 708 from the signal line driving circuit C1. At this time, a drain current corresponding to this signal voltage is supplied from the power supply line 703 to the EL light source section 200 as a signal current. As a result, the EL light source section 200 emits light according to the supplied signal current.

2-2. EL light source unit 200
2-2-1. Anode 2
The anode 2 has a function of supplying holes from an external power supply to the light-emitting layer 5 . The constituent material (anode material) of the anode 2 is not particularly limited. Metal oxides such as tin (SnO ₂ ) and zinc oxide (ZnO) are included. These may be used individually by 1 type, or may use 2 or more types together.

Although the thickness of the anode 2 is not particularly limited, it is preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 200 nm.

The anode 2 can be formed, for example, by a dry film-forming method such as a vacuum deposition method or a sputtering method. At this time, the anode 2 having a predetermined pattern may be formed by a photolithography method or a method using a mask.

2-2-2. cathode 8
The cathode 8 has a function of supplying electrons from an external power source toward the light emitting layer 5 . The constituent material of the cathode 8 (cathode material) is not particularly limited, but examples include lithium, sodium, magnesium, aluminum, silver, sodium-potassium alloy, magnesium/aluminum mixture, magnesium/silver mixture, magnesium/indium mixture, and aluminum. / aluminum oxide (Al ₂ O ₃ ) mixtures, rare earth metals and the like. These may be used individually by 1 type, or may use 2 or more types together.

Although the thickness of the cathode 8 is not particularly limited, it is preferably in the range of 0.1 to 1,000 nm, more preferably in the range of 1 to 200 nm.

The cathode 3 can be formed, for example, by a dry film-forming method such as a vapor deposition method or a sputtering method.

2-2-3. hole injection layer 3
The hole injection layer 3 has a function of receiving holes supplied from the anode 2 and injecting them into the hole transport layer 4 . The hole injection layer 3 may be provided as required, and may be omitted.

The constituent material (hole injection material) of the hole injection layer 3 is not particularly limited, but for example, a phthalocyanine compound such as copper phthalocyanine; 4,4′,4″-tris[phenyl(m-tolyl)amino ] triphenylamine derivatives such as triphenylamine; 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, 2,3,5,6-tetrafluoro-7,7,8,8- cyano compounds such as tetracyano-quinodimethane; metal oxides such as vanadium oxide and molybdenum oxide; amorphous carbon; polyaniline (emeraldine), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT -PSS), polymers such as polypyrrole, and the like. Among these, the hole injection material is preferably a polymer, more preferably PEDOT-PSS. Moreover, one of the above hole injection materials may be used alone, or two or more thereof may be used in combination.

The thickness of the hole injection layer 3 is not particularly limited, but is preferably in the range of 0.1 to 500 nm, more preferably in the range of 1 to 300 nm, and further preferably in the range of 2 to 200 nm. preferable. The hole injection layer 3 may have a single layer structure or a laminated structure in which two or more layers are laminated.

Such a hole injection layer 4 can be formed by a wet film formation method or a dry film formation method. When the hole injection layer 3 is formed by a wet film formation method, usually, an ink containing the hole injection material is applied by various coating methods, and the resulting coating is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. mentioned. On the other hand, when the hole injection layer 3 is formed by a dry film-forming method, a vacuum vapor deposition method, a sputtering method, or the like can be preferably used.

2-2-4. hole transport layer 4
The hole transport layer 4 has a function of receiving holes from the hole injection layer 3 and transporting them efficiently to the light emitting layer 6 . Further, the hole transport layer 4 may have a function of preventing transport of electrons. The hole transport layer 4 may be provided as required, and may be omitted.

The constituent material (hole transport material) of the hole transport layer 4 is not particularly limited, but for example, TPD (N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1' -biphenyl-4,4'diamine), α-NPD (4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl), m-MTDATA (4,4',4''- low-molecular-weight triphenylamine derivatives such as tris(3-methylphenylphenylamino)triphenylamine); polyvinylcarbazole; poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl) -benzidine] (poly-TPA), polyfluorene (PF), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine (Poly-TPD), poly[( Conjugated systems such as 9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(sec-butylphenyl)diphenylamine)) (TFB), polyphenylene vinylene (PPV) compound polymers; and copolymers containing these monomer units.

Among these, the hole-transporting material is preferably a polymer compound obtained by polymerizing a triphenylamine derivative or a triphenylamine derivative into which a substituent is introduced. A polymer compound obtained by polymerizing a phenylamine derivative is more preferable. Moreover, the above hole-transporting materials may be used singly or in combination of two or more.

Although the thickness of the hole transport layer 4 is not particularly limited, it is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 300 nm, even more preferably in the range of 10 to 200 nm. The hole transport layer 4 may have a single layer structure or a laminated structure in which two or more layers are laminated.

Such a hole transport layer 4 can be formed by a wet film formation method or a dry film formation method. When the hole transport layer 4 is formed by a wet film-forming method, usually, an ink containing the above hole transport material is applied by various coating methods, and the resulting coating is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. mentioned. On the other hand, when the hole transport layer 4 is formed by a dry film-forming method, a vacuum vapor deposition method, a sputtering method, or the like can be preferably used.

2-2-5. electron injection layer 7
The electron injection layer 7 has a function of receiving electrons supplied from the cathode 8 and injecting them into the electron transport layer 6 . The electron injection layer 7 may be provided as required, and may be omitted.

The constituent material (electron injection material) of the electron injection layer 7 is not particularly limited, but examples thereof include alkali metal chalcogenides such as Li ₂ O, LiO, Na ₂ S, Na ₂ Se and NaO; alkaline earth metal chalcogenides such as BeO, BaS, MgO, CaSe; alkali metal halides such as CsF, LiF, NaF, KF, LiCl, KCl, NaCl; alkalis such as 8-hydroxyquinolinolatritium (Liq) Metal salts; alkaline earth metal halides such as _CaF2 , _BaF2 , _SrF2 , _MgF2 , _BeF2 , and the like. Among these, alkali metal chalcogenides, alkaline earth metal halides and alkali metal salts are preferred. Moreover, the above electron injection materials may be used singly or in combination of two or more.

The thickness of the electron injection layer 7 is not particularly limited, but is preferably in the range of 0.1 to 100 nm, more preferably in the range of 0.2 to 50 nm, and more preferably in the range of 0.5 to 10 nm. is more preferred. The electron injection layer 7 may have a single-layer structure or a laminated structure in which two or more layers are laminated.

Such an electron injection layer 7 can be formed by a wet film formation method or a dry film formation method. When the electron injection layer 7 is formed by a wet film formation method, usually, an ink containing the above-described electron injection material is applied by various coating methods, and the resulting coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. mentioned. On the other hand, when the electron injection layer 7 is formed by a dry film-forming method, a vacuum deposition method, a sputtering method, or the like can be applied.

2-2-6. electron transport layer 8
The electron transport layer 8 has a function of receiving electrons from the electron injection layer 7 and efficiently transporting them to the light emitting layer 5 . Further, the electron transport layer 8 may have a function of preventing transport of holes. The electron transport layer 8 may be provided as required, and may be omitted.

The constituent material (electron transport material) of the electron transport layer 8 is not particularly limited, but examples thereof include tris(8-quinolinolato)aluminum (Alq3), tris(4-methyl-8-quinolinolato)aluminum (Almq3), bis( Quinolines such as 10-hydroxybenzo[h]quinolinato)beryllium (BeBq2), bis(2-methyl-8-quinolinolato)(p-phenylphenolato)aluminum (BAlq), bis(8-quinolinolato)zinc (Znq) metal complexes having a backbone or a benzoquinoline backbone; metal complexes having a benzoxazoline backbone such as bis[2-(2'-hydroxyphenyl)benzoxazolato]zinc (Zn(BOX)2); bis[2-( 2′-Hydroxyphenyl)benzothiazolate]zinc (Zn(BTZ)2), a metal complex having a benzothiazoline skeleton; 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ), 1,3- Bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (OXD-7), 9-[4-(5-phenyl-1,3,4- tri- or diazole derivatives such as oxadiazol-2-yl)phenyl]carbazole (CO11); 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H- benzimidazole) (TPBI), 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (mDBTBIm-II); quinoline derivatives; perylene derivatives; pyridine derivatives such as 7-diphenyl-1,10 _- phenanthroline (BPhen); pyrimidine derivatives; triazine derivatives; quinoxaline derivatives; metal oxides and the like. Among these, imidazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, and metal oxides (inorganic oxides) are preferred as electron transport materials. Moreover, the above-mentioned electron transport materials may be used singly or in combination of two or more.

Although the thickness of the electron transport layer 7 is not particularly limited, it is preferably in the range of 5 to 500 nm, more preferably in the range of 5 to 200 nm. The electron transport layer 6 may be a single layer or a laminate of two or more layers.

Such an electron transport layer 7 can be formed by a wet film formation method or a dry film formation method. When the electron-transporting layer 6 is formed by a wet film-forming method, the ink containing the above-described electron-transporting material is usually applied by various coating methods, and the resulting coating is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. mentioned. On the other hand, when the electron transport layer 6 is formed by a dry film-forming method, a vacuum vapor deposition method, a sputtering method, or the like can be applied.

2-2-7. Light-emitting layer 5
The light-emitting layer 5 has a function of emitting light using energy generated by recombination of holes and electrons injected into the light-emitting layer 5 . The light-emitting layer 5 of the present embodiment emits blue light with a wavelength in the range of 400-500 nm, more preferably in the range of 420-480 nm.

The light-emitting layer 5 preferably contains a light-emitting material (guest material or dopant material) and a host material. In this case, the mass ratio of the host material and the light-emitting material is not particularly limited, but is preferably in the range of 10:1 to 300:1. A compound capable of converting singlet excitation energy into light or a compound capable of converting triplet excitation energy into light can be used as the light-emitting material. In addition, the light-emitting material preferably contains at least one selected from the group consisting of organic low-molecular-weight fluorescent materials, organic high-molecular-weight fluorescent materials, and organic phosphorescent materials.

Compounds capable of converting singlet excitation energy into light include organic low-molecular fluorescent materials and organic high-molecular fluorescent materials that emit fluorescence.

Compounds having an anthracene structure, tetracene structure, chrysene structure, phenanthrene structure, pyrene structure, perylene structure, stilbene structure, acridone structure, coumarin structure, phenoxazine structure, or phenothiazine structure are preferred as organic low-molecular-weight fluorescent materials.

Specific examples of organic low-molecular-weight fluorescent materials include, for example, 5,6-bis[4-(10-phenyl-9-anthryl)phenyl]-2,2'-bipyridine, 5,6-bis[4'-( 10-phenyl-9-anthryl)biphenyl-4-yl]-2,2′-bipyridine (,N,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenyl Stilbene-4,4'-diamine, 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine, 4-(9H-carbazol-9-yl)-4 '-(9,10-diphenyl-2-anthryl)triphenylamine, N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine, 4- (10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine, 4-[4-(10-phenyl-9-anthryl)phenyl]-4′- (9-phenyl-9H-carbazol-3-yl)triphenylamine, perylene, 2,5,8,11-tetra(tert-butyl)perylene, N,N'-diphenyl-N,N'-bis[4 -(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis[3-(9-phenyl -9H-fluoren-9-yl)phenyl]-pyrene-1,6-diamine, N,N'-bis(dibenzofuran-2-yl)-N,N'-diphenylpyrene-1,6-diamine, N, N'-bis(dibenzothiophen-2-yl)-N,N'-diphenylpyrene-1,6-diamine, N,N''-(2-tert-butylanthracene-9,10-diyldi-4,1 -phenylene)bis[N,N′,N′-triphenyl-1,4-phenylenediamine], N,9-diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H -carbazol-3-amine, N-[4-(9,10-diphenyl-2-anthryl)phenyl]-N,N',N'-triphenyl-1,4-phenylenediamine, N,N,N' ,N′,N″,N″,N′″,N′″-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetraamine, coumarin 30, N-(9, 10-diphenyl-2-anthryl)-N,9-diph phenyl-9H-carbazol-3-amine, N-(9,10-diphenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine, N,N,9-triphenyl anthracen-9-amine, coumarin 6, coumarin 545T, N,N'-diphenylquinacridone, rubrene, 5,12-bis(1,1'-biphenyl-4-yl)-6,11-diphenyltetracene, 2-( 2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyran-4-ylidene)propanedinitrile, 2-{2-methyl-6-[2-(2,3, 6,7-tetrahydro-1H,5H-benzo[ij]quinolidin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile, N,N,N',N'-tetrakis(4-methyl phenyl)tetracene-5,11-diamine, 7,14-diphenyl-N,N,N',N'-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine, 2 -{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolidin-9-yl)ethenyl]- 4H-pyran-4-ylidene}propanedinitrile, 2-{2-tert-butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H-benzo[ij]quinolidin-9-yl)ethenyl]-4H-pyran-4-ylidene}propandinitrile, 2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}- 4H-pyran-4-ylidene)propanedinitrile, 2-{2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H ,5H-benzo[ij]quinolidin-9-yl)ethenyl]-4H-pyran-4-ylidene}propandinitrile, 5,10,15,20-tetraphenylbisbenzo[5,6]indeno[1,2 ,3-cd:1′,2′,3′-lm]perylene and the like.

Specific examples of organic polymeric fluorescent materials include, for example, homopolymers composed of units based on fluorene derivatives, copolymers composed of units based on fluorene derivatives and units based on tetraphenylphenylenediamine derivatives, and units based on terphenyl derivatives. and homopolymers composed of units based on diphenylbenzofluorene derivatives.

As the compound capable of converting triplet excitation energy into light, an organic phosphorescent material that emits phosphorescence is preferable. Specific examples of organic phosphorescent materials include metals containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, palladium, silver, gold, and aluminum. complexes. Among them, the organic phosphorescent material is preferably a metal complex containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium and palladium. and ruthenium, more preferably a metal complex containing at least one metal atom, and more preferably an iridium complex or a platinum complex.

As the host material, it is preferable to use at least one compound having an energy gap larger than that of the light-emitting material. Furthermore, when the light-emitting material is a phosphorescent material, a compound having a triplet excitation energy greater than the triplet excitation energy (the energy difference between the ground state and the triplet excited state) of the light-emitting material can be selected as the host material. preferable.

Examples of host materials include tris(8-quinolinolato)aluminum (III), tris(4-methyl-8-quinolinolato)aluminum (III), bis(10-hydroxybenzo[h]quinolinato)beryllium (II), bis (2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III), bis(8-quinolinolato)zinc(II), bis[2-(2-benzoxazolyl)phenolato]zinc(II) , bis[2-(2-benzothiazolyl)phenolato]zinc(II), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 1,3- Bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene, 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl )-1,2,4-triazole, 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole), bathophenanthroline, bathocuproine, 9-[ 4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole, 9,10-diphenylanthracene, N,N-diphenyl-9-[4-(10-phenyl -9-anthryl)phenyl]-9H-carbazol-3-amine, 4-(10-phenyl-9-anthryl)triphenylamine, N,9-diphenyl-N-{4-[4-(10-phenyl- 9-anthryl)phenyl]phenyl}-9H-carbazol-3-amine, 6,12-dimethoxy-5,11-diphenylchrysene, 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9H-carbazole , 3,6-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H -carbazole, 7-[4-(10-phenyl-9-anthryl)phenyl]-7H-dibenzo[c,g]carbazole, 6-[3-(9,10-diphenyl-2-anthryl)phenyl]-benzo [b] naphtho[1,2-d]furan, 9-phenyl-10-{4-(9-phenyl-9H-fluoren-9-yl)biphenyl-4′-yl}anthracene, 9,10-bis( 3,5-diphenylphenyl)anthracene, 9,1 0-di(2-naphthyl)anthracene, 2-tert-butyl-9,10-di(2-naphthyl)anthracene, 9,9'-bianthryl, 9,9'-(stilbene-3,3'-diyl) Diphenanthrene, 9,9′-(stilbene-4,4′-diyl)diphenanthrene, 1,3,5-tri(1-pyrenyl)benzene, 5,12-diphenyltetracene or 5,12-bis(biphenyl- 2-yl)tetracene and the like. These host materials may be used individually by 1 type, or may use 2 or more types together.

Although the thickness of the light-emitting layer 5 is not particularly limited, it is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm.

Such a light-emitting layer 5 can be formed by a wet film-forming method or a dry film-forming method. When the light-emitting layer 5 is formed by a wet film-forming method, the ink containing the above-described light-emitting material and host material is usually applied by various coating methods, and the resulting coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet ejection method), a spin coating method, a casting method, an LB method, a letterpress printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. mentioned. On the other hand, when the light-emitting layer 5 is formed by a dry film-forming method, a vacuum deposition method, a sputtering method, or the like can be applied.

The EL light source section 200 may further have a bank (partition wall) that partitions the hole injection layer 3, the hole transport layer 4 and the light emitting layer 5, for example. The bank height is not particularly limited, but is preferably in the range of 0.1 to 5 μm, more preferably in the range of 0.2 to 4 μm, and further preferably in the range of 0.2 to 3 μm. preferable.

The width of the bank opening is preferably in the range of 10 to 200 μm, more preferably in the range of 30 to 200 μm, even more preferably in the range of 50 to 100 μm. The length of the bank opening is preferably in the range of 10 to 400 μm, more preferably in the range of 20 to 200 μm, even more preferably in the range of 50 to 200 μm. Also, the inclination angle of the bank is preferably in the range of 10 to 100°, more preferably in the range of 10 to 90°, even more preferably in the range of 10 to 80°.

2-3. light conversion layer 12
The light conversion layer 12 converts the light emitted from the EL light source unit 200 to re-emit light, or transmits the light emitted from the EL light source unit 200 . As shown in FIG. 3, as the pixel unit 20, a first pixel unit 20a that converts light having a wavelength in the above range and emits red light, and a second pixel unit 20a that converts light having a wavelength in the above range and emits green light. and a third pixel portion 20c that transmits light having a wavelength in the above range. A plurality of first pixel units 20a, second pixel units 20b, and third pixel units 20c are arranged in a grid so as to repeat this order. Between adjacent pixel portions, that is, between the first pixel portion 20a and the second pixel portion 20b, between the second pixel portion 20b and the third pixel portion 20c, and between the third pixel portion A light blocking portion 30 for blocking light is provided between 20c and the first pixel portion 20a. In other words, these adjacent pixel portions are separated by the light shielding portion 30 . The first pixel portion 20a and the second pixel portion 20b may contain coloring materials corresponding to respective colors.

The first pixel portion 20a and the second pixel portion 20b each contain a cured product of the nanocrystal-containing composition of the embodiment described above. The cured product essentially contains the light-emitting fine particles 90 and a curing component, and further preferably contains light scattering particles in order to scatter light and reliably extract it to the outside. The curing component is a cured product of a thermosetting resin, such as a cured product obtained by polymerization of a resin containing an epoxy group. That is, the first pixel portion 20a includes a first curing component 22a, and first light emitting fine particles 90a and first light scattering particles 21a dispersed in the first curing component 22a. Similarly, the second pixel portion 20b includes a second curing component 22b, and first luminescent fine particles 90b and first light scattering particles 21b dispersed in the second curing component 22b, respectively. In the first pixel portion 20a and the second pixel portion 20b, the first curing component 22a and the second curing component 22b may be the same or different, and may be the first light scattering particles 22a. It may be the same as or different from the second light scattering particles 22b.

The first light emitting fine particles 90a are red light emitting fine particles that absorb light with a wavelength in the range of 420 to 480 nm and emit light with an emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel section 20a can be rephrased as a red pixel section for converting blue light into red light. The second light-emitting fine particles 90b are green light-emitting fine particles that absorb light with a wavelength in the range of 420 to 480 nm and emit light with an emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel section 20b can be rephrased as a green pixel section for converting blue light into green light.

The content of the light-emitting fine particles 90 in the pixel portions 20a and 20b containing the cured product of the nanocrystal-containing composition is the same as that of the nanocrystal-containing composition, from the viewpoint of improving the external quantum efficiency and obtaining excellent emission intensity. It is preferably 1% by mass or more based on the total mass of the cured product. From the same point of view, the content of the light-emitting fine particles 90 may be 5% by mass or more, 10% by mass or more, or 15% by mass, based on the total mass of the cured product of the nanocrystal-containing composition. % or more. The content of the light-emitting fine particles 90 is preferably 40% by mass or less based on the total mass of the nanocrystal-containing composition, from the viewpoint of obtaining excellent reliability of the pixel portions 20a and 20b and excellent emission intensity. . From a similar point of view, the content of the luminescent particles 90 may be 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total mass of the cured product of the nanocrystal-containing composition. % by mass or more.

The content of the light-scattering particles 21a and 21b in the pixel portions 20a and 20b containing the cured product of the nanocrystal-containing composition is the total mass of the cured product of the nanocrystal-containing composition, from the viewpoint of improving the external quantum efficiency. Based on the, it may be 0.1% by mass or more, may be 1% by mass or more, may be 5% by mass or more, may be 7% by mass or more, and may be 10% by mass or more. It may be present, and may be 12% by mass or more. The content of the light-scattering particles 21a and 21b is 60 mass based on the total mass of the cured product of the nanocrystal-containing composition, from the viewpoint of improving the external quantum efficiency and the reliability of the pixel section 20. % or less, may be 50% by mass or less, may be 40% by mass or less, may be 30% by mass or less, may be 25% by mass or less, or may be 20% by mass It may be less than or equal to 15% by mass or less.

The third pixel portion 20c has a transmittance of 30% or more for light with a wavelength in the range of 420-480 nm. Therefore, the third pixel section 20c functions as a blue pixel section when using a light source that emits light with a wavelength in the range of 420 to 480 nm. The third pixel portion 20c includes, for example, a cured product of the composition containing the thermosetting resin described above. The cured product contains 22 cc of the third cured component. The third curing component 22c is a cured product of a thermosetting resin, specifically a cured product obtained by polymerization of a resin containing an epoxy group. That is, the third pixel portion 20c includes the third curing component 22c. When the third pixel portion 20c contains the above-described cured product, the composition containing the thermosetting resin has a transmittance of 30% or more for light with a wavelength in the range of 420 to 480 nm. Among the components contained in the crystal-containing composition, components other than the thermosetting resin, curing agent and solvent may be further contained. Note that the transmittance of the third pixel section 20c can be measured with a microspectroscope.

The thickness of the pixel portion (the first pixel portion 20a, the second pixel portion 20b, and the third pixel portion 20c) is not particularly limited, but may be, for example, 1 μm or more, or may be 2 μm or more. , 3 μm or more. The thickness of the pixel portion (the first pixel portion 20a, the second pixel portion 20b, and the third pixel portion 20c) may be, for example, 30 μm or less, 25 μm or less, or 20 μm or less. may

The light conversion layer 12 having the first to third pixel portions 20a to 20c can be formed by drying and heating a coating film formed by a wet film forming method to cure the film. The first pixel portion 20a and the second pixel portion 20b can be formed using the nanocrystal-containing composition of the present invention. On the other hand, the third pixel portion 20c can be formed using a resin composition that does not contain the luminescent fine particles 90 contained in the nanocrystal-containing composition.

Hereinafter, a method for forming a coating film as the light conversion layer 12 using an ink composition using the nanocrystal-containing composition of the present invention will be described. The coating method for obtaining the coating film is not particularly limited, but for example, inkjet printing method (piezo method or thermal droplet ejection method), spin coating method, casting method, LB method, letterpress printing method, gravure printing. method, screen printing method, nozzle printing method, and the like. Here, the nozzle printing method is a method in which the ink composition is applied in stripes from nozzle holes as liquid columns. Among them, an inkjet printing method (particularly, a piezoelectric droplet discharging method) is preferable as the coating method. As a result, the heat load when ejecting the ink composition can be reduced, and the deterioration of the light-emitting fine particles 90 due to heat can be prevented.

The conditions for the inkjet printing method are preferably set as follows. The ejection amount of the ink composition is not particularly limited, but is preferably 1 to 50 pL/time, more preferably 1 to 30 pL/time, and even more preferably 1 to 20 pL/time.

Moreover, the opening diameter of the nozzle hole is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 30 μm. This can improve ejection accuracy of the ink composition while preventing clogging of the nozzle holes.

The temperature at which the coating film is formed is not particularly limited, but is preferably in the range of 10 to 50°C, more preferably in the range of 15 to 40°C, and preferably in the range of 15 to 30°C. More preferred. By ejecting droplets at such a temperature, crystallization of various components contained in the ink composition can be suppressed.

In addition, the relative humidity when forming the coating film is not particularly limited, but it is preferably in the range of 0.01 ppm to 80%, more preferably in the range of 0.05 ppm to 60%, and 0.1 ppm It is more preferably in the range of ~15%, particularly preferably in the range of 1 ppm to 1%, and most preferably in the range of 5 to 100 ppm. When the relative humidity is equal to or higher than the above lower limit, it becomes easy to control the conditions for forming the coating film. On the other hand, when the relative humidity is equal to or less than the above upper limit, the amount of water adsorbed to the coating film, which may adversely affect the light conversion layer 12 obtained, can be reduced.

The obtained coating film may be dried by leaving it at room temperature (25° C.) or by heating. From the viewpoint of productivity, it is preferable to dry by heating. When drying is performed by heating, the drying temperature is not particularly limited, but the temperature is preferably set in consideration of the boiling point and vapor pressure of the organic solvent used in the ink composition. The drying temperature is preferably 50 to 130.degree. C., more preferably 60 to 120.degree. C., and particularly preferably 70 to 110.degree. If the drying temperature is 50°C or less, the organic solvent cannot be removed. I don't like it. Drying is preferably carried out under reduced pressure, more preferably under reduced pressure of 0.001 to 100 Pa. Furthermore, the drying time is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, particularly preferably 1 to 10 minutes. By drying the coating film under such drying conditions, the organic solvent is reliably removed from the coating film, and the external quantum efficiency of the resulting light conversion layer 12 can be further improved.

The ink composition of the present invention can be completely cured by further heating after the pre-baking step of the coating film. The heating temperature for complete curing is preferably 150 to 260°C, more preferably 160 to 230°C, and particularly preferably 170 to 210°C.

The heating time for complete curing is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, particularly preferably 1 to 10 minutes. Furthermore, the heating for complete curing can be carried out in the air or in an inert gas, but is more preferably carried out in an inert gas in order to suppress oxidation of the coating film. Nitrogen, argon, carbon dioxide, etc. are mentioned as an inert gas. By curing the coating film under such heating conditions, the coating film can be completely cured, so that the external quantum efficiency of the resulting light conversion layer 9 can be further improved.

The ink composition of the present invention may be cured by irradiation with active energy rays (eg, ultraviolet rays) in addition to curing by heating. As an irradiation source (light source), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like is used.
The wavelength of the irradiated light is preferably 200 nm or more, and more preferably 440 nm or less. Also, the light irradiation amount (exposure amount) is preferably 10 mJ/cm ² or more, and more preferably 4000 mJ/cm ² or less.

As described above, the nanocrystal-containing composition of the present invention is excellent in stability against heat, so that even the pixel section 20, which is a molded body after heat curing, can achieve good light emission. Furthermore, since the luminescent fine particle composition of the present invention is excellent in dispersibility, the luminescent fine particles 910 and 90 are excellent in dispersibility, and a flat pixel portion 20 can be obtained.

Furthermore, since the light-emitting fine particles 90 contained in the first pixel portion 20a and the second pixel portion 20b contain semiconductor nanocrystals made of metal halide, they have a large absorption in the wavelength range of 300 to 500 nm. Therefore, in the first pixel portion 20a and the second pixel portion 20b, the blue light incident on the first pixel portion 20a and the second pixel portion 20b is transmitted to the upper substrate 13 side. Leakage to the substrate 13 side can be prevented. Therefore, according to the first pixel portion 20a and the second pixel portion 20b of the present invention, red light and green light with high color purity can be extracted without mixing blue light.

The light blocking section 30 is a so-called black matrix provided for the purpose of separating the adjacent pixel sections 20 to prevent color mixture and for the purpose of preventing light leakage from the light source. The material constituting the light shielding part 30 is not particularly limited, and in addition to metals such as chromium, curing of a resin composition in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, organic pigments, etc. are contained in a binder polymer. objects, etc. can be used. As the binder polymer used here, one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, etc., photosensitive resin, O/W An emulsion-type resin composition (for example, an emulsified reactive silicone) can be used. The thickness of the light shielding portion 30 may be, for example, 1 μm or more and 15 μm or less.

The light emitting device 100 can be configured as a bottom emission type instead of a top emission type.
Also, the light emitting element 100 can use another light source instead of the EL light source section 200 .

As described above, the nanocrystal-containing composition, the ink composition, the method for producing the same, and the light-emitting device provided with the light conversion layer produced using the ink composition of the present invention have been described. It is not limited to the configuration of the form. For example, the luminescent fine particles, the luminescent fine particle dispersion, the nanocrystal-containing composition, the ink composition, and the light-emitting device of the present invention each have any other configuration in addition to the configurations of the above-described embodiments. , or may be replaced with any structure that performs a similar function. In addition, the method for producing luminescent fine particles of the present invention may have other arbitrary steps in the configuration of the above-described embodiment, or may be replaced with arbitrary steps that exhibit similar effects. good.

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited only to the following examples. All the materials used in the examples were obtained by introducing argon gas to replace dissolved oxygen with argon gas. Before mixing, titanium oxide was heated at 120° C. for 2 hours under a reduced pressure of 1 mmHg and allowed to cool in an argon gas atmosphere. The liquid materials used in the examples were previously dehydrated with molecular sieves 3A for 48 hours or more before mixing.

<Preparation of luminescent fine particles>
(Preparation of luminescent fine particles A)
Cesium carbonate (0.815 g), 1-octadecene (40 ml), and oleic acid (2.5 ml) were added to a three-necked flask, dried under vacuum at 120°C for 1 hour, and then heated to 150°C to remove cesium oleate. prepared.

After adding lead (II) bromide (55 mg), 1-octadecene (5 ml), oleylamine (0.5 ml), and oleic acid (0.5 ml) to another three-necked flask and heating at 110° C. for 30 minutes under vacuum , and heated to 180° C. under an argon stream. Furthermore, the above cesium oleate solution (0.8 ml) heated at 150° C. was added with a syringe, reacted for 15 seconds, and then rapidly cooled in an ice bath.

The resulting reaction solution was centrifuged (8000 G×5 minutes) to collect solid matter. Toluene (20 ml) was added to the obtained solid to obtain a suspension. This suspension was subjected to centrifugation (8000 G×5 minutes), precipitates containing impurities were removed by decantation, and the supernatant toluene solution was recovered. Ethyl acetate (20 ml) was added to the recovered toluene solution to reprecipitate the solid, thereby obtaining luminous microparticles A. The obtained light-emitting fine particles A have a ligand consisting of oleylamine and oleic acid on the surface of lead tribromide cesium crystals having a perovskite crystal structure and exhibiting light emission. corresponds to The average particle diameter of the luminescent fine particles A was 10 nm. The average particle size of the luminous fine particles A was measured by Nanotrac Wave II (manufactured by Microtrac) and found to be 10 nm on average.

(Preparation of luminescent fine particles B)
A toluene solution (0.05M) of N-1(1-adamantyl)ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared. The luminous fine particles A, oleic acid (50 ml), and the N-1(1-adamantyl)ethylenediamine solution (2 ml) were added to an eggplant flask and stirred for 1 minute. At this time, the luminescent fine particles A were added so that the concentration was 15 mg/mL. Ethyl acetate (100 ml) was added to the resulting solution, followed by centrifugation (8000 G×5 minutes) to obtain luminous fine particles B. The light-emitting fine particles B have a ligand composed of N-1(1-adamantyl)ethylenediamine on the surface of a cesium lead tribromide crystal that has a perovskite-type crystal structure and exhibits light emission. It corresponds to the fine particle 910 . The average particle size of the light-emitting fine particles B was 10 nm.

(Preparation of luminescent fine particles C)
Cesium carbonate (0.81 g), 1-octadecene (40 ml) and oleic acid (2.5 ml) were mixed to obtain a mixture. Next, this mixed solution was dried under reduced pressure at 120° C. for 10 minutes, and then heated at 150° C. under an argon atmosphere. This gave a cesium-oleic acid solution.

On the other hand, lead (II) bromide (138.0 mg) and 1-octadecene (10 mL) were mixed to obtain a mixture. Next, this mixed solution was dried under reduced pressure at 120° C. for 10 minutes, and then 3-aminopropyltriethoxysilane (1 ml) was added to this mixed solution in an argon atmosphere to obtain a mixed solution (1).

After that, the mixture (1) was heated to 140° C., the cesium-oleic acid solution (1.3 ml) was added, and the mixture was reacted by heating and stirring for 5 seconds, and then cooled in an ice bath. .

Then, the resulting reaction solution was stirred in the atmosphere (23° C., 45% humidity) for 60 minutes, and then ethanol (20 ml) was added to obtain a suspension. The resulting suspension was centrifuged (3,000 rpm, 5 minutes) to collect solids.

By adding the collected solid matter to 16 ml of hexane, a hexane dispersion liquid of the light-emitting fine particles C was obtained. The light-emitting fine particles C are composed of a ligand of oleic acid and a ligand of 3-aminopropyltriethoxysilane having a reactive group on the surface of lead tribromide cesium crystals having a perovskite crystal structure and exhibiting light emission. and a silica coating layer corresponding to the inorganic coating layer 91 containing Si in FIG. The average particle size of the luminescent fine particles C was 10 nm, and the thickness of the inorganic coating layer was 1 nm.

<Preparation of monomer solution>
(Monomer solution 1)
1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate as a photopolymerizable monomer (8.85 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), light acrylate DCP-A (0.5 parts by mass) , manufactured by Kyoeisha Chemical Co., Ltd.) and stirred at room temperature to dissolve uniformly, thereby obtaining a monomer solution 1.

(Monomer solution 2)
Except that isobornyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate in the method for preparing the monomer solution 1. obtained a monomer solution 2 in the same manner as the method for preparing the monomer solution 1.

(Monomer solution 3)
In the method for preparing the monomer solution 1, dicyclopentanyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. A monomer solution 3 was obtained in the same manner as the method for preparing the monomer solution 1, except that it was used.

(Monomer solution 4)
In the method for preparing the monomer solution 1, 1-adamantyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) is used instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. A monomer solution 4 was obtained in the same manner as the method for preparing the monomer solution 1, except that

(Monomer solution 5)
In the method for preparing the monomer solution 1, 2-methyl-2-adamantyl methacrylate (Tokyo Chemical Industry Co., Ltd. A monomer solution 5 was obtained in the same manner as the preparation method of the monomer solution 1, except that the product was used.

(Monomer solution 6)
In the method for preparing the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, isobornyl methacrylate (4.85 parts by mass, Tokyo Chemical Industry Co., Ltd. (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 1-adamantyl methacrylate (4.00 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) were used.

(Monomer solution 7)
In the method for preparing the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, Light Ester L (0.30 parts by mass, manufactured by Kyoeisha Chemical Co., Ltd. ), and 1-adamantyl methacrylate (8.55 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were used in the same manner as for the preparation of the monomer solution 1 to obtain a monomer solution 7.

(Monomer solution 8)
In the method for preparing the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, Light Ester L (3.00 parts by mass, manufactured by Kyoeisha Chemical Co., Ltd. ), and 1-adamantyl methacrylate (5.85 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were used in the same manner as for the preparation of the monomer solution 1 to obtain a monomer solution 8.

(Monomer solution 9)
In the method for preparing the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, Light Ester L (8.85 parts by mass, manufactured by Kyoeisha Chemical Co., Ltd. ) was used to obtain a monomer solution 9 in the same manner as for the preparation of the monomer solution 1.

(Monomer solution 10)
In the method for preparing the monomer solution 1, isobornyl methacrylate (8.85 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. ) was used, and TMPTA (0.5 parts by mass, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of light acrylate DCP-A. rice field.

(Monomer solution 11)
In the method for preparing the monomer solution 1, Light Ester L (8.85 parts by mass, manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate. A monomer solution 11 was obtained in the same manner as the monomer solution 1 except that TMPTA (0.5 parts by mass, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of the light acrylate DCP-A. .

(Monomer solution 12)
In the method for preparing the monomer solution 1, light ester PO-A (8.85 parts by mass, Kyoeisha Chemical Co., Ltd. A monomer solution 12 was obtained in the same manner as in the preparation method of the monomer solution 1, except for using

<Preparation of QD dispersion>
(Example 1)
Light-emitting fine particles A (0.015 parts by mass) were mixed with monomer solution 1 (0.935 parts by mass), and the mixture was stirred at room temperature for uniform dispersion. The resulting dispersion was filtered through a filter with a pore size of 5 μm to obtain QD Dispersion 1 as a nanocrystal-containing composition.

(Examples 2 to 8, 10, 40)
QD dispersions 2 to 8 and QD dispersion 10 were prepared in the same manner as in the method for preparing QD dispersion 1, except that monomer solutions 2 to 8, monomer solution 10, and monomer solution 12 were used instead of monomer solution 1. , and QD dispersion 13 were obtained.

(Example 9)
QD Dispersion 9 was obtained in the same manner as in the preparation method of QD Dispersion 1, except that Monomer Solution 9 was used instead of Monomer Solution 1, and Light-Emitting Fine Particles B were used instead of Light-Emitting Fine Particles A.

(Example 11)
QD Dispersion 11 was obtained in the same manner as in the preparation method of QD Dispersion 1, except that Monomer Solution 11 was used instead of Monomer Solution 1, and Light-Emitting Fine Particle B was used instead of Light-Emitting Fine Particle A.

(Example 12)
A QD dispersion 12 was obtained in the same manner as in the preparation method of the QD dispersion 1 except that the monomer solution 4 was used instead of the monomer solution 1 and the luminescent fine particles C were used instead of the luminescent fine particles A.

(Comparative example 1)
QD Dispersion C1 was obtained in the same manner as in the method for preparing QD Dispersion 1, except that Monomer Solution 9 was used instead of Monomer Solution 1.

The following table shows the contents of the monomer solutions 1 to 11 and the luminescent fine particles A to C in the QD dispersions 1 to 12 of Examples 1 to 12 and the QD dispersion C1 of Comparative Example 1. In addition, the unit of a numerical value is a mass part.

<Preparation of monomer solution containing initiator>
(Monomer solution B1)
Photopolymerization was initiated in the same manner as in the method for preparing monomer solution 1, except that two photopolymerization initiators were added in addition to the above-described photopolymerizable monomers, and that stirring was performed at 60 ° C. instead of room temperature. A monomer solution B1 containing the agent was obtained. As two types of photopolymerization initiators, 0.3 parts by mass of "Omnirad TPO" manufactured by IGM Resin and 0.2 parts by mass of "Omnirad 819" manufactured by IGM Resin were added.

(Monomer solution B2 to monomer solution B11, 13)
Monomer solution B2 to monomer solution B11 containing a photopolymerization initiator and monomer solution B13 are obtained in the same manner as in the method for preparing monomer solution B1, except that monomer solution 2 to monomer solution 11 are used instead of monomer solution 1. rice field.

(Monomer solution B12)
In the method for preparing the monomer solution B1, a photopolymerization initiator was added in the same manner, except that the monomer solution 2 was used instead of the monomer solution 1, and only one type of photopolymerization initiator was added instead of the two types of photopolymerization initiators. A monomer solution B12 containing As one type of photopolymerization initiator, 0.5 parts by mass of "Omnirad TPO" manufactured by IGM Resin was added.

The table below shows the contents of the monomer solutions B1 to B12. The unit of numerical values in the table is parts by mass.

<Preparation of QD dispersion B>
(QD dispersion B1)
Light-emitting fine particles A (0.015 parts by mass) are mixed with a monomer solution B1 (0.985 parts by mass) containing a photopolymerization initiator, and uniformly dispersed by stirring at room temperature to obtain a QD dispersion B1. rice field.

(QD dispersion B2 to QD dispersion B8)
QD dispersions B2 to B8 were obtained in the same manner as in the method for preparing QD dispersion B1, except that monomer solutions B2 to B8 containing photopolymerization initiators were used instead of monomer solution B1 containing photopolymerization initiators. .

(QD dispersion B9)
In the method for preparing QD dispersion B1, the monomer solution B9 containing a photopolymerization initiator is used instead of the monomer solution B1 containing a photopolymerization initiator, and the light-emitting fine particles B are used instead of the light-emitting fine particles A. , to obtain QD dispersion B9.

(QD dispersion B10)
A QD dispersion B10 was obtained in the same manner as in the method for preparing QD dispersion B1, except that monomer solution B10 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator.

(QD dispersion B11)
In the method for preparing the QD dispersion B1, the monomer solution B11 containing a photopolymerization initiator is used instead of the monomer solution B1 containing a photopolymerization initiator, and the light-emitting fine particles B are used instead of the light-emitting fine particles A. , to obtain QD dispersion B11.

(QD dispersion B12)
In the method for preparing the QD dispersion B1, the monomer solution B4 containing a photopolymerization initiator is used instead of the monomer solution B1 containing a photopolymerization initiator, and the light-emitting fine particles C are used instead of the light-emitting fine particles A. , to obtain QD dispersion B12.

(QD dispersion B13)
A QD dispersion B13 was obtained in the same manner as in the method for preparing QD dispersion B1, except that monomer solution B12 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator.
(QD dispersion B14)
A QD dispersion B14 was obtained in the same manner as in the method for preparing QD dispersion B1, except that monomer solution B13 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator.

(QD dispersion BC1)
QD dispersion BC1 was obtained in the same manner as in the preparation method of QD dispersion B9, except that luminescent fine particles A were used instead of luminescent fine particles B.

The table below shows the contents of QD dispersions B1 to B14 and QD dispersion BC1. The unit of numerical values in the table is parts by mass.

<Preparation of light-scattering particle dispersion>
(Light-scattering particle dispersion 1)
Titanium oxide particles (55 parts by mass, manufactured by Ishihara Sangyo Co., Ltd., "CR-60-2") and a photopolymerizable monomer dicyclopentanyl methacrylate (45 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) Mixed. Note that the average particle size (volume average size) of the titanium oxide particles is 300 nm. Next, after adding zirconia beads (diameter: 0.3 mm) to the resulting formulation, the formulation was dispersed by shaking for 2 hours using a paint conditioner. Thus, a light scattering particle dispersion 1 was obtained.

(Light-scattering particle dispersion 2)
In the method for preparing light-scattering particle dispersion 1, the same as the method for preparing light-scattering particle dispersion 1, except that Light Ester L (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. Then, a light-scattering particle dispersion 2 was obtained.

<Preparation of QD ink>
(Example 13)
Light-scattering particle dispersion 1 (6 parts by mass) was mixed with QD dispersion B1 (94 parts by mass) and stirred at room temperature for uniform dispersion. A QD ink 1 as a nanocrystal-containing composition and an ink composition was obtained by filtering the resulting dispersion through a filter with a pore size of 5 μm.

(Examples 14 to 24, 41)
In the method for preparing QD ink 1 of Example 13, in the same manner as the method for preparing QD ink 1, except that QD dispersions B2 to 12 and QD dispersion B14 were used instead of QD dispersion B1. QD Inks 2-12 and QD Ink 14 were obtained.

(Example 25)
In the method for preparing QD ink 1 of Example 13, QD Ink 1 was used, except that QD Dispersion B13 was replaced with QD Dispersion B1, and Light Scattering Dispersion 2 was replaced with Light Scattering Dispersion 1. QD ink 13 was obtained in the same manner as in the preparation method of .

(Comparative example 2)
QD ink C1 was obtained in the same manner as in the method for preparing QD ink 1 of Example 13, except that QD dispersion CB1 was used instead of QD dispersion B1.

The contents of QD ink 1 of Example 13 to QD ink 13 of Example 25, QD ink 14 of Example 41, and QD ink C1 of Comparative example 2 are shown in the table below. The unit of numerical values in the table is parts by mass.

<Preparation of light conversion layer>
(Example 26)
The obtained QD ink 1 of Example 13 was applied onto a glass substrate (manufactured by Corning, "EagleXG") by a spin coater so that the film thickness after drying was 10 µm.

The coating film thus obtained was irradiated with UV light having a wavelength of 365 nm from an LED lamp at an exposure amount of 2000 mJ/cm ² in a nitrogen atmosphere. As a result, the QD ink 1 of Example 13 was cured to form a layer of the cured ink composition on the glass substrate, which was used as the light conversion layer 1 of Example 26.

(Examples 27-38, 42)
In the method for producing the light conversion layer 1 of Example 26, QD ink 2 of Example 14 to QD ink 13 of Example 25 and QD ink 14 of Example 41 were used instead of QD ink 1 of Example 13. In the same way, the light conversion layer 2 of Example 27 to the light conversion layer 13 of Example 38 and the light conversion layer 14 of Example 42 were produced.

(Comparative Example 3)
A light conversion layer C1 of Comparative Example 3 was produced in the same manner as in the method of producing the light conversion layer 1 of Example 26, except that the QD ink C1 of Comparative Example 2 was used instead of the QD ink 1 of Example 13. .

<Evaluation>
[Quantum yield (PLQY) retention]
The quantum yields (PLQY) of QD dispersions 1 to 12 of Example 1 to QD dispersions 1 to 12 of Example 12, QD dispersion 13 of Example 40, and QD dispersion C1 of Comparative Example 1 are expressed as absolute PL quantum Measured with a yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., "Quantaurus-QY"), the quantum yield retention rate (quantum yield after standing for 10 days in the atmosphere after preparation, the quantum yield immediately after preparation ) was calculated. It means that the higher the quantum yield retention rate, the higher the stability of the light-emitting fine particles to oxygen gas and water vapor.

[Dispersion stability]
After leaving the QD inks 1 to 13 of Examples 13 to 25, the QD ink 14 of Example 41, and the QD ink C1 of Comparative Example 2 in the atmosphere, the presence or absence of precipitates was checked and evaluated according to the following criteria. .
〔Evaluation criteria〕
A: No precipitate was formed after 10 days.
B: After 10 days, a very small amount of precipitate is formed. The precipitate is dissolved by shaking.
C: After 10 days, a slightly large amount of precipitate is formed. Precipitate remains even after shaking.

[External Quantum Efficiency Retention Rate of Light Conversion Layer]
The external quantum efficiencies of the light conversion layers 1 to 13 of Examples 26 to 38, the light conversion layer 14 of Example 42, and the light conversion layer C1 of Comparative Example 3 were measured as follows. Efficiency retention (value obtained by dividing the external quantum efficiency 10 days after the formation of the light conversion layer by the external quantum efficiency immediately after the formation of the light conversion layer) was calculated.

A blue LED (peak emission wavelength: 450 nm; manufactured by CCS Co., Ltd.) was used as a surface emitting light source, and a light conversion layer was placed on the light source with the glass substrate side facing downward. The integrating sphere was connected to a radiation spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., "MCPD-9800"), and brought close to the light conversion layer placed on the blue LED. In this state, the blue LED was turned on, the quantum numbers of the excitation light and the emission (fluorescence) of the light conversion layer were measured, and the external quantum efficiency was calculated. It means that the higher the external quantum efficiency retention rate, the higher the stability of the light conversion layer containing light-emitting fine particles against oxygen gas and water vapor.

[3D parameters]
The table below shows the structural formulas of the compounds used as ligands coordinated to the surface of the luminescent nanocrystals described above.

The table below shows the structural formulas of the compounds used as monomers for the preparation of the QD dispersions and QD inks described above.

式（Ｃ）中、ｎは屈折率を表し、Ｍは分子量を表し、ｄは密度を表す。密度、及び屈折率は２０℃または２５℃の値を用いた。算出した立体パラメーターＭＲを下表に示す。For the compounds described above, the steric parameter MR was calculated using the following formula (C).

In formula (C), n represents refractive index, M represents molecular weight, and d represents density. Values at 20°C or 25°C were used for density and refractive index. The calculated steric parameters MR are shown in the table below.

<Evaluation of QD dispersion>
QD dispersions 1 to 12 of Examples 1 to 12, QD dispersion 13 of Example 40, and QD dispersion C1 of Comparative Example 1 are discussed below.

First, for the QD dispersion C1 of Comparative Example 1, the absolute value of the difference between the steric parameter MR of each monomer and the steric parameter MR of the ligand |ΔMR| A mean|ΔMR| _{weighted average} was calculated. Furthermore, when the PLQY retention rate was measured for the QD dispersion C1 of Comparative Example 1, it was 53.0%.

(1) |ΔMR| _PY in combination of light ester L and oleic acid
=|(MR of light ester L)−(MR of oleic acid)|
=|78.6-88.3|
= 9.7
(2) |ΔMR| _PZ in combination of light ester L and oleylamine
=|(MR of light ester L)−(MR of oleylamine)|
=|78.6-86.9|
= 8.3
(3) |ΔMR| _QX in combination of light acrylate DCP-A and oleic acid
=|(MR of light acrylate DCP-A)−(MR of oleic acid)|
=|82.2-88.3|
= 6.1
(4) |ΔMR| _QZ in combination of light acrylate DCP-A and oleylamine
=|(MR of light acrylate DCP-A)−(MR of oleylamine)|
=|82.2-86.9|
= 4.7

(5) Weighted average |ΔMR| _{weighted average} of |MR|
= {(|ΔMR| _PY × 0.5 + |ΔMR| _PZ × 0.5) × m _P + (|ΔMR| _QY × 0.5 + |ΔMR| _QZ × 0.5) × m _Q }/(m _P + m _Q )
= {(9.7*0.5+8.3*0.5)*8.85+(6.1*0.5+4.7*0.5)*0.5}/(8.85+0.5)
=8.8
However, the |ΔMR| _{weighted average} was calculated with the coordination ratio of oleic acid and oleylamine coordinated to the surface of the luminescent nanocrystal being 0.5:0.5.

Next, for the QD dispersions 1 to 12 of Examples 1 to 12 and the QD dispersion 13 of Example 40, the |ΔMR| and |ΔMR| _{weighted averages} were calculated in the same manner as in Comparative Example 1. , PLQY retention was measured. In each QD dispersion 1 to 12, two types of ligands were used, and the ΔMR| _{weighted average} was calculated with the coordination ratio of each ligand set to 0.5:0.5. However, in the QD dispersion 12 of Example 12, a ligand made of oleic acid and a ligand made of 3-aminopropyltriethoxysilane were coordinated on the surface of the luminescent nanocrystal made of lead tribromide cesium crystal. is ranked. 3-Aminopropyltriethoxysilane coordinates to the surface of the luminescent nanocrystal and then forms a siloxane bond to cover the surface of the luminescent nanocrystal in a network. It is believed that the exchange of oleic acid and photopolymerizable monomer in the QD dispersion is inhibited. Therefore, for Example 12, the |ΔMR| _{weighted average} was calculated assuming that only oleic acid was coordinated to the surface of the luminescent nanocrystal, that is, the coordination ratio of oleic acid was 1. The results are shown in the table below.

As shown in the above table, the QD dispersions of Examples 1 to 12 and the QD dispersion of Example 40 have a maximum value of |ΔMR| of 12 or more, and a weighted average |ΔMR| of all |ΔMR| A _{weighted average} of 12 or more. On the other hand, the QD dispersion of Comparative Example 1 has a maximum value of | _ΔMR | It can be seen that the QD dispersions of Examples 1 to 12 and the QD dispersion of Example 40 exhibit higher PLQY retention than the QD dispersion of Comparative Example 1.

The QD dispersions of Examples 1 to 8, 10 and Comparative Example 1 contain cationic oleylamine and anionic oleic acid-coordinated light-emitting fine particles, whereas the QD dispersions of Examples 9 and 11 contains luminescent fine particles coordinated with cationic N-(1-adamantyl)ethylenediamine and anionic oleic acid. Also in Examples 9 and 11 in which N-(1-adamantyl)ethylenediamine was used instead of oleylamine and oleic acid as ligands, the PLQY retention rate of the QD dispersion was superior to that of Comparative Example 1. . From this, when a compound having no cyclic structure is used as a ligand and a compound having a cyclic structure is used as a monomer, and when a compound having a cyclic structure is used as a ligand and a cyclic structure is used as a monomer, It is clear that high PLQY retention is obtained in all cases of using compounds that do not have. Moreover, from the results of Examples 1 to 5 and Example 40, it can be seen that high PLQY is exhibited even if the cyclic structure is aromatic as well as aliphatic.

Further, from the results of Examples 1 to 12, it is clear that the higher the |ΔMR| _{weighted average} , the higher the PLQY retention rate tends to be.

Furthermore, the presence or absence of an inorganic coating layer in the light-emitting fine particles will be examined. In the QD dispersion of Example 12, 3-aminopropyltriethoxysilane was coordinated to the surface of the luminescent nanocrystals instead of oleylamine as a cationic ligand, and this ligand formed a siloxane bond. , is the same as the QD dispersion of Example 4, except that the surface of the luminescent nanocrystals is provided with an inorganic coating layer containing Si. The |ΔMR| _{weighted average} for the QD dispersion of Example 4 is 24.8, while the QD dispersion of Example 12 is 24.1, which is 0.7 smaller. However, the PLQY retention rate in the QD dispersion of Example 4 was 71.9, while that of the QD dispersion of Example 12 was 75.8, which was 3.9 higher. From this result, in the QD dispersion of Example 12, the luminescent nanocrystals were protected by forming an inorganic coating layer containing Si on the surface of the luminescent nanocrystals, and oleic acid and the photopolymerizable monomer It is thought that the PLQY retention rate increased as a result of the suppression of the exchange of .

<Evaluation of QD ink>
For the obtained QD inks of Examples 13 to 25, Example 41, and Comparative Example 2, the maximum |ΔMR| maximum value and ΔMR| _{weighted average} were calculated in the same manner as the QD dispersion. The maximum value of |ΔMR| and the _{weighted average} of ΔMR| were calculated in consideration of the steric parameter MR of dicyclopentanyl methacrylate and light ester L used in the preparation of light-scattering particle dispersions 1 and 2 as well. Furthermore, the dispersion stability of the QD ink was evaluated. The results are shown in the table below.

As shown in the table above, the QD inks of Examples 13 to 25 and the QD ink of Example 41 have | _ΔMR | is 12 or more. On the other hand, the QD ink of Comparative Example 2 has a maximum |ΔMR| of 12 or more, but the _{weighted average} of |ΔMR| It can be seen that the QD inks of Examples 13 to 25 are superior to the QD ink of Comparative Example 2 in dispersion stability. In particular, when the |ΔMR| _{weighted average} is 20 or more, all of them are "A", indicating excellent dispersion stability.

<Evaluation of light conversion layer>
Next, a light conversion layer was produced and evaluated by the method described above. The results are shown in the table below.

As shown in the above table, the light conversion layer C1 of Comparative Example 3 has a low external quantum efficiency retention rate of 67.0%, whereas the light conversion layers 1 to 13 of Examples 26 to 38 and Example The light conversion layer 14 of No. 42 showed a higher value than the light conversion layer C1 of Comparative Example 3.

From the results of the QD dispersions 1 to 12 of Examples 1 to 12, the QD dispersion 13 of Example 40, the QD inks 1 to 13 of Examples 13 to 25, and the QD ink 14 of Example 41, photopolymerization A nanocrystal-containing composition containing a metal halide luminescent nanocrystal having a ligand on its surface and having a |ΔMR| _{weighted average} of 12 or more has a |ΔMR| _{weighted average} of It is clear that not only is the PLQY retention rate superior to that of less than 12, but also the dispersion stability is superior.

Furthermore, from the results of the light conversion layers 1 to 13 of Examples 26 to 38 and the light conversion layer 14 of Example 42, the light conversion layer containing a cured product of a nanocrystal-containing composition having a |ΔMR| _{weighted average} of 12 or more _. From this, it can be expected that a light-emitting device having a light conversion layer formed from the nanocrystal-containing composition of the present invention also has excellent external quantum efficiency retention.

90 Light-emitting fine particles, inorganic-coated light-emitting fine particles, silica-coated light-emitting fine particles 91 Inorganic coating layer, silica-coating layer 910 Light-emitting fine particles, uncoated light-emitting fine particles 911 Nanocrystals 912 Ligand layer 100 Light emitting element 200 EL light source section 1 Lower substrate 2 Anode 3 hole injection layer 4 hole transport layer 5 light emitting layer 6 electron transport layer 7 electron injection layer 8 cathode 9 sealing layer 10 filling layer 11 protective layer 12 light conversion layer 13 upper substrate 14 EL layer 20 pixel section,
20a first pixel portion 20b second pixel portion 20c third pixel portion 21a first light scattering particles 21b second light scattering particles 21c third light scattering particles 22a first curing component 22b second curing Component 22c Third curing component 90a First luminescent fine particle 90b First luminescent fine particle 30 Light shielding part 701 Capacitor 702 Driving transistor 705 Common electrode 706 Signal line 707 Scanning line 708 Switching transistor C1 Signal line driving circuit C2 Scanning line driving circuit C3 Control circuit PE, R, G, B Pixel electrode X Copolymer XA Aggregate x1 Aliphatic polyamine chain x2 Hydrophobic organic segment YA Core-shell type silica nanoparticles Z Solution containing raw material compounds for semiconductor nanocrystals

Claims (7)

Containing one or more photopolymerizable monomers and luminescent fine particles having one or more ligands on the surfaces of luminescent nanocrystals made of metal halides and having a perovskite structure,
When the absolute value |ΔMR| of the difference between the steric parameter MR of an arbitrary photopolymerizable monomer and the steric parameter MR of an arbitrary ligand is calculated, the photopolymerizable monomer and ligand satisfying the following formula (A) One or more combinations exist, and
For all combinations of each photopolymerizable monomer and each ligand contained in the nanocrystal-containing composition, the content of each photopolymerizable monomer and each ligand is A _weighted average value |ΔMR| of |ΔMR| calculated in consideration of the ratio coordinated to the surface satisfies the following formula (B),
In the combination of the photopolymerizable monomer and the ligand that satisfy the formula (A), either the photopolymerizable monomer or the ligand contains a compound containing a cyclic structure,
In a combination of a photopolymerizable monomer and a ligand that satisfy the formula (A), when the photopolymerizable monomer contains a compound containing a cyclic structure, the ligand contains a linear molecular structure. wherein the steric parameter MR of the photopolymerizable monomer is in the range of 50 to 70 and the steric parameter MR of the ligand is in the range of 80 to 90,
In a combination of a photopolymerizable monomer and a ligand that satisfy the formula (A), when the ligand contains a compound containing a cyclic structure, the photopolymerizable monomer is a compound containing a linear molecular structure. wherein the steric parameter MR of the photopolymerizable monomer is in the range of 60-100 and the steric parameter MR of the ligand is in the range of 40-80
A nanocrystal-containing composition characterized by:
|ΔMR|=|(steric parameter MR of photopolymerizable monomer)−(steric parameter MR of ligand)|≧12 (A)
|ΔMR| _{weighted average} ≧12 (B)
(However, the steric parameter MR is the following formula (C)

In formula (C), n represents the refractive index, M represents the molecular weight, and d represents the density. ) The nanocrystal-containing composition according to claim 1 , wherein the compound containing a cyclic structure contains a cyclic structure represented by the following formulas (1-2) to (1-24).

1 or 2, wherein the luminescent fine particles have a ligand having a reactive group capable of forming a siloxane bond on the surface of the luminescent nanocrystal, and the ligand forms an inorganic coating layer containing Si. 3. The nanocrystal-containing composition of claim 2 . 4. The nanocrystal-containing composition according to any one of claims 1 to 3 , further comprising at least one of a photopolymerization initiator, a light scattering agent and a dispersing agent. An ink composition using the nanocrystal-containing composition according to any one of claims 1 to 4 . A light conversion layer comprising a cured product of the ink composition according to claim 5 . A light-emitting device comprising the light conversion layer according to claim 6 .

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