KR102547607B1 - Nanocrystal-containing composition, ink composition, light conversion layer and light emitting device - Google Patents

Abstract

The problem to be solved by the present invention is a composition containing nanocrystals having excellent dispersion stability and light emitting properties, an ink composition containing the composition, a light conversion layer containing a cured product of the ink composition, and a light conversion layer provided with the light conversion layer. It is to provide a light emitting element. The nanocrystal-containing composition of the present invention contains at least one photopolymerizable monomer and luminescent particulates having at least one ligand on the surface of a metal halide-containing luminescent nanocrystal, and the steric parameter MR of the photopolymerizable monomer is and the absolute value of the difference between the steric parameter MR of any ligand |ΔMR| is 12 or more, and in all combinations of each of the photopolymerizable monomers and each of the ligands contained in the nanocrystal-containing composition, | The weighted average value of ΔMR||ΔMR| characterized by _{a weighted average} of 12 or greater.

Description

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

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 element provided with the light conversion layer.

BT2020, which is required as a next-generation display device, is a very ambitious standard, and it is difficult to satisfy this even with color filters and organic EL using current pigments. On the other hand, quantum dots are materials that emit fluorescence such as red, green, and blue with a narrow half-value width of the emission wavelength, and are attracting attention as a light-emitting material capable of clearing BT2020. In the early quantum dots, core-shell type nanoparticles using CdSe or the like were used, but InP or the like has recently been used to avoid the harmfulness thereof. 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 diameter in order to obtain emission with a narrow half-value width, and there are many problems in their production.

In recent years, luminescent nanocrystals containing metal halide, in particular, quantum dots having a perovskite-type crystal structure have been discovered and are attracting attention. A general perovskite quantum dot (hereinafter sometimes referred to as “PeQD”) is a nano-sized crystal particle having a structure represented by CsPbX ₃ (X=Cl, Br, I). PeQD is advantageous in terms of productivity compared to conventional quantum dots in that the emission wavelength can be controlled by the ratio of halogen elements and the particle size can be easily controlled compared to InP quantum dots and the like.

Non-Patent Document 1 reports an ink composition containing PeQD and poly(methyl methacrylate) (hereinafter sometimes referred to as "PMMA"). On the other hand, Patent Literature 1 points out that the ink composition containing PeQD and PMMA has a problem that the solvent resistance of the coating film is not necessarily sufficient. Patent Literature 1 discloses an ink composition containing PeQD and a photopolymerizable monomer, which may further contain a solvent, and in which the ratios of carbon, oxygen, and nitrogen contained in the photopolymerizable monomer and the solvent are specified. Further, as a technique similar to Patent Document 1, Patent Document 2 includes nanocrystals as a curable composition containing fluorescent particles containing a perovskite compound, a photopolymerizable monomer, and a photopolymerization initiator, and specifying the LogP value of the photopolymerizable monomer. The containing composition is disclosed. The technical points of Patent Literature 1 and Patent Literature 2 focus on the polarity of the photopolymerizable monomer, and it is thought that the low polarity is preferable. However, as in the ink compositions or nanocrystal-containing compositions disclosed in these known documents, there was a problem that only focusing on the polarity of the photopolymerizable monomer was not sufficient to achieve both the dispersibility and light emitting properties of PeQD.

Japanese Patent No. 6506488 Japanese Patent Publication No. 2020-70443

Nano Lett. 2015, 15, 3692-3696

Therefore, the problem to be solved by the present invention is to provide a nanocrystal-containing composition having excellent dispersion stability and luminous properties, an ink composition containing the composition, a light conversion layer containing a cured product of the ink composition, and the light conversion layer. It is to provide the provided light emitting element.

As a result of intensive examination to solve the above problems, the present inventors have provided a ligand on the surface of a luminescent nanocrystal containing a metal halide, and used a ligand and a photopolymerizable monomer that satisfy specific conditions to achieve dispersion stability. and a nanocrystal-containing composition having excellent luminescent properties, and thus completed the present invention.

That is, the present invention contains light-emitting fine particles having one or two or more ligands on the surface of light-emitting nanocrystals containing one or two or more monomers and a metal halide, and the steric parameters of any photopolymerizable monomer. When the absolute value |ΔMR| of the difference between MR and any steric parameter MR is calculated, one or more combinations of photopolymerizable monomers and ligands satisfying the following formula (A) exist, and each contained in the nanocrystal-containing composition For all combinations of the photopolymerizable monomer and each ligand, the weighted average value |ΔMR| Provided is a composition containing nanocrystals characterized in that _{the weighted average} satisfies the following formula (B).

(However, the three-dimensional parameter MR is the following formula (C)

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

The present invention provides an ink composition comprising the nanocrystal-containing composition 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 element characterized by having the light conversion layer described above.

1 is a cross-sectional view showing an embodiment of luminescent fine particles contained in a composition containing luminescent nanocrystals according to the present invention.
Fig. 2 is a cross-sectional view showing another embodiment of the luminescent fine particles contained in the composition containing luminescent nanocrystals according to the present invention.
3 is a cross-sectional view showing an embodiment of a light emitting device according to the present invention.
4 is a schematic diagram showing the configuration of an active matrix circuit.
5 is a schematic diagram showing the configuration of an active matrix circuit.

Hereinafter, embodiments of the nanocrystal-containing composition, ink composition, light conversion layer, and light emitting element of the present invention, and their manufacturing method will be described in detail.

1. Compositions containing nanocrystals

The nanocrystal-containing composition of the embodiment of the present invention contains light-emitting fine particles having one or two or more ligands on the surface of light-emitting nanocrystals containing one or two or more photopolymerizable monomers and a metal halide. The specific structure of the luminescent fine particles will be described later.

1-1. Conditions Regarding Solid Parameters

The nanocrystal-containing composition of the present invention comprises a photopolymerizable monomer that satisfies the following formula (A) 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; and There is one or more combinations of ligands, and for all combinations of each of the photopolymerizable monomers and each of the ligands included in the nanocrystal-containing composition, the content of each of the photopolymerizable monomers and the ligands of each of the luminescent nanocrystals The weighted average value of |ΔMR| calculated by considering the ratio of coordination to the surface |ΔMR| It is characterized in that _{the weighted average} satisfies the following formula (B).

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

The steric parameter MR is, for example, an index representing the three-dimensional size of the entire compound used to investigate the correlation between molecular structure and pharmacological activity, and is described in, for example, "Operations Research, (25) 394 401, July issue, 1982” or “Nihon Noyaku Journal Experimental Technology Lecture Vol.38, No.2, 195-203 (2013)”. Since the steric parameter MR is an indicator of the overall size of a molecule, it is considered suitable as an indicator of differences in the steric structure of compounds.

In the present invention, this steric parameter MR is applied as an index showing the difference in steric structure of the photopolymerizable monomer or compound constituting the ligand. When the compound constituting the photopolymerizable monomer and the compound constituting the ligand in the nanocrystal-containing composition have structures similar to each other, |ΔMR| becomes a small value (eg, 10 or less). In that case, in the nanocrystal-containing composition, since the compound constituting the photopolymerizable monomer and the compound constituting the ligand have structures similar to each other, the ligand coordinated to the luminescent nanocrystal is easily exchanged with the photopolymerizable monomer. As a result, When the energy level of the nanocrystal maintained by the ligand is changed, the light emitting property is changed and the dispersion stability is also reduced, making it difficult to maintain excellent light emitting properties.

On the other hand, when |ΔMR| satisfies Formula (A), it means that the compound constituting the photopolymerizable monomer and the compound constituting the ligand have structures significantly different from each other. In this case, in the nanocrystal-containing composition, exchange between the ligand coordinated to the luminescent nanocrystal and the photopolymerizable monomer can be suppressed.

|ΔMR| is preferably 12 or more, more preferably 15 or more, and particularly preferably 20 or more. In addition, although there is no particular regulation on the upper limit of |ΔMR|, if the difference in the three-dimensional structure between the photopolymerizable monomer and the compound constituting the ligand is too great, the light-emitting fine particles having the ligand on the surface of the light-emitting nanocrystal containing a metal halide It is preferable that it is 50 or less from the point which the compatibility of a photopolymerizable monomer becomes low.

In the case where the nanocrystal-containing composition of the present invention includes two or more types of photopolymerizable monomers and two or more types of ligands, |ΔMR| satisfies the above-described formula (A) in a combination of at least one of the photopolymerizable monomers and ligands. However, |ΔMR| does not limit the use of photopolymerizable monomers and ligands that do not satisfy the above formula (A). For example, a nanocrystal-containing composition uses two types of photopolymerizable monomers P and Q and two types of ligands Y and Z, and |ΔMR| When _PY satisfies formula (A), |ΔMR| in the combination of photopolymerizable monomer P and ligand Z _PZ , |ΔMR| in the combination of photopolymerizable monomer Q and ligand Y _QY and |ΔMR| in the combination of photopolymerizable monomer Q and ligand Z _QZ may or may not satisfy Formula (A).

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

Weighted average of |ΔMR||ΔMR| The fact that _{the weighted average} satisfies the above-mentioned formula (B) means that in most combinations of the photopolymerizable monomer and the ligand included in the nanocrystal-containing composition, the compound constituting the photopolymerizable monomer and the compound constituting the ligand are significantly different from each other. It means having a structure. In the nanocrystal-containing composition, since the above-described effect of suppressing the exchange of the photopolymerizable monomer with the ligand coordinated to the luminescent nanocrystal can be obtained reliably, excellent dispersion stability and excellent luminescent properties can be achieved.

On the other hand, in the nanocrystal-containing composition, the weighted average |ΔMR| of |ΔMR| If _{the weighted average} does not satisfy the above formula (B), exchange of the ligand and the photopolymerizable monomer cannot be suppressed, so good dispersion stability and luminescent properties cannot be secured.

|ΔMR| _{The weighted average} is calculated in consideration of the content of each photopolymerizable monomer included in the nanocrystal-containing composition and the coordination ratio of each ligand to the surface of the nanocrystal. For example, the nanocrystal-containing composition contains two types of photopolymerizable monomer P (steric parameter MR _P ) of m _P mass parts and photopolymerizable monomer Q (steric parameter MR _Q ) of m _Q mass parts, and luminescent nanocrystals When two types of ligand Y (steric parameter MR _Y ) and anionic ligand Z (steric parameter MR _Z ) are coordinated on the surface of , it can be calculated as follows. In addition, even if one type or three or more types of photopolymerizable monomers are included in the nanocrystal-containing composition, and even if one type or three or more types of ligands are present, |ΔMR| _{A weighted average} can be calculated similarly.

First, the absolute value |ΔMR| of the difference in the steric parameter in each combination of a photopolymerizable monomer and a ligand is calculated, respectively.

Next, the obtained |ΔMR| _PY to |ΔMR| By weighting with respect to _QZ by the compounding ratio of photopolymerizable monomers (in terms of mass) and the coordination ratio of ligands, |ΔMR| Calculate _{the weighted average} . If the coordinated ratio of the cationic ligand to the anionic ligand is known, it is preferable to calculate according to the ratio. For example, when ligand Y and ligand Z are coordinated on the surface of the luminescent nanocrystal at a ratio of r _Y : r _Z , the calculation is as follows.

However, when the coordination ratio between ligand Y and Z is not clear, it is assumed that they are coordinated on the surface of the luminescent nanocrystal at a ratio of 0.5:0.5, and calculated as follows.

In the combination of the photopolymerizable monomer and the ligand satisfying the above formula (A), it is preferable that at least one of the photopolymerizable monomer or the ligand is a compound containing a cyclic structure. In particular, a linear compound such as oleylamine or oleic acid is often used as a ligand on the surface of a metal halide-containing luminescent nanocrystal. 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. Since it is difficult for the photopolymerizable monomer containing a cyclic structure with high steric hindrance to enter the surface covered with the ligand having a linear molecular structure, exchange of the photopolymerizable monomer and the ligand is difficult to occur. On the other hand, when a compound containing a cyclic structure is used as a ligand, since entering a linear photopolymerizable monomer having a different shape from the ligand into the luminescent nanocrystal is energetically unfavorable, the photopolymerizable monomer and the ligand are exchanged. It becomes difficult for this to happen. In this way, by using a compound containing a cyclic structure for at least one of the photopolymerizable monomer and the ligand, exchange of the photopolymerizable monomer and the ligand can be suppressed. As a result, the surface of the luminescent nanocrystals containing metal halide can be stably covered with the ligand, and no energy levels trapped in the luminescent nanocrystals can be maintained, thereby maintaining good luminescent properties.

In order to obtain a combination of a photopolymerizable monomer and a ligand that satisfy the above formula (A), when the photopolymerizable monomer is a compound containing a cyclic structure or when the ligand is a compound containing a cyclic structure compound, respectively, preferable steric parameters It is preferable that the range of becomes 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. , which is preferable for maintaining a state in which the surface of the luminescent nanocrystal is stably covered with the ligand. Furthermore, when 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, the coating stability of the ligand, the dispersion stability of the luminescent nanocrystal, and the luminescent properties are improved. It is particularly preferable in exerting.

(2) When a compound containing a cyclic structure as a ligand is used, a photopolymerizable monomer having a linear molecular structure having a steric parameter of 60 to 100 and a steric parameter of the ligand in the range of 40 to 80 exhibits luminescent properties. It is preferable in maintaining a state in which the surface of the nanocrystal is stably covered with the ligand. Furthermore, when the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 75 to 85 and the steric parameter of the ligand is in the range of 55 to 65, the coating stability of the ligand, the dispersion stability of the luminescent nanocrystal, and the luminescence properties are improved. It is particularly preferable in exerting.

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

Optional -CH ₂ - in the formulas (1-2) to (1-24) may be substituted with -O-, -S-, -N=, or -NH-. At least one of the photopolymerizable monomers or ligands has formulas (1-3), (1-4), (1-6), (1-8), (1-10), (1-15) and (1- 19) to (1-24) are preferable because they have excellent compatibility with the luminescent fine particles and can improve dispersibility. Further, when 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), light emission In addition to dispersibility with fine particles, it is more preferable because a high quantum yield can be secured. In particular, compounds containing cyclic structures represented by formulas (1-3), (1-19) and (1-21) are more preferable in that they can be used for both the photopolymerizable monomer and the ligand.

Any hydrogen atom in the above formulas (1-2) to (1-24) may be substituted with R ₁ . When R ₁ is a functional group, as R ₁ , a carboxyl group, a carboxylic acid 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, a sulfonic acid group, a boronic acid group, An amide group and a thioamide group are mentioned. Particularly, when the ligand is a compound having a cyclic structure in which R ₁ is a carboxyl group, an amino group, a mercapto group, an amide group, or a thioamide group, it is preferable because the coordination ability with respect to light-emitting fine particles can be improved.

When R ₁ is an alkyl group, it represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms, and -CH ₃ at the terminal of the alkyl group is -NH ₂ , -OH, -SH, -COOH, -CONH ₂ , -CSNH ₂ may be substituted with -CH ₂ - in the alkyl group may be substituted with -Si-, -NH- or -O-, even if -(CH ₂ ) ₂ - in the alkyl group is substituted with -(CH=CH)- do. The number of carbon atoms of R ₁ is preferably 1 to 10 to increase the dispersibility with the luminescent fine particles, and the number of carbon atoms in R ₁ is particularly preferably 1 to 5 to increase the dispersibility with the luminescent fine particles and the quantum yield. In order to increase the quantum yield retention of the light emitting fine particles, it is preferable to include 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 straight-chain alkoxyl group having 1 to 20 carbon atoms. -CH ₃ at the terminal of the alkoxy group may be substituted with -NH ₂ , -OH, -SH, -COOH, -CONH ₂ , or -CSNH ₂ , and -CH ₂ - in the alkoxy group is -Si-, - NH- or -O- may be substituted, and -(CH ₂ ) ₂ - in the alkoxy group may be substituted with -(CH=CH)-. The number of carbon atoms of R ₁ is preferably 1 to 10 to increase the dispersibility with the luminescent fine particles, and the number of carbon atoms in R ₁ is particularly preferably 1 to 5 to increase the dispersibility with the luminescent fine particles and the quantum yield. In order to increase the quantum yield retention of the light emitting fine particles, it is preferable to include a polyalkoxysilane, polysilanol, or polysilazane structure capable of forming an inorganic coating layer containing Si.

Any hydrogen atom in the above formulas (1-2) to (1-24) may be substituted with P. P is each independently represented by the following general formulas (P-1) to (P-16). Black dots in the formula represent bonding hands. When a plurality of P's exist, they may be the same or different.

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

When using a compound containing a cyclic structure represented by the above (1-2) to (1-24) as the photopolymerizable monomer, more specifically, the following formulas (1-3-1) to (1-3-8) ), (1-4-1) to (1-4-8), (1-19-1) to (1-19-16), (1-21-1) to (1-21-8), (1-22-1) to (1-22-4), (1-23-1) to (1-23-8) and (1-24-1) to (1-24-4) A compound can be used suitably. As for x and z in the following formula, 0 to 18 are each independently preferable, and as for y and zz, 1 to 18 are each independently preferable. In addition, in order for the steric parameter of the photopolymerizable monomer containing 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, respectively It is preferable to be 1 to 5 independently. The following formulas (1-3-1) to (1-3-6), (1-4-1) to (1-4- 8), (1-19-1) to (1-19-8), (1-21-1) to (1-21-4), (1-22-1) to (1-22-4) , (1-23-5) to (1-23-8) are preferred, x and z in the following formula are each independently preferably 0 to 5, and y and zz are each independently It is preferable to be 1 to 5. Further, when the steric parameter is desired to be higher than 65 as a cyclic structure, (1-19-1) to (1-19-8) or 1,2,2,6,6-pentamethyl- having an adamantyl structure Particularly preferred are (1-23-5) to (1-23-8) having a 4-piperidyl structure, x and z in the following formula are each independently preferably 0 to 5, and y and zz are , are particularly preferably 1 to 5 each independently.

As described above, when a compound in which the steric parameter of the photopolymerizable monomer having a cyclic molecular structure is 40 to 90 is used, a ligand that is a suitable combination has a steric parameter of the ligand having a linear molecular structure of 60 to 90 It is preferably in the range of 110, more preferably, the steric parameter of the photopolymerizable monomer having a cyclic molecular structure 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 more desirable to be As a ligand compound that satisfies these conditions, a ligand in which a terminal functional group is a carboxylic acid or an amine is preferable. In addition, it is preferable to use the ligand in which these terminal functional groups become carboxylic acids or amines in a ratio of 1:1.

As a ligand having a linear molecular structure in which a terminal functional group becomes a 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, petroseric 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, nonadecanoic acid, arachidic acid, heneicosanoic acid, cis-4,7,10, 13,16,19-Docosahexaenoic acid, erucic acid, behenic acid, lignoceric acid, and trichosanoic acid are preferred as a coordination having a steric parameter of 60 to 110, (2) more preferably, Pentadecanoic acid, cis-9-hexadecenoic acid, palmitic acid, 2-hexadecenoic acid, heptadecanoic acid, petroseric 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, nonadecananoic acid, arachidic acid, heneicosanoic acid, the conformation of the ligand It is preferable as a coordination with a parameter of 70 to 100, and (3) particularly preferably, heptadecanoic acid, petroseric acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid, or oleic acid have a steric parameter of 80 to 90 It is particularly preferable as a ligand to be.

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

On the other hand, when a compound containing a cyclic structure represented by (1-2) to (1-24) is used as a ligand coordinated to the surface of a metal halide-containing luminescent nanocrystal, a compound containing a cyclic structure In order for the steric parameter of the ligand to be contained within the range of 40 to 80, compounds represented by the following (1-19-A) to (1-19-H) can be suitably used, and (1-19-A) Compounds represented by (1-19-F) to 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 more preferably 1 to 5 .

In the case of using a compound having a steric parameter of 40 to 80 for a ligand having a cyclic molecular structure, a suitable combination of a photopolymerizable monomer having a linear molecular structure is a steric of a photopolymerizable monomer having a linear molecular structure. The parameter 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 steric parameter of the photopolymerizable monomer having a linear molecular structure is 75 to 65. It is more preferable to be in the range of 85. Specifically, it is preferable to use a compound shown below.

That is, (1) as the methacrylate compound, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, Hexadecyl methacrylate, as an acrylate compound, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate has a steric parameter of 60 to 100 It is preferable as a photopolymerizable monomer having a linear molecular structure in the range of (2) more preferably, as the methacrylate compound, dodecyl methacrylate and tridecyl methacrylate, and as the acrylate compound, acrylic acid Decyl, undecyl acrylate, dodecyl acrylate and tetradecyl acrylate are particularly preferred as the photopolymerizable monomer having a linear molecular structure with a steric parameter in the range of 75 to 85.

More specifically, the preferred combination of the photopolymerizable monomer and the ligand satisfying the above formula (A) is preferably the following combination.

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. A photopolymerizable monomer having a steric parameter of 40 to 90 is preferable for maintaining a state in which the surface of the crystal is stably covered with the ligand, and specifically, formulas (1-3-1) to (1-3-8) , (1-4-1) to (1-4-8), (1-19-1) to (1-19-16), (1-21-1) to (1-21-8), ( Compounds represented by 1-22-1) to (1-22-4), (1-23-1) to (1-23-8) and (1-24-1) to (1-24-4) In the formula, x and z are each independently 0 to 5, and y and zz are each independently 1 to 5 photopolymerizable monomers, and a terminal functional group having a steric parameter of 60 to 110 is carboxylic acid. As the ligand having a chain molecular structure, tridecanoic acid, 2-tridecenoic acid, myristic acid, pentadecanoic acid, cis-9-hexadecenoic acid, palmitic acid, 2-hexadecenoic acid, heptadecanoic acid, petro Seric 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-eico Satrienoic acid, arachidonic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, cis-4,7,10,13,16,19-docosahexaenoic acid, erucic acid, behenic acid, lignocer Examples of ligands having a linear molecular structure in which an acid or trichosanoic acid has a terminal functional group having a steric parameter of 60 to 110 become an amine include dodecylamine, tetradecylamine, 1-aminotridecane, 1-aminopentadecane, Combining a ligand selected from hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecan-9-amine, oleylamine, 1-aminononadecane, and 2-n-octyl-1-dodecylamine desirable.

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, the coating stability of the ligand, the dispersion stability of the luminescent nanocrystal, Particularly preferred for exhibiting luminescent properties, specifically, as photopolymerizable monomers having a steric parameter of 50 to 70, formulas (1-3-1) to (1-3-6), (1-4- 1) to (1-4-8), (1-19-1) to (1-19-8), (1-21-1) to (1-21-4), (1-22-1) to (1-22-4), (1-23-5) to (1-23-8), (1-24-1) to (1-24-4) are preferred, and luminescent nano In order to increase the luminescent properties of the crystal, methacrylate compounds rather than acrylate compounds, (1-3-5), (1-3-6), (1-4-5) to (1-4-8), (1-19-3) to (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) Preferably, among (1-24-3) and (1-24-4), in order to increase the PLQY retention rate of the QD dispersion and the light conversion layer while maintaining the dispersion stability of the QD dispersion or QD ink (1-24 -4) is preferable, and when the steric parameter is desired to be higher than 65 as a photopolymerizable monomer having a cyclic structure, (1-19-1) to (1-19-8) or 1,2 having an adamantyl structure (1-23-5) to (1-23-8) having a 2,6,6-pentamethyl-4-piperidyl structure are particularly preferred, and x and z in the formula are independently 0 to 0 5, y and zz each independently have a photopolymerizable monomer of 1 to 5, and a ligand having a linear molecular structure in which a terminal functional group having a steric parameter of 80 to 90 is a carboxylic acid, heptadecanoic acid, petro Seric acid, linoleic acid, γ-linolenic acid, stearic acid, linolenic acid, oleic acid, as a ligand having a linear molecular structure in which the terminal functional group having a steric parameter of 80 to 90 becomes an amine, hexadecylamine, 1-aminoheptadecane , It is preferable to combine a ligand selected from stearylamine, heptadecan-9-amine, and oleylamine. Particularly, as the ligand, petroseric acid, linoleic acid, γ-linolenic acid, linolenic acid, and oleic acid having a double bond in the alkyl chain and oleylamine are particularly preferred for exhibiting the coating stability of the ligand, the dispersion stability of the luminescent nanocrystals, and the luminescent properties.

(2) When a compound containing a cyclic structure is used as a ligand, a photopolymerizable monomer having a linear molecular structure having a steric parameter of 60 to 100 and a steric parameter of the ligand in the range of 40 to 80 exhibits luminescent properties. It is preferable for maintaining the state in which the surface of the nanocrystal is stably covered with a ligand, and specifically, a photopolymerizable monomer having a linear molecular structure having a steric parameter of 60 to 100, and an acrylic having 6 to 17 carbon atoms. A late compound or a methacrylate compound is preferable, and as a ligand having a cyclic structure having a steric parameter of 40 to 80, compounds represented by (1-19-A) to (1-19-H) are preferable. .

More preferably, as a photopolymerizable monomer having a linear molecular structure with a steric parameter of 75 to 85, an acrylate compound or a methacrylate compound having 11 to 13 carbon atoms is preferable, and the luminescent properties of the luminescent nanocrystals In order to increase, a methacrylate compound is more preferable than an acrylate compound, and the steric parameter is in the range of 55 to 65, and as the ligand, the compound represented by the formulas (1-19-A) to (1-19-F) This is particularly preferable for exhibiting the coating stability of the ligand, the dispersion stability of the luminescent nanocrystal, and the luminescent properties.

1-2. luminescent particles

The luminescent fine particles included in the nanocrystal-containing composition described above will be described. In the luminescent fine particles 910 shown in FIG. 1 , one or two or more ligands are provided on the surface of the luminescent nanocrystal 911 . A ligand layer 912 is formed by a plurality of ligands coordinated on the surface of the luminescent nanocrystal 911 .

1-2-1. luminescent nanocrystals

First, the luminescent nanocrystal 911 (hereinafter, simply referred to as "nanocrystal 911") will be described. The luminescent nanocrystal is a nano-sized semiconductor nanocrystal (nanocrystal particle) that contains a metal halide and emits fluorescence or phosphorescence by absorbing excitation light.

As light-emitting nanocrystals containing metal halide, for example, quantum dots having a perovskite-type crystal structure described later are widely known. The luminescent nanocrystals are crystals having a maximum particle diameter (may be an average particle diameter) of 100 nm or less as measured by a transmission electron microscope or a scanning electron microscope, for example. The luminescent nanocrystals may emit fluorescence or phosphorescence by being excited by, for example, light energy or electric energy of a predetermined wavelength.

Luminescent nanocrystals containing a metal halide include a compound represented by the general formula: A _a M _m X _x .

In formula, A is at least 1 sort(s) of an organic cation and a metal cation. Examples of organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, and protonated thiourea. Examples of metal cations include Cs, Rb, K, Na, Li, and the like. cations of

M is at least one metal cation. As the metal cation, a metal cation selected from group 1, group 2, group 3, group 4, group 5, group 6, group 7, group 8, group 9, group 10, group 11, group 13, group 14 and group 15 can be heard More preferably, Ag, Au, Bi, Ca, Ce, Co, Cr, Cu, Eu, Fe, Ga, Ge, Hf, In, Ir, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os , Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, and Zr cations.

X is at least one kind of anion. Examples of the anion include chloride ion, bromide ion, iodide ion, cyanide ion and the like, and at least one kind of halogen is included.

a is an integer from 1 to 7, m is an integer from 1 to 4, and x is an integer from 3 to 16.

A compound represented by the general formula _{A a} M _m X _x , specifically, AMX, A ₄ MX, AMX ₂ , AMX ₃ , A ₂ MX 3 , AM _{2 X 3} , A ₂ MX ₄ , A ₂ MX ₅ , A ₃ MX ₅ , A ₃ M ₂ X ₅ , A ₃ MX ₆ , A ₄ MX ₆ , AM ₂ X ₆ , A ₂ MX ₆ , A ₄ M ₂ X ₆ , A ₃ MX ₈ , A ₃ M ₂ X ₉ , A ₃ M ₃ X ₉ , A ₂ M ₂ X ₁₀ , A ₇ M ₃ X ₁₆ compounds are preferred.

In formula, A is at least 1 sort(s) of an organic cation and a metal cation. Examples of organic cations include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, and protonated thiourea. Examples of metal cations include Cs, Rb, K, Na, Li, and the like. cations of

In formula, M is at least 1 sort(s) of metal cation. Specifically, one type of metal cation (M ¹ ), two types of metal cations (M ¹ _α M ² _β ), three types of metal cations (M ¹ _α M ² _β M ³ _γ ), and four types of metal cations (M ¹ _α M ² _β M ³ _γ M ⁴ _δ ) and the like. However, α, β, γ, and δ represent real numbers of 0 to 1, respectively, and represent α+β+γ+δ = 1. As the metal cation, a metal cation selected from group 1, group 2, group 3, group 4, group 5, group 6, group 7, group 8, group 9, group 10, group 11, group 13, group 14 and group 15 can be heard More preferably, Ag, Au, Bi, Ca, Ce, Co, Cr, Cu, Eu, Fe, Ga, Ge, Hf, In, Ir, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os , Pb, Pd, Pt, Re, Rh, Ru, Sb, Sc, Sm, Sn, Sr, Ta, Te, Ti, V, W, Zn, and Zr cations.

In formula, X is an anion containing at least 1 type of halogen. Specifically, one type of halogen anion (X ¹ ), two types of halogen anion (X ¹ _α X ² _β ), and the like are exemplified. Examples of the anion include chloride ion, bromide ion, iodide ion, cyanide ion and the like, and at least one kind of halogen is included.

A compound containing a metal halide represented by the general formula A _a M _m X _x is one to which metal ions such as Bi, Mn, Ca, Eu, Sb, Yb are added (doped) to improve light emitting properties. It can be done.

Among the metal halide-containing compounds represented by the general formula A _a M _m X _x , the compound having a perovskite-type crystal structure adjusts its particle size, the type and abundance of metal cations constituting the M site, Furthermore, it is particularly preferable for use as luminescent nanocrystals because the emission wavelength (emission color) can be controlled by adjusting the type and abundance of anions constituting 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 preferable. A, M and X in the formula are as described above. As described above, the compound having a perovskite-type crystal structure may be one to which metal ions such as Bi, Mn, Ca, Eu, Sb, Yb or the like are added (doped).

Among the compounds exhibiting a perovskite-type crystal structure, A is Cs, Rb, K, Na, Li, and M is one metal cation (M1) or two metal cations in order to exhibit better light emitting characteristics. (M ¹ _α M ² _β ), and X is preferably a chloride ion, bromide ion, or iodide ion. However, α and β represent real numbers of 0 to 1, respectively, and represent α+β=1. Specifically, M is preferably selected from Ag, Au, Bi, Cu, Eu, Fe, Ge, K, In, Na, Mn, Pb, Pd, Sb, Si, Sn, Yb, Zn, and Zr. .

As a specific composition of luminescent nanocrystals containing metal halide showing a perovskite-type crystal structure, luminescent nanocrystals using Pb as M such as CsPbBr ₃ , CH ₃ NH ₃ PbBr ₃ , CHN ₂ H ₄ PbBr ₃ , It is preferable from the point of being excellent in quantum efficiency while being excellent in intensity|strength. In addition, luminescent nanocrystals using a metal cation other than Pb as M such as CsSnBr ₃ , CsEuBr ₃ CsYbI ₃ , etc. are preferred because of their low toxicity and low environmental impact.

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

The red luminescent 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. It is preferable to have an emission peak in a wavelength range of 640 nm or less, 637 nm or less, 635 nm or less, 632 nm or less, or 630 nm or less, and 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more. It is preferable to have an emission peak in a wavelength range of 610 nm or more, 607 nm or more, or 605 nm or more. These upper and lower limit values can be arbitrarily combined. In addition, also in the same description below, the upper limit value and the lower limit value described individually can be combined arbitrarily.

Green luminescent luminescent nanocrystals are 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 It is preferable to have an emission peak in a wavelength range of 528 nm or more, 525 nm or more, 523 nm or more, 520 nm or more, 515 nm or more, 510 nm or more, 507 nm or more, 505 nm or more, 503 nm or more. It is preferable to have an emission peak in a wavelength range of 500 nm or more or 500 nm or more.

Blue luminescent luminescent nanocrystals are 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 It is preferable to have an emission peak in a wavelength range of 450 nm or less, 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. It is preferable to have an emission peak in the wavelength range of nm or more.

The shape of the luminescent nanocrystal is not particularly limited, and may be an arbitrary geometric shape or an arbitrary irregular shape. Examples of the shape of the luminescent nanocrystal include a rectangular parallelepiped shape, a cubic shape, a spherical shape, a regular tetrahedral shape, an ellipsoidal shape, a pyramid shape, a disk shape, a branch shape, a net shape, and a rod shape. Further, as the shape of the luminescent nanocrystal, a rectangular parallelepiped shape, a cubic shape, or a spherical shape is preferable.

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

1-2-2. ligand

The ligand is essential for obtaining nano-sized crystals by suppressing crystal growth by coordinating to the surface of the formed luminescent nanocrystals when synthesizing luminescent nanocrystals containing metal halide. In addition, since the ligand can maintain a state in which the surface of the luminescent nanocrystal containing metal halide is stably covered, generation of trap states on the surface of the luminescent nanocrystal can be prevented and good light emission characteristics can be maintained. In addition, the ligand also has a function of enhancing the compatibility with the photopolymerizable monomer and ensuring the dispersibility of the luminescent nanocrystal by coordinating to the surface of the luminescent nanocrystal containing an inorganic material. Therefore, loss of the ligand from the surface of the luminescent nanocrystal causes aggregation of the luminescent nanocrystal or deterioration of luminescent properties and dispersibility, so that the ligand is stably deposited on the surface of the luminescent nanocrystal without exchange with the photopolymerizable monomer. Coordination becomes important. As the ligand coordinated on the surface of the luminescent nanocrystal, it is essential to use at least one ligand that satisfies the above formula (A) when combined with any photopolymerizable monomer included in the nanocrystal-containing composition. A ligand that does not satisfy Formula (A) may be used. Moreover, as a ligand, a compound containing a linear structure without a cyclic structure can also be used other than the compound containing the said cyclic structure.

As the ligand that forms such a linear structure, a compound having a bonding group that binds to a cation or anion contained in the luminescent nanocrystal is preferable. Examples of the bondable group include a carboxyl group, a carboxylic acid 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, a sulfonic acid group, an amide group, and a thioamide group. And it is preferable that it is at least 1 sort(s) of a boronic acid group, and it is more preferable that it is at least 1 sort(s) of a carboxyl group and an amino group. Examples of such a ligand include compounds containing a carboxyl group or an amino group, and among these, one type may be used alone or two or more types may be used in combination.

As a carboxyl group-containing compound, C1-C30 linear or branched aliphatic carboxylic acid is mentioned, for example. Specific examples of such carboxyl group-containing compounds include, for example, arachidonic acid, crotonic acid, trans-2-decenoic acid, erucic acid, 3-decenoic acid, cis-4,7,10,13,16,19-docosahexa Enic 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, petroseric acid, elaidic acid, oleic acid, 3-octenoic acid, trans-2-pentenoic acid, trans-3-pentenoic acid, ricinolic acid, sorbic acid, 2-tridecenoic acid, cis-15- Tetracosenoic acid, 10-undecenoic 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, la Uric acid, myristic acid, melissic acid, octacosanoic acid, nonadecanoic acid, nonacosanoic acid, n-octanoic acid, palmitic acid, pentadecanoic acid, propionic acid, pentacosanoic acid, nonanoic acid, stearic acid, lignocer acids, trichosanoic acid, tridecanoic acid, undecanoic acid, valeric acid and the like.

As an amino group containing compound, C1-C30 linear or branched aliphatic amine is mentioned, for example. Specific examples of such an amino group-containing compound include 1-aminoheptadecane, 1-aminononadecane, heptadecan-9-amine, stearylamine, oleylamine, 2-n-octyl-1-dodecylamine, Allylamine, amylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, isobutylamine, isoamylamine, 3-methoxypropylamine, 2-methoxyethylamine, 2-methylbutylamine, neopentyl Amine, propylamine, methylamine, ethylamine, butylamine, hexylamine, heptylamine, n-octylamine, 1-aminodecane, nonylamine, 1-aminoundecane, dodecylamine, 1-aminopentadecane, 1 - Aminotridecane, hexadecylamine, tetradecylamine, etc. are mentioned.

1-2-3. Method for preparing luminescent fine particles

Next, a method for preparing the luminescent fine particles 910 shown in FIG. 1 will be described. The light-emitting fine particles 910 have one or two or more of the above-mentioned ligands on the surface of the light-emitting nanocrystals 911, and the ligand layer 912 is formed by a plurality of ligands coordinated on the surface of the light-emitting nanocrystals 911. ) is provided. As a method for producing such light-emitting fine particles 910, there are a method of heating and a method of not heating.

First, an example of a method for producing 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 A _a M _b X _c described above (hereinafter sometimes referred to as "solution containing semiconductor raw materials") are prepared. Among the two types of solutions containing semiconductor raw materials, 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 satisfying the above formula (A) is added to at least one of the semiconductor raw material-containing solutions.

Then, these two kinds of semiconductor raw material-containing solutions are mixed under an inert gas atmosphere and reacted under temperature conditions of 140 to 260°C. Subsequently, nanocrystals are precipitated by cooling to -20 to 30°C and stirring. A ligand layer 912 containing coordinated ligands is formed on the surface of the precipitated nanocrystals 911 . By recovering the nanocrystals 911 by a conventional method such as centrifugation, the luminescent fine particles 910 can be obtained.

Specifically, a solution containing, for example, cesium carbonate as a semiconductor raw material and oleic acid serving as a ligand in an organic solvent is prepared. As the organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. At this time, it is preferable to prepare each addition amount so that cesium carbonate is 0.2 to 2 g and oleic acid is 0.1 to 10 mL with respect to 40 mL of the organic solvent. After drying the obtained solution under reduced pressure at 90 to 150°C for 10 to 180 minutes, the cesium-oleic acid solution is obtained by heating at 100 to 200°C under an inert gas atmosphere such as argon or nitrogen.

On the other hand, a solution containing lead (II) bromide as 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 obtained solution is dried under reduced pressure at 90 to 150°C for 10 to 180 minutes.

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

A solid substance is recovered by centrifuging the resulting suspension, and the solid substance is added to toluene, whereby light-emitting fine particles 910 having a ligand layer 912 of oleic acid and oleylamine on the surface of nanocrystals 911 coordinated with oleic acid are obtained. A dispersion of luminescent fine particles dispersed in toluene can be obtained.

Next, an example of a method for manufacturing the luminescent 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 satisfying the above formula (A) is added to the solution containing the starting compound. Next, by adding the obtained solution to a large amount of an organic solvent serving as a poor solvent for nanocrystals, nanocrystals in which ligands are coordinated on the surface are deposited. At this time, the amount of the organic solvent used is preferably 10 to 1000 times the mass of the semiconductor nanocrystal.

Specifically, as a semiconductor raw material-containing solution, a solution containing, for example, lead (II) bromide, cesium bromide, a compound that forms a ligand satisfying the above formula (A), and an organic solvent is prepared. The organic solvent may be a good solvent for nanocrystals, but is preferably dimethyl sulfoxide, N,N-dimethylformamide, N-methylformamide or a mixed solvent thereof from the point of compatibility. At this time, it is preferable to adjust the respective addition amounts so that lead (II) bromide is 50 to 200 mg and cesium bromide is 10 to 100 mg with respect to 10 mL of the organic solvent.

Then, 0.1 to 5 mL of the above-described solution containing lead (II) bromide and cesium bromide is added to a large amount of co-solvent, stirred in the air for 5 to 180 seconds, and then the solid is recovered by centrifugation. When the mixture is added to a large amount of co-solvent, nanocrystals 911 are precipitated, and a compound forming a ligand satisfying the above formula (A) is coordinated on the surface of nanocrystals 911.

By adding this recovered solid material to toluene, biluminous fine particles 910 having a ligand layer 912 made of a compound that forms a ligand satisfying the above formula (A) on the surface of the nanocrystal 911 are toluene It is possible to obtain a dispersion of light emitting fine particles dispersed in

1-3. photopolymerizable monomer

As the photopolymerizable monomer used in the present invention, in addition to the photopolymerizable monomer containing the above cyclic structure, a general radical photopolymerizable monomer that polymerizes by irradiation of light can be used, and a photopolymerizable monomer or oligomer may be used. 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 a polyfunctional (meth)acrylate having a plurality of (meth)acryloyl groups.

When the nanocrystal-containing composition is used as an ink composition, from the viewpoint of excellent fluidity, better ejection stability, and the viewpoint of suppressing the decrease in smoothness due to curing shrinkage during the production of a light emitting fine particle coating film, monofunctional (method ) It is preferable to use a combination of acrylate and polyfunctional (meth)acrylate.

Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, and 2-ethyl Hexyl(meth)acrylate, Octyl(meth)acrylate, Nonyl(meth)acrylate, Dodecyl(meth)acrylate, Hexadecyl(meth)acrylate, Octadecyl(meth)acrylate, Cyclohexyl(meth)acrylate Acrylates, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethyl Aminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl Oxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate LATE, Phenylbenzyl(meth)acrylate, Succinic acid mono(2-acryloyloxyethyl), N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy) ethyl] tetrahydrophthalimide and the like.

The polyfunctional (meth)acrylate may be bifunctional (meth)acrylate, trifunctional (meth)acrylate, tetrafunctional (meth)acrylate, pentafunctional (meth)acrylate, hexafunctional (meth)acrylate, or the like. and, for example, di(meth)acrylate in which two hydroxyl groups of a diol compound are substituted by a (meth)acryloyloxy group, and two or three hydroxyl groups of a triol compound are replaced by a (meth)acryloyloxy group. A substituted di- or tri(meth)acrylate may be used.

Specific examples of the bifunctional (meth)acrylate include 1,3-butylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, and 1,5-pentanedioldi(meth)acrylate. Acrylate, 3-methyl-1,5-pentanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, 1,8-octanedioldi (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, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, Di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl)isocyanurate are substituted by (meth)acryloyloxy groups, 4 moles or more of ethylene oxide or propylene oxide per mole of neopentyl glycol Di(meth)acrylate in which two hydroxyl groups of the diol obtained by adding (meth)acryloyloxy groups are substituted, and diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A. Di(meth)acrylate in which the hydroxyl group is substituted by a (meth)acryloyloxy group, and two hydroxyl groups of a triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane are (meth)acrylic Di(meth)acrylates substituted with royloxy groups, diols in which two hydroxyl groups of diols obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A are substituted with (meth)acryloyloxy groups (meth)acrylate etc. are mentioned.

Specific examples of the trifunctional (meth)acrylate include, for example, trimethylolpropane tri(meth)acrylate, glycerin triacrylate, pentaerythritol tri(meth)acrylate, and 3 moles or more of 1 mole of trimethylolpropane ethylene and tri(meth)acrylates in which three hydroxyl groups of a triol obtained by adding oxide or propylene oxide are substituted with (meth)acryloyloxy groups.

As a specific example of tetrafunctional (meth)acrylate, pentaerythritol tetra (meth)acrylate etc. are mentioned, for example.

As a specific example of a pentafunctional (meth)acrylate, dipentaerythritol penta (meth)acrylate etc. are mentioned, for example.

As a specific example of 6 functional (meth)acrylate, dipentaerythritol hexa(meth)acrylate etc. are mentioned, for example.

The polyfunctional (meth)acrylate may be a poly(meth)acrylate in which a plurality of hydroxyl groups of dipentaerythritol, such as dipentaerythritol hexa(meth)acrylate, are substituted with (meth)acryloyloxy groups.

The (meth)acrylate compound may be ethylene oxide-modified phosphoric acid (meth)acrylate or ethylene oxide-modified alkyl phosphoric acid (meth)acrylate having a phosphoric acid group.

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

The amount of the photopolymerizable monomer contained in the nanocrystal-containing composition is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and still more preferably 70 to 99% by mass. By setting the amount of the photopolymerizable monomer in the nanocrystal-containing composition within the above range, the luminous efficiency of the luminescent nanoparticles can be increased. In addition, in a light emitting layer (light conversion layer) obtained by curing an ink composition containing nanocrystals, the dispersion state of the light emitting fine particles becomes better, and thus the external quantum efficiency can be further increased.

1-4. Other structural examples of luminescent fine particles

In the above, the nanocrystal-containing composition containing the luminescent fine particles 910 having one or more ligands on the surface of the luminescent nanocrystal 911 has been described, but the configuration of the luminescent fine particles is not limited to that shown in FIG. does not For example, a ligand having a reactive group capable of forming a siloxane bond is coordinated to the surface of the luminescent nanocrystal 911 in addition to a ligand satisfying the above formula (A), and the ligand having a reactive group capable of forming a siloxane bond Light-emitting fine particles having an inorganic coating layer containing Si formed by Next, the luminescent fine particles provided with this inorganic coating layer will be described. In some cases, light emitting fine particles having an inorganic coating layer are referred to as "inorganic coated light emitting fine particles", and light emitting fine particles without an inorganic coating layer are sometimes described as "uncoated light emitting fine particles".

The luminescent fine particles 90 (inorganic coated luminescent fine particles) shown in FIG. 2 have, on the surface of the luminescent nanocrystals 911, at least a ligand that satisfies the above formula (A) and a ligand having a reactive group capable of forming a siloxane bond. is coordinated, and the molecular length of a ligand satisfying at least the above formula (A) is preferably longer than that of 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 has luminescent properties By forming siloxane bonds in the vicinity of the nanocrystal 911, a mesh structure containing a large number of siloxane bonds is formed, and the inorganic coating layer 91 containing Si is formed. The ligands that are coordinated on the surface of the luminescent nanocrystals 911 and satisfy at least the above formula (A) form the ligand layer 912 in a form exposed from between the mesh structures of the inorganic coating layer 91 .

Since the ligands of the inorganic coated light emitting fine particles 90 are exposed from the inorganic coated layer 91, dispersibility can be ensured when mixed with a 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, since the inorganic coated light-emitting fine particles 90 can protect the light-emitting nanocrystals 911 from light, heat, moisture, etc. by providing the inorganic coating layer 91 containing Si, the uncoated light-emitting fine particles 910 ), the quantum yield retention rate and the external quantum efficiency retention rate can be further improved.

The thickness of the inorganic coating layer 91 is preferably 0.5 to 50 nm, and more preferably 1.0 to 30 nm. In the case of the light emitting fine particles 90 having the inorganic coating layer 91 having such a thickness, the stability of the nanocrystals 911 against light, heat, moisture, and the like can be sufficiently increased. In addition, the thickness of the inorganic coating layer 91 can be changed by adjusting the number of atoms (chain length) of the linking structure linking 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 is preferably a hydrolyzable silyl group such as a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms, since a siloxane bond is easily formed.

In addition, the ligand having a reactive group capable of forming a siloxane bond preferably has a binding group that binds to a cation or anion included in the light emitting nanocrystal 911 including a metal halide.

Examples of the bondable group include a carboxyl group, a carboxylic acid 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, a sulfonic acid group, and a boronic acid group. there is. Especially, as a bondable group, it is preferable that it is at least 1 sort(s) of a carboxyl group and an amino group. These bondable groups have higher affinity (reactivity) to cations or anions contained in the luminescent nanocrystals having a perovskite-type crystal structure than reactive groups. For this reason, the bonding 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 siloxane bonds can be more easily and reliably formed. there is.

From this point of view, examples of the ligand having a reactive group capable of forming the siloxane bond include a carboxyl group or an amino group-containing silicon compound, and one of these may be used alone or two or more may be used in combination.

Specific examples of the carboxyl group-containing silicon compound 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, etc. are mentioned.

On the other hand, specific examples of amino group-containing silicon compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropylmethylethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldipropoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl Idiisopropoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl) -3-aminopropyltripropoxysilane, N-(2-aminoethyl)-3-aminopropyltriisopropoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N- (2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylsilane Triol, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N,N-bis[3-(trimethyx) Toxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl)phenyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, (aminoethylaminoethyl)phenyltripropoxysilane, (aminoethylaminoethyl) Phenyltriisopropoxysilane, (aminoethylaminomethyl)phenyltrimethoxysilane, (aminoethylaminomethyl)phenyltriethoxysilane, (aminoethylaminomethyl)phenyltripropoxysilane, (aminoethylaminomethyl)phenyl Triisopropoxysilane, 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-amino Propyltrimethoxysilane, N-β-(N-di(vinylbenzyl)aminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxysilane, methylbenzylaminoethylaminopropyltrimeth Toxysilane, dimethylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidpropyltriethoxysilane, 3-(N-phenyl ) Aminopropyltrimethoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminoethyl)phenethyltriethoxysilane , (aminoethylaminoethyl)phenethyltripropoxysilane, (aminoethylaminoethyl)phenethyltriisopropoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxy Silane, (aminoethylaminomethyl)phenethyltripropoxysilane, (aminoethylaminomethyl)phenethyltriisopropoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine , N-[2-[3-(triethoxysilyl)propylamino]ethyl]ethylenediamine, N-[2-[3-(tripropoxysilyl)propylamino]ethyl]ethylenediamine, N-[2- [3-(triisopropoxysilyl) propylamino] ethyl] ethylenediamine etc. are mentioned.

Specific examples of the silicon compound containing a mercapto group include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxy. Silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-[ethoxybis(3 ,6,9,12,15-pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol; and the like.

The inorganic coated light emitting fine particles 90 described above form a solution containing a semiconductor raw material and a ligand having a reactive group capable of forming an inorganic coating layer containing Si, and a ligand satisfying the above formula (A) A ligand having a reactive group capable of forming an inorganic coating layer on the surface of the semiconductor nanocrystal and satisfying the above formula (A) It can be produced by a method of coordinating a ligand to be made and then forming the inorganic coating layer 91 having the reactive group. As a method for producing the inorganic coated light-emitting fine particles 90, there are a method in which heating is performed and a method in which heating is not performed.

First, a method of producing inorganic coated light-emitting fine particles 91 by heating will be described. Two types of raw material compound-containing solutions are prepared respectively. At this time, a compound that forms a ligand satisfying the above formula (A) and a compound having a reactive group capable of forming a siloxane bond by containing Si are added to one or both of the two raw material compound-containing solutions. . Then, these are mixed under an inert gas atmosphere and reacted under temperature conditions of 140 to 260°C. Next, a method of precipitating nanocrystals by cooling to -20 to 30°C and stirring is exemplified. The precipitated nanocrystals are those in which ligands are coordinated on the surface of the nanocrystals 911 and an inorganic coating layer 91 having siloxane bonds is formed. Thereafter, the silica-coated light-emitting fine particles 91 can be obtained by recovering the obtained particles by a conventional method such as centrifugation.

Specifically, a solution containing cesium carbonate, oleic acid, and an organic solvent is prepared, for example. As the organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. At this time, it is preferable to prepare each addition amount so that cesium carbonate is 0.2 to 2 g and oleic acid is 0.1 to 10 mL with respect to 40 mL of the organic solvent. After drying the obtained solution under reduced pressure at 90 to 150°C for 10 to 180 minutes, the cesium-oleic acid solution is obtained by heating at 100 to 200°C under an inert gas atmosphere such as argon or nitrogen.

On the other hand, 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 obtained solution under reduced pressure at 90 to 150°C for 10 to 180 minutes, 0.1 to 2 mL of 3-aminopropyltriethoxysilane is added under an inert gas atmosphere such as argon or nitrogen.

Then, the solution containing lead (II) bromide and 3-aminopropyltriethoxysilane is heated to 140 to 260° C., and the above-mentioned cesium-oleic acid solution is added, followed by heating and stirring for 1 to 10 seconds to react. , The obtained 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, the nanocrystals 911 are precipitated, and 3-aminopropyltriethoxysilane and oleic acid are coordinated on the surface of the nanocrystals 911.

Then, after stirring the obtained reaction solution under air at room temperature (10 to 30°C, 5 to 60% humidity) for 5 to 300 minutes, a suspension is obtained by adding 0.1 to 50 mL of ethanol. During stirring at room temperature under air, the alkoxysilyl groups of 3-aminopropyltriethoxysilane condense, and the inorganic coating layer 91 having siloxane bonds is formed on the surface of the nanocrystals 911 to which oleic acid is coordinated.

A solid substance is recovered by centrifuging the resulting suspension, and the solid substance is added to toluene, thereby providing an inorganic coating layer 91 having a siloxane bond on the surface of the nanocrystal 911, and oleic acid on the surface of the nanocrystal 911. A dispersion of light-emitting fine particles in which silica-coated light-emitting fine particles 90, which are coordinated and exposed from between inorganic coated particles and have a ligand layer 912, are dispersed in toluene, can be obtained.

Next, a method for producing the silica-coated light-emitting fine particles 90 without heating is 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 under air, and then the resulting mixture is mixed with a large amount of a poor solvent for the nanocrystals. A method of precipitating nanocrystals by adding to an organic solvent of . The amount of organic solvent used is preferably 10 to 1000 times the mass of semiconductor nanocrystals. In addition, the precipitated nanocrystal becomes one in which an inorganic coating layer 91 having a siloxane bond is formed on the surface of the nanocrystal 911 . Silica-coated light-emitting fine particles 90 can be obtained by recovering the obtained particles by a conventional method such as centrifugation.

Specifically, as a solution containing raw material compounds for semiconductor nanocrystals, for example, a solution containing lead (II) bromide and methylamine hydrobromide in an organic solvent is prepared. The organic solvent may be a good solvent for nanocrystals, but is preferably dimethyl sulfoxide, N,N-dimethylformamide, N-methylformamide, or a mixed solvent thereof from the viewpoint of compatibility. At this time, it is preferable to adjust the respective addition amounts so that lead (II) bromide is 50 to 200 mg and methylamine hydrobromide is 10 to 100 mg with respect 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, etc. can be used. At this time, it is preferable to adjust the respective addition amounts so that 3-aminopropyltriethoxysilane is 0.01 to 0.5 mL and oleic acid is 0.01 to 0.5 mL with respect to 5 mL of the poor solvent.

Then, 5 mL of the solution containing the above-described 3-aminopropyltriethoxysilane was added to 0.1 to 5 mL of the solution containing the above-described lead (II) bromide and methylamine hydrobromide at 0 to 60 ° C. under air. Add to get a mixture. Immediately thereafter, the obtained mixture is added to a large amount of co-solvent and stirred under the atmosphere for 5 to 180 seconds, after which the solid is recovered by centrifugation. When the mixture is added to a large amount of co-solvent, nanocrystals 911 are precipitated, and 3-aminopropyltriethoxysilane and oleic acid are coordinated on the surface of nanocrystals 911. Then, during stirring in the air, the alkoxysilyl group of 3-aminopropyltriethoxysilane condenses to form a surface layer 91 having siloxane bonds on the surface of the nanocrystal 911 .

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

1-5. photopolymerization initiator

The nanocrystal-containing composition of the present invention preferably further contains a polymerization initiator. It is preferable that a photoinitiator is at least 1 sort(s) chosen from the group containing an alkylphenone type compound, an acylphosphine oxide type compound, and an oxime ester type compound.

As an alkylphenone type photoinitiator, the compound represented by Formula (b-1) is mentioned, for example.

In formula (b-1), R1a represents a group selected from the following formulas (R ^1a -1) to (R ^1a -6), and R ^2a , R ^2b and R ^2c are each independently represented by the following formula ( R ² -1) to a group selected from formulas (R ² -7).

As specific examples of the compound represented by the formula (b-1), compounds represented by the following formulas (b-1-1) to (b-1-6) are preferable, and the following formula (b-1-1) , a compound represented by formula (b-1-5) or formula (b-1-6) is more preferred.

As an acylphosphine oxide type photoinitiator, the compound represented by Formula (b-2) is mentioned, for example.

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 represent an alkyl group, an aryl group, a heterocyclic group, or an alkanoyl group; It may be substituted with an alkyl group, a hydroxyl group, a carboxyl group, a sulfone group, an aryl group, an alkoxy group, or an arylthio group.

As specific examples of the compound represented by the formula (b-2), compounds represented by the following formulas (b-2-1) to (b-2-5) are preferable, and the following formula (b-2-1) Or the compound represented by formula (b-2-5) is more preferable.

As an oxime ester type photoinitiator, the compound represented by the following formula (b-3-1) or a formula (b-3-2) is mentioned, for example.

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 represent a halogen atom or a carbon atom may be substituted with a substituent selected from the group consisting of an alkoxyl group having 1 to 6 atoms and a phenyl group, X ¹ represents an oxygen atom or a nitrogen atom, X ² represents an oxygen atom or NR, and R represents the number of carbon atoms An alkyl group of 1 to 6 is shown.

As specific examples of the compounds represented by the formulas (b-3-1) and (b-3-2), the following formulas (b-3-1-1) to (b-3-1-2) and the following Compounds represented by formulas (b-3-2-1) to (b-3-2-2) are preferred, and the following formulas (b-3-1-1) and formulas (b-3-2-1) Or the compound represented by formula (b-3-2-2) is more preferable.

The compounding amount of the photopolymerization initiator is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and still more preferably 1 to 6% by mass with respect to the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition. desirable. In addition, a photoinitiator may be used individually by 1 type, and may mix and use 2 or more types. The nanocrystal-containing composition containing the photopolymerization initiator in such an amount sufficiently maintains photosensitivity during photocuring, and prevents crystals of the photopolymerization initiator from precipitating when the coating film is dried, so that deterioration of the physical properties of the coating film can be suppressed.

When dissolving the photopolymerization initiator in the nanocrystal-containing composition, it is preferable to use it after dissolving it in the photopolymerizable monomer in advance.

In order to dissolve in the photopolymerizable monomer, it is preferable to uniformly dissolve the photopolymerizable monomer by adding a photopolymerizable monomer while stirring so that the reaction by heat is not initiated.

The dissolution temperature of the photopolymerization initiator may be appropriately adjusted in consideration of the solubility of the photopolymerization initiator to the photopolymerizable monomer and the heat-induced polymerization of the photopolymerizable monomer, but from the viewpoint of not initiating polymerization of the photopolymerizable monomer, the temperature is 10 to 60°C. It is preferably , more preferably 10 to 40 ° C, and even more preferably 10 to 30 ° C.

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 in the form of particulates, it is described below as "light-scattering particles". Light-scattering particles are, for example, optically inactive inorganic fine particles. Light-scattering particles can scatter light from an irradiated 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.

Examples of the material constituting the light-scattering particles include simple metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; Silica, barium sulfate, barium carbonate, calcium carbonate, talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, metal oxides such as zinc oxide; metal carbonates such as magnesium carbonate, barium carbonate, bismuth carbonate, and calcium carbonate; metal hydroxides such as aluminum hydroxide; and complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, and metal salts such as bismuth nitrate. Among them, as the material constituting the light-scattering particles, at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silica is selected from the viewpoint of a more excellent light leakage reduction effect. It is preferable to contain, and it is more preferable to include at least 1 sort(s) selected from the group which consists of titanium oxide, barium sulfate, and calcium carbonate.

The light-scattering particles may have a spherical shape, a filament shape, or an irregular shape. However, as the light-scattering particles, the use of less directional particles (eg, spherical, tetrahedral, etc.) as the particle shape can further improve the uniformity, fluidity and light scattering properties of the nanocrystal-containing composition. preferred in

The average particle diameter (volume average diameter) of the light-scattering particles in the nanocrystal-containing composition may be 0.05 μm or more, 0.2 μm or more, or 0.3 μm or more from the viewpoint of a more excellent light leakage reduction effect. The average particle diameter (volume average diameter) of the light-scattering particles in the nanocrystal-containing composition may be 1.0 µm or less, 0.6 µm or less, or 0.4 µm or less from the viewpoint of excellent ejection stability. 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 to 1.0 μm, 0.2 to 0.6 μm, 0.2 to 0.4 μm, and 0.3 μm. to 1.0 µm, 0.3 to 0.6 µm, or 0.3 to 0.4 µm. From the standpoint of obtaining such an average particle diameter (volume average diameter) easily, 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 nanotrack particle size distribution analyzer and calculating the volume average diameter. In addition, the average particle diameter (volume average diameter) of the light-scattering particles to be used is obtained by measuring the particle diameter of each particle with a transmission electron microscope or a scanning electron microscope, for example, and calculating the volume average diameter.

The content of the light-scattering particles may be 0.1% by mass or more, 1% by mass or more, or 5% by mass or more based on the mass of the non-volatile content of the nanocrystal-containing composition, from the viewpoint of a more excellent light leakage reduction effect. 7 mass % or more may be sufficient, 10 mass % or more may be sufficient, and 12 mass % or more may be sufficient as it. The content of the light-scattering particles may be 60% by mass or less, and may be 50% by mass or less, based on the mass of the non-volatile content of the nanocrystal-containing composition, from the viewpoint of further excellent light leakage reduction effect and excellent discharge stability. , 40 mass % or less may be sufficient, 30 mass % or less may be sufficient, 25 mass % or less may be sufficient, 20 mass % or less may be sufficient, and 15 mass % or less may be sufficient. In this embodiment, since the nanocrystal-containing composition contains a polymer dispersing agent, the light-scattering particles can be well 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-scattering fine particles (light-scattering particles/luminescent nanocrystals) may be 0.1 or more, 0.2 or more, or 0.5 or more, from the viewpoint of a more excellent light leakage reduction effect. The mass ratio (light scattering particles/luminescent nanocrystals) may be 5.0 or less, 2.0 or less, or 1.5 or less, from the viewpoint of further excellent light leak reduction effect and excellent continuous ejection property during inkjet printing. In addition, it is thought that the light leakage reduction by light-scattering particle|grains is based on the following mechanism. That is, in the case where light-scattering particles do not exist, it is considered that the backlight light only passes substantially straight through the inside of the pixel portion, and there is little chance of being 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 backlight light is scattered in all directions within the pixel portion and the light-emitting fine particles can receive it, so even if the same backlight is used, in the pixel portion It is believed that the light absorption of As a result, it is thought that it has become possible to prevent leakage light with this mechanism.

1-7. dispersant

The nanocrystal-containing composition of the present invention preferably further contains a dispersing agent. 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. A dispersing agent is classified into a low molecular dispersing agent and a high molecular dispersing agent. In this specification, a "low molecule" means a molecule having a weight average molecular weight (Mw) of 5,000 or less, and a "high molecule" means a molecule having a weight average molecular weight (Mw) of more than 5,000. In addition, in this specification, "weight average molecular weight (Mw)" can employ the value measured using gel permeation chromatography (GPC) using polystyrene as a standard substance.

As a low molecular dispersing agent, it is oleic acid, for example; phosphorus atom-containing compounds such as triethyl phosphate, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA); nitrogen atom-containing compounds such as oleylamine, octylamine, trioctylamine, and hexadecylamine; and sulfur atom-containing compounds such as 1-decanethiol, octanethiol, dodecanethiol, and amyl sulfide.

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

Commercially available polymer dispersants include, for example, the DISPERBYK series made by Big Chemie, the TEGO Dispers series made by Evonik, the EFKA series made by BASF, the SOLSPERSE series made by Nippon Lubrizol, the Aji Super series made by Ajinomoto Fine Techno, Kusumoto Kasei's DISPARLON series, Kyoeisha Kagaku's Floren series, etc. 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, based on 100 parts by mass of the light emitting fine particles 910 and 90.

However, in the case of forming a color filter pixel portion by an inkjet method using a conventional ink composition, there is a case where the ejection stability from the inkjet nozzle is lowered due to aggregation of light-emitting fine particles and light-scattering particles. Further, it is conceivable to improve discharge stability by miniaturizing the light-emitting fine particles and light-scattering particles, reducing the content of the light-emitting fine particles and light-scattering particles, etc. It was difficult to achieve both stability and the effect of reducing leaked light. In contrast, according to the nanocrystal-containing composition of the present invention further containing a dispersant, light leakage can be further reduced while ensuring sufficient ejection stability. The reason why such an effect is obtained is not clear, but it is presumed that aggregation of light-emitting fine particles and light-scattering particles (particularly, light-scattering particles) is remarkably suppressed by the dispersant.

Examples of functional groups having affinity for light-scattering particles include acidic functional groups, basic functional groups and nonionic functional groups. The acidic functional group has a dissociable proton and may be neutralized with a base such as an amine or hydroxide ion, and the basic functional group may be neutralized with an acid such as an organic acid or an inorganic acid.

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

Examples of the basic functional group include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.

Examples of the nonionic functional group include a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO ₂ -), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, A ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group are mentioned.

From the viewpoint of the dispersion stability of the light-scattering particles, the difficulty of causing 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, as the acidic functional group, a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group is preferably used, and as the basic functional group, an amino group is preferably used. Among these, a carboxyl group, a phosphonic acid group, and an amino group are more preferably used, and an amino group is most preferably used.

A dispersant having an acidic functional group has an acid value. The acid value of the polymer dispersing agent 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 easily 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.

In addition, the dispersing agent having a basic functional group has an amine value. The amine value of the dispersing agent having a basic functional group is preferably 1 to 200 mgKOH/g in terms of solid content. When the amine value is 1 or more, sufficient dispersibility of the light-scattering particles is easily obtained, and when the amine value is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) is difficult to decrease.

The weight average molecular weight of the dispersing agent may be 750 or more, 1000 or more, 2000 or more, or 3000 or more from the viewpoint of being able to favorably disperse the light scattering particles and further improving the effect of reducing light leakage. . In addition, the weight average molecular weight of the dispersant can favorably disperse the light scattering particles, can further improve the effect of reducing light leakage, and also makes the viscosity of the inkjet ink capable of ejection and suitable for stable ejection From the viewpoints, 100000 or less may be sufficient, 50000 or less may be sufficient, and 30000 or less may be sufficient.

The content of the dispersing agent may be 0.5 parts by mass or more, 2 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the light-scattering particles from the viewpoint of the dispersibility of the light-scattering particles. The content of the polymer dispersion may be 50 parts by mass or less, 30 parts by mass or less, or 10 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 picture element portion (cured product of the ink composition). do.

1-8. other ingredients

The nanocrystal-containing composition used in the present invention may contain components other than the luminescent fine particles 910 and 90, photopolymerizable monomers, photopolymerization initiators, and light scattering particles within a range that does not impair the effects of the present invention. Examples of these other components include polymerization inhibitors, antioxidants, leveling agents, chain transfer agents, dispersing aids, thermoplastic resins, and sensitizers.

1-8-1. polymerization inhibitor

Examples of the polymerization inhibitor include p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, and 2,2'-methylenebis(4-methyl- 6-t-butyl phenol), 2,2'-methylenebis (4-ethyl-6-t-butyl phenol), 4,4'-thiobis (3-methyl-6-t-butyl phenol), 4- phenolic compounds such as methoxy-1-naphthol and 4,4'-dialkoxy-2,2'-bi-1-naphthol; Hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naph quinone compounds such as toquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone; p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-i-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'-di amine compounds such as cumyl-diphenylamine and 4,4'-dioctyl-diphenylamine; thioether compounds such as phenothiazine and distearylthiodipropionate; 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylphenyl N-oxyl compounds such as peridine-1-oxyl free radical; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinapthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthyl, N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrondimethylamine, p-nitron-N,N-diethylamine, N-nitrosoethanolamine, N-nitroso -Di-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-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-butylnitronbenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitro So-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso- and nitroso-based compounds such as 5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, and Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

It is preferable that it is 0.01-1.0 mass % with respect to the total amount of photopolymerizable monomers contained in a nanocrystal containing composition, and, as for the addition amount of polymerization inhibitor, it is more preferable that it is 0.02-0.5 mass %.

1-8-2. antioxidant

As an antioxidant, 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" (above, BASF Corporation make); 「Adecas Staff AO-20」, 「Adecas Staff AO-30」, 「Adecas Staff AO-40」, 「Adecas Staff AO-50」, 「Adecas Staff AO-60」, 「Adecas Staff AO -80” (above, manufactured by ADEKA Co., Ltd.); "JP-360", "JP-308E", "JPE-10" (above, manufactured by Johoku Chemical Industry Co., Ltd.); "Smilizer BHT", "Smilizer BBM-S", "Smilizer GA-80" (above, Sumitomo Chemical Co., Ltd. make), etc. are mentioned.

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

1-8-3. leveling agent

The leveling agent is not particularly limited, but is preferably a compound capable of reducing unevenness in film thickness in the case of forming a thin film of the light emitting fine particles 90.

Examples of such leveling agents include alkyl carboxylates, alkyl phosphates, alkylsulfonates, fluoroalkylcarboxylates, fluoroalkylphosphates, fluoroalkylsulfonates, polyoxyethylene derivatives, and fluoroalkylethylene oxide derivatives. , polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts and the like.

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

As other specific examples of the leveling agent, for example, "Ptergent 100", "Ptergent 100C", "Ptergent 110", "Ptergent 150", "Ptergent 150CH", "Ptergent 100A-K", "Ptergent 100A-K" 「Ptergent 300」, 「Ptergent 310」, 「Ptergent 320」, 「Ptergent 400SW」, 「Ptergent 251」, 「Ptergent 215M」, 「Ptergent 212M」, 「Ptergent 215M」, 「Ptergent 250 」, 「Ptergent 222F」, 「Ptergent 212D」, 「FTX-218」, 「Ptergent 209F」, 「Ptergent 245F」, 「Ptergent 208G」, 「Ptergent 240G」, 「Ptergent 212P」, 「Phtergent 220P」, 「Ptergent 228P」, 「DFX-18」, 「Ptergent 601AD」, 「Ptergent 602A」, 「Ptergent 650A」, 「Ptergent 750FM」, 「FTX-730FM」, 「Ptergent 601AD」 Gent 730FL", "Ptergent 710FS", "Ptergent 710FM", "Ptergent 710FL", "Ptergent 750LL", "FTX-730LS", "Ptergent 730LM", (above, manufactured by Neos, Inc.), etc. can be heard

As another specific example of a leveling agent, "BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", for example ”, “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” ”, “BYK-Silclean 3700” (above, manufactured by BYK Co., Ltd.), and the like.

As other specific examples of the leveling agent, for example, "TEGO Rad2100", "TEGO Rad2011", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2600", "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 Glide B1484”, “TEGO Glide ZG400”, 「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", "TEGO Wet KL245" (above, manufactured by Evonik Industries, Ltd.), etc. are mentioned.

As another specific example of a leveling agent, it is "FC-4430", "FC-4432" (above, 3M Japan Co., Ltd. make), "Unidigm NS" (above, Daikin Kogyo Co., Ltd. make), for example; 「Suplon S-241」, 「Suplon S-242」, 「Suplon S-243」, 「Suplon S-420」, 「Suplon S-611」, 「Suplon S-651」, 「Suplon S-651」 Ron S-386" (above, manufactured by AGC Semichemical Co., Ltd.) and the like.

As other specific examples of the leveling agent, for example, "DISPARLON OX-880EF", "DISPARLON OX-881", "DISPARLON OX-883", "DISPARLON OX-77EF", "DISPARLON OX-710", "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" (above, manufactured by Kusumoto Kasei Co., Ltd.), etc. are mentioned.

As other specific examples of the leveling agent, for example, "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-652-NF", "PF -3320” (above, manufactured by OMNOVA SOLUTIONS); "Polyflow No.7", "Polyflow No.50E", "Polyflow No.50EHF", "Polyflow No.54N", "Polyflow No.75", "Polyflow No.77", "Polyflow “Polyflo No.85”, “Polyflo No.85HF”, “Polyflo No.90”, “Polyflo No.90D-50”, “Polyflo No.95”, “Polyflo No.99C”, “Polyflo No.90D-50” "Polyflo KL-400K", "Polyflo KL-400HF", "Polyflo KL-401", "Polyflo KL-402", "Polyflo KL-403", "Polyflo KL-404", "Polyflo KL -100”, “Polyflo LE-604”, “Polyflo 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" (above, Kyoeisha Chemical Co., Ltd. make), etc. are mentioned.

In addition, as another specific example of a leveling agent, "L-7001", "L-7002", "8032ADDITIVE", "57ADDTIVE", "L-7064", "FZ-2110", "FZ-2105", "67ADDTIVE", "8616ADDTIVE" (above, Toray-Dow Silicone Co., Ltd. make), etc. are mentioned.

The added amount of the leveling agent is preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition.

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 a substrate when the nanocrystal-containing composition is used as an ink composition.

As a chain transfer agent, it is aromatic hydrocarbons, for example; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane; Mercaptan such as octylmercaptan, n-butylmercaptan, n-pentylmercaptan, n-hexadecylmercaptan, n-tetradecylmer, n-dodecylmercaptan, t-tetradecylmercaptan, t-dodecylmercaptan captan compounds; Hexanedithiol, decanedithiol, 1,4-butanediolbisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanetrithioglycol Late, trimethylolpropanetrithiopropionate, trimethylolpropanetris (3-mercaptobutyrate), pentaerythritol tetrakithioglycolate, pentaerythritoltetrakithiopropionate, trimercaptopropionic acid tris (2-hydroxy Roxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- thiol compounds such as s-triazine; sulfide compounds such as dimethylxantogen disulfide, diethylxantogen disulfide, diisopropylxantogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide; N,N-dimethylaniline, N,N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-terbinene, dipentene, etc. However, 2,4-diphenyl-4-methyl-1-pentene and thiol compounds are preferred.

As a specific example of a chain transfer agent, the compound represented by the following general formula (9-1) - (9-12) is preferable, for example.

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be straight-chain or branched-chain, and at least one methylene group in the alkyl group does not directly bond an oxygen atom and a sulfur atom to each other, an oxygen atom, It may be substituted by a sulfur atom, -CO-, -OCO-, -COO- or -CH=CH-.

R ⁹⁶ represents an alkylene group having 2 to 18 carbon atoms, and at least one methylene group in the alkylene group is an oxygen atom, a sulfur atom, -CO-, -OCO-, -, without direct bonding of oxygen atoms and sulfur atoms to each other. It may be substituted by COO- or -CH=CH-.

The added amount of the chain transfer agent is preferably 0.1 to 10% by mass, more preferably 1.0 to 5% by mass, based on the total amount of photopolymerizable monomers contained in the nanocrystal-containing composition.

1-8-5. dispersing aid

Examples of the dispersing aid include organic pigments such as phthalimidemethyl derivatives, phthalimidesulfonic acid derivatives, phthalimide N-(dialkylamino)methyl derivatives, and phthalimide N-(dialkylaminoalkyl)sulfonic acid amide derivatives. Derivatives etc. are mentioned. These dispersion auxiliary agents may be used individually by 1 type, and may use 2 or more types together.

1-8-6. thermoplastic

Examples of the thermoplastic resin 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, photopolymerizable monomers and amines that do not cause an addition reaction can be used. Examples of such a sensitizer include trimethylamine, methyl dimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N,N-dimethylbenzylamine. , 4,4'-bis (diethylamino) benzophenone, etc. are mentioned.

1-9. Method for preparing nanocrystal-containing composition

The nanocrystal-containing composition as described above can be prepared by dispersing the light-emitting fine particles 910 and 90 described above in a solution in which a photopolymerizable monomer and a photopolymerization initiator are mixed. Dispersion of the light emitting fine particles 910 and 90 can be carried out by using a ball mill, sand mill, bead mill, three roll mill, paint conditioner, attritor, dispersion stirrer, and a dispersing machine such as ultrasonic waves, for example.

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, still more preferably 1 to 40% by mass. By setting the content of the luminescent fine particles 910 and 90 in the nanocrystal-containing composition to the above range, the ejection stability can be further improved when the ink composition composed of the nanocrystal-containing monomer is ejected by the inkjet printing method. can In addition, the uncoated light emitting fine particles 910 or the inorganic coated light emitting fine particles 91 are less likely to aggregate with each other, so that the external quantum efficiency of the resulting light emitting layer (light conversion layer) can be increased.

The nanocrystal-containing composition of the present invention can be cured by forming a film on a substrate by various methods such as an inkjet printer, photolithography, or spin coater, and curing the film by heating. Among them, the nanocrystal-containing composition of the present invention is particularly suitable as an ink composition used in an inkjet printer.

The viscosity of the nanocrystal-containing composition as an 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, and 7 to 12 mPa·s. It is more preferable that it is the range of s. In this case, since the meniscus shape of the nanocrystal-containing composition in the ink ejection hole of the ejection head is stabilized, ink ejection control (for example, control of ejection amount and ejection timing) becomes easy. Also, ink can be smoothly ejected from the ink ejection hole. In addition, the viscosity of the nanocrystal-containing composition can be measured, for example, with an E-type viscometer.

In addition, the surface tension of the nanocrystal-containing composition as an ink composition is preferably a surface tension suitable for inkjet printing. It is preferable that it is the range of 20-40 mN/m, and, as for the specific value of surface tension, it is more preferable that it is the range of 25-35 mN/m. By setting the surface tension within the above range, it is possible to suppress the occurrence of flight bending of ink droplets. In addition, flight bending means the deviation of the landing position of the ink by 30 µm or more from the target position when the ink is ejected from the ink ejection hole.

2. Light-emitting device formed using nanocrystal-containing composition

The above-described nanocrystal-containing composition can be cured by forming a film on a substrate by various methods such as inkjet printer, photolithography, and spin coater, and heating and curing the film. Hereinafter, a case in which a color filter pixel portion of a light emitting device having a blue organic LED backlight is formed using a nanocrystal-containing composition as an ink composition will be described as an example.

Fig. 3 is a cross-sectional view showing one embodiment of the light emitting element of the present invention, and Figs. 4 and 5 are schematic diagrams each showing the configuration of an active matrix circuit. In addition, in FIG. 3, for convenience, the dimensions of each part and their ratio are exaggerated and shown, and may differ from reality. In addition, the materials, dimensions, etc. shown below are examples, and the present invention is not limited thereto, and can be appropriately changed within a range that does not change the gist thereof. Hereinafter, for convenience of explanation, the upper side in Fig. 3 is 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, description of hatching which shows a cross section is abbreviate|omitted in order to avoid complicating a drawing.

As shown in FIG. 3, the light emitting element 100 includes a lower substrate 1, an EL light source unit 200, a filling layer 10, a protective layer 11, and the above-described light emitting fine particles. It has a structure in which a light conversion layer 12 acting as a layer and an 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 unit 200 includes an anode 2, an EL layer 14 including 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 sequentially stacked from the anode 2 side. includes

This light emitting element 100 absorbs and re-radiates or transmits the light emitted from the EL light source unit 200 (EL layer 14) by the light conversion layer 12, and transmits the light from the upper substrate 13 side to the outside. It is a photoluminescent element taken out with. At this time, light of a predetermined color is converted into light by the light emitting particles 910 or 90 included in the light conversion layer 12 . Hereinafter, each layer is sequentially demonstrated.

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 element 100 . When the light emitting device 100 is a top emission type, the upper substrate 13 is made of a transparent substrate. Meanwhile, when the light emitting device 100 is a bottom emission type, the lower substrate 1 is formed of a transparent substrate. Here, the transparent substrate means a substrate capable of transmitting light of a wavelength in the visible light region, and includes colorless transparent, colored transparent, and translucent transparent substrates.

As the transparent substrate, for example, quartz glass, Pyrex (registered trademark) glass, transparent glass substrates such as synthetic quartz plates, quartz substrates, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (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 an alkali-free glass that does not contain an alkali component in the glass. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" by Corning, "AN100" by Asahi Glass, "OA-10G" and "OA-10G" by Nippon Denki Glass Co., Ltd. 11” is suitable. These are raw materials with a small coefficient of thermal expansion and are excellent in dimensional stability and workability in high-temperature heat treatment. In the case of imparting flexibility to the light emitting element 100, each of the lower substrate 1 and the upper substrate 13 includes a plastic substrate (a substrate composed of a polymer material as a main material) and a metal substrate having a relatively small thickness. is selected

The thickness of the lower substrate 1 and the upper substrate 13 is not particularly limited, respectively, but is preferably in the range of 100 to 1,000 μm, and more preferably in the range of 300 to 800 μm.

In addition, either one or both of the lower substrate 1 and the upper substrate 13 may be omitted depending on the type of use of the light emitting element 100 .

As shown in FIG. 4, on the lower substrate 1, a signal line driving circuit C1 and a scanning line driving circuit ( C2), a control circuit C3 for controlling the operation of these circuits, a plurality of signal lines 706 connected to the signal line driver circuit C1, and a plurality of scan lines 707 connected to the scan line driver circuit C2 is provided. In the vicinity of the intersection of each signal line 706 and each scan line 707, as shown in Fig. 5, a capacitor 701, a driving transistor 702, and a switching transistor 708 are provided.

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 driving 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 supplying driving current, and a drain electrode. It is connected to the anode 4 of this EL light source section 200.

The switching transistor 708 has a gate electrode connected to the scan line 707, a source electrode connected to the signal line 706, and a drain electrode connected to the gate electrode of the driving transistor 702. In this embodiment, the common electrode 705 constitutes the cathode 8 of the EL light source unit 200. In addition, the driving transistor 702 and the switching transistor 708 can be constituted by, for example, thin film transistors or the like.

The scan line driving circuit C2 supplies or blocks a scan voltage according to a scan signal to the gate electrode of the switching transistor 708 via the scan line 707 to turn the switching transistor 708 on or off. In this way, the scan line driver circuit C2 adjusts the timing at which the signal line driver circuit C1 writes the signal voltage. On the other hand, the signal line driving circuit C1 supplies or cuts off a signal voltage according to a video signal to the gate electrode of the driving transistor 702 through the signal line 706 and the switching transistor 708, so that the EL light source unit 200 Adjust the amount of signal current supplied.

Therefore, when the scan voltage from the scan line driver circuit C2 is supplied to the gate electrode of the switching transistor 708 and the switching transistor 708 is turned on, the signal voltage from the signal line driver circuit C1 is applied to the gate electrode of the switching transistor 708. supplied to the gate electrode. At this time, the 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 unit 200 emits light according to the supplied signal current.

2-2. EL light source (200)

2-2-1. Anode(2)

The anode 2 has a function of supplying holes toward the light emitting layer 5 from an external power source. The constituent material (anode material) of the anode 2 is not particularly limited, and examples thereof include metals such as gold (Au), metal halides such as copper iodide (CuI), indium tin oxide (ITO), and tin oxide ( and metal oxides such as SnO ₂ ) and zinc oxide (ZnO). These may be used individually by 1 type, and may use 2 or more types together.

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

The anode 2 can be formed by, for example, 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 supply toward the light emitting layer 5 . The constituent material (negative electrode material) of the negative electrode 8 is not particularly limited, and examples thereof include lithium, sodium, magnesium, aluminum, silver, a sodium-potassium alloy, a magnesium/aluminum mixture, a magnesium/silver mixture, and magnesium/indium. mixtures, aluminum/aluminum oxide (Al ₂ O ₃ ) mixtures, rare earth metals, and the like. These may be used individually by 1 type, and may use 2 or more types together.

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

The cathode 3 can be formed by, for example, 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 . In addition, the hole injection layer 3 may be provided as needed, and may be omitted.

The constituent material (hole injection material) of the hole injection layer 3 is not particularly limited, but examples thereof include phthalocyanine compounds such as copper phthalocyanine; Triphenylamine derivatives such as 4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine; 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile, 2 Cyano compounds such as 3,5,6-tetrafluoro-7,7,8,8-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, etc. Among these, the hole injecting material is preferably a polymer, and PEDOT-PSS It is more preferable that it is PSS In addition, the hole injection material mentioned above may be used individually by 1 type, and may use 2 or more types together.

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

Such a hole injection layer 4 can be formed by a wet film forming method or a dry film forming method. In the case where the hole injection layer 3 is formed by a wet film forming method, usually, ink containing the hole injection material described above is applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include inkjet printing (droplet dispensing method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, screen printing method, nozzle print printing method, and the like. can be heard On the other hand, in the case of forming the hole injection layer 3 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like can be suitably 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 . In addition, the hole transport layer 4 may have a function of preventing electron transport. In addition, the hole transport layer 4 may be provided as needed and may be omitted.

The constituent material (hole transport material) of the hole transport layer 4 is not particularly limited, but is, 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 [(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(sec-butylphenyl)diphenylamine))(TFB), polyphenylenevinylene conjugated compound polymers such as (PPV), and copolymers containing these monomer units.

Among these, the hole transport material is preferably a triphenylamine derivative or a polymer compound obtained by polymerizing a triphenylamine derivative introduced with a substituent, and more preferably a polymer compound obtained by polymerizing a triphenylamine derivative introduced with a substituent. do. In addition, the hole transport materials described above may be used alone or in combination of two or more.

The thickness of the hole transport layer 4 is not particularly limited, but is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 300 nm, and still 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 forming method or a dry film forming method. In the case where the hole transport layer 4 is formed by a wet film forming method, usually ink containing the hole transport material described above is applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include inkjet printing (droplet dispensing method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, screen printing method, nozzle print printing method, and the like. can be heard On the other hand, in the case of forming the hole transport layer 4 by a dry film forming method, a vacuum evaporation method, a sputtering method, or the like can be suitably 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 . In addition, the electron injection layer 7 may be provided as needed and may be omitted.

The constituent material (electron injection material) of the electron injection layer 7 is not particularly limited, and 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 CaO, BaO, SrO, BeO, BaS, MgO, CaSe; alkali metal halides such as CsF, LiF, NaF, KF, LiCl, KCl, NaCl; alkali metal salts such as lithium 8-hydroxyquinolinolate (Liq); and alkaline earth metal halides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , and BeF ₂ . Among these, alkali metal chalcogenides, alkaline earth metal halides, and alkali metal salts are preferable. In addition, the electron injecting materials described above may be used alone 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, still more preferably in the range of 0.5 to 10 nm. . The electron injection layer 7 may have a single-layer structure or a laminated structure in which two or more layers are stacked.

Such an electron injection layer 7 can be formed by a wet film forming method or a dry film forming method. In the case where the electron injection layer 7 is formed by a wet film forming method, usually ink containing the electron injection material described above is applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include inkjet printing (droplet dispensing method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, screen printing method, nozzle print printing method, and the like. can be heard On the other hand, in the case of forming the electron injection layer 7 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may 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 . In addition, the electron transport layer 8 may have a function of preventing transport of holes. In addition, the electron transport layer 8 may be provided as needed, and may be omitted.

The constituent material (electron transport material) of the electron transport layer 8 is not particularly limited, and examples thereof include tris(8-quinolilator) aluminum (Alq3) and tris(4-methyl-8-quinolinolate). Aluminum (Almq3), bis(10-hydroxybenzo[h]quinolinate)beryllium (BeBq2), bis(2-methyl-8-quinolinolate)(p-phenylphenolate)aluminum (BAlq), bis metal complexes having a quinoline skeleton or a benzoquinoline skeleton such as (8-quinolinolate) zinc (Znq); metal complexes having a benzoxazoline skeleton such as bis[2-(2'-hydroxyphenyl)benzoxazolato]zinc (Zn(BOX)2); metal complexes having a benzothiazoline skeleton such as bis[2-(2'-hydroxyphenyl)benzothiazolato]zinc (Zn(BTZ)2); 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-oxadiazole-2- tris or diazole derivatives such as yl]benzene (OXD-7), 9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]carbazole (CO11); 2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole)(TPBI), 2-[3-(dibenzothiophen-4-yl) Imidazole derivatives such as phenyl]-1-phenyl-1H-benzimidazole (mDBTBIm-II); quinoline derivatives; perylene derivatives; pyridines such as 4,7-diphenyl-1,10-phenanthroline (BPhen) derivatives; pyrimidine derivatives; triazine derivatives; quinoxaline derivatives; diphenylquinone derivatives; nitro-substituted fluorene derivatives; metal oxides such as zinc oxide (ZnO) and titanium oxide (TiO ₂ ). Among these, As the electron transport material, preferably imidazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, metal oxides (inorganic oxides). You may use more than one species together.

The thickness of the electron transport layer 7 is not particularly limited, but is preferably in the range of 5 to 500 nm, and 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 forming method or a dry film forming method. In the case where the electron transport layer 6 is formed by a wet film forming method, usually ink containing the electron transport material described above is applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include inkjet printing (droplet dispensing method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, screen printing method, nozzle print printing method, and the like. can be heard On the other hand, in the case of forming the electron transport layer 6 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may be applied.

2-2-7. Light emitting layer (5)

The light emitting layer 5 has a function of generating light emission using energy generated by recombination of holes and electrons injected into the light emitting layer 5 . The light emitting layer 5 of this embodiment emits blue light with a wavelength in the range of 400 to 500 nm, more preferably in the range of 420 to 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. For the light emitting material, a compound capable of converting singlet excitation energy into light or a compound capable of converting triplet excitation energy into light can be used. Further, the light-emitting material preferably includes at least one selected from the group consisting of organic low-molecular-weight fluorescent materials, organic high-molecular fluorescent materials, and organic phosphorescent materials.

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

The organic low-molecular-weight fluorescent material has an anthracene structure, a tetracene structure, a chrysene structure, a phenanthrene structure, a pyrene structure, a perylene structure, a stilbene structure, an acridone structure, a coumarin structure, a phenoxazine structure, or a phenothiazine structure. compounds are preferred.

Specific examples of the organic low molecular weight fluorescent material include 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 '-diphenylstilbene-4,4'-diamine, 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine, 4-(9H-carbazole Bazol-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(dibenzo Furan-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-phenyl rendiamine], 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-diphenyl-9H-carbazol-3-amine, N-(9,10-diphenyl-2-anthryl) -N,N',N'-triphenyl-1,4-phenylene Diamine, N,N,9-triphenylanthracene-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)propanedi Nitrile, 2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran- 4-ylidene} propanedinitrile, N,N,N',N'-tetrakis(4-methylphenyl)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]quinolizin-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]quinolizin-9-yl )ethenyl]-4H-pyran-4-ylidene}propanedinitrile, 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] quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene} propanedinitrile, 5,10,15,20-tetraphenylbisbenzo[5,6]indeno[1,2 ,3-cd:1',2',3'-lm] perylene; and the like.

Specific examples of the organic polymer fluorescent material include, for example, homopolymers containing units based on fluorene derivatives, copolymers containing units based on fluorene derivatives and units based on tetraphenylphenylenediamine derivatives, and terphenyl. A homopolymer comprising a unit based on a derivative, a homopolymer comprising a unit based on a diphenylbenzoflorene derivative, and the like are exemplified.

As the compound capable of converting triplet excitation energy into light, an organic phosphorescent material that emits phosphorescence is preferable. Specific examples of the organic phosphorescent material include, for example, a metal complex 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. can be heard Among them, as the organic phosphorescent material, 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 is preferable, and iridium, rhodium, A metal complex containing at least one metal atom selected from the group consisting of platinum and ruthenium is more preferable, and an iridium complex or a platinum complex is still more preferable.

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. In addition, when the light emitting material is a phosphorescent material, it is preferable to select a compound having a higher triplet excitation energy than the triplet excitation energy (energy difference between the ground state and the triplet excited state) of the light emitting material as the host material.

As the host material, for example, tris(8-quinolinolato) aluminum (III), tris(4-methyl-8-quinolinolato) aluminum (III), bis(10-hydroxybenzo[h]quin Nolinato) 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-benzenetri yl)tris(1-phenyl-1H-benzimidazole), vasophenanthroline, vasocuproin, 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-carbazole- 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, 9,10-di(2-naphthyl)anthracene, 2-tert-butyl-9,10-di(2-naphthyl)anthracene, 9,9 '-Bianthril, 9,9'-(stilbene-3,3'-diyl)diphenanthrene, 9,9'-(stilbene-4,4'-diyl)diphenanthrene, 1,3,5 -Tri (1-pyrenyl) benzene, 5,12-diphenyl tetracene or 5,12-bis (biphenyl-2-yl) tetracene, etc. are mentioned. These host materials may be used individually by 1 type, and may use 2 or more types together.

The thickness of the light emitting layer 5 is not particularly limited, but is preferably in the range of 1 to 100 nm, and 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. In the case where the light emitting layer 5 is formed by a wet film forming method, usually, ink containing the light emitting material and the host material described above is applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include inkjet printing (droplet dispensing method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, screen printing method, nozzle print printing method, and the like. can be heard On the other hand, in the case of forming the light emitting layer 5 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may be applied.

Further, the EL light source unit 200 may further include banks (partition walls) partitioning the hole injection layer 3, the hole transport layer 4, and the light emitting layer 5, for example. The height of the banks 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, still more preferably in the range of 0.2 to 3 μm.

The width of the opening of the bank is preferably in the range of 10 to 200 μm, more preferably in the range of 30 to 200 μm, still more preferably in the range of 50 to 100 μm. The length of the opening of the bank is preferably in the range of 10 to 400 μm, more preferably in the range of 20 to 200 μm, still more preferably in the range of 50 to 200 μm. Further, the inclination angle of the bank is preferably in the range of 10 to 100°, more preferably in the range of 10 to 90°, and still 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 and re-emits it, or transmits the light emitted from the EL light source unit 200. As shown in FIG. 3, the pixel unit 20 includes a first pixel unit 20a that converts light having a wavelength in the above range to emit red light, and a second pixel unit 20a that converts light having a wavelength in the above range to emit green light. It has a portion 20b and a third pixel portion 20c that transmits light having a wavelength in the above range. A plurality of first pixel portions 20a, second pixel portions 20b, and third pixel portions 20c are arranged in a grid pattern so as to be repeated in this order. And, between adjacent pixel units, that is, between the first pixel unit 20a and the second pixel unit 20b, between the second pixel unit 20b and the third pixel unit 20c, and the third pixel unit 20c ) and the first pixel portion 20a, a light blocking portion 30 for shielding light is provided. In other words, these adjacent pixel parts are separated from each other by the light-shielding part 30 . In addition, the first pixel portion 20a and the second pixel portion 20b may contain color 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 above-described embodiment. The cured product preferably contains light-emitting fine particles 90 and a curing component as essential, and further 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, for example, a cured product obtained by polymerization of a resin containing an epoxy group. That is, the first pixel portion 20a includes the first curing component 22a, and first light-emitting fine particles 90a and first light scattering particles 21a respectively dispersed in the first curing component 22a. Similarly, the second pixel portion 20b includes a second curing component 22b, and first light-emitting fine particles 90b and first light scattering particles 21b respectively dispersed in the second curing component 22b. 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 the first light-scattering particles 22a and the second curing component 22b may be the same or different. The two light-scattering particles 22b may be the same or different.

The first light-emitting fine particles 90a are red light-emitting fine particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a peak emission wavelength in the range of 605 to 665 nm. That is, the first pixel portion 20a may be referred to as a red pixel portion for converting blue light into red light. In addition, the second light-emitting fine particles 90b are green light-emitting fine particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a peak emission wavelength in the range of 500 to 560 nm. That is, the second pixel portion 20b may be referred to as a green pixel portion 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 nanocrystals from the viewpoint of further improving the external quantum efficiency and obtaining excellent luminous intensity. Based on the total mass of the cured product of the containing composition, it is preferably 1% by mass or more. From the same point of view, the content of the luminescent fine particles 90 may be 5% by mass or more, 10% by mass or more, or 15% by mass or more based on the total mass of the cured product of the nanocrystal-containing composition. The content of the luminescent fine particles 90 is preferably 40% by mass or less based on the total mass of the nanocrystal-containing composition from the viewpoint of excellent reliability of the pixel portions 20a and 20b and excellent luminous intensity. . From the same 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 more based on the total mass of the cured product of the nanocrystal-containing composition.

The content of the light-scattering particles 21a, 21b in the pixel portions 20a, 20b containing the cured product of the nanocrystal-containing composition is the curing of the nanocrystal-containing composition from the viewpoint of further improving the external quantum efficiency. Based on the total mass of water, 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, may be 10% by mass or more, may be 12% by mass or more. The content of the light-scattering particles 21a and 21b is, based on the total mass of the cured product of the nanocrystal-containing composition, 60 It may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less.

The third pixel portion 20c has a transmittance of 30% or more to light having a wavelength in the range of 420 to 480 nm. Therefore, the third pixel portion 20c functions as a blue pixel portion when a light source emitting light having a wavelength in the range of 420 to 480 nm is used. The third pixel portion 20c includes, for example, a cured product of a composition containing the thermosetting resin described above. The cured product contains the third cured component 22c. 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 includes the cured product described above, the composition containing the thermosetting resin has a transmittance to light having a wavelength in the range of 420 to 480 nm of 30% or more, as long as it is 30% or more. Among the components contained in the nanocrystal-containing composition, components other than a thermosetting resin, a curing agent, and a solvent may be further contained. In addition, the transmittance of the third pixel portion 20c can be measured by a microscopy device.

The thickness of the pixel portions (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 2 μm or more. It may be 3 μm or more. The thickness of the pixel portions (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. do.

The light conversion layer 12 including the above first to third pixel portions 20a to 20c can be formed by drying, heating, and curing a coating film formed by a wet film forming method. 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 light-emitting fine particles 90 included in the nanocrystal-containing composition.

Hereinafter, a method of forming a coating film as the light conversion layer 12 using the 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, and examples thereof include inkjet printing method (piezo method or thermal method droplet discharging method), spin coating method, cast method, LB method, iron plate printing method, gravure printing method, A screen printing method, a nozzle print printing method, etc. are mentioned. Here, the nozzle print printing method is a method of applying an ink composition in a stripe shape from a nozzle hole as a column of liquid. Among them, as the coating method, an inkjet printing method (particularly, a piezo-type droplet discharging method) is preferable. This makes it possible to reduce the thermal load when discharging the ink composition, and to prevent deterioration of the light emitting fine particles 90 due to heat.

The conditions of the inkjet printing method are preferably set as follows. The discharge 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 still more preferably 1 to 20 pL/time.

Further, the opening diameter of the nozzle hole is preferably in the range of 5 to 50 µm, and more preferably in the range of 10 to 30 µm. As a result, the ejection accuracy of the ink composition can be increased while clogging of the nozzle hole is prevented.

The temperature at the time of forming the coating film 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 still more preferably in the range of 15 to 30°C. If liquid droplets are discharged at such a temperature, crystallization of various components included in the ink composition can be suppressed.

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

Drying of the obtained coating film may be performed by leaving it at room temperature (25°C) or by heating, but from the viewpoint of productivity, it is preferable to perform drying by heating. When drying is performed by heating, the drying temperature is not particularly limited, but is preferably a temperature considering the boiling point and vapor pressure of the organic solvent used in the ink composition. The drying temperature is preferably 50 to 130°C, more preferably 60 to 120°C, particularly preferably 70 to 110°C, as a prebaking step for removing the organic solvent in the coating film. If the drying temperature is 50 ° C. or less, the organic solvent cannot be removed, while if the drying temperature is 130 ° C. or more, the organic solvent is removed and the coating film is cured simultaneously, so the appearance of the cured coating film is remarkably deteriorated, which is not preferable. In addition, it is preferable to perform drying under reduced pressure, and it is more preferable to perform it under reduced pressure of 0.001-100 Pa. The drying time is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, and 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 obtained light conversion layer 12 can be further improved.

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

The heating time for complete curing is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, and particularly preferably 1 to 10 minutes. Further, although heating for complete curing can be performed in air or in an inert gas, in order to suppress oxidation of the coating film, it is more preferable to perform in an inert gas. As an inert gas, nitrogen, argon, carbon dioxide, etc. are mentioned. By curing the coating film under such heating conditions, the external quantum efficiency of the obtained light conversion layer 9 can be further improved since the coating film can be completely cured.

In addition to curing by heating, the ink composition of the present invention may be cured by using an active energy ray (eg, ultraviolet ray) irradiation in combination. As an irradiation source (light source), a mercury lamp, a metal halide lamp, a xenon lamp, LED etc. are used, for example.

It is preferable that it is 200 nm or more, and, as for the wavelength of the light to irradiate, it is more preferable that it is 440 nm or less. Moreover, it is preferable that it is 10 mJ/cm<2> or more, and, as for the irradiation amount (exposure amount) of light, it is more preferable that it is 4000 mJ/cm<2> or less.

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

In addition, since the light emitting particles 90 included in the first pixel portion 20a and the second pixel portion 20b include semiconductor nanocrystals including metal halide, absorption in the wavelength range of 300 to 500 nm is reduced. big. 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, that is, , leakage of blue light to the upper substrate 13 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 having high color purity can be extracted without mixing blue light.

The light blocking unit 30 is a so-called black matrix provided for the purpose of preventing color mixing by separating adjacent pixel units 20 and preventing light leakage from a light source. The material constituting the light-shielding portion 30 is not particularly limited, and a cured product of a resin composition in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a binder polymer in addition to metals such as chromium, 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, photosensitive resin, O/W An emulsion-type resin composition (for example, one obtained by emulsifying reactive silicone) or the like can be used. The thickness of the light-blocking portion 30 may be, for example, 1 μm or more and 15 μm or less.

The light emitting element 100 may be configured as a bottom emission type instead of a top emission type.

In addition, instead of the EL light source unit 200, the light emitting element 100 may use another light source.

In the above, the nanocrystal-containing composition and ink composition of the present invention, their production method, and the light emitting element provided with the light conversion layer produced using the ink composition have been described. It is not limited. For example, the luminescent fine particles, the luminescent fine particle dispersion, the nanocrystal-containing composition, the ink composition, and the light emitting element of the present invention may each have other arbitrary configurations added to the configuration of the above-described embodiment, and the same It may be substituted with an arbitrary structure exhibiting the function of. In the configuration of the above-described embodiment, the method for producing luminescent fine particles of the present invention may have other arbitrary steps, or may be substituted with an arbitrary step exhibiting the same effect.

Example

Hereinafter, the present invention will be specifically described by examples. However, the present invention is not limited only to the following examples. All of the materials used in the Examples are obtained by introducing argon gas to replace dissolved oxygen with argon gas. Titanium oxide was heated at 120°C for 2 hours under a reduced pressure of 1 mmHg before mixing, and allowed to cool in an argon gas atmosphere. The liquid material used in the examples was dehydrated in the molecular sieve 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 prepare cesium oleate.

In another three-necked flask, lead (II) bromide (55 mg), 1-octadecene (5 ml), oleylamine (0.5 ml) and oleic acid (0.5 ml) were added, and after heating at 110 ° C. for 30 minutes under vacuum, The temperature was raised to 180°C under an argon stream. Further, the cesium oleate solution (0.8 ml) being heated at 150°C was added with a syringe and reacted for 15 seconds, followed by rapid cooling in an ice bath.

The obtained reaction solution was centrifuged (8000 G x 5 minutes) to recover a solid. Toluene (20 ml) was added to the obtained solid to obtain a suspension. This suspension was centrifuged (8000 G x 5 minutes), precipitates containing impurities were removed by decantation, and a supernatant toluene solution was recovered. Ethyl acetate (20 ml) was added to the recovered toluene solution to reprecipitate the solid to obtain luminescent fine particles A. The obtained luminescent fine particles A have a perovskite type crystal structure and exhibit light emission, and the surface of a lead cesium tribromide crystal is provided with a ligand containing oleylamine and oleic acid, and is equivalent to the above-described uncoated luminescent fine particles 910. do. The average particle diameter of the luminescent fine particles A was 10 nm. The average particle diameter of the luminescent fine particles A was measured by Nanotrac Wave II (manufactured by Microtrac), and was 10 nm on average.

(Preparation of luminescent fine particles B)

A toluene solution (0.05 M) of N-1(1-adamantyl)ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared. The luminescent fine particles A, oleic acid (50 ml), and the N-1 (1-adamantyl) ethylenediamine solution (2 ml) were added to an eggplant flask, and the mixture was stirred for 1 minute. At this time, the luminescent fine particles A were added to a concentration of 15 mg/mL. After adding ethyl acetate (100 ml) to the obtained solution, it was centrifuged (8000 G x 5 minutes) to obtain luminescent fine particles B. The luminescent fine particles B have a ligand containing N-1(1-adamantyl)ethylenediamine on the surface of a lead cesium tribromide crystal that has a perovskite crystal structure and exhibits luminescence, and has the above-described bare luminescence. Corresponds to the fine particles 910. The average particle diameter of the luminescent 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 liquid mixture. Next, after drying this liquid mixture under reduced pressure at 120°C for 10 minutes, it was heated at 150°C in an argon atmosphere. In this way, a cesium-oleic acid solution was obtained.

On the other hand, lead (II) bromide (138.0 mg) and 1-octadecene (10 mL) were mixed to obtain a mixed solution. Next, after drying this liquid mixture at 120 degreeC for 10 minutes under reduced pressure, 3-aminopropyl triethoxysilane (1 ml) was added to this liquid mixture in an argon atmosphere, and liquid mixture (1) was obtained.

Thereafter, after raising the temperature of the liquid mixture (1) to 140°C, the cesium-oleic acid solution (1.3 ml) was added and reacted by heating and stirring for 5 seconds, followed by cooling in an ice bath.

Next, after stirring the obtained reaction solution under air (23°C, 45% humidity) for 60 minutes, ethanol (20 ml) was added to obtain a suspension. The resulting suspension was centrifuged (3,000 revolutions/minute, 5 minutes) to recover a solid.

A hexane dispersion of the luminescent fine particles C was obtained by adding the collected solid matter to 16 ml of hexane. The luminescent fine particles C have a perovskite-type crystal structure and the surface of a lead cesium tribromide crystal exhibiting light emission is provided with a ligand containing oleic acid and a ligand containing 3-aminopropyltriethoxysilane having a reactive group, It corresponds to the inorganic-coated light-emitting fine particles 90 described above further having a silica coating layer corresponding to the inorganic coating layer 91 containing Si in FIG. 2 by reacting with the reactive group. The average particle diameter 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 (8.85 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a photopolymerizable monomer, light acrylate DCP-A (0.5 parts by mass) , Kyoeisha Chemical Co., Ltd.), and it was made to dissolve uniformly by stirring at room temperature, and the monomer solution 1 was obtained.

(monomer solution 2)

In the preparation method of monomer solution 1, isobornyl methacrylate (Tokyo Kasei Kogyo Co., Ltd. A monomer solution 2 was obtained in the same manner as in the preparation method of the monomer solution 1 except that the first) was used.

(Monomer Solution 3)

In the preparation method of the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, dicyclopentanyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) ) was used, and the monomer solution 3 was obtained in the same manner as in the preparation method of the monomer solution 1.

(monomer solution 4)

In the preparation method of the monomer solution 1, instead of the photopolymerizable monomer 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1-adamantyl methacrylate (Tokyo Chemical Industry Co., Ltd.) Except having used Shikigai Co., Ltd. product), it carried out similarly to the preparation method of monomer solution 1, and obtained monomer solution 4.

(Monomer solution 5)

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

(Monomer Solution 6)

In the preparation method of monomer solution 1, isobornyl methacrylate (4.85 parts by mass, Tokyo Kasei Monomer solution 6 was obtained in the same manner as in the preparation method of monomer solution 1 except that Kogyo Co., Ltd. make) and 1-adamantyl methacrylate (4.00 parts by mass, Tokyo Kasei Kogyo Co., Ltd. make) were used.

(monomer solution 7)

In the preparation method of 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, Kyoeisha Chemical Co., Ltd.) and 1-adamantyl methacrylate (8.55 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were used, but the monomer solution 7 was obtained in the same manner as in the preparation method of the monomer solution 1.

(monomer solution 8)

In the preparation method of 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, Kyoeisha Chemical Co., Ltd.) and 1-adamantyl methacrylate (5.85 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were used, but the monomer solution 8 was obtained in the same manner as in the preparation method of the monomer solution 1.

(monomer solution 9)

In the preparation method of 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, Kyoeisha Chemical Except having used (made by Co., Ltd.), it carried out similarly to the preparation method of monomer solution 1, and obtained monomer solution 9.

(monomer solution 10)

In the preparation method of monomer solution 1, isobornyl methacrylate (8.85 parts by mass, Tokyo Kasei Kogyo Co., Ltd.) was used, except that TMPTA (0.5 parts by mass, Osaka Yuki Chemical Kogyo Co., Ltd.) was used instead of light acrylate DCP-A, in the same manner as in the preparation method of monomer solution 1, Monomer solution 10 was obtained.

(monomer solution 11)

In the preparation method of monomer solution 1, light ester L (8.85 parts by mass, Kyoeisha Chemical Co., Ltd. Monomer solution in the same manner as in the preparation method for monomer solution 1, except that TMPTA (0.5 parts by mass, manufactured by Osaka Yuki Chemical Industry Co., Ltd.) was used instead of light acrylate DCP-A. got 11

(monomer solution 12)

In the preparation method of monomer solution 1, light ester PO-A (8.85 parts by mass, Kyoeisha Kaga Monomer solution 12 was obtained in the same manner as in the preparation method of monomer solution 1, except that Kokuro Co., Ltd. product) was used.

<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 stirred at room temperature to obtain uniform dispersion. The resulting dispersion was filtered through a filter having a pore diameter of 5 μm to obtain QD dispersion 1 as a nanocrystal-containing composition.

(Examples 2 to 8, 10, 40)

In the method for preparing QD dispersion 1, QD dispersions 2 to 8, QD dispersions 10, and QD dispersions are similarly performed except that Monomer solutions 2 to 8, Monomer solution 10, and Monomer solution 12 are used instead of Monomer solution 1, respectively. Dispersion 13 was 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 luminescent microparticles B were used instead of luminescent microparticles A.

(Example 11)

In the method for preparing QD dispersion 1, QD dispersion 11 was obtained in the same manner except that monomer solution 11 was used instead of monomer solution 1 and luminescent fine particles B was used instead of luminescent fine particles A.

(Example 12)

QD dispersion 12 was obtained in the same manner as in the preparation method of QD dispersion 1, except that monomer solution 4 was used instead of monomer solution 1 and luminescent microparticles C were used instead of luminescent microparticles A.

(Comparative Example 1)

QD dispersion C1 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.

The table below shows the contents of monomer solutions 1 to 11 and luminescent fine particles A to C in QD dispersions 1 to 12 of Examples 1 to 12 and 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)

In the preparation method of monomer solution 1, in addition to the photopolymerizable monomer described above, two types of photopolymerization initiators were added, and the point was stirred at 60 ° C. instead of room temperature. Monomer solution B1 containing photopolymerization initiator in the same way got 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)

In the preparation method of Monomer Solution B1, Monomer Solutions B2 to Monomer Solution B11 and Monomer Solution B13 containing a photopolymerization initiator were obtained in the same manner except that Monomer Solutions 2 to 11 were used instead of Monomer Solution 1.

(Monomer Solution B12)

In the preparation method of Monomer Solution B1, Monomer Solution 2 was used instead of Monomer Solution 1, and Monomer Solution B12 containing a photopolymerization initiator was similarly prepared except that only one photopolymerization initiator was added instead of two photopolymerization initiators. got it As one type of photopolymerization initiator, 0.5 parts by mass of "Omnirad TPO" manufactured by IGM Resin was added.

In the table below, the contents of the monomer solutions B1 to B12 are shown. In addition, the unit of the numerical value in a table|surface is a mass part.

<Preparation of QD dispersion B>

(QD dispersion B1)

Light-emitting fine particles A (0.015 parts by mass) were mixed with monomer solution B1 (0.985 parts by mass) containing a photopolymerization initiator, and stirred at room temperature to uniformly disperse the mixture, thereby obtaining QD dispersion B1.

(QD Dispersion B2 to QD Dispersion B8)

In the preparation method of QD dispersion B1, QD dispersions B2 to B8 were obtained in the same manner except that monomer solutions B2 to B8 containing a photopolymerization initiator were used instead of monomer solution B1 containing a photopolymerization initiator.

(QD dispersion B9)

In the method for preparing the QD dispersion B1, the monomer solution B9 containing the photopolymerization initiator was used instead of the monomer solution B1 containing the photopolymerization initiator, and the luminescent fine particles B were used instead of the light emitting fine particles A. QD dispersion in the same manner Sieve B9 was obtained.

(QD dispersion B10)

In the preparation method of QD dispersion B1, QD dispersion B10 was obtained similarly 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 the photopolymerization initiator was used instead of the monomer solution B1 containing the photopolymerization initiator, and the luminescent fine particles B were used instead of the light emitting fine particles A. QD dispersion in the same manner Sieve B11 was obtained.

(QD dispersion B12)

In the method for preparing the QD dispersion B1, the monomer solution B4 containing the photopolymerization initiator was used instead of the monomer solution B1 containing the photopolymerization initiator, and the light emitting fine particles C was used instead of the light emitting fine particles A. In the same way, QD dispersion Sieve B12 was obtained.

(QD dispersion B13)

In the preparation method of QD dispersion B1, QD dispersion B13 was obtained similarly except that monomer solution B12 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator.

(QD dispersion B14)

QD dispersion B14 was obtained in the same manner as in the preparation method of 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. In addition, the unit of the numerical value in a table|surface is a mass part.

<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 dicyclopentanyl methacrylate (45 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), which is a photopolymerizable monomer, were mixed. . In addition, the average particle diameter (volume average diameter) of the titanium oxide particles is 300 nm. Then, after adding zirconia beads (diameter: 0.3 mm) to the obtained formulation, dispersion treatment of the formulation was performed by shaking for 2 hours using a paint conditioner. In this way, a light-scattering particle dispersion 1 was obtained.

(Light Scattering Particle Dispersion 2)

In the preparation method of the light-scattering particle dispersion 1, in the same manner as in the preparation method of the light-scattering particle dispersion 1, except that light ester L (manufactured by Kyoesha Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. Thus, 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 to obtain uniform dispersion. The resulting dispersion was filtered through a filter having a pore diameter of 5 μm to obtain a nanocrystal-containing composition and QD Ink 1 as an ink composition.

(Examples 14 to 24, 41)

In the preparation method of QD Ink 1 of Example 13, QD Ink 2 was prepared in the same manner as in the preparation method of QD Ink 1, except that QD Dispersion B2 to 12 and QD Dispersion B14 were respectively used instead of QD Dispersion B1. to 12 and QD ink 14.

(Example 25)

In the preparation method of QD Ink 1 of Example 13, QD Dispersion B13 instead of QD Dispersion B1 and Light Scattering Dispersion 2 were used instead of Light Scattering Dispersion 1, respectively. Similarly, QD Ink 13 was obtained.

(Comparative Example 2)

In the preparation method of QD Ink 1 of Example 13, QD Ink C1 was obtained in the same manner as in the preparation method of QD Ink 1 except that QD Dispersion CB1 was used instead of QD Dispersion B1.

In the table below, 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 addition, the unit of the numerical value in a table|surface is a mass part.

<Production of Light Conversion Layer>

(Example 26)

The obtained QD Ink 1 of Example 13 was applied onto a glass substrate (“EagleXG” manufactured by Corning) by a spin coater so that the film thickness after drying was 10 μm.

The obtained coating film was irradiated with ultraviolet light having an LED lamp wavelength of 365 nm at an exposure amount of 2000 mJ/cm 2 in a nitrogen atmosphere. This cured the QD Ink 1 of Example 13 to form a layer containing a cured ink composition on the glass substrate, which was referred to as Light Conversion Layer 1 of Example 26.

(Examples 27 to 38, 42)

In the method for producing the light conversion layer 1 of Example 26, QD Ink 2 to Example 14 QD Ink 13 of Example 25 and QD Ink 14 of Example 41 were used instead of QD Ink 1 of Example 13. Similarly, 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)

In the method for producing the light conversion layer 1 of Example 26, the light conversion layer C1 of Comparative Example 3 was similarly produced except that QD Ink C1 of Comparative Example 2 was used instead of QD Ink 1 of Example 13.

<evaluation>

[Quantum Yield (PLQY) retention rate]

Quantum yields (PLQY) of QD dispersions 1 to 12 of Example 1, QD dispersion 13 of Example 40, and QD dispersion C1 of Comparative Example 1 were measured as absolute PL quantum yields. It was measured with an apparatus ("Quantaurus-QY", manufactured by Hamamatsu Photonics Co., Ltd.), and the quantum yield retention rate (the quantum yield after being left in the air for 10 days after preparation divided by the quantum yield immediately after preparation) was calculated. The higher the quantum yield retention rate, the higher the stability of the luminescent fine particles to oxygen gas and water vapor.

[Dispersion stability]

QD Inks 1 to 13 of Examples 13 to 25, QD Ink 14 of Example 41, and QD Ink C1 of Comparative Example 2 were left in the air, and then the presence or absence of precipitate was checked and evaluated according to the following criteria.

〔Evaluation standard〕

A: After 10 days, no precipitate was generated.

B: After 10 days, a precipitate was very slightly generated. Shaking dissolves the precipitate.

C: After 10 days, a lot of precipitate was generated. Shaking also leaves a precipitate.

[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, and the external quantum efficiency retention rate of the light conversion layer (The value obtained by dividing the external quantum efficiency 10 days after formation of the light conversion layer by the external quantum efficiency immediately after 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 emission light source, and a light conversion layer was provided on this light source with the glass substrate side facing downward. An integrating sphere was connected to a radiation spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., "MCPD-9800"), and the integrating sphere was brought closer to the light conversion layer provided on the blue LED. In this state, the blue LED was turned on, and the quantum numbers of the excitation light and light emission (fluorescence) of the light conversion layer were measured to calculate the external quantum efficiency. The higher the external quantum efficiency retention rate, the higher the stability of the light conversion layer including light-emitting particles to oxygen gas and water vapor.

[Stereoscopic parameters]

The following table shows structural formulas of compounds used as ligands coordinated on the surface of the above-described luminescent nanocrystals.

In the table below, structural formulas of compounds used as monomers used for preparing the QD dispersions and QD inks described above are shown.

For the above compound, the steric parameter MR was calculated using the following formula (C).

In Formula (C), n represents a refractive index, M represents a molecular weight, and d represents a density. Values of 20 °C or 25 °C were used for density and refractive index. The calculated steric parameter MR is shown in the table below.

<Evaluation of QD dispersion>

Hereinafter, 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 reviewed.

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| and the weighted average |ΔMR| of the entire |ΔMR| _{A weighted average} was calculated. In addition, the PLQY retention rate of QD dispersion C1 of Comparative Example 1 was measured and found to be 53.0%.

(1) |ΔMR| in the combination of light ester L and oleic acid _PY

=|(MR of light ester L)-(MR of oleic acid)|

=|78.6-88.3|

=9.7

(2) |ΔMR| in the combination of light ester L and oleylamine _PZ

=|(MR of light ester L)-(MR of oleylamine)|

=|78.6-86.9|

=8.3

(3) |ΔMR| in the combination of light acrylate DCP-A and oleic acid _QX

=|(MR of light acrylate DCP-A)-(MR of oleic acid)|

=|82.2-88.3|

=6.1

(4) |ΔMR| in the combination of light acrylate DCP-A and oleylamine _QZ

=|(MR of light acrylate DCP-A)-(MR of oleylamine)|

=|82.2-86.9|

=4.7

(5) the weighted average of |MR||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 )

={(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 coordination ratio of oleic acid and oleylamine coordinated to the surface of the luminescent nanocrystal is 0.5:0.5, |ΔMR| _{A weighted average} was calculated.

Next, QD dispersions 1 to 12 of Examples 1 to 12 and QD dispersion 13 of Example 40 were carried out in the same manner as in Comparative Example 1, and each |ΔMR| and |ΔMR| _{A weighted average} was calculated to determine PLQY retention. In each of the QD dispersions 1 to 12, two types of ligands were used, and the coordination ratio of each ligand was set to 0.5:0.5, and ΔMR| _{A weighted average} was calculated. However, in QD dispersion 12 of Example 12, a ligand containing oleic acid and a ligand containing 3-aminopropyltriethoxysilane are coordinated on the surface of the luminescent nanocrystal containing lead cesium tribromide crystal. After 3-aminopropyltriethoxysilane is coordinated to the surface of the luminescent nanocrystal, it forms a siloxane bond to cover the surface of the luminescent nanocrystal in a mesh shape, so as will be described later, oleic acid and QD dispersion used as a ligand. It is thought that the exchange of the photopolymerizable monomer in the inside is suppressed. From this, regarding Example 12, only oleic acid is coordinated on the surface of the luminescent nanocrystal, that is, assuming that the coordination ratio of oleic acid is 1, |ΔMR| _{A weighted average} was calculated. Results are shown in the table below.

As shown in the table above, in the QD dispersions of Examples 1 to 12 and the QD dispersion of Example 40, the maximum value of |ΔMR| is 12 or more, and the weighted average |ΔMR| of all |ΔMR| _{The weighted average} is 12 or higher. In contrast, the QD dispersion of Comparative Example 1 had a maximum value of |ΔMR| far below 12, and |ΔMR| _{The weighted average} is well below 12. In addition, it can be seen that the QD dispersions of Examples 1 to 12 and the QD dispersion of Example 40 exhibit higher PLQY retention rates compared to the QD dispersion of Comparative Example 1.

The QD dispersions of Examples 1 to 8 and 10 and Comparative Example 1 contain luminescent particulates coordinated with cationic oleylamine and anionic oleic acid, whereas the QD dispersions of Examples 9 and 11 have cationic oleylamine and anionic oleic acid. It contains luminescent fine particles coordinated with N-(1-adamantyl)ethylenediamine and anionic oleic acid. Also in Examples 9 and 11 in which N-(1-adamantyl)ethylenediamine was used as a ligand instead of oleylamine or oleic acid, the PLQY retention rate of the QD dispersion was superior to that of Comparative Example 1. In this respect, 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 compound having no cyclic structure is used as a monomer, In either case, it is clear that a high PLQY retention rate is exhibited. Further, from the results of Examples 1 to 5 and Example 40, it is understood that even if the cyclic structure is aromatic as well as aliphatic, high PLQY is exhibited.

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

In addition, the presence or absence of an inorganic coating layer in the luminescent fine particles is examined. In the QD dispersion of Example 12, 3-aminopropyltriethoxysilane is coordinated on the surface of the luminescent nanocrystal instead of oleylamine as a cationic ligand, and this ligand forms a siloxane bond, and the luminescent nanocrystal It is the same as the QD dispersion of Example 4 except that the inorganic coating layer containing Si is provided on the surface. |ΔMR| in the QD dispersion of Example 4 Compared to _{the weighted average} of 24.8, the QD dispersion of Example 12 is 24.1, which is 0.7 less. By the way, the PLQY retention rate in the QD dispersion of Example 4 was 71.9, whereas the QD dispersion of Example 12 was 75.8, which was 3.9 higher. From this result, in the QD dispersion of Example 12, by forming an inorganic coating layer containing Si on the surface of the luminescent nanocrystals, the luminescent nanocrystals were protected and the exchange of oleic acid with the photopolymerizable monomer was suppressed. , it is thought that the PLQY retention rate has increased.

<Evaluation of QD ink>

For the obtained QD inks of Examples 13 to 25, Example 41, and Comparative Example 2, the maximum values of |ΔMR| and ΔMR| _{A weighted average} was calculated. The maximum value of |ΔMR| and ΔMR| _{The weighted average} was calculated in consideration of the steric parameter MR of dicyclopentanyl methacrylate and light ester L used for the preparation of the light scattering particle dispersions 1 to 2. In addition, the dispersion stability of the QD ink was evaluated. Results are shown in the table below.

As shown in the table above, in the QD inks of Examples 13 to 25 and the QD ink of Example 41, the maximum value of |ΔMR| is 12 or more, and the weighted average |ΔMR| of all |ΔMR| _{The weighted average} is 12 or higher. In contrast, the QD ink of Comparative Example 2 had a maximum value of |ΔMR| of 12 or more, but |ΔMR| _{The weighted average} is well below 12. And it turns out that the QD inks of Examples 13 to 25 are superior in dispersion stability compared to the QD inks of Comparative Example 2. In particular, |ΔMR| When _{the weighted average} is 20 or more, all are "A", and it is understood that excellent dispersion stability is exhibited.

<Evaluation of light conversion layer>

Next, a light conversion layer was produced and evaluated by the method described above. Results are shown in the table below.

As shown in the table above, 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 the light conversion layer 14 of Example 42 showed a higher value than that of the light conversion layer C1 of Comparative Example 3.

From the results of QD dispersions 1 to 12 of Examples 1 to 12, QD dispersions 13 of Example 40, QD inks 1 to 13 of Examples 13 to 25, and QD ink 14 of Example 41, the photopolymerizable monomer and , containing luminescent microparticles having ligands on the surface of luminescent nanocrystals containing metal halide, |ΔMR| A composition containing nanocrystals having _{a weighted average} of 12 or more has |ΔMR| Compared to those with _{a weighted average} of less than 12, it is clear that not only the PLQY retention is excellent, but also the dispersion stability is excellent.

Further, 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, |ΔMR| A light conversion layer comprising a cured product of a nanocrystal-containing composition having _{a weighted average} of 12 or more has |ΔMR| Comparing the light conversion layer comprising a cured product of a nanocrystal-containing composition having _{a weighted average} of less than 12, it is clear that the retention rate of external quantum efficiency is excellent. From this point of view, it can be expected that a light emitting element having a light conversion layer formed from the nanocrystal-containing composition of the present invention also has an excellent external quantum efficiency retention rate.

90: luminescent fine particles, inorganic coated luminescent fine particles, silica coated luminescent fine particles
91: inorganic coating layer, silica coating layer
910: light-emitting fine particles, uncoated light-emitting fine particles
911: nanocrystal
912: ligand layer
100: light emitting element
200: EL light source
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: packed layer
11: protective layer
12: light conversion layer
13: upper board
14: EL layer
20: pixel unit
20a: first pixel unit
20b: second pixel unit
20c: third pixel unit
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 light-emitting fine particles
90b: first light-emitting fine particles
30: light blocking part
701: capacitor
702 drive transistor
705 common electrode
706: signal line
707 scan line
708: switching transistor
C1: signal line driving circuit
C2: scan line driving circuit
C3: control circuit
PE, R, G, B: pixel electrode
X: copolymer
XA: association
x1: aliphatic polyamine chain
x2: hydrophobic organic segment
YA: core-shell silica nanoparticles
Z: solution containing raw material compounds for semiconductor nanocrystals

Claims (8)

Containing light-emitting fine particles having one or two or more ligands on the surface of a light-emitting nanocrystal having a perovskite-type structure containing one or two or more photopolymerizable monomers and a metal halide,
When the absolute value |ΔMR| of the difference between the steric parameter MR of any photopolymerizable monomer and the steric parameter MR of any ligand is calculated, one or more combinations of photopolymerizable monomers and ligands that satisfy the following formula (A) exist, also
For all combinations of each of the photopolymerizable monomers and each of the ligands included in the nanocrystal-containing composition, the content of each of the photopolymerizable monomers and the ligands are calculated considering the coordinated ratio on the surface of the luminescent nanocrystal. The weighted average value of |ΔMR||ΔMR| _{The weighted average} satisfies the following formula (B),
In the combination of the photopolymerizable monomer and the ligand that satisfy the above formula (A), either the photopolymerizable monomer or the ligand contains a compound containing a cyclic structure,
In the combination of a photopolymerizable monomer and a ligand that satisfy the formula (A), when the photopolymerizable monomer contains a compound containing the cyclic structure, the ligand contains a compound containing a linear molecular structure, 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 the combination of a photopolymerizable monomer and a ligand that satisfy the formula (A), when the ligand contains a compound containing the cyclic structure, the photopolymerizable monomer contains a compound containing a linear molecular structure, The steric parameter MR of the photopolymerizable monomer is in the range of 60 to 100 and the steric parameter MR of the ligand is in the range of 40 to 80
A composition containing nanocrystals, characterized in that.

(However, the three-dimensional parameter MR is the following formula (C)

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

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 an inorganic coating layer containing Si is formed by the ligand. Compositions containing nanocrystals. The composition containing nanocrystals according to claim 1 or 2, further comprising at least one of a photopolymerization initiator, a light scattering agent and a dispersing agent. An ink composition characterized by using the nanocrystal-containing composition according to claim 1 or 2. A light conversion layer comprising a cured product of the ink composition according to claim 5. A light emitting element comprising the light conversion layer according to claim 6. delete

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