CN116390997A

CN116390997A - Nanocrystalline-containing composition, ink composition, light conversion layer, and light-emitting element

Info

Publication number: CN116390997A
Application number: CN202180067110.8A
Authority: CN
Inventors: 初阪一辉; 延藤浩一; 青木良夫; 野中祐贵
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2020-10-15
Filing date: 2021-09-30
Publication date: 2023-07-04
Also published as: JPWO2022080143A1; KR20230051596A; KR102547607B1; WO2022080143A1; JP7151914B2; TW202227589A

Abstract

The invention aims to solve the problems that: provided are a composition containing nanocrystals and having excellent dispersion stability and light-emitting characteristics, an ink composition containing the composition, a light-converting layer containing a cured product of the ink composition, and a light-emitting element provided with the light-converting layer. The nanocrystalline-containing composition of the present invention is characterized in that: a luminescent microparticle comprising 1 or more photopolymerizable monomers and 1 or more ligands on the surface of a luminescent nanocrystal composed of a metal halide, wherein 1 or more combinations exist in which 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 12 or more, and all of the photopolymerizable monomers and the ligands contained in the nanocrystal-containing compositionWeighted average of |Δmr| in combination |Δmr| _{Weighted average} Is 12 or more.

Description

Nanocrystalline-containing composition, ink composition, light conversion layer, and light-emitting element

Technical Field

The present invention relates to a composition containing nanocrystals, an ink composition using the composition, a light conversion layer containing a cured product of the ink composition, and a light emitting element including the light conversion layer.

Background

BT2020, which is a very active standard required for next-generation display devices, is not easy to satisfy BT2020 even with color filters or organic ELs using current pigments. On the other hand, quantum dots are materials that emit fluorescence such as red fluorescence, green fluorescence, and blue fluorescence having a relatively narrow half-value width of the emission wavelength, and have been attracting attention as light-emitting materials that can satisfy BT2020. While core-shell nanoparticles using CdSe and the like are used for the early quantum dots, inP and the like have recently been used in order to avoid the harmful effects thereof. However, since the wavelength of luminescence of the core-shell quantum dot is determined by the particle size, in order to obtain luminescence with a narrow half-width, it is necessary to precisely control the degree of dispersion of the particle size, and there are many problems in production.

In recent years, luminescent nanocrystals composed of metal halides, particularly quantum dots having perovskite crystal structures, have been found and have been attracting attention. A general perovskite quantum dot (hereinafter, sometimes referred to as "PeQD") is CsPbX ₃ (x=cl, br, I). The PeQD is advantageous in terms of productivity as compared with conventional quantum dots because it can control the emission wavelength by the ratio of halogen and can control the particle size more easily than InP quantum dots and the like.

Non-patent document 1 reports an ink composition containing peqds and poly (methyl methacrylate) (hereinafter, sometimes referred to as "PMMA"). In this regard, patent document 1 discloses the following problems: the solvent resistance of the coating film of the ink composition containing PeQD and PMMA is not necessarily sufficient. Patent document 1 discloses an ink composition containing PeQD and a photopolymerizable monomer, and further containing a solvent, wherein the ratio of carbon, oxygen, and nitrogen contained in the photopolymerizable monomer and the solvent is specified. Further, as a technique similar to patent document 1, patent document 2 discloses a nanocrystal-containing composition as a curable composition, which contains: the fluorescent particles of the perovskite compound, the photopolymerizable monomer and the photopolymerization initiator, and the LogP value of the photopolymerizable monomer is specified. The technical points of patent document 1 and patent document 2 are considered to be: in view of the polarity of the photopolymerizable monomer, it is preferable that the polarity is low. However, if attention is paid only to the polarity of the photopolymerizable monomer as in the ink compositions or nanocrystal-containing compositions disclosed in these known documents, there is a disadvantage that the dispersibility and the luminescence characteristics of the PeQD are not sufficiently compatible.

Prior art literature

Patent literature

Patent document 1: japanese patent No. 6506488

Patent document 2: japanese patent laid-open No. 2020-70443

Non-patent literature

Non-patent document 1: nano Lett.2015,15,3692-3696

Disclosure of Invention

Problems to be solved by the invention

Accordingly, the present invention aims to solve the problems: provided are a composition containing nanocrystals and having excellent dispersion stability and light-emitting characteristics, an ink composition containing the composition, a light-converting layer containing a cured product of the ink composition, and a light-emitting element provided with the light-converting layer.

Means for solving the problems

The present inventors have made an intensive study to solve the above problems, and as a result, found that: the present invention has been accomplished by providing a ligand on the surface of a luminescent nanocrystal composed of a metal halide, and using a ligand and a photopolymerizable monomer satisfying specific conditions as the ligand and the photopolymerizable monomer, it is possible to provide a nanocrystal-containing composition excellent in dispersion stability and luminescence characteristics.

Namely, the present invention provides a composition containing nanocrystals, characterized in that: when the absolute value |Δmr| of the difference between the three-dimensional parameter MR of an arbitrary photopolymerizable monomer and the arbitrary three-dimensional parameter MR is calculated, the combination of the photopolymerizable monomer and the ligand satisfying the following formula (a) is present in 1 or more, and the weighted average |Δmr| of the |Δmr| calculated in consideration of the content of each photopolymerizable monomer and the coordination ratio of each ligand on the surface of the luminescent nanocrystal in all the combinations of each photopolymerizable monomer and each ligand contained in the composition containing nanocrystals _{Weighted average} The following formula (B) is satisfied.

|Δmr|= | (steric parameter MR of monomer) - (steric parameter MR of ligand) |gtoreq 12 (a)

|ΔMR| _{Weighted average} ≥12(B)

(wherein, the stereoscopic parameter MR is represented by the following formula (C),

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

The invention provides an ink composition comprising the composition containing nanocrystals.

The invention provides a light conversion layer, which is characterized in that: a cured product comprising the above ink composition.

The invention provides a light-emitting element, which is characterized in that: the light conversion layer is provided.

Drawings

FIG. 1 is a cross-sectional view showing an embodiment of luminescent particles contained in the luminescent nanocrystal composition of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of luminescent particles contained in the luminescent nanocrystal composition of the present invention.

FIG. 3 is a cross-sectional view showing an embodiment of a light-emitting element according to the present invention.

Fig. 4 is a schematic diagram showing the structure of an active matrix circuit.

Fig. 5 is a schematic diagram showing the structure of an active matrix circuit.

Detailed Description

Hereinafter, embodiments of the nanocrystal-containing composition, the ink composition, the light-converting layer, the light-emitting element, and the method for producing the same according to the present invention will be described in detail.

1. Compositions containing nanocrystals

The nanocrystal-containing composition of the embodiment of the present invention contains: 1 or 2 or more photopolymerizable monomers, and luminescent particles each having 1 or 2 or more ligands on the surface of luminescent nanocrystals composed of a metal halide. The specific structure of the luminescent particles will be described later.

1-1 conditions for stereoscopic parameters

The nanocrystalline-containing composition of the present invention is characterized in that: 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, there are 1 or more combinations of photopolymerizable monomers and ligands satisfying the following formula (a), and the weighted average |Δmr| of |Δmr| calculated in consideration of the content of each photopolymerizable monomer and the coordination ratio of each ligand on the surface of the luminescent nanocrystal in all combinations of each photopolymerizable monomer and each ligand contained in the nanocrystal-containing composition _{Weighted average} The following formula (B) is satisfied.

|ΔMR| _{Weighted average} ≥12(B)

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

The above-mentioned steric parameter MR is an index of the three-dimensional size of the whole compound for investigating the correlation between the molecular structure and the pharmacological activity, and is disclosed in, for example, "Operations Research, (25) 394-401,7 month," journal of the experimental technique of the journal of the pesticide science, vol 38, no.2,195-203 (2013) ". The steric parameter MR is considered to be suitable as an index indicating a difference in the steric structure of a compound because it is an index indicating the overall size of a molecule.

In the present invention, the three-dimensional parameter MR is used as an index indicating the difference in the three-dimensional structure of the compound constituting the photopolymerizable monomer or ligand. When the compound constituting the photopolymerizable monomer and the compound constituting the ligand contained in the composition containing nanocrystals have structures similar to each other, the value of |Δmr| becomes small (for example, 10 or less). In this case, in the composition containing nanocrystals, since the structures of the compound constituting the photopolymerizable monomer and the compound constituting the ligand are similar to each other, the ligand coordinated to the luminescent nanocrystals is easily exchanged with the photopolymerizable monomer, and as a result, the energy level of the nanocrystals held by the ligand is changed, thereby causing a change in light emission characteristics, a decrease in dispersion stability, and the like, and it becomes difficult to maintain excellent light emission characteristics.

On the other hand, when |Δmr| satisfies the formula (a), it means that the compound constituting the photopolymerizable monomer and the compound constituting the ligand have structures that are greatly different from each other. In this case, in the composition containing nanocrystals, the exchange of the ligand coordinated to the luminescent nanocrystals with the photopolymerizable monomer can be suppressed.

The |Δmr| is preferably 12 or more, more preferably 15 or more, and particularly preferably 20 or more. The upper limit of the |Δmr| is not particularly limited, but if the difference in the three-dimensional structures of the compound constituting the photopolymerizable monomer and the ligand becomes too large, the compatibility between the photopolymerizable monomer and the luminescent fine particles having the ligand on the surface of the luminescent nanocrystal composed of the metal halide becomes low, and therefore, it is preferably 50 or less.

When the composition containing nanocrystals of the present invention contains 2 or more photopolymerizable monomers and 2 or more ligands, the use of the photopolymerizable monomers and ligands for which |Δmr| does not satisfy the above formula (a) is not limited as long as |Δmr| satisfies the above formula (a) in at least 1 or more combinations of the photopolymerizable monomers and ligands. For example, a composition containing nanocrystals uses 2 photopolymerizable monomers, P, Q, and 2 ligands, Y, Z, and |ΔMR| in the combination of photopolymerizable monomers P and ligands Y _PY When the formula (A) is satisfied, |ΔMR| in the combination of the photopolymerizable monomer P and the ligand Z _PZ |ΔMR| in combination of photopolymerizable monomer Q and ligand Y _QY And |ΔMR| in combination of photopolymerizable monomer Q and ligand Z _QZ The formula (A) may be satisfied or may not be satisfied.

In the nanocrystalline-containing composition of the present invention, the |Δmr| in at least 1 combination of the photopolymerizable monomer and the ligand satisfies the above formula (a), and the weighted average |Δmr| of the |Δmr| in all combinations of the photopolymerizable monomer and the ligand is further calculated _{Weighted average} The following formula (B) is satisfied. Wherein, |ΔMR| _{Weighted average} Is calculated by taking into consideration the content of each photopolymerizable monomer contained in the composition containing nanocrystals and the coordination ratio of each ligand on the surface of the nanocrystals.

|ΔMR| _{Weighted average} ≥12 (B)

So-called |Δmr| weighted average |ΔMR| _{Weighted average} The fact that the above formula (B) is satisfied means that the photopolymerizable monomer-constituting compound and the ligand-constituting compound have structures that are greatly different from each other in most combinations of the photopolymerizable monomer and the ligand contained in the nanocrystal-containing composition. The nanocrystal-containing composition can reliably achieve the above-described effect of suppressing the exchange of the ligand coordinated to the luminescent nanocrystal and the photopolymerizable monomer, and thus can achieve both excellent dispersion stability and excellent light-emitting characteristics.

On the other hand, in the composition containing nanocrystals, the addition of the surfactant at |ΔMR|Weight average |ΔMR| _{Weighted average} When the above formula (B) is not satisfied, the exchange of the ligand and the photopolymerizable monomer cannot be suppressed, and thus good dispersion stability and light emission characteristics cannot be ensured.

|ΔMR| _{Weighted average} Is calculated by taking into consideration the content of each photopolymerizable monomer contained in the composition containing nanocrystals and the coordination ratio of each ligand on the surface of the nanocrystals. For example, in nanocrystalline-containing compositions containing m _P Mass parts of photopolymerizable monomers P (stereo parameter MR _P ) M _Q Mass parts of photopolymerizable monomers Q (stereo parameter MR _Q ) Both of them, a cationic ligand Y (steric parameter MR _Y ) Anionic ligand Z (steric parameter MR _Z ) In both cases, the calculation can be performed as follows. Even if the photopolymerizable monomers contained in the nanocrystalline-containing composition are 1 or 3 or more and the ligands are 1 or 3 or more, the |Δmr| can be calculated in the same manner _{Weighted average} 。

First, the absolute value |Δmr| of the difference between the three-dimensional parameters in each combination of the photopolymerizable monomer and the ligand is calculated.

|ΔMR| _PY ＝|MR _P －MR _Y |

|ΔMR| _PZ ＝|MR _P －MR _Z |

|ΔMR| _QY ＝|MR _Q －MR _Y |

|ΔMR| _QZ ＝|MR _Q －MR _Z |

Next, for the obtained |ΔMR| _PY ～|ΔMR| _QZ The |ΔMR| is calculated by weighting the mixing ratio (mass conversion) of the photopolymerizable monomers and the ligand coordination ratio _{Weighted average} . In the case where the coordination ratio of the cationic ligand to the anionic ligand is known, calculation is preferably performed based on the ratio. For example, in the case of ligand Y and ligand Z at r _Y ：r _Z When the ratio of (2) is coordinated to the surface of the luminescent nanocrystal, the ratio is calculated as follows.

|ΔMR| _{Weighted flatAre all} ＝{(|ΔMR| _PY ×r _Y +|ΔMR| _PZ ×r _Z )×m _P +(|ΔMR| _QY ×r _Y +|ΔMR| _QZ ×r _Z )×m _Q }/(m _P +m _Q )

In the case where the coordination ratio of the ligand Y to the ligand Z is not clear, it is assumed that the ratio is 0.5: the ratio of 0.5 was coordinated to the surface of the luminescent nanocrystal, and was calculated as follows.

|ΔMR| _{Weighted average} ＝{(|ΔMR| _PY ×0.5+|ΔMR| _PZ ×0.5)×m _P +(|ΔMR| _QY ×0.5+|ΔMR| _QZ ×0.5)×m _Q }/(m _P +m _Q )

In the combination of the photopolymerizable monomer and the ligand 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, linear compounds such as oleylamine and oleic acid are often used as ligands on the surface of luminescent nanocrystals composed of metal halides. In the case where the ligand is a compound having such a linear molecular structure, a photopolymerizable monomer having a cyclic structure is particularly preferably used. Since a photopolymerizable monomer having a cyclic structure with a large steric hindrance is difficult to enter the surface covered with a ligand having a linear molecular structure, exchange between the photopolymerizable monomer and the ligand is difficult to occur. On the other hand, in the case of using a compound having a cyclic structure as a ligand, it is energetically unfavorable when a linear photopolymerizable monomer having a shape different from that of the ligand enters into luminescent nanocrystals, and therefore exchange of the photopolymerizable monomer with the ligand is difficult to occur. In this way, by using a compound having a cyclic structure for at least one of the photopolymerizable monomer and the ligand, exchange between the photopolymerizable monomer and the ligand can be suppressed. The result is that: the surface of the luminescent nanocrystal composed of the metal halide is stably covered with the ligand, and the energy level trapped in the luminescent nanocrystal is not generated, thereby maintaining good luminescence characteristics.

In order to satisfy the above formula (a) by the combination of the photopolymerizable monomer and the ligand, when the photopolymerizable monomer is a compound containing a cyclic structure or when the ligand is a compound containing a cyclic structure, the preferable range of the steric parameters is preferably the range shown below.

(1) When a compound having a cyclic structure is used as the photopolymerizable monomer, it is preferable that the stereoparameter of the photopolymerizable monomer is in the range of 40 to 90 and the stereoparameter of the ligand having a linear molecular structure is in the range of 60 to 110 in order to maintain a state in which the surface of the luminescent nanocrystal is stably covered with the ligand. Further, in view of exhibiting coating stability of the ligand, dispersion stability of the luminescent nanocrystal, and luminescence property, it is particularly preferable that 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.

(2) When a compound having a cyclic structure is used as the ligand, it is preferable that the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 60 to 100 and the steric parameter of the ligand is in the range of 40 to 80 in order to maintain a state in which the surface of the luminescent nanocrystal is stably covered with the ligand. Further, in view of exhibiting coating stability of the ligand, dispersion stability of the luminescent nanocrystal, and luminescence property, it is particularly preferable that 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 cyclic structure of the compound having a cyclic structure is specifically represented by the following formulas (1-2) to (1-24). Each of the cyclic structures represented by the formulas (1-2) to (1-24) may be bonded to other structural parts at any carbon atom in the cyclic structure.

The above formulae (1-2) to (1-24)arbitrary-CH ₂ -can be substituted with-O-, -S-, -n=, or-NH-. In the case where at least one of the photopolymerizable monomers or the ligands is a compound containing a cyclic structure represented by the formulae (1-3), (1-4), (1-6), (1-8), (1-10), (1-15) and (1-19) to (1-24), compatibility with the luminescent particles is excellent, and dispersibility can be improved, and therefore, it is preferable. Further, in the case where at least one of the photopolymerizable monomer and the ligand is a compound containing a cyclic structure represented by the formulae (1-3), (1-4) and (1-19) to (1-24), it is more preferable because not only dispersibility with luminescent particles but also a high quantum yield can be ensured. In particular, compounds containing the cyclic structures represented by the formulae (1-3), (1-19) and (1-21) are further preferable in that they can be used for both the photopolymerizable monomer and the ligand.

Any hydrogen atom in the above formulae (1-2) to (1-24) may be substituted with R ₁ . At R ₁ In the case of functional groups, R is ₁ Examples of the method include: carboxyl group, carboxylic anhydride group, amino group, ammonium group, mercapto group, phosphine oxide group, phosphate group, phosphonate group, phosphinic acid group, sulfonate group, borate group, amide group, and sulfonamide group. In particular the ligand is a ligand comprising R ₁ In the case of a compound having a cyclic structure such as a carboxyl group, an amino group, a mercapto group, an amide group or a sulfonamide group, the ability to coordinate to the luminescent particles can be improved, which is preferable.

At R ₁ In the case of an alkyl group, a branched or straight-chain alkyl group having 1 to 20 carbon atoms is represented by-CH at the terminal of the alkyl group ₃ Can be substituted by-NH ₂ 、-OH、-SH、-COOH、-CONH ₂ 、-CSNH ₂ -CH in the alkyl group ₂ Can be substituted is-Si-, -NH-or-O-, - (CH) in the alkyl group ₂ ) ₂ Can be substituted by- (ch=ch) -. In order to improve dispersibility with luminescent particles, R ₁ The carbon number of (2) is preferably 1 to 10, and R is preferably 1 to 10 in order to improve dispersibility with the luminescent particles and also to improve quantum yield ₁ The carbon number of (2) is particularly preferably 1 to 5. In order to improve the quantum yield retention of the luminescent particles, it is preferable to include a polyalkoxysilane, polysilanol, polysilazane structure capable of forming an inorganic coating layer containing Si.

At R ₁ In the case of an alkoxy group, a branched or straight chain alkoxy group having 1 to 20 carbon atoms is represented. -CH at the end of the above alkoxy group ₃ Can be substituted by-NH ₂ 、-OH、-SH、-COOH、-CONH ₂ 、-CSNH ₂ -CH in the alkoxy group ₂ Can be substituted is-Si-, -NH-or-O-, of- (CH) in the alkoxy radical ₂ ) ₂ Can be substituted by- (ch=ch) -. In order to improve dispersibility with luminescent particles, R ₁ The carbon number of (2) is preferably 1 to 10, and R is preferably 1 to 10 in order to improve dispersibility with the luminescent particles and also to improve quantum yield ₁ The carbon number of (2) is particularly preferably 1 to 5. In order to improve the quantum yield retention of the luminescent particles, it is preferable to include a polyalkoxysilane, polysilanol, polysilazane structure capable of forming an inorganic coating layer containing Si.

Any hydrogen atom in the above formulae (1-2) to (1-24) may be substituted with P. P is represented by the following general formulae (P-1) to (P-16) independently of each other. The black dots in the formula represent bond bonds. Where there are multiple P's, they may be the same or different.

More preferably, (P-1), (P-2) and (P-3) are preferable, and (P-2) and (P-3) are particularly preferable, since the decrease in quantum yield of the luminescent particles can be suppressed.

When a compound having a cyclic structure represented by the above (1-2) to (1-24) is used as the photopolymerizable monomer, more specifically, a compound represented by 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) can be preferably used. X and z in the following formula are each independently preferably 0 to 18, and y and zz are each independently preferably 1 to 18. Further, in order to make the three-dimensional parameter of the photopolymerizable monomer composed of the compound containing the cyclic structure 40 to 90, x and z in the following formula are preferably 0 to 5 and y and zz are preferably 1 to 5, respectively. In order to maintain dispersibility with the luminescent particles and to set the three-dimensional parameter to 60 to 70, the compounds represented by 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), and (1-23-5) to (1-23-8) are preferable, x and z in the following formulas are each independently preferably 0 to 5, and y and zz are each independently preferably 1 to 5. Further, when the three-dimensional parameter is to be higher than 65, (1-19-1) to (1-19-8) having an adamantyl structure as a cyclic structure, or (1-23-5) to (1-23-8) having a 1,2, 6-pentamethyl-4-piperidinyl structure as a cyclic structure are particularly preferable, x and z in the following formulae are each independently preferably 0 to 5, and y and zz are each independently particularly preferably 1 to 5.

As described above, in the case of using a compound having a stereoparameter of 40 to 90 as a photopolymerizable monomer having a cyclic molecular structure, the ligand to be a preferable combination is preferably one having a linear molecular structure, the stereoparameter is preferably in the range of 60 to 110, more preferably one having a cyclic molecular structure, the stereoparameter is in the range of 50 to 70, and the stereoparameter is preferably in the range of 80 to 90. As the ligand compound satisfying such a condition, a ligand whose terminal functional group is carboxylic acid or amine is preferable. In addition, ligands whose terminal functional groups are carboxylic acids or amines are preferably selected from the group consisting of 1: a ratio of 1 was used.

The ligand having a linear molecular structure in which the terminal functional group is carboxylic acid is specifically preferably (1) tridecanoic acid, 2-tridecenic acid, tetradecanoic acid, pentadecanoic acid, cis-9-hexadecenoic acid, hexadecanoic acid, 2-hexadecenoic acid, heptadecanoic acid, apigenin acid, linolenic 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, arachic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, cis-4, 7,10,13,16, 19-docosahexaenoic acid, erucic acid, docosylic acid, tetracosylic acid, tricosylic acid, and the ligand having a steric parameter of 60 to 110; (2) More preferably pentadecanoic acid, cis-9-hexadecenoic acid, hexadecanoic acid, 2-hexadecenoic acid, heptadecanoic acid, apinic acid, linoleic acid, gamma-linolenic acid, stearic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid, cis-8, 11, 14-eicosatrienoic acid, arachic acid, nonadecanoic acid, eicosanoic acid, and heneicosanoic acid are preferable as ligands having a steric parameter of 70 to 100; (3) Heptadecanoic acid, apinic acid, linoleic acid, gamma-linolenic acid, stearic acid, linolenic acid and oleic acid are particularly preferred as ligands with a steric parameter of 80 to 90.

The ligand having a linear molecular structure in which the terminal functional group is an amine is specifically preferable, and (1) a ligand having a steric parameter of 60 to 110, which is preferably selected from the group consisting of ethylenediamine, 1-aminotridecane, 1-aminopentadecane, hexadecylamine, 1-aminopentadecane, stearylamine, heptadec-9-amine, oleylamine, 1-aminononadecane, 2-n-octyl-1-dodecylamine, and (2) a ligand having a steric parameter of 70 to 100, which is more preferably selected from the group consisting of 1-aminopentadecane, hexadecylamine, 1-aminoheptadecane, stearylamine, heptadec-9-amine, oleylamine, 1-aminononadecane, 2-n-octyl-1-dodecylamine, and (3) a ligand having a steric parameter of 80 to 90, which is particularly preferably selected from the group consisting of hexadecylamine, 1-aminoheptadecane, stearylamine, heptadecylamine and oleylamine.

On the other hand, in the case of using a compound containing the cyclic structures represented by the above (1-2) to (1-24) as a ligand to be disposed on the surface of a luminescent nanocrystal composed of a metal halide, in order to bring the steric parameter of the ligand composed of the compound containing the cyclic structure into a range of 40 to 80, the compounds represented by the following (1-19-a) to (1-19-H) are preferably used, and the compounds represented by the following (1-19-a) to (1-19-F) are particularly preferably used. Preferably, xx and yy in the following formulae are each independently 1 to 18, and more preferably, xx and yy in the following formulae are each independently 1 to 5 so that the steric parameters of the ligand are in the range of 55 to 65.

When a compound having a ligand with a cyclic molecular structure with a steric parameter of 40 to 80 is used, the steric parameter of the photopolymerizable monomer having a linear molecular structure, which is a preferable combination, is preferably in the range of 50 to 100, more preferably in the range of 55 to 65, and the steric parameter of the photopolymerizable monomer having a linear molecular structure is in the range of 75 to 85. Specifically, the compounds shown below are preferably used.

Namely, (1) nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate as the methacrylate compound, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate as the acrylate compound, are preferably as photopolymerizable monomers having a linear molecular structure in the range of 60 to 100 in terms of steric parameters; (2) More preferably, dodecyl methacrylate and tridecyl methacrylate as the methacrylate compound, decyl acrylate, undecyl acrylate, dodecyl acrylate and tetradecyl acrylate as the acrylate compound, and a photopolymerizable monomer having a linear molecular structure and having a steric parameter in the range of 75 to 85.

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

In the case of using a compound having a cyclic structure as the photopolymerizable monomer, in order to maintain a state in which the surface of the luminescent nanocrystal is stably covered with the ligand, it is preferable that the stereoparameters of the photopolymerizable monomer be in the range of 40 to 90 and the stereoparameters of the ligand having a linear molecular structure be in the range of 60 to 110, specifically, it is preferable that the photopolymerizable monomer having a stereoparameters of 40 to 90 and having the formulae (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 the compound represented by (1-24-1) to (24-4) be combined with the ligand in which x and z are each independently 0 to 5 and y and zz are each independently 1 to 5, and the ligand having the terminal end groups of 60-hexadecanoic acid, and tridecanoic acid, pentadecanoic acid, and pentadecanoic acid are present as the terminal groups of the compound or the terminal groups of 2-hexadecanoic acid, and tridecanoic acid Gamma-linolenic acid, stearic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid, cis-8, 11, 14-eicosatrienoic acid, arachidic acid, nonadecanoic acid, eicosanoic acid, heneicosanic acid, cis-4, 7,10,13,16, 19-docosahexaenoic acid, erucic acid, behenic acid, tetracosanoic acid, tricosanoic acid, and ligands having a straight chain molecular structure and having a terminal functional group with a steric parameter of 60 to 110 are selected from dodecylamine, tetracosamine, 1-aminotridecane, 1-aminopentadecane, hexadecylamine, 1-aminopentadecane, stearylamine, heptadec-9-amine, oleylamine, 1-aminononadecane, and 2-n-octyl-1-dodecylamine.

Further, it is preferable that the photopolymerizable monomer has a steric parameter in the range of 50 to 70 and the ligand having a linear molecular structure has a steric parameter in the range of 80 to 90, which is particularly preferable in terms of exhibiting coating stability of the ligand, dispersion stability of the luminescent nanocrystals, and luminescence characteristics, and specifically, it is preferable that the photopolymerizable monomer is combined with the following ligand, and in order to improve luminescence characteristics of the luminescent nanocrystals, the photopolymerizable monomer having a steric parameter of 50 to 70 is preferably a compound represented by the formulae (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) to (1-22-1) to (1-22-4), (1-23-5) to (1-23-8) to (1-24-1) to (24-4), and more preferably (1-3-5) to (1-3-6) to (1-4) to (1-3-4) to (1-4) be used as the methacrylate compound In (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), and (1-24-4), in order to maintain the dispersion stability of the QD dispersion or QD ink and to improve the PLQY retention rate of the QD dispersion and the light conversion layer, it is preferable that (1-24-4) be a photopolymerizable monomer having a cyclic structure, and in the case where the three-dimensional parameter is to be higher than 65, (1-19-1) to (1-19-8) having an adamantyl structure, or (1-23-5) to (1-23-8) having a 1,2, 6-pentamethyl-4-piperidinyl structure, x and z in the formulae are each independently 0 to 5 and y and zz are each independently 1 to 5; the ligand having a linear molecular structure and having a terminal functional group of 80 to 90 as a steric parameter is selected from the group consisting of heptadecanoic acid, apinic acid, linolic acid, γ -linolenic acid, stearic acid, linolenic acid, and oleic acid, and the ligand having a linear molecular structure and having a terminal functional group of 80 to 90 as a steric parameter is selected from the group consisting of hexadecylamine, 1-aminoheptadecane, stearylamine, heptadec-9-amine, and oleylamine, and is particularly preferably selected from the group consisting of apigenin, linolenic acid, γ -linolenic acid, oleic acid, and oleylamine having a double bond in the alkyl chain, in terms of the coating stability of the ligand, the dispersion stability of the luminescent nanocrystal, and the luminescent property.

(2) When a compound having a cyclic structure is used as the ligand, it is preferable that the photopolymerizable monomer having a linear molecular structure has a steric parameter in the range of 60 to 100 and the ligand has a steric parameter in the range of 40 to 80, specifically, the photopolymerizable monomer having a steric parameter of 60 to 100 and a linear molecular structure is preferable to be an acrylate compound or a methacrylate compound having 6 to 17 carbon atoms, and the ligand having a steric parameter of 40 to 80 and a cyclic structure is preferable to be the compound represented by (1-19-a) to (1-19-H) in terms of maintaining the state that the surface of the luminescent nanocrystal is stably covered with the ligand.

Further preferred is: the photopolymerizable monomer having a linear molecular structure with a steric parameter of 75 to 85 is preferably an acrylic acid ester compound or a methacrylic acid ester compound having 11 to 13 carbon atoms, and the compound represented by the formulae (1-19-a) to (1-19-F) is particularly preferable in that the ligand having a steric parameter of 55 to 65 is more preferable than the acrylic acid ester compound in order to improve the luminescence characteristics of the luminescent nanocrystal.

1-2 luminescent particles

Luminescent particles contained in the above-described nanocrystal composition are described. The luminescent microparticle 910 shown in fig. 1 has 1 or 2 or more ligands on the surface of the luminescent nanocrystal 911. The ligand layer 912 is formed by a large number of ligands coordinated to the surface of the luminescent nanocrystal 911.

1-2-1. Luminescent nanocrystals

First, luminescent nanocrystal 911 (hereinafter, may be simply referred to as "nanocrystal 911") will be described. Luminescent nanocrystals are nano-sized semiconductor nanocrystals (nanocrystals) that are composed of a metal halide and absorb excitation light to emit fluorescence or phosphorescence.

As luminescent nanocrystals composed of metal halides, for example, the following quantum dots having a perovskite crystal structure are known. The luminescent nanocrystals are crystals having a maximum particle diameter (average particle diameter) of 100nm or less, as measured by a transmission electron microscope or a scanning electron microscope, for example. The luminescent nanocrystals can be excited by light energy or electric energy of a predetermined wavelength to emit fluorescence or phosphorescence, for example.

Luminescent nanocrystals composed of metal halides are represented by the general formula: a is that _a M _m X _x The indicated compounds constitute.

Wherein A is at least 1 of an organic cation and a metal cation. Examples of the organic cation include ammonium, formamidinium, guanidinium, imidazolium, pyridinium, pyrrolidinium, and protonated thiourea, and examples of the metal cation include cations such as Cs, rb, K, na, li.

M is at least 1 metal cation. Examples of the metal cations include: 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, group 15. More preferably, the cation may be Ag, au, bi, ca, ce, co, cr, cu, eu, fe, ga, ge, hf, in, ir, mg, mn, mo, na, nb, nd, ni, os, pb, pd, pt, re, rh, ru, sb, sc, sm, sn, sr, ta, te, ti, V, W, zn, zr.

X is at least 1 anion. Examples of the anions include chloride ion, bromide ion, iodide ion, cyanide ion, and the like, and contain at least 1 halogen.

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

General formula A _a M _m X _x The compounds represented are preferably AMX, A ₄ MX、AMX ₂ 、AMX ₃ 、A ₂ MX ₃ 、AM ₂ X ₃ 、A ₂ MX ₄ 、A ₂ MX ₅ 、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 The compound represented.

Wherein M is at least 1 metal cation. Specifically, there may be mentioned: 1 metal cation (M) ¹ ) 2 metal cations (M) ¹ _α M ² _β ) 3 metal cations (M) ¹ _α M ² _β M ³ _γ ) 4 metal cations (M) ¹ _α M ² _β M ³ _γ M ⁴ _δ ) Etc. Wherein α, β, γ, δ represent real numbers of 0 to 1, respectively, and α+β+γ+δ=1. Examples of the metal cation include metal cations selected from

groups

1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, and 15. More preferably, there may be mentioned: ag. Au, bi, ca, ce, co, cr, cu, eu, fe, ga, ge, hf, in, ir, mg, mn, mo, na, nb, nd, ni, os, pb, pd, pt, re, rh, ru, sb, sc, sm, sn, sr, ta, te, ti, V, W, zn, zr, etc.

Wherein X is an anion comprising at least 1 halogen. Specifically, 1 halogen anion (X ¹ ) 2 halogen anions (X) ¹ _α X ² _β ) Etc. Examples of the anions include chloride ion, bromide ion, iodide ion, cyanide ion, and the like, and includeContaining at least 1 halogen.

From the general formula A _a M _m X _x The compound composed of the metal halide may be added (doped) with a metal ion such as Bi, mn, ca, eu, sb, yb to improve the light-emitting property.

With respect to the above formula A _a M _m X _x Among the compounds represented by the metal halides, compounds having a perovskite crystal structure are particularly preferably used in the form of luminescent nanocrystals, since the emission wavelength (emission color) can be controlled by adjusting the particle size, the type and the presence ratio of the metal cations constituting the M site, and the type and the presence ratio of the anions constituting the X site. Specifically, AMX is preferable ₃ 、A ₃ MX ₅ 、A ₃ MX ₆ 、A ₄ MX ₆ 、A ₂ MX ₆ The compound represented. A, M and X in the formula are as described above. In addition, a compound having a perovskite crystal structure may be added (doped) with a metal ion such as Bi, mn, ca, eu, sb, yb as described above.

In order to exhibit further excellent light-emitting characteristics, among the compounds having a perovskite crystal structure, it is preferable that A be Cs, rb, K, na, li and M be 1 metal cation (M ¹ ) Or 2 metal cations (M ¹ _α M ² _β ) X is chloride ion, bromide ion, iodide ion. Wherein α and β each represent a real number of 0 to 1, and α+β=1. In particular, M is preferably selected from Ag, au, bi, cu, eu, fe, ge, K, in, na, mn, pb, pd, sb, si, sn, yb, zn, zr.

CsPbBr as a specific composition of luminescent nanocrystals composed of metal halides in perovskite crystal structure ₃ 、CH ₃ NH ₃ PbBr ₃ 、CHN ₂ H ₄ PbBr ₃ Luminescent nanocrystals using Pb as M are preferred because of their excellent light intensity and quantum efficiency. In addition, csSnBr ₃ 、CsEuBr ₃ CsYbI ₃ Etc. use of metal cations other than PbLuminescent nanocrystals in which the seed is M are preferable because they have low toxicity and little environmental impact.

The luminescent nanocrystals may be red luminescent crystals that emit light having a luminescence peak in a wavelength range of 605 to 665nm (red light), green luminescent crystals that emit light having a luminescence peak in a wavelength range of 500 to 560nm (green light), or blue luminescent crystals that emit light having a luminescence peak in a wavelength range of 420 to 480nm (blue light). In one embodiment, a plurality of luminescent nanocrystals may be used in combination. The wavelength of the luminescence peak of the luminescent nanocrystal can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using an absolute PL quantum yield measurement apparatus.

The luminescent nanocrystals having red luminescence preferably have luminescence peaks in wavelength ranges of 665nm or less, 663nm or less, 660nm or less, 658nm or less, 655nm or less, 653nm or less, 651nm or less, 650nm or less, 647nm or less, 645nm or less, 643nm or less, 640nm or less, 637nm or less, 635nm or less, 632nm or less, or 630nm or less, and preferably have luminescence peaks in wavelength ranges of 628nm or more, 625nm or more, 623nm or more, 620nm or more, 615nm or more, 610nm or more, 607nm or more, or 605nm or more. These upper and lower limits may be arbitrarily combined. In the following description, the upper limit value and the lower limit value described individually may be arbitrarily combined.

The green luminescent nanocrystals preferably have a luminescent peak in a wavelength range of 560nm or less, 557nm or less, 555nm or less, 550nm or less, 547nm or less, 545nm or less, 543nm or less, 540nm or less, 537nm or less, 535nm or less, 532nm or less, or 530nm or less, and preferably have a luminescent peak in a wavelength range of 528nm or more, 525nm or more, 523nm or more, 520nm or more, 515nm or more, 510nm or more, 507nm or more, 505nm or more, 503nm or more, or 500nm or more.

The blue light-emitting luminescent nanocrystals preferably have a luminescence peak in a wavelength range of 480nm or less, 477nm or less, 475nm or less, 470nm or less, 467nm or less, 465nm or less, 463nm or less, 460nm or less, 457nm or less, 455nm or less, 452nm or less, or 450nm or less, and preferably have a luminescence peak in a wavelength range of 450nm or more, 445nm or more, 440nm or more, 435nm or more, 430nm or more, 428nm or more, 425nm or more, 422nm or more, or 420nm or more.

The shape of the luminescent nanocrystals is not particularly limited, and may be any geometric shape or any irregular shape. Examples of the shape of the luminescent nanocrystals include rectangular parallelepiped, cube, sphere, regular tetrahedron, ellipsoid, pyramid, disk, dendrite, network, and rod. The shape of the luminescent nanocrystals is preferably a rectangular parallelepiped, a cube, or a sphere.

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

1-2-2 ligands

The ligand is necessary for obtaining a nano-sized crystal by being disposed on the surface of the formed luminescent nanocrystal when synthesizing the luminescent nanocrystal composed of the metal halide. In addition, since the ligand can maintain a state of stably covering the surface of the luminescent nanocrystal composed of the metal halide, generation of a trap level on the surface of the luminescent nanocrystal can be prevented, and good luminescence characteristics can be maintained. Further, the ligand is disposed on the surface of the luminescent nanocrystal made of an inorganic material, thereby improving the compatibility with the photopolymerizable monomer and also ensuring the dispersibility of the luminescent nanocrystal. Therefore, loss of the ligand from the surface of the luminescent nanocrystal leads to aggregation of the luminescent nanocrystal, and a decrease in the luminescent characteristics and dispersibility, and therefore it is important that the ligand is stably coordinated to the surface of the luminescent nanocrystal without exchanging with the photopolymerizable monomer. As the ligand coordinated to the surface of the luminescent nanocrystal, 1 or more kinds of ligands satisfying the above formula (a) must be used when combined with any photopolymerizable monomer contained in the nanocrystal-containing composition, but ligands not satisfying the above formula (a) may be further used. In addition, as the ligand, in addition to the above-described compound having a cyclic structure, a compound having a linear structure without having a cyclic structure may be used.

As the ligand having such a linear structure, a compound having a bonding group bonded to a cation or anion contained in the luminescent nanocrystal is preferable. The bonding group is preferably at least 1 of a carboxyl group, a carboxylic anhydride group, an amino group, an ammonium group, a mercapto group, a phosphine oxide group, a phosphate group, a phosphonate group, a phosphinate group, a sulfonate group, an amide group, a thioamide group, and a borate group, and more preferably at least 1 of a carboxyl group and an amino group. Examples of such ligands include compounds containing a carboxyl group or an amino group, and 1 kind of these compounds may be used alone or 2 or more kinds of these compounds may be used in combination.

Examples of the carboxyl group-containing compound include: straight-chain or branched aliphatic carboxylic acids having 1 to 30 carbon atoms. Specific examples of such a carboxyl group-containing compound include: eicosanoic acid, butenoic acid, trans-2-decenoic acid, erucic acid, 3-decenoic acid, cis-4, 7,10,13,16, 19-docosahexaenoic acid, 4-decenoic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid, 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, gamma-linolenic acid, 3-nonenoic acid, 2-nonenoic acid, trans-2-octenoic acid, apinic acid, trans-oleic acid, 3-octenoic acid, trans-2-pentenoic acid trans-3-pentenoic acid, ricinoleic acid, sorbic acid, 2-tridecenoic acid, cis-15-twenty-decenoic acid, 10-undecylenic acid, 2-undecylenic acid, acetic acid, butyric acid, docosyl acid, cerotic acid, capric acid, eicosanoic acid, heneicosanoic acid, heptadecanoic acid, enanthic acid, caproic acid, heptadecanoic acid, dodecanoic acid, tetradecanoic acid, triacontanoic acid, octacosanoic acid, nonadecanoic acid, n-octanoic acid, hexadecanoic acid, pentadecanoic acid, propionic acid, pentacosanoic acid, nonanoic acid, stearic acid, tetracosanoic acid, tricosanoic acid, tridecanoic acid, undecanoic acid, valeric acid, and the like.

Examples of the amino group-containing compound include: a linear or branched aliphatic amine having 1 to 30 carbon atoms. Specific examples of such an amino group-containing compound include: 1-aminoheptadecane, 1-aminononadecane, heptadec-9-amine, stearylamine, oleylamine, 2-n-octyl-1-dodecylamine, allylamine, pentylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, isobutylamine, isopentylamine, 3-methoxypropylamine, 2-methoxyethylamine, 2-methylbutylamine, neopentylamine, propylamine, methylamine, ethylamine, butylamine, hexylamine, heptylamine, n-octylamine, 1-aminodecane, nonylamine, 1-aminoundecane, dodecylamine, 1-aminopentadecane, 1-aminotridecylamine, hexadecylamine, dodecylamine and the like.

1-2-3. Preparation method of luminous particles

Next, a method for producing the luminescent microparticles 910 shown in fig. 1 will be described. The luminescent microparticle 910 has 1 or 2 or more kinds of the above-mentioned ligands on the surface of the luminescent nanocrystal 911, and a ligand layer 912 is provided by a large number of ligands coordinated to the surface of the luminescent nanocrystal 911. As a method for producing such luminescent microparticles 910, there are a method of heating and a method of not heating.

First, an example of a method of producing the luminescent particles 910 by heating will be described. First, 2 compounds containing compounds capable of synthesizing the above formula A are prepared _a M _b X _c A solution of a raw material compound of the compound (hereinafter, may be referred to as a "semiconductor raw material-containing solution"). Among the solutions of 2 semiconductor-containing 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. In this case, a compound capable of forming a ligand satisfying the above formula (a) is added in advance to at least one of the solutions containing the semiconductor raw materials.

Next, the 2 solutions containing the semiconductor raw materials are mixed under an inert gas atmosphere, and reacted at a temperature of 140 to 260 ℃. Then, the mixture was cooled to-20 to 30℃and stirred, whereby nanocrystals were precipitated. The precipitated nanocrystal 911 is formed with a ligand layer 912 composed of ligands coordinated to the surface thereof. The nanocrystals 911 are recovered by a conventional method such as centrifugation, whereby luminescent microparticles 910 can be obtained.

Specifically, for example, a solution containing cesium carbonate as a semiconductor raw material, oleic acid as a ligand, and an organic solvent is prepared. As the organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. In this case, the amount of each additive is preferably adjusted so that cesium carbonate is 0.2 to 2g and oleic acid is 0.1 to 10mL relative to 40mL of the organic solvent. The obtained solution is dried at 90 to 150 ℃ for 10 to 180 minutes under reduced pressure, and then heated to 100 to 200 ℃ under an inert gas atmosphere such as argon, nitrogen, etc., thereby obtaining cesium-oleic acid solution.

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

Then, the cesium-oleic acid solution was added in a state where the solution containing lead (II) bromide was heated to 140 to 260 ℃, and the reaction was performed by heating and stirring for 1 to 10 seconds, and then the obtained reaction solution was cooled by an ice bath. In this case, it is preferable to add 0.1 to 1mL of cesium-oleic acid solution to 5mL of the solution containing lead (II) bromide. In the process of stirring at the temperature of between 20 ℃ below zero and 30 ℃, nano crystals 911 formed by lead cesium tribromide are separated out, and oleic acid and oleylamine are coordinated on the surfaces of the nano crystals 911.

The obtained suspension is centrifuged to collect a solid, and the solid is added to toluene to obtain a luminescent particle dispersion in which luminescent particles 910 each having a ligand layer 912 of oleic acid and oleylamine on the surface of a nanocrystal 911 coordinated with oleic acid are dispersed in toluene.

Next, an example of a method for producing the luminescent particles 910 without heating will be described. First, a solution containing a raw material compound capable of synthesizing semiconductor nanocrystals by a reaction is prepared. In this case, a compound capable of forming a ligand satisfying the above formula (a) is added in advance to the above raw material compound-containing solution. Then, the obtained solution is added to a large amount of organic solvent which is a poor solvent for the nanocrystals, thereby precipitating the nanocrystals with ligands coordinated to the surface. In this case, the amount of the organic solvent to be used is preferably 10 to 1000 times the amount of the semiconductor nanocrystal in terms of mass.

Specifically, for example, the following solutions are prepared as a semiconductor-containing raw material solution, which contains: lead (II) bromide and cesium bromide, a compound forming a ligand satisfying the above formula (a), and an organic solvent. The organic solvent may be a good solvent for the nanocrystals, and is preferably dimethylsulfoxide, N-dimethylformamide, N-methylformamide, or a mixed solvent thereof, in view of compatibility. In this case, the amount of each of the lead (II) bromide to be added is preferably adjusted so that the amount of the lead (II) bromide is 50 to 200mg and the amount of cesium bromide is 10 to 100mg, based on 10mL of the organic solvent.

Then, the mixture is added to a large amount of poor solvent, 0.1 to 5mL, relative to the solution containing lead (II) bromide and cesium bromide, and stirred under atmospheric conditions for 5 to 180 seconds, and then the solids are recovered by centrifugation. When the mixture is added to a large amount of poor solvent, the nanocrystal 911 is precipitated, and the compound forming the ligand satisfying the above formula (a) is coordinated to the surface of the nanocrystal 911.

By adding the recovered solid to toluene, a luminescent particle dispersion liquid in which luminescent particles 910 having a ligand layer 912 on the surface of nanocrystal 911 are dispersed in toluene can be obtained, wherein ligand layer 912 is formed of a compound that forms a ligand satisfying formula (a).

1-3 photopolymerizable monomers

The photopolymerizable monomer used in the present invention may be a general photopolymerizable monomer which is polymerized by irradiation with light, or may be a photopolymerizable monomer or oligomer, in addition to the photopolymerizable monomer having the above-described cyclic structure. They may be used together with photopolymerization initiators. The photopolymerizable monomers may be used alone or in combination of 1 or more than 2.

Examples of such a photoradically polymerizable monomer include (meth) acrylate compounds. The (meth) acrylate compound may be a monofunctional (meth) acrylate having 1 (meth) acryloyl group, or may be a multifunctional (meth) acrylate having a plurality of (meth) acryloyl groups.

From the viewpoint of excellent fluidity and more excellent ejection stability when the nanocrystalline-containing composition is used as an ink composition, and from the viewpoint of being able to suppress the decrease in smoothness due to cure shrinkage when producing a luminescent microparticle coating film, it is preferable to use a monofunctional (meth) acrylate in combination with a multifunctional (meth) acrylate.

Examples of the monofunctional (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dipentenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylbenzyl (meth) acrylate, mono (2-acryloyloxy) 2-benzoyl ] 2-phthalyl (meth) acrylate, N- [ 2-phthalyl ] oxyethyl (meth) acrylate, N- (o-phenyl) acrylate, N- (meth) 2-hydroxy-propyl (meth) acrylate, N- (meth-butyl (meth) acrylate, N-butyl (meth) acrylate, N-2-hydroxy (meth-hydroxy) acrylate N- [2- (acryloyloxy) ethyl ] tetrahydrophthalimide, and the like.

The multifunctional (meth) acrylate is a 2-functional (meth) acrylate, a 3-functional (meth) acrylate, a 4-functional (meth) acrylate, a 5-functional (meth) acrylate, a 6-functional (meth) acrylate, or the like. For example, di (meth) acrylate in which 2 hydroxyl groups of the diol compound are substituted with (meth) acryloyloxy groups, di (meth) acrylate in which 2 or 3 hydroxyl groups of the triol compound are substituted with (meth) acryloyloxy groups, and the like can be used.

Specific examples of the 2-functional (meth) acrylate include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane dimethanol 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 hydroxypivalate di (meth) acrylate, 2 hydroxyl groups of tris (2-hydroxyethyl) isocyanurate are substituted with (meth) acryloyloxy groups to give di (meth) acrylate, 2 hydroxyl groups of ethylene oxide or propylene oxide diol obtained by adding more than 4 moles of ethylene oxide to 1 mole of neopentyl glycol are substituted with (meth) acryloyloxy groups to give di (meth) acrylate, and 2 hydroxyl groups obtained by adding 2 moles of ethylene oxide to 2 (meth) diol obtained by 2 to give (meth) acrylate, and (3) a di (meth) acrylate obtained by substituting 2 hydroxyl groups of a triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane with (meth) acryloyloxy groups, a di (meth) acrylate obtained by substituting 2 hydroxyl groups of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a with (meth) acryloyloxy groups.

Specific examples of the 3-functional (meth) acrylate include: trimethylolpropane tri (meth) acrylate, glycerol triacrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and substitution of 3 hydroxyl groups of the triol with (meth) acryloyloxy groups.

Specific examples of the 4-functional (meth) acrylate include: pentaerythritol tetra (meth) acrylate, and the like.

Specific examples of the 5-functional (meth) acrylate include: dipentaerythritol penta (meth) acrylate, and the like.

Specific examples of the 6-functional (meth) acrylate include: dipentaerythritol hexa (meth) acrylate, and the like.

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 an ethylene oxide-modified phosphoric acid (meth) acrylate having a phosphoric acid group, an ethylene oxide-modified alkyl phosphoric acid (meth) acrylate, or the like.

In the nanocrystal composition of the present invention, in the case where the curable component is composed of only a photopolymerizable monomer or the curable component is composed of a photopolymerizable monomer as a main component, the use of a polyfunctional photopolymerizable monomer having 2 or more functional groups in 1 molecule, which is a polyfunctional photopolymerizable monomer having 2 or more polymerizable functional groups, as described above, is more preferable because the durability (strength, heat resistance, etc.) of the cured product can be further improved.

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 contained in the nanocrystal-containing composition to the above range, the light-emitting efficiency of the light-emitting nanoparticle can be improved. Further, in the light-emitting layer (light-converting layer) obtained by curing the ink composition containing the nanocrystalline-containing composition, the dispersion state of the light-emitting fine particles becomes good, and therefore the external quantum efficiency can be further improved.

1-4 other examples of the composition of luminescent particles

The above describes the nanocrystal composition containing the luminescent microparticles 910 having 1 or 2 or more ligands on the surface of the luminescent nanocrystals 911, but the structure of the luminescent microparticles is not limited to that shown in fig. 1. For example, luminescent fine particles having a ligand satisfying the above formula (a) and a ligand having a reactive group capable of forming a siloxane bond coordinated thereto on the surface of luminescent nanocrystal 911 can be used, and thus having an inorganic coating layer containing Si formed of a ligand having a reactive group capable of forming a siloxane bond. Next, luminescent particles having the inorganic coating layer will be described. The luminescent particles having an inorganic coating layer may be referred to as "inorganic coated luminescent particles", and luminescent particles not having an inorganic coating layer may be referred to as "non-coated luminescent particles".

In the luminescent microparticle 90 (inorganic coated luminescent microparticle) shown in fig. 2, it is preferable that at least a ligand satisfying the above formula (a) and a ligand having a reactive group capable of forming a siloxane bond are coordinated to the surface of the luminescent nanocrystal 911, and that the ligand satisfying at least the above formula (a) has a longer molecular length than the ligand having a reactive group capable of forming a siloxane bond, and in this case, a siloxane bond is formed in the vicinity of the luminescent nanocrystal 911 by the ligand having a reactive group capable of forming a siloxane bond, thereby forming a network structure composed of a plurality of siloxane bonds, and an inorganic coating layer 91 containing Si is formed. The ligand satisfying at least the above formula (a) coordinated to the surface of the luminescent nanocrystal 911 forms a ligand layer 912 in a form exposed between the network structures of the inorganic coating layer 91.

Since the inorganic coating luminescent particles 90 are exposed from the inorganic coating layer 91, dispersibility can be ensured when mixing with the photopolymerizable monomer. In this case, since at least 1 ligand is a ligand satisfying the above formula (a), exchange of the photopolymerizable monomer and the ligand can be made less likely to occur. Further, by providing the inorganic coated luminescent particles 90 with the inorganic coating layer 91 containing Si, the luminescent nanocrystals 911 can be protected from light, heat, moisture, and the like, and therefore the quantum yield retention and external quantum efficiency retention can be further improved as compared with the uncoated luminescent particles 910.

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

Among the above-mentioned ligands having a reactive group capable of forming a siloxane bond, a hydrolyzable silyl group such as a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms is preferable as the reactive group in terms of easy formation of a siloxane bond.

The ligand having a reactive group capable of forming a siloxane bond preferably has a bonding group bonded to a cation or anion contained in the luminescent nanocrystal 911 composed of a metal halide.

Examples of the bonding group include: carboxyl group, carboxylic anhydride group, amino group, ammonium group, mercapto group, phosphine oxide group, phosphate group, phosphonate group, phosphinate group, sulfonate group, borate group, etc. Among them, at least 1 of a carboxyl group and an amino group is preferable as the bonding group. These bonding groups have higher affinity (reactivity) for cations or anions contained in the luminescent nanocrystals having a perovskite crystal structure than the reactive groups. Therefore, the bonding group present in the ligand coordinates to the luminescent nanocrystals 911 constituting the inorganic coating luminescent particles 90, and the inorganic coating layer 91 formed of siloxane bonds can be formed more easily and reliably.

In these cases, examples of the ligand having a reactive group capable of forming a siloxane bond include a silicon compound containing a carboxyl group or an amino group, and 1 kind of the ligand may be used alone or 2 or more kinds of the ligand may be used in combination.

Specific examples of the silicon compound containing a carboxyl group include: trimethoxysilylpropionic acid, triethoxysilylpropionic acid, N- [3- (trimethoxysilyl) propyl ] -N ' -carboxymethyl ethylenediamine, N- [3- (trimethoxysilyl) propyl ] phthalimide, N- [3- (trimethoxysilyl) propyl ] ethylenediamine-N, N ', N ' -triacetic acid, and the like.

On the other hand, specific examples of the amino group-containing silicon compound include: 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methylethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldipropoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiisopropyloxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl tripropoxysilane, N- (2-aminoethyl) -3-aminopropyl triisopropoxysilane, N- (2-aminoethyl) -3-aminoisobutyl dimethylmethoxysilane, N- (2-aminoethyl) -3-aminoisobutyl methyldimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-triol, 3-triethoxysilyl-N- (1, 3-dimethylbenzylidene-propylamine, N-aminopropyl trimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl ] ethylenediamine, (aminoethylaminoethyl) phenyltrimethoxysilane, (aminoethylaminoethyl) phenyltriethoxysilane, (aminoethylaminoethyl) phenyltripropoxysilane, (aminoethylaminoethyl) phenyltriisopropoxysilane, (aminoethylaminomethyl) phenyltrimethoxysilane, (aminoethylaminomethyl) phenyltriethoxysilane, (aminoethylaminomethyl) phenyltripropoxysilane, (aminoethylaminomethyl) phenyltriisopropoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl methyldimethoxysilane, N-beta- (N-vinylbenzyl aminoethyl) -N-gamma- (N-vinylbenzyl) -gamma-aminopropyl trimethoxysilane, N-beta- (N-di (vinylbenzyl) aminoethyl) -N-gamma-aminopropyl trimethoxysilane, N-beta- (N-vinylbenzyl) -gamma-aminopropyl trimethoxysilane, and trimethoxy-ethyl-3-aminopropyl silane, dimethylbenzylaminopropyl trimethoxysilane, benzylaminoethylaminopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, 3- (N-phenyl) aminopropyl trimethoxysilane, N-bis [3- (trimethoxysilyl) propyl ] ethylenediamine, (aminoethylaminoethyl) phenethyl trimethoxysilane, (aminoethylaminoethyl) phenethyl triethoxysilane, (aminoethylaminoethyl) phenethyl tripropoxysilane, (aminoethylaminoethyl) phenethyl triisopropoxysilane, (aminoethylaminomethyl) phenethyl trimethoxysilane, (aminoethylaminomethyl) phenethyl triethoxysilane, (aminoethylaminomethyl) phenethyl tripropoxysilane, N- [2- [3- (trimethoxysilyl) propylamino ] ethyl ] ethylenediamine, N- [2- [3- (triethoxysilyl) propylamino ] ethyl ] ethylenediamine, N- [2- [3- (tripropoxysilyl) ethyl ] ethylenediamine, N- [2- [3- (triisopropylsilyl ] ethylenediamine, and the like.

Specific examples of the mercapto group-containing silicon compound include: 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl methyl diethoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl triethoxysilane, 2-mercaptoethyl methyl dimethoxysilane, 2-mercaptoethyl methyl diethoxysilane, 3- [ ethoxybis (3, 6,9,12, 15-pentaoxaoctacosan-1-yloxy) silyl ] -1-propanethiol, and the like.

The inorganic coated luminescent particles 90 may be produced by the following method: the solution containing a semiconductor raw material, the solution containing a ligand having a reactive group capable of forming an inorganic coating layer containing Si, and a compound forming a ligand satisfying the above formula (a) are mixed, whereby a semiconductor nanocrystal having a light-emitting property and composed of a metal halide is precipitated, and the ligand having a reactive group capable of forming an inorganic coating layer, and the ligand satisfying the above formula (a) are coordinated to the surface of the semiconductor nanocrystal, and then an inorganic coating layer 91 having the above reactive group is formed. As a method for producing the inorganic coated luminescent particles 90, there are a method of heating and a method of not heating.

First, a method of producing the inorganic coated luminescent particles 91 by heating will be described. 2 solutions containing the starting compounds were prepared separately. In this case, the following methods are exemplified: a compound forming a ligand satisfying the above formula (a) and a compound having a reactive group which contains Si and can form a siloxane bond are previously added to either or both of 2 kinds of solutions containing a raw material compound; then, they are mixed under an inert gas atmosphere and reacted at a temperature of 140 to 260 ℃. Then, the mixture was cooled to-20 to 30℃and stirred, whereby nanocrystals were precipitated. The precipitated nanocrystals are nanocrystals in which a ligand is coordinated to the surface of the nanocrystal 911, and an inorganic coating layer 91 having a siloxane bond is further formed. Then, the obtained particles are recovered by a conventional method such as centrifugal separation, whereby the silica-coated luminescent particles 91 can be obtained.

Specifically, for example, a solution containing cesium carbonate, oleic acid, and an organic solvent is prepared. As the organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. In this case, the addition amounts of cesium carbonate and oleic acid are preferably adjusted so that the amount of cesium carbonate is 0.2 to 2g and the amount of oleic acid is 0.1 to 10mL, respectively, relative to 40mL of the organic solvent. The obtained solution is dried under reduced pressure at 90-150 ℃ for 10-180 minutes, and then heated to 100-200 ℃ under an inert gas atmosphere such as argon, nitrogen and the like, thereby obtaining cesium-oleic acid solution.

On the other hand, a solution containing lead (II) bromide and the same organic solvent as described above was prepared. At this time, 20 to 100mg of lead (II) bromide was added to 5mL of the organic solvent. The obtained solution was dried at 90 to 150℃for 10 to 180 minutes under reduced pressure, and then 0.1 to 2mL of 3-aminopropyl triethoxysilane was added under an inert gas atmosphere such as argon or nitrogen.

Then, the cesium-oleic acid solution was added in a state where a solution containing lead (II) bromide and 3-aminopropyl triethoxysilane had been heated to 140 to 260 ℃, and the mixture was heated and stirred for 1 to 10 seconds to react, and then the obtained reaction solution was cooled by an ice bath. In this case, it is preferable to add 0.1 to 1mL of cesium-oleic acid solution to 5mL of the solution containing lead (II) bromide and 3-aminopropyl triethoxysilane. In the process of stirring at the temperature of between 20 ℃ below zero and 30 ℃, the nano crystal 911 is separated out, and meanwhile, the 3-aminopropyl triethoxysilane and the oleic acid are coordinated on the surface of the nano crystal 911.

Then, the obtained reaction solution was stirred at room temperature (10 to 30 ℃ C., humidity 5 to 60%) under atmospheric pressure for 5 to 300 minutes, and then 0.1 to 50mL of ethanol was added thereto, thereby obtaining a suspension. The alkoxysilyl group of 3-aminopropyl triethoxysilane is condensed during stirring at room temperature under the atmosphere, and an inorganic coating layer 91 having siloxane bonds is formed on the surface of the nanocrystal 911 to which oleic acid is coordinated.

The obtained suspension is centrifuged to collect a solid, and the solid is added to toluene to obtain a luminescent particle dispersion in which silica-coated luminescent particles 90 are dispersed in toluene, wherein the silica-coated luminescent particles 90 have an inorganic coating layer 91 having siloxane bonds on the surface of the nanocrystal 911, and oleic acid is coordinated to the surface of the nanocrystal 911 and exposed from between the inorganic coating particles to provide a ligand layer 912.

Next, a method for producing the silica-coated luminescent particles 90 without heating will be described. The following methods may be mentioned: the solution containing the raw material compound of the semiconductor nanocrystal and the solution containing the compound having a reactive group which contains Si and can form a siloxane bond are mixed under the atmosphere, and then the obtained mixture is added to a large amount of organic solvent which is a poor solvent for the nanocrystal, thereby precipitating the nanocrystal. The amount of the organic solvent to be used is preferably 10 to 1000 times the amount of the semiconductor nanocrystal in terms of mass. The deposited nanocrystals have an inorganic coating layer 91 having siloxane bonds formed on the surface of the nanocrystal 911. The obtained particles are recovered by a conventional method such as centrifugation, whereby the silica-coated luminescent fine particles 90 can be obtained.

Specifically, for example, a solution containing lead (II) bromide and methylamine hydrobromide, and an organic solvent is prepared as a solution containing a raw material compound of semiconductor nanocrystals. The organic solvent may be a good solvent for the nanocrystals, and is preferably dimethylsulfoxide, N-dimethylformamide, N-methylformamide, or a mixed solvent thereof, in view of compatibility. In this case, the amount of each of the lead (II) bromide to be added is preferably adjusted so that the amount of the lead (II) bromide is 50 to 200mg and the amount of the methylamine hydrobromide to be added is 10 to 100mg, based on 10mL of the organic solvent.

On the other hand, for example, a solution containing 3-aminopropyl triethoxysilane, oleic acid, and a poor solvent is prepared as a solution containing a compound having a reactive group that contains Si and can form a siloxane bond. As the poor solvent, isopropyl alcohol, toluene, hexane, or the like can be used. In this case, the addition amounts of the respective solvents are preferably adjusted so that 5mL of 3-aminopropyl triethoxysilane and 0.01 to 0.5mL of oleic acid are used as the poor solvents, respectively.

Then, 5mL of the solution containing 3-aminopropyl triethoxysilane was added to 0.1 to 5mL of the solution containing lead (II) bromide and methyl amine hydrobromide at 0 to 60℃under the atmosphere to obtain a mixture. Then, the obtained mixture was immediately added to a large amount of poor solvent, stirred under atmospheric pressure for 5 to 180 seconds, and then centrifuged to collect the solid. When the mixture is added to a large amount of poor solvent, the nanocrystals 911 are precipitated, and at the same time, the 3-aminopropyl triethoxysilane and oleic acid coordinate to the surface of the nanocrystals 911. Then, in the course of stirring under the atmosphere, the alkoxysilyl group of 3-aminopropyl triethoxysilane condenses, and a surface layer 91 having siloxane bonds is formed on the surface of the nanocrystal 911.

By adding the recovered solid to toluene, a luminescent particle dispersion liquid in which the silica-coated luminescent particles 90 are dispersed in toluene can be obtained, wherein the silica-coated luminescent particles 90 have a surface layer 91 having siloxane bonds on the surface of a nanocrystal 911 composed of a lead methyl ammonium tribromide crystal.

1-5 photopolymerization initiator

The nanocrystal-containing composition of the present invention preferably further contains a polymerization initiator. The photopolymerization initiator is preferably at least 1 selected from the group consisting of an alkylbenzene-based compound, an acylphosphine oxide-based compound, and an oxime ester-based compound.

Examples of the alkyl benzophenone photopolymerization initiator include compounds represented by the formula (b-1).

In the formula (b-1), R ^1a Is selected from the following formula (R) ^1a -1) to formula (R) ^1a -the radical in 6), R ^2a 、R ^2b R is R ^2c Each independently represents a compound selected from the following formula (R ² -1) to formula (R) ² -7).

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

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

In the formula (b-2), R ²⁴ Represents alkyl, aryl or heterocyclyl, R ²⁵ R is R ²⁶ Each independently represents an alkyl group, an aryl group, a heterocyclic group or an alkanoyl group (alkenoyl group), which groups may be substituted with an alkyl group, a hydroxyl group, a carboxyl group, a sulfone group, an aryl group, an alkoxy group, an arylthio group.

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

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

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

Specific examples of the compounds represented by the above-mentioned formulae (b-3-1) and (b-3-2) are preferably compounds represented by the following formulae (b-3-1-1) to (b-3-1-2) and (b-3-2-1) to (b-3-2-2), more preferably compounds represented by the following formulae (b-3-1-1), formula (b-3-2-1) or formula (b-3-2-2).

The amount of the photopolymerization initiator to be blended is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and even more preferably 1 to 6% by mass, based on the total amount of the photopolymerizable monomers contained in the nanocrystal-containing composition. The photopolymerization initiator may be used alone or in combination of 1 or more than 2. The nanocrystalline-containing composition containing the photopolymerization initiator in such an amount sufficiently maintains the sensitivity at the time of photocuring, and the crystallization of the photopolymerization initiator is less likely to precipitate at the time of drying the coating film, so that deterioration of the physical properties of the coating film can be suppressed.

When the photopolymerization initiator is dissolved in the composition containing nanocrystals, it is preferably used after being dissolved in the photopolymerizable monomer in advance.

In order to dissolve in the photopolymerizable monomer, it is preferable to add the photopolymerization initiator while stirring the photopolymerizable monomer so that the reaction does not start by heat, thereby uniformly dissolving the photopolymerization initiator.

The dissolution temperature of the photopolymerization initiator may be appropriately adjusted in consideration of the solubility of the photopolymerization initiator to be used in the photopolymerizable monomer and the polymerizability of the photopolymerizable monomer by heat, and is preferably 10 to 60 ℃, more preferably 10 to 40 ℃, and even more preferably 10 to 30 ℃ from the viewpoint of not starting the polymerization of the photopolymerizable monomer.

1-6 light scattering agent

The nanocrystal-containing composition of the present invention preferably further contains a light scattering agent. The light scattering agent is generally in the form of particles, and will be hereinafter referred to as "light scattering particles". The light scattering particles are, for example, optically inactive inorganic fine particles. The light-scattering particles can scatter the light from the light source unit irradiated to the light-emitting layer (light conversion layer) formed by curing the composition containing nanocrystals or the ink composition containing the composition.

Examples of the material constituting the light scattering particles include: elemental metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, gold, and the like; metal oxides such as 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, and zinc oxide; metal carbonates such as magnesium carbonate, barium carbonate, bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; and metal salts such as barium zirconate, calcium titanate, barium titanate, strontium titanate and the like. Among them, the material constituting the light scattering particles preferably contains at least 1 selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silicon dioxide, and more preferably contains at least one selected from the group consisting of titanium oxide, barium sulfate, and calcium carbonate, from the viewpoint of more excellent effect of reducing light leakage.

The light scattering particles may have a spherical shape, a long thread shape, an indefinite shape, or the like. However, from the viewpoint of further improving the uniformity, flowability, and light scattering properties of the composition containing nanocrystals, it is preferable to use particles having less directionality as the particle shape (for example, particles in a spherical shape, a regular tetrahedron shape, or the like) as the light scattering particles.

The average particle diameter (volume average diameter) of the light scattering particles in the composition containing nanocrystals may be 0.05 μm or more, may be 0.2 μm or more, or may be 0.3 μm or more from the viewpoint of more excellent effect of reducing light leakage. The average particle diameter (volume average diameter) of the light scattering particles in the nanocrystalline-containing composition may be 1.0 μm or less, may be 0.6 μm or less, or may be 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 nanocrystalline-containing composition may also be 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, 0.3 to 1.0 μm, 0.3 to 0.6 μm, or 0.3 to 0.4 μm. The average particle diameter (volume average diameter) of the light scattering particles used may be 50nm or more and 1000nm or less from the viewpoint of easy obtaining of such average particle diameter (volume average diameter). The average particle diameter (volume average diameter) of the light scattering particles in the nanocrystal-containing composition can be obtained by measuring the particle diameter by a dynamic light scattering Nanotrac particle size distribution meter and calculating the volume average diameter. The average particle diameter (volume average diameter) of the light scattering particles used can be obtained by measuring the particle diameter of each particle by 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 mass% or more, 1 mass% or more, 5 mass% or more, 7 mass% or more, 10 mass% or more, or 12 mass% or more based on the mass of the nonvolatile component of the nanocrystalline-containing composition, from the viewpoint of more excellent effect of reducing light leakage. The content of the light scattering particles may be 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 25 mass% or less, or 20 mass% or less, or 15 mass% or less, based on the mass of the nonvolatile component of the nanocrystal-containing composition, from the viewpoint of more excellent light leakage reduction effect and excellent ejection stability. In this embodiment, since the composition containing nanocrystals contains the polymeric dispersant, the light-scattering particles can be well dispersed even when the content of the light-scattering particles is within the above range.

From the viewpoint of more excellent effect of reducing light leakage, the mass ratio of the content of the light scattering particles to the content of the luminescent particles (light scattering particles/luminescent nanocrystals) may be 0.1 or more, or 0.2 or more, or 0.5 or more. The mass ratio (light scattering particles/luminescent nanocrystals) may be 5.0 or less, or 2.0 or less, or 1.5 or less, from the viewpoint of more excellent light leakage reduction effect and excellent continuous ejection property at the time of inkjet printing. The light leakage reduction by using light scattering particles is thought to be based on the following mechanism. That is, when the light scattering particles are not present, it is considered that the backlight passes through the pixel portion only substantially in a straight line, and the light-emitting particles have less chance to absorb the backlight. On the other hand, if the light scattering particles and the luminescent particles are present in the same pixel portion, the backlight is scattered in all directions in the pixel portion, and the luminescent particles can receive light, so that the light absorption amount in the pixel portion increases even if the same backlight is used. As a result, it is considered that light leakage can be prevented by such a mechanism.

1-7 dispersant

The nanocrystal-containing composition of the present invention preferably further contains a dispersant. The dispersant is not particularly limited as long as it is a compound capable of further improving the dispersion stability of the luminescent particles in the composition containing nanocrystals. The dispersant is divided into a low molecular dispersant and a high molecular dispersant. In the present specification, "low molecular weight" means a molecule having a weight average molecular weight (Mw) of 5,000 or less, and "high molecular weight" means a molecule having a weight average molecular weight (Mw) of more than 5,000. In this specification, the "weight average molecular weight (Mw)" may be a value measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard substance.

Examples of the low-molecular dispersant include: oleic acid; 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; sulfur atom-containing compounds such as 1-decanethiol, octanethiol, dodecanethiol and pentylsulfide.

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, polyamine resins (polyethyleneimine, polyallylamine, etc.), epoxy resins, polyimide resins, wood rosin, gum rosin, natural rosin such as tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleic rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin derivative such as rosin modified phenol, and the like.

Examples of the commercially available polymer dispersants include DISPRBYK series manufactured by BYK-Chemie, TEGO Dispers series manufactured by Evonik, EFKA series manufactured by BASF, SOLSPERSE series manufactured by Nippon Lumbrin, ajinsper series manufactured by Ajinomoto Fine-Techno, DISPARALON series manufactured by Nanyon chemical, flowlen series manufactured by Cogrong chemical, and the like.

The amount of the dispersant to be blended is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the

luminescent particles

910, 90, respectively.

In addition, when a color filter pixel portion is formed by an inkjet method using a conventional ink composition, there are cases where ejection stability from a nozzle is lowered due to aggregation of light-emitting particles and light-scattering particles or the like. In addition, it is considered that the ejection stability is improved by making the luminescent particles and the light scattering particles finer, reducing the content of the luminescent particles and the light scattering particles, and the like, but in this case, the effect of reducing light leakage is liable to be reduced, and it is difficult to achieve both sufficient ejection stability and the effect of reducing light leakage. In contrast, according to the nanocrystal composition of the present invention further containing a dispersant, sufficient ejection stability can be ensured and light leakage can be further reduced. The reason for obtaining such an effect is not clear, and is presumed to be: by the dispersant, aggregation of the luminescent particles and the light scattering particles (particularly, the light scattering particles) is significantly suppressed.

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

Examples of the acidic functional group include: carboxyl (-COOH), sulfo (-SO) ₃ H) Sulfuric acid group (-OSO) ₃ H) Phosphonic acid groups (-PO (OH) ₃ ) Phosphate (-OPO (OH)) ₃ ) Phosphinic acid groups (-PO (OH) -) and mercapto groups (-SH).

As basic functional groups, there may be mentioned: primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, triazole, and the like.

Examples of the nonionic functional group include: hydroxy, ether, thioether, sulfinyl (-SO-), sulfonyl (-SO-) ₂ (-), carbonyl, formyl, ester, carbonate, amide, carbamoyl, ureido, thioamide, thiourea, sulfamoyl, cyano, alkenyl, alkynyl, phosphine oxide, thiophosphino.

From the viewpoint of dispersion stability of the light scattering particles, the viewpoint of side effects such as difficulty in occurrence of sedimentation of luminescent particles, the viewpoint of ease of synthesis of the polymer dispersant, and the viewpoint of stability of the functional group, carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid groups can be preferably used as the acidic functional groups, and amino groups can be preferably used as the basic functional groups. Among them, carboxyl, phosphonic acid and amino groups are more preferably used, and amino groups are most preferably used.

The dispersant having an acidic functional group has an acid value. The acid value of the polymer dispersant having an acidic functional group is preferably 1 to 150mgKOH/g in terms of solid content conversion. 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 not easily lowered.

In addition, dispersants having basic functional groups have amine numbers. The amine value of the dispersant having a basic functional group is preferably 1 to 200mgKOH/g in terms of solid content conversion. If the amine value is 1 or more, sufficient dispersibility of the light scattering particles is easily obtained, and if the amine value is 200 or less, the storage stability of the pixel portion (cured product of the ink composition) is not easily lowered.

The weight average molecular weight of the dispersant may be 750 or more, 1000 or more, 2000 or more, or 3000 or more, from the viewpoint of enabling the light scattering particles to be well dispersed and further improving the effect of reducing light leakage. The weight average molecular weight of the dispersant may be 100000 or less, 50000 or less, or 30000 or less, from the viewpoint that the light scattering particles can be satisfactorily dispersed, the effect of reducing light leakage can be further improved, and the viscosity of the inkjet ink can be set to a viscosity suitable for stable ejection.

The content of the dispersant may be 0.5 parts by mass or more, or 2 parts by mass or more, or 5 parts by mass or more, based on 100 parts by mass of the light-scattering particles, from the viewpoint of dispersibility of the light-scattering particles. From the viewpoint of the wet heat stability of the pixel portion (cured product of the ink composition), 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 relative to 100 parts by mass of the light scattering particles.

1-8 other ingredients

The composition containing nanocrystals used in the present invention may contain other components than the

luminescent microparticles

910 and 90, the photopolymerizable monomer, the photopolymerization initiator, and the light scattering particles within a range that does not inhibit the effects of the present invention. Examples of such other components include: polymerization inhibitor, antioxidant, leveling agent, chain transfer agent, dispersing aid, thermoplastic resin, sensitizer, etc.

1-8-1 polymerization inhibitor

Examples of the polymerization inhibitor include: phenolic compounds such as p-methoxyphenol, cresol, t-butylcatechol, 3, 5-di-t-butyl-4-hydroxytoluene, 2' -methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4' -thiobis (3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, and 4,4' -dialkoxy-2, 2' -bi-1-naphthol; quinone compounds such as hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, p-benzoquinone, methyl p-benzoquinone, tert-butyl p-benzoquinone, 2, 5-diphenyl benzoquinone, 2-hydroxy-1, 4-naphthoquinone, 2, 3-dichloro-1, 4-naphthoquinone, anthraquinone, and diphenoquinone; amine compounds such as p-phenylenediamine, 4-aminodiphenylamine, N '-diphenylp-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N' -di-2-naphthylp-phenylenediamine, diphenylamine, N-phenyl-beta-naphthylamine, 4 '-diisopropylphenyldiphenylamine, and 4,4' -dioctyldiphenylamine; thioether compounds such as phenothiazine and distearyl thiodipropionate; 2, 6-tetramethylpiperidine-1-oxyl, 2, 6-tetramethylpiperidine N-oxide compounds such as 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl; n-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrobenzene, p-nitrosodiphenylamine, alpha-nitroso-beta-naphthol, N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-N-butylamine, N-nitroso-N-N-butyl-4-butanolamine, N-nitrosodiisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt (FUJIFILM Wako Pure Chemical Co., ltd., "Q-1300"), nitrobenzene, 2,4, 6-tri-tert-butylnitrobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylcarbamate, N-nitroso-N-propylcarbamate, 1-nitroso-2-naphthol, 1-nitroso-2-naphthol-3, 6-sodium 2-nitroso-N-ethyl-4-butanolate, sodium 2-methyl-phenolsulfonate, 5-nitrosophenolsulfonate, 5-nitrosophenolate, sodium-methyl-phenolsulfonate, nitroso compounds such as Q-1301 (manufactured by FUJIFILM Wako Pure Chemical Co., ltd.).

The amount of the polymerization inhibitor to be added is preferably 0.01 to 1.0 mass%, more preferably 0.02 to 0.5 mass% based on the total amount of the photopolymerizable monomers contained in the nanocrystal composition.

1-8-2 antioxidant

Examples of the antioxidant include: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] ("IRGANOX 1010"), thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] ("IRGANOX 1035"), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ("IRGANOX 1076"), "IRGANOX1135", "IRGANOX1330", 4, 6-bis (octylmethylthio) orthocresol ("IRGANOX 1520L"), "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX565", manufactured by BASF corporation, above); "Adekastab AO-20", "Adekastab AO-30", "Adekastab AO-40", "Adekastab AO-50", "Adekastab AO-60", "Adekastab AO-80" (manufactured above by ADEKA Co., ltd.); "JP-360", "JP-308E", "JPE-10" (manufactured by Tokubei chemical industries Co., ltd.); "Sumizer BHT", "Sumizer BBM-S", "Sumizer GA-80" (manufactured by Sumitomo chemical Co., ltd.) and the like.

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

1-8-3 leveling agent

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

Examples of such leveling agents include: alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, and the like.

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

Examples of other specific leveling agents include: "FTERGENT 100", "FTERGENT 100C", "FTERGENT 110", "FTERGENT 150CH", "FTERGENT 100A-K", "FTERGENT 300", "FTERGENT 310", "FTERGENT 320", "FTERGENT 400SW", "FTERGENT 251", "FTERGENT 215M", "FTERGENT 212M", "FTERGENT 215M", "FTERGENT 250", "FTERGENT 222F", "FTERGENT 212D", "FTX-218", "FTERGENT 209F", "FTERGENT 245F", "FTERGENT 208G", "FTERGENT 240G", "FTERGENT 212P", "FTERGENT 220P", "FTGENT-18", "FTERGENT 601AD", "FTERGENT 602A", "FTERGENT 650A", "FTERGENT 750F", "FTFM", "X-730 FM", "FTERGENT 730FL", "FTFM-730 FL", "FTFM-FM-730, and the like manufacturing methods.

Examples of other specific leveling agents include: "BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", "BYK-322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-340", "BYK-344", "BYK-370", "BYK-375", "BYK-377", "BYK-350", "BYK-352", "BYK-354", "BYK-355", "BYK-356", "BYK-358N", "BYK-361N", "BYK-357", "BYK-390", "BYK-392", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-Silean 3700", manufactured by KCo., ltd.) and the like.

Examples of other specific leveling agents include: "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 ATF2", "TEGO Flow ZFS460", "TEGO Glide100", "TEGO Glide110", "TEGO Glide130", "TEGO Glide410", "TEGO Glide411", "TEGO Glide415", "TEGO Glide432", "TEGO Glide440", TEGO Flow370"," TEGO Flow425"," TEGO "TEGO Glide450", "TEGO Glide482", "TEGO Glide A115", "TEGO Glide B1484", "TEGO Glide ZG400", "TEGO Tain 4000", "TEGO Tain 4100", "TEGO Tain 4200", "TEGO Wet240", "TEGO Wet250", "TEGO Wet260", "TEGO Wet265", "TEGO Wet270", "TEGO Wet280", "TEGO Wet500", "TEGO Wet505", "TEGO Wet510", "TEGO Wet520", "TEGO Wet 245" (manufactured by Evonik Industries Corp.) and the like.

Examples of other specific leveling agents include: "FC-4430", "FC-4432" (above 3M Japan Co., ltd.) "and" Unidyne NS "(above Dain Co., ltd.); "Surflon S-241", "Surflon S-242", "Surflon S-243", "Surflon S-420", "Surflon S-611", "Surflon S-651", "Surflon S-386" (manufactured by AGC cleaning and beautification Co., ltd.) and the like.

Examples of other specific leveling agents include: "DISPARON OX-880EF", "DISPARON OX-881", "DISPARON OX-883", "DISPARON OX-77EF", "DISPARON OX-710", "DISPARON 1922", "DISPARON 1927", "DISPARON P-410EF", "DISPARON P-420", "DISPARON P-425", "DISPARON PD-7", "DISPARON 1970", "DISPARON 230", "DISPARON LF-1980", "DISPARON LF-1982", "DISPARON LF-1084", "DISPARON LF-1985", "DISPARON LHP-90", "DISPARON LHP-91", "DISPARON LHP-95", "DIPARON LHP-96", "DISPARON P-1930N", "DIARON 1931", "DIPARON 3", "DIARON 4", "DIARON 1", "DIARON-1751", "DIARON-1760", "DIARON-1931", "DIARON-17", and the like, DIARPARARON being manufactured by DISPARON-1931 "," DISPARON-17, DISPARON-1931 "," DIARON-17, etc.

Examples of other specific leveling agents include: "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-652-NF", "PF-3320" (above manufactured by OMNOVASOLUTIONS Co.); "Polyflow No.7", "Polyflow No.50E", "Polyflow No.50EHF", "Polyflow No.54N", "Polyflow No.75", "Polyflow No.77", "Polyflow No.85", "Polyflow No.85HF", "Polyflow No.90", "Polyflow No.90D-50", "Polyflow No.95", "Polyflow No.99C", "Polyflow KL-400K", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-100", "Polyflow LE-604", "Polyflow KL-700", "FlowAC-300", "FlowAC-303", "FlowAC-324", "FlowAC-326F", "FlowAC-530", "FlowAC-903", "WAC-903", "HF", "FlowAC-1160", "FlowAC-1190", "Polyflow KL-2000", "Polyflow KL-82", kside "KOJ-UK", "KOK-UK", "KOK", etc. Chen ", etc.

Further, specific examples of the leveling agent include: "L-7001", "L-7002", "8032ADDITIVE", "57 ADTIVE", "L-7064", "FZ-2110", "FZ-2105", "67 ADTIVE", "8616 ADTIVE" (manufactured by Dow Corning Toray Silicone Co., ltd.) and the like.

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

1-8-4 chain transfer agent

When the composition containing nanocrystals is used as the ink composition, the chain transfer agent is a component used for the purpose of further improving the adhesion between the ink composition and the substrate.

Examples of the chain transfer agent include: aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide and bromotrichloromethane; thiol compounds such as octanethiol, n-butanethiol, n-pentanethiol, n-hexadecanethiol, n-tetradecanethiol, n-dodecyl mercaptan, t-tetradecanethiol, t-dodecyl mercaptan, and the like; thiol compounds such as hexane dithiol, decanedithiol, 1, 4-butanediol dithiopropionate, 1, 4-butanediol dithioacetate, ethylene glycol dithiopropionate, trimethylolpropane trithioacetate, trimethylolpropane trithiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioacetate, pentaerythritol tetrathiopropionate, tris (2-hydroxyethyl) isocyanurate of trimercapto propionic acid, 1, 4-dimethylmercapto benzene, 2,4, 6-trimercapto s-triazine, and 2- (N, N-dibutylamino) -4, 6-dimercapto-triazine; sulfide compounds such as dimethyl xanthate, diethyl xanthate, diisopropyl xanthate, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; n, N-dimethylaniline, N-divinylaniline, pentaphenyl ethane, alpha-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, alpha-terpinene, gamma-terpinene, dipentene and the like, but 2, 4-diphenyl-4-methyl-1-pentene, thiol compounds are preferable.

Specific examples of the chain transfer agent include compounds represented by the following general formulae (9-1) to (9-12).

Wherein R is ⁹⁵ Represents an alkyl group having 2 to 18 carbon atoms, which may be straight-chain or straight-chainThe alkyl group may be branched, and 1 or more methylene groups in the alkyl group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or-ch=ch-without directly bonding an oxygen atom and a sulfur atom to each other.

R ⁹⁶ An alkylene group having 2 to 18 carbon atoms, wherein 1 or more methylene groups in the alkylene group may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-or-ch=ch-without directly bonding an oxygen atom and a sulfur atom to each other.

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

1-8-5 dispersing auxiliary

Examples of the dispersing aid include: and organic pigment derivatives such as phthalimide methyl derivatives, phthalimide sulfonic acid derivatives, phthalimide N- (dialkylamino) methyl derivatives, and phthalimide N- (dialkylaminoalkyl) sulfonic acid amide derivatives. These dispersing aids may be used alone or in combination of 1 or more than 2.

1-8-6. Thermoplastic resin

Examples of the thermoplastic resin include: urethane-based resins, acrylic-based resins, polyamide-based resins, polyimide-based resins, styrene-maleic anhydride-based resins, acrylic-polyester-based resins, and the like.

1-8-7. Sensitizer

As the sensitizer, amines which do not undergo an addition reaction with the photopolymerizable monomer can be used. Examples of such a sensitizer include: trimethylamine, methyldimethanol amine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N-dimethylbenzylamine, 4' -bis (diethylamino) benzophenone, and the like.

1-9 Process for the preparation of compositions containing nanocrystals

The above-described composition containing nanocrystals can be prepared by dispersing the

luminescent particles

910 and 90 in a solution in which a photopolymerizable monomer, a photopolymerization initiator, and the like are mixed. The dispersion of the

luminescent particles

910 and 90 can be performed by using a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersing mixer, or ultrasonic waves.

The content of the

luminescent particles

910 and 91 in the nanocrystal composition is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 1 to 40% by mass. When the content of the

luminescent particles

910 and 90 in the nanocrystal composition is set to the above range, the ejection stability can be further improved when the ink composition composed of the nanocrystal monomer is ejected by the inkjet printing method. In addition, the non-coated luminescent particles 910 or the inorganic coated luminescent particles 91 are less likely to aggregate with each other, and the external quantum efficiency of the obtained luminescent layer (light conversion layer) can be improved.

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

The viscosity of the nanocrystal-containing composition as the ink composition is preferably in the range of 2 to 20mpa·s, more preferably in the range of 5 to 15mpa·s, and even more preferably in the range of 7 to 12mpa·s, from the viewpoint of ejection stability at the time of inkjet printing. In this case, since the meniscus shape of the nanocrystalline-containing composition in the ink ejection hole of the ejection head is stable, the ejection of the ink is easy to control (for example, the ejection amount and the ejection timing are controlled). In addition, ink can be smoothly ejected from the ink ejection holes. The viscosity of the composition containing the nanocrystals can be measured by, for example, an E-type viscometer.

The surface tension of the nanocrystalline-containing composition as the ink composition is preferably a surface tension suitable for the inkjet printing method. The specific value of the surface tension is preferably in the range of 20 to 40mN/m, more preferably in the range of 25 to 35 mN/m. By setting the surface tension to the above range, the occurrence of flight deviation of the ink droplets can be suppressed. The flying shift means that when the ink is ejected from the ink ejection hole, the landing position of the ink is shifted by 30 μm or more from the target position.

2. Light emitting device formed using nanocrystalline-containing composition

The composition containing nanocrystals can be obtained by forming a coating film on a substrate by various methods such as an inkjet printer, photolithography, spin coater, and the like, and heating and curing the coating film. The following will be described by taking the following cases as examples: a color filter pixel portion including a light emitting element of a blue organic LED backlight is formed using a composition containing nanocrystals as an ink composition.

Fig. 3 is a cross-sectional view showing an embodiment of a light-emitting element according to the present invention, and fig. 4 and 5 are schematic diagrams showing the configuration of an active matrix circuit, respectively. In fig. 3, the dimensions of each part and the ratio thereof are exaggerated for convenience, and may be different from actual ones. The materials, dimensions, and the like shown below are examples, and the present invention is not limited to these, and can be appropriately modified within a range that does not change the gist thereof. Hereinafter, for convenience of explanation, the upper side of fig. 3 will be referred to as "upper side" or "upper side", and the lower side will be referred to as "lower side" or "lower side". In fig. 3, hatching showing a cross section is omitted to avoid complication of the drawing.

As shown in fig. 3, the light-emitting element 100 has a structure in which a lower substrate 1, an EL light source unit 200, a filler layer 10, a protective layer 11, a light conversion layer 12 containing the light-emitting particles and functioning as a light-emitting layer, and an upper substrate 13 are stacked in this order. The luminescent particles contained in the light conversion layer 12 may be non-coated luminescent particles 910 that are not provided with the inorganic coating layer or the resin coating layer, or may be inorganic coated luminescent particles 90. The EL light source section 200 includes, in order: an anode 2, an EL layer 14 composed of a plurality of layers, a cathode 8, a polarizing plate not shown, and a sealing layer 9. The EL layer 14 includes a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7, which are stacked in this order from the anode 2 side.

The light emitting element 100 is a photoluminescent element that absorbs and re-emits light emitted from the EL light source section 200 (EL layer 14) through the light conversion layer 12 or transmits the light, and extracts the light from the upper substrate 13 side to the outside. At this time, the light emitted from the

luminescent particles

910 or 90 included in the light conversion layer 12 is converted into light of a predetermined color. The respective layers will be described in order below.

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. In the case where the light-emitting element 100 is of a top emission type, the upper substrate 13 is constituted by a transparent substrate. On the other hand, in the case where the light-emitting element 100 is of the bottom emission type, the lower substrate 1 is constituted by a transparent substrate. Here, the transparent substrate means a substrate through which light having a wavelength in the visible light region can pass, and transparent includes colorless transparent, colored transparent, and semitransparent.

As the transparent substrate, for example, a transparent glass substrate such as quartz glass, pyrex (registered trademark) glass, or a synthetic quartz plate, or a quartz substrate; plastic substrates (resin substrates) made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyimide (PI), polycarbonate (PC), and the like; a metal substrate made of iron, stainless steel, aluminum, copper, or the like; a silicon substrate; gallium arsenide substrates, and the like. Among them, a glass substrate made of alkali-free glass containing no alkali component in the glass is preferably used. Specifically, "7059 glass", "1737 glass", "Eagle 200" and "Eagle XG" manufactured by Corning corporation, and "AN100" manufactured by Asahi Kara corporation, and "OA-10G" and "OA-11" manufactured by Nippon Electric Glass are preferable. These materials have a small thermal expansion coefficient, and are excellent in dimensional stability and workability in high-temperature heat treatment. In addition, when flexibility is provided to the light-emitting element 100, a plastic substrate (a substrate made of a polymer material as a main material) and a metal substrate having a relatively small thickness are selected for the lower substrate 1 and the upper substrate 13, respectively.

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

Either or both of the lower substrate 1 and the upper substrate 13 may be omitted depending on the use form of the light emitting element 100.

As shown in fig. 4, the lower substrate 1 includes: a signal line driver circuit C1 and a scanning line driver circuit C2 for controlling current supply to the anode 2 constituting the pixel electrode PE shown in R, G, B, a control circuit C3 for controlling operation of these circuits, a plurality of signal lines 706 connected to the signal line driver circuit C1, and a plurality of scanning lines 707 connected to the scanning line driver circuit C2. In addition, as shown in fig. 5, a capacitor 701, a driving transistor 702, and a switching transistor 708 are provided near the intersection of each signal line 706 and each scanning line 707.

With respect to the capacitor 701, one electrode is connected to the gate electrode of the driving transistor 702, and the other electrode is connected to the source electrode of the driving 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 for supplying a driving current, and a drain electrode connected to the anode 4 of the EL light source unit 200.

In the switching transistor 708, a gate electrode is connected to the scanning line 707, a source electrode is connected to the signal line 706, and a drain electrode is connected to the gate electrode of the driving transistor 702. In the present embodiment, the common electrode 705 forms the cathode 8 of the EL light source unit 200. The driving transistor 702 and the switching transistor 708 may be formed of, for example, thin film transistors.

The scanning line driving circuit C2 supplies or blocks a scanning voltage corresponding to a scanning signal to or from the gate electrode of the switching transistor 708 via the scanning line 707, and turns on or off the switching transistor 708. Thereby, the scanning line driving circuit C2 adjusts timing of writing the signal voltage to the signal line driving circuit C1. On the other hand, the signal line driving circuit C1 supplies or blocks a signal voltage corresponding to the video signal to the gate electrode of the driving transistor 702 via the signal line 706 and the switching transistor 708, and adjusts the amount of signal current supplied to the EL light source unit 200.

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

2-2.EL light source section 200

2-2-1 anode 2

The anode 2 has a function of supplying holes from an external power source toward the light-emitting layer 5. The constituent material (anode material) of the anode 2 is not particularly limited, and examples thereof include: metals such as gold (Au); halogenated metals such as copper iodide (CuI); indium Tin Oxide (ITO), tin oxide (SnO) ₂ ) Metal oxides such as zinc oxide (ZnO), and the like. They may be used alone or in combination of 1 kind or 2 or more kinds.

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

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

2-2-2 cathode 8

The cathode 8 has a function of supplying electrons from an external power source toward the light-emitting layer 5. The constituent material (cathode material) of the cathode 8 is not particularly limited, and examples thereof include: lithium, sodium, magnesium, aluminum, silver, sodium-potassium alloy, magnesium/aluminum mixture, magnesium/silver mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al) ₂ O ₃ ) Mixtures, rare earth metals, and the like. They may be used alone or in combination of 1 kind or 2 or more kinds.

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

The cathode 3 may be formed by a dry film forming method such as a vapor deposition method or a sputtering method.

2-2-3 hole injection layer 3

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

The constituent material (hole injection material) of the hole injection layer 3 is not particularly limited, and examples thereof include: phthalocyanine compounds such as copper phthalocyanine; triphenylamine derivatives such as 4,4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine; cyano compounds such as 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonyl nitrile, 2,3,5, 6-tetrafluoro-7, 8-tetracyanoquinodimethane; metal oxides such as vanadium oxide and molybdenum oxide; amorphous carbon; polyaniline (aniline green), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS), polymer such as polypyrrole, and the like. Among them, the hole injection material is preferably a polymer, more preferably PEDOT-PSS. The hole injecting material may be used alone or in combination of 1 or 2 or more.

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

Such a hole injection layer 4 can be formed by a wet film forming method or a dry film forming method. When the hole injection layer 3 is formed by a wet film formation method, an ink containing the hole injection material is generally 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 discharge method), spin coating, casting, LB, relief printing, gravure printing, screen printing, nozzle printing, and the like. 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 preferably used.

2-2-4 hole transport layer 4

The hole transport layer 4 has a function of receiving holes from the hole injection layer 3 and efficiently transporting the holes to the light emitting layer 6. In addition, the hole transport layer 4 may also have a function of preventing electron transport. The hole transport layer 4 may be provided as needed, or may be omitted.

The constituent material (hole transport material) of the hole transport layer 4 is not particularly limited, and examples thereof include: low molecular triphenylamine derivatives such as TPD (N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), α -NPD (4, 4 '-bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl), m-MTDATA (4, 4',4 "-tris (3-methylphenyl phenylamino) triphenylamine); polyvinylcarbazole; conjugated compound polymers such as 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), and polyphenylacetylene (PPV); and copolymers containing the monomer units thereof.

Among them, the hole transporting material is preferably a polymer compound obtained by polymerizing a triphenylamine derivative or a triphenylamine derivative having a substituent introduced therein, and more preferably a polymer compound obtained by polymerizing a triphenylamine derivative having a substituent introduced therein. In addition, 1 kind of the hole transporting material may be used alone, or 2 or more kinds may be used in combination.

The thickness of the hole transport layer 4 is not particularly limited, but is preferably in the range of 1 to 500nm, more preferably in the range of 5 to 300nm, and even more preferably in the range of 10 to 200 nm. The hole transport layer 4 may be a single layer or a laminate structure in which 2 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. When the hole transport layer 4 is formed by a wet film formation method, an ink containing the hole transport material is generally 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 discharge method), spin coating, casting, LB, relief printing, gravure printing, screen printing, nozzle printing, and the like. On the other hand, in the case of forming the hole transport layer 4 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like can be preferably used.

2-2-5. Electron injection layer 7

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

The constituent material (electron injection material) of the electron injection layer 7 is not particularly limited, and examples thereof include: li (Li) ₂ O、LiO、Na ₂ S、Na ₂ Alkali metal chalcogenides such as Se, naO; an alkaline earth metal chalcogenide such as CaO, baO, srO, beO, baS, mgO, caSe; an alkali metal halide such as CsF, liF, naF, KF, liCl, KCl, naCl; alkali metal salts such as lithium 8-hydroxyquinoline (Liq); caF (CaF) ₂ 、BaF ₂ 、SrF ₂ 、MgF ₂ 、BeF ₂ And the like. Among them, alkali metal chalcogenides, alkaline earth metal halides and alkali metal salts are preferable. The electron injection material may be used alone or in combination of 1 or more than 2.

The thickness of the electron injection layer 7 is not particularly limited, but is preferably in the range of 0.1 to 100nm, more preferably in the range of 0.2 to 50nm, and even more preferably in the range of 0.5 to 10 nm. The electron injection layer 7 may be a single layer or a laminate structure in which 2 or more layers are laminated.

Such an electron injection layer 7 can be formed by a wet film forming method or a dry film forming method. When the electron injection layer 7 is formed by a wet film formation method, an ink containing the electron injection material is generally 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 discharge method), spin coating, casting, LB, relief printing, gravure printing, screen printing, nozzle printing, and the like. 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 to the light emitting layer 5. In addition, the electron transport layer 8 may also have a function of preventing hole transport. The electron transport layer 8 may be provided as needed, or 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-hydroxyquinoline) aluminum (Alq 3), tris (4-methyl-8-hydroxyquinoline) aluminum (Almq 3), bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (BeBq 2), bis (2-methyl-8-hydroxyquinoline) (p-phenylphenol) aluminum (BAlq), bis (8-hydroxyquinoline) zinc (Znq), and the like, and has a quinoline skeleton or a benzoquinoline skeleton; bis [2- (2' -hydroxyphenyl) benzoxazoles]Metal complexes having a benzoxazole skeleton such as zinc (Zn (BOX) 2); bis [2- (2' -hydroxyphenyl) benzothiazoles]Metal complexes having benzothiazole skeletons such as zinc (Zn (BTZ) 2); 2- (4-Biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (4-Biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl ]Benzene (OXD-7), 9- [4- (5-phenyl-1, 3, 4-oxadiazol-2-yl) phenyl]Tri-or diazole derivatives such as carbazole (CO 11); 2,2' - (1, 3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole) (TPBI), 2- [3- (dibenzothiophen-4-yl) phenyl]-imidazole derivatives such as 1-phenyl-1H-benzimidazole (mdtbim-II); quinoline derivatives; perylene derivatives; pyridine derivatives such as 4, 7-diphenyl-1, 10-phenanthroline (BPhen); pyrimidine derivatives; triazine derivatives; quinoxaline derivatives; diphenyl quinone derivatives; nitro-substituted fluorene derivatives; zinc oxide (ZnO), titanium oxide (TiO ₂ ) Metal oxides such as the like. Among them, the electron transport material is preferably an imidazole derivative, a pyridine derivative, a pyrimidine derivative, a triazine derivative, or a metal oxide (inorganic oxide). The electron transport material may be used alone or in combination of 1 or more than 2.

The thickness of the electron transport layer 7 is not particularly limited, but is preferably in the range of 5 to 500nm, and more preferably in the range of 5 to 200 nm. The electron transport layer 6 may be a single layer or may be laminated with 2 or more layers.

Such an electron transport layer 7 can be formed by a wet film forming method or a dry film forming method. When the electron transport layer 6 is formed by a wet film forming method, the ink containing the electron transport material is generally 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 discharge method), spin coating, casting, LB, relief printing, gravure printing, screen printing, nozzle printing, and the like. 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. Luminescent layer 5

The light-emitting layer 5 has a function of emitting light by energy generated by recombination of holes and electrons injected into the light-emitting layer 5. The light-emitting layer 5 of the present embodiment emits blue light having a wavelength in the range of 400 to 500nm, and 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 to the light-emitting material is not particularly limited, and is preferably 10:1 to 300: 1. The light-emitting material may use a compound capable of converting singlet excitation energy into light or a compound capable of converting triplet excitation energy into light. The light-emitting material preferably contains at least 1 selected from the group consisting of an organic low-molecular fluorescent material, an organic high-molecular fluorescent material, and an organic phosphorescent material.

As a compound capable of converting singlet excitation energy into light, there are listed: an organic low-molecular fluorescent material or an organic high-molecular fluorescent material which emits fluorescence.

The organic low-molecular fluorescent material is preferably a compound having an anthracene structure, an naphthacene structure, a 1, 2-benzophenanthrene 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.

Specific examples of the organic low-molecular 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 [ o ]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-carbazol-9-yl) -4' - (9, 10-diphenyl-2-anthryl) triphenylamine, N, 9-diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazol-3-amine, 4- (10-phenyl-9-anthryl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine, 4- [4- (10-phenyl-9-anthryl) phenyl]-4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine, perylene, 2,5,8, 11-tetra (t-butyl) perylene, N ' -diphenyl-N, N ' -bis [4- (9-phenyl-9H-fluoren-9-yl) phenyl ]]Pyrene-1, 6-diamine, N '-bis (3-methylphenyl) -N, N' -bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl ]]-pyrene-1, 6-diamine, N ' -bis (dibenzofuran-2-yl) -N, N ' -diphenylpyrene-1, 6-diamine, N ' -bis (dibenzothiophene-2-yl) -N, N ' -diphenylpyrene-1, 6-diamine, N ' - (2-tert-butylanthracene-9, 10-diylbis-4, 1-phenylene) bis [ N, N ', N ' -triphenylene-1, 4-phenylene diamine ]N, 9-diphenyl-N- [4- (9, 10-diphenyl-2-anthracenyl) phenyl group]-9H-carbazol-3-amine, N- [4- (9, 10-diphenyl-2-anthracenyl) phenyl ]]-N, N ', N ' -triphenyl-1, 4-phenylene diamine, N, N, N ', N ', N ", N", N ' "-octaphenyl dibenzo [ g, p ]]

-2,7,10,15-tetramine, 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-phenylenediamine, 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 ]]Vinyl } -6-methyl-4H-pyran-4-ylidene) malononitrile, 2- { 2-methyl-6- [2- (2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, N, N, N ', N' -tetrakis (4-methylphenyl) naphthacene-5, 11-diamine, 7, 14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) acenaphthene [1,2-a]-1, 2-Benzonaphthene-3, 10-diamine, 2- { 2-isopropyl-6- [2- (1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 2- { 2-tert-butyl-6- [2- (1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ] ]Quinolin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 2- (2, 6-bis {2- [4- (dimethylamino) phenyl)]Vinyl } -4H-pyran-4-ylidene) malononitrile, 2- {2, 6-bis [2- (8-methoxy-1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 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: homopolymers consisting of units based on fluorene derivatives; copolymers composed of units based on fluorene derivatives and units based on tetraphenylphenylenediamine derivatives; homopolymers consisting of units based on a biphenyl derivative; homopolymers made up of units based on diphenylbenzofluorene derivatives, and the like.

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: a metal complex comprising at least 1 metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, palladium, silver, gold, and aluminum. Among them, the organic phosphorescent material is preferably a metal complex containing at least 1 metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, and palladium, more preferably a metal complex containing at least 1 metal atom selected from the group consisting of iridium, rhodium, platinum, and ruthenium, and still more preferably an iridium complex or a platinum complex.

As the host material, at least 1 kind of compound having an energy gap larger than that of the light-emitting material is preferably used. Further, in the case where the light-emitting material is a phosphorescent material, a compound having a triplet excitation energy larger than the triplet excitation energy (energy difference between the ground state and the triplet excitation state) of the light-emitting material is preferably selected as the host material.

Examples of the host material include: tris (8-hydroxyquinoline) aluminum (III), tris (4-methyl-8-hydroxyquinoline) aluminum (III), bis (10-hydroxybenzo [ h ]]Quinolinyl) beryllium (II), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III), bis (8-hydroxyquinoline) zinc (II), bis [2- (2-benzoxazolyl) phenol]Zinc (II), bis [2- (2-benzothiazolyl)) Phenol (P)]Zinc (II), 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole, 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl]Benzene, 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-triazole, 2' - (1, 3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole), bathophenanthroline, bathocuproine, 9- [4- (5-phenyl-1, 3, 4-oxadiazol-2-yl) phenyl]-9H-carbazole, 9, 10-diphenylanthracene, N-diphenyl-9- [4- (10-phenyl-9-anthracenyl) phenyl]-9H-carbazol-3-amine, 4- (10-phenyl-9-anthryl) triphenylamine, N, 9-diphenyl-N- {4- [4- (10-phenyl-9-anthryl) phenyl ] ]Phenyl } -9H-carbazol-3-amine, 6, 12-dimethoxy-5, 11-diphenyl

9- [4- (10-phenyl-9-anthracenyl) phenyl group]-9H-carbazole, 3, 6-diphenyl-9- [4- (10-phenyl-9-anthracenyl) phenyl ]]-9H-carbazole, 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl ]]-9H-carbazole, 7- [4- (10-phenyl-9-anthracenyl) phenyl ]]-7H-dibenzo [ c, g]Carbazole, 6- [3- (9, 10-diphenyl-2-anthryl) phenyl group]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-bis (2-naphthyl) anthracene, 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene, 9' -bianthracene, 9'- (stilbene-3, 3' -diyl) diphenanthrene, 9'- (stilbene-4, 4' -diyl) diphenanthrene, 1,3, 5-tris (1-pyrenyl) benzene, 5, 12-diphenyl tetracene, or 5, 12-bis (biphenyl-2-yl) tetracene, and the like. These host materials may be used alone or in combination of 1 or more than 2.

The thickness of the light-emitting layer 5 is not particularly limited, but is preferably in the range of 1 to 100nm, 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. When the light-emitting layer 5 is formed by a wet film formation method, the ink containing the light-emitting material and the host material is generally applied by various application methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case of forming the light-emitting layer 5 by a dry film forming method, a vacuum vapor deposition method, a sputtering method, or the like may be applied.

The EL light source unit 200 may further include, for example, banks (partition walls) that divide the hole injection layer 3, the hole transport layer 4, and the light emitting layer 5. The height of the bank is not particularly limited, but is preferably in the range of 0.1 to 5. Mu.m, more preferably in the range of 0.2 to 4. Mu.m, and still more preferably in the range of 0.2 to 3. Mu.m.

The opening width of the bank is preferably in the range of 10 to 200. Mu.m, more preferably in the range of 30 to 200. Mu.m, and even more preferably in the range of 50 to 100. Mu.m. The opening length of the bank is preferably in the range of 10 to 400. Mu.m, more preferably in the range of 20 to 200. Mu.m, and even more preferably in the range of 50 to 200. Mu.m. 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 even more preferably in the range of 10 to 80 °.

2-3 light conversion layer 12

The light conversion layer 12 converts light emitted from the EL light source unit 200 to re-emit light or transmits light emitted from the EL light source unit 200. As shown in fig. 3, the pixel unit 20 includes: a 1 st pixel unit 20a that converts light having a wavelength in the above range to emit red light; a 2 nd pixel unit 20b that converts light having the wavelength in the above range to emit green light; and a 3 rd pixel portion 20c that transmits light having a wavelength in the above range. The 1 st pixel portion 20a, the 2 nd pixel portion 20b, and the 3 rd pixel portion 20c are sequentially and repeatedly arranged in a lattice shape. A light shielding portion 30 for shielding light is provided between the adjacent pixel portions, that is, between the 1 st pixel portion 20a and the 2 nd pixel portion 20b, between the 2 nd pixel portion 20b and the 3 rd pixel portion 20c, and between the 3 rd pixel portion 20c and the 1 st pixel portion 20 a. In other words, these adjacent pixel portions are separated from each other by the light shielding portion 30. The 1 st pixel portion 20a and the 2 nd pixel portion 20b may contain coloring materials corresponding to the respective colors.

The 1 st pixel portion 20a and the 2 nd pixel portion 20b each contain a cured product of the composition containing nanocrystals according to the above embodiment. The cured product preferably contains luminescent particles 90 and a curing component as essential components, and further contains light scattering particles to scatter light and extract it to the outside with certainty. 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 1 st pixel section 20a includes: the 1 st curing component 22a, and the 1 st light-emitting particles 90a and the 1 st light-scattering particles 21a dispersed in the 1 st curing component 22a, respectively. Similarly, the 2 nd pixel portion 20b includes: the 2 nd curing component 22b, and the 1 st light-emitting particles 90b and the 1 st light-scattering particles 21b dispersed in the 2 nd curing component 22b, respectively. In the 1 st pixel portion 20a and the 2 nd pixel portion 20b, the 1 st curing component 22a and the 2 nd curing component 22b may be the same or different, and the 1 st light scattering particle 22a and the 2 nd light scattering particle 22b may be the same or different.

The 1 st light-emitting particle 90a is a red light-emitting particle that absorbs light having a wavelength in the range of 420 to 480nm and emits light having a light emission peak wavelength in the range of 605 to 665 nm. That is, the 1 st pixel portion 20a may be modified as a red pixel portion for converting blue light into red light. The 2 nd luminescent particles 90b are green luminescent particles that absorb light having a wavelength in the range of 420 to 480nm and emit light having a luminescent peak wavelength in the range of 500 to 560 nm. That is, the 2 nd pixel portion 20b may be modified as a green pixel portion for converting blue light into green light.

The content of the luminescent particles 90 in the

pixel portions

20a and 20b including the cured product of the composition containing nanocrystals is preferably 1 mass% or more based on the total mass of the cured product of the composition containing nanocrystals, from the viewpoint of further improving the external quantum efficiency and obtaining excellent luminous intensity. From the same viewpoint, the content of the luminescent particles 90 may be 5 mass% or more, 10 mass% or more, or 15 mass% or more based on the total mass of the cured product of the nanocrystalline-containing composition. The content of the luminescent particles 90 is preferably 40 mass% or less based on the total mass of the composition containing nanocrystals, from the viewpoint of excellent reliability of the

pixel portions

20a, 20b and excellent light emission intensity. From the same viewpoint, the content of the luminescent particles 90 may be 30 mass% or less, 25 mass% or less, or 20 mass% or more based on the total mass of the cured product of the nanocrystalline-containing composition.

The content of the

light scattering particles

21a, 21b in the

pixel portions

20a, 20b containing the cured product of the composition containing nanocrystals may be 0.1 mass% or more, may be 1 mass% or more, may be 5 mass% or more, may be 7 mass% or more, may be 10 mass% or more, or may be 12 mass% or more, based on the total mass of the cured product of the composition containing nanocrystals, from the viewpoint of further excellent effect of improving external quantum efficiency. The content of the

light scattering particles

21a, 21b may be 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 25 mass% or less, or 20 mass% or less, or 15 mass% or less based on the total mass of the cured product of the nanocrystal-containing composition, from the viewpoint of further excellent effect of improving external quantum efficiency and excellent reliability of the pixel portion 20.

The 3 rd pixel portion 20c has a transmittance of 30% or more with respect to light having a wavelength in the range of 420 to 480 nm. Therefore, when a light source that emits light having a wavelength in the range of 420 to 480nm is used, the 3 rd pixel portion 20c functions as a blue pixel portion. The 3 rd pixel portion 20c includes, for example, a cured product of a composition containing the thermosetting resin. The cured product contains the 3 rd curing component 22c. The 3 rd 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 3 rd pixel portion 20c includes the 3 rd curing component 22c. When the 3 rd pixel portion 20c contains the cured product, the thermosetting resin-containing composition may further contain components other than the thermosetting resin, the curing agent, and the solvent among the components contained in the luminescent particle-containing ink composition, as long as the transmittance of light having a wavelength in the range of 420 to 480nm is 30% or more. The transmittance of the 3 rd pixel portion 20c can be measured by a microscopic spectroscopic device.

The thickness of the pixel portion (1 st pixel portion 20a, 2

nd pixel portion

20b, and 3 rd pixel portion 20 c) is not particularly limited, and may be, for example, 1 μm or more, or may be 2 μm or more, or may be 3 μm or more. The thickness of the pixel portion (1 st pixel portion 20a, 2

nd pixel portion

20b, and 3 rd pixel portion 20 c) may be, for example, 30 μm or less, 25 μm or less, or 20 μm or less.

The light conversion layer 12 including the 1 st to 3 rd pixel portions 20a to 20c described above can be formed by drying and heating a coating film formed by a wet film forming method, and curing the coating film. The 1 st pixel portion 20a and the 2 nd pixel portion 20b can be formed using the composition containing nanocrystals of the present invention. On the other hand, the 3 rd pixel portion 20c may be formed using a resin composition that does not contain the luminescent particles 90 included in the nanocrystal composition.

Hereinafter, a method of forming a coating film as the light conversion layer 12 using the ink composition containing the nanocrystalline 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 (piezo-electric or thermal droplet discharge), spin coating, casting, LB, relief, gravure, screen, nozzle, etc. Here, the nozzle printing method is a method of applying an ink composition in a stripe form from a nozzle hole in the form of a liquid column. Among them, the coating method is preferably an inkjet printing method (particularly a piezoelectric droplet discharge method). This reduces the heat load at the time of ejecting the ink composition, and prevents the luminescent particles 90 from being degraded by 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.

The opening diameter of the nozzle hole is preferably in the range of 5 to 50. Mu.m, more preferably in the range of 10 to 30. Mu.m. Thus, clogging of the nozzle holes can be prevented, and the ejection accuracy of the ink composition can be improved.

The temperature at the time of forming the coating film is not particularly limited, but is preferably in the range of 10 to 50 ℃, more preferably in the range of 15 to 40 ℃, and even more preferably in the range of 15 to 30 ℃. If the droplets are ejected at the above temperature, crystallization of various components contained in the ink composition can be suppressed.

The relative humidity at the time of forming the coating film is not particularly limited, and is preferably in the range of 0.01ppm to 80%, more preferably in the range of 0.05ppm to 60%, even more preferably in the range of 0.1ppm to 15%, particularly preferably in the range of 1ppm to 1%, and most preferably in the range of 5ppm to 100%. If the relative humidity is not less than the lower limit, the control of the conditions at the time of forming the coating film becomes easy. On the other hand, if the relative humidity is equal to or less than the upper limit value, the amount of moisture adsorbed to the coating film, which may adversely affect the obtained light-converting layer 12, can be reduced.

The drying of the obtained coating film may be carried out at room temperature (25 ℃) or by heating, and is preferably carried out by heating from the viewpoint of productivity. In the case of drying by heating, the drying temperature is not particularly limited, and is preferably set to a temperature in consideration of the boiling point and vapor pressure of the organic solvent used in the ink composition. The drying temperature is preferably 50 to 130 ℃, more preferably 60 to 120 ℃, and particularly preferably 70 to 110 ℃ as the pre-baking step for removing the organic solvent in the coating film. If the drying temperature is 50 ℃ or lower, the organic solvent cannot be removed, whereas if it is 130 ℃ or higher, the removal of the organic solvent and the curing of the coating film occur simultaneously, so that the appearance of the cured coating film is markedly deteriorated, which is not preferable. The drying is preferably performed under reduced pressure, more preferably under reduced pressure of 0.001 to 100 Pa. Further, 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 can be surely 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 pre-baking step of the coating film. The heating temperature for complete curing is preferably 150 to 260 ℃, more preferably 160 to 230 ℃, particularly preferably 170 to 210 ℃.

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, the heating for complete curing may be performed in air or in an inert gas, but in order to suppress oxidation of the coating film, it is more preferable to perform in an inert gas. As the inert gas, there may be mentioned: nitrogen, argon, carbon dioxide, and the like. By curing the coating film under such heating conditions, the coating film can be completely cured, and thus the external quantum efficiency of the obtained light conversion layer 9 can be further improved.

The ink composition of the present invention may be cured by irradiation with active rays (for example, ultraviolet rays) in addition to curing by heating. As the irradiation source (light source), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like is used.

The wavelength of the irradiated light is preferably 200nm or more, more preferably 440nm or less. The irradiation amount (exposure amount) of light is preferably 10mJ/cm ² Above, more preferably 4000mJ/cm ² The following is given.

As described above, the composition containing nanocrystals of the present invention is excellent in stability against heat, and therefore good light emission can be achieved even in the pixel portion 20, which is a molded body after heat curing. Further, the light-emitting fine particle composition of the present invention is excellent in dispersibility, so that the light-emitting

fine particles

910 and 90 are excellent in dispersibility, and a flat pixel portion 20 can be obtained.

Further, since the light-emitting fine particles 90 included in the 1 st pixel portion 20a and the 2 nd pixel portion 20b contain semiconductor nanocrystals including metal halides, absorption in a wavelength region of 300 to 500nm is large. Therefore, in the 1 st pixel portion 20a and the 2 nd pixel portion 20b, blue light incident on the 1 st pixel portion 20a and the 2 nd pixel portion 20b can be prevented from penetrating toward the upper substrate 13 side, that is, blue light leaks toward the upper substrate 13 side. Therefore, according to the 1 st pixel portion 20a and the 2 nd 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 shielding portion 30 is a so-called black matrix that is provided to separate adjacent pixel portions 20 to prevent color mixing and light leakage from the light source. The material constituting the light shielding portion 30 is not particularly limited, and a cured product of a resin composition containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a binder polymer may be used in addition to metals such as chromium. As the binder polymer used herein, 1 or 2 or more kinds of resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, etc., a photosensitive resin, an O/W emulsion type resin composition (for example, a reactive silicone emulsion type) and the like can be used. The thickness of the light shielding portion 30 may be, for example, 1 μm or more and 15 μm or less.

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

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

The nanocrystalline-containing composition, the ink composition, the method for producing the same, and the light-emitting element including the light-converting layer produced using the ink composition of the present invention have been described above, but the present invention is not limited to the configuration of the above embodiment. For example, the luminescent particles, luminescent particle dispersion, nanocrystalline-containing composition, ink composition, and light-emitting element according to the present invention may have any other structure in addition to the structures of the above embodiments, or may be replaced with any structure that exhibits the same function. The method for producing luminescent particles according to the present invention may have any other steps for the above-described embodiment, and may be replaced with any steps that exert the same effects.

Examples

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. All materials used in the examples were obtained by introducing argon gas and replacing dissolved oxygen with argon gas. Titanium oxide was heated at 120℃for 2 hours under reduced pressure of 1mmHg before mixing, and left to cool under an argon atmosphere. The liquid material used in the examples was dehydrated by the molecular sieve 3A for 48 hours or more before mixing.

< preparation of luminescent particles >

(preparation of luminescent particle A)

Cesium carbonate (0.815 g), 1-octadecene (40 ml), and oleic acid (2.5 ml) were added to a three-necked flask, and dried at 120℃for 1 hour under vacuum, and then heated to 150℃to prepare cesium oleate.

To the other 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℃for 30 minutes under vacuum, the temperature was raised to 180℃under an argon gas flow. Further, the cesium oleate solution (0.8 ml) heated at 150℃was added by syringe, reacted for 15 seconds, and then quenched by ice bath.

The obtained reaction solution was subjected to centrifugal separation (8000 G.times.5 minutes), and a solid was recovered. Toluene (20 ml) was added to the obtained solid to obtain a suspension. The suspension was subjected to centrifugal separation (8000 g×5 minutes), and the precipitate containing impurities was removed by decantation, and a toluene solution of the supernatant was recovered. Ethyl acetate (20 ml) was added to the recovered toluene solution to reprecipitate the solid matter, thereby obtaining luminescent particles A. The obtained luminescent particle a has a ligand composed of oleylamine and oleic acid on the surface of lead cesium tribromide crystal having a perovskite crystal structure and exhibiting luminescence, and corresponds to the above-mentioned non-coated luminescent particle 910. The average particle diameter of the luminescent particles A was 10nm. The average particle diameter of the luminescent particles A was measured by Nanotrac waveII (Microtrac Co., ltd.) and found to be an average of 10nm.

(preparation of luminescent particle B)

A toluene solution (0.05M) of N-1 (1-adamantyl) ethylenediamine (manufactured by Tokyo chemical Co., ltd.) was prepared. To an eggplant type flask, the luminescent fine particles A, oleic acid (50 ml) and the N-1 (1-adamantyl) ethylenediamine solution (2 ml) were added and stirred for 1 minute. At this time, the luminescent particles A were added so that the concentration became 15 mg/mL. After ethyl acetate (100 ml) was added to the obtained solution, centrifugal separation (8000 g×5 minutes) was performed, whereby luminescent particles B were obtained. The luminescent particles B have a ligand composed of N-1 (1-adamantyl) ethylenediamine on the surface of lead cesium tribromide crystals having a perovskite crystal structure and exhibiting luminescence, and correspond to the non-coated luminescent particles 910. The average particle diameter of the luminescent particles B was 10nm.

(preparation of luminescent particle C)

Cesium carbonate (0.81 g), 1-octadecene (40 ml), and oleic acid (2.5 ml) were mixed to obtain a mixed solution. Subsequently, the mixture was dried under reduced pressure at 120℃for 10 minutes, and then heated at 150℃under an argon atmosphere. Thus, cesium-oleic acid solution was obtained.

On the other hand, lead (II) bromide (138.0 mg) was mixed with 1-octadecene (10 mL) to obtain a mixed solution. Subsequently, the mixture was dried at 120 ℃ under reduced pressure for 10 minutes, and then 3-aminopropyl triethoxysilane (1 ml) was added to the mixture under an argon atmosphere, thereby obtaining a mixture (1).

Then, after the temperature of the mixed solution (1) was raised to 140 ℃, the cesium-oleic acid solution (1.3 ml) was added thereto, and the mixture was heated and stirred for 5 seconds to perform a reaction, and then cooled by an ice bath.

Subsequently, the obtained reaction solution was stirred under atmospheric conditions (23 ℃ C., 45% humidity) for 60 minutes, and then ethanol (20 ml) was added thereto to obtain a suspension. The obtained suspension was subjected to centrifugal separation (3,000 rpm, 5 minutes) to recover a solid.

The recovered solid was added to 16ml of hexane, thereby obtaining a hexane dispersion of luminescent particles C. The luminescent particle C has a ligand composed of oleic acid and a ligand composed of 3-aminopropyl triethoxysilane having a reactive group on the surface of a lead cesium tribromide crystal having a perovskite crystal structure and exhibiting luminescence, and the reactive group reacts to form a silica coating layer corresponding to the inorganic coating layer 91 containing Si in fig. 2, and corresponds to the inorganic coated luminescent particle 90. The average particle diameter of the luminescent particles C was 10nm, and the thickness of the inorganic coating layer was 1nm.

< preparation of monomer solution >

(monomer solution 1)

1,2, 6-pentamethyl-4-piperidyl methacrylate (8.85 parts by mass, manufactured by tokyo chemical Co., ltd.) as a photopolymerizable monomer was mixed with Light acrylate DCP-A (0.5 parts by mass, manufactured by co-Rong chemical Co., ltd.) and stirred at room temperature to be uniformly dissolved, thereby obtaining a monomer solution 1.

(monomer solution 2)

Monomer solution 2 was obtained in the same manner as in the preparation method of monomer solution 1 except that isobornyl methacrylate (manufactured by tokyo chemical industry co., ltd.) was used instead of 1,2, 6-pentamethyl-4-piperidyl methacrylate as the photopolymerizable monomer.

(monomer solution 3)

Monomer solution 3 was obtained in the same manner as in the preparation method of monomer solution 1, except that dicyclopentanyl methacrylate (manufactured by tokyo chemical industry co., ltd.) was used instead of 1,2, 6-pentamethyl-4-piperidine methacrylate as the photopolymerizable monomer.

(monomer solution 4)

Monomer solution 4 was obtained in the same manner as in the preparation method of monomer solution 1, except that 1-adamantyl methacrylate (manufactured by tokyo chemical industry Co., ltd.) was used instead of 1,2, 6-pentamethyl-4-piperidyl methacrylate as the photopolymerizable monomer.

(monomer solution 5)

A monomer solution 5 was obtained in the same manner as in the preparation method of the monomer solution 1, except that 2-methyl-2-adamantyl methacrylate (manufactured by tokyo chemical industry co., ltd.) was used instead of 1,2, 6-pentamethyl-4-piperidyl methacrylate as the photopolymerizable monomer in the preparation method of the monomer solution 1.

(monomer solution 6)

In the production method of the monomer solution 1, a monomer solution 6 was obtained in the same manner as in the production method of the monomer solution 1 except that isobornyl methacrylate (4.85 parts by mass, manufactured by tokyo chemical industry co., ltd.) and 1-adamantyl methacrylate (4.00 parts by mass, manufactured by tokyo chemical industry co., ltd.) were used instead of 1,2, 6-pentamethyl-4-piperidine methacrylate as the photopolymerizable monomer.

(monomer solution 7)

In the production method of the monomer solution 1, a monomer solution 7 was obtained in the same manner as in the production method of the monomer solution 1 except that Light ester L (0.30 parts by mass, manufactured by co-polymer chemical Co., ltd.) and 1-adamantyl methacrylate (8.55 parts by mass, manufactured by tokyo chemical industry Co., ltd.) were used instead of 1,2, 6-pentamethyl-4-piperidine methacrylate as the photopolymerizable monomer.

(monomer solution 8)

In the production method of the monomer solution 1, a monomer solution 8 was obtained in the same manner as in the production method of the monomer solution 1 except that Light ester L (3.00 parts by mass, manufactured by co-Rong chemical Co., ltd.) and 1-adamantyl methacrylate (5.85 parts by mass, manufactured by tokyo chemical industry Co., ltd.) were used instead of 1,2, 6-pentamethyl-4-piperidine methacrylate as the photopolymerizable monomer.

(monomer solution 9)

The production method of the monomer solution 1 was performed in the same manner as the production method of the monomer solution 1 except that Light ester L (8.85 parts by mass, manufactured by co-polymer chemical company) was used instead of methacrylic acid-1, 2, 6-pentamethyl-4-piperidine ester as a photopolymerizable monomer, to obtain a monomer solution 9.

(monomer solution 10)

In the production method of the monomer solution 1, a monomer solution 10 was obtained in the same manner as in the production method of the monomer solution 1 except that isobornyl methacrylate (8.85 parts by mass, manufactured by tokyo chemical industry co., ltd.) was used instead of 1,2, 6-pentamethyl-4-piperidyl methacrylate as a photopolymerizable monomer, and TMPTA (0.5 parts by mass, manufactured by osaka organic chemical industry co., ltd.) was used instead of Light acrylate DCP-a.

(monomer solution 11)

In the production method of the monomer solution 1, a monomer solution 11 was obtained in the same manner as in the production method of the monomer solution 1 except that Light ester L (8.85 parts by mass, manufactured by co-polymer chemical Co., ltd.) was used instead of methacrylic acid-1, 2, 6-pentamethyl-4-piperidine ester as a photopolymerizable monomer, and TMPTA (0.5 parts by mass, manufactured by osaka organic chemical industry Co., ltd.) was used instead of Light acrylate DCP-a.

(monomer solution 12)

The production method of the monomer solution 1 was carried out in the same manner as in the production method of the monomer solution 1 except that Light ester PO-A (8.85 parts by mass, manufactured by KyowA Kagaku Co., ltd.) was used instead of methacrylic acid-1, 2, 6-pentamethyl-4-piperidine ester as A photopolymerizable monomer, to obtain A monomer solution 12.

Preparation of the QD Dispersion

Example 1

Luminescent particles a (0.015 parts by mass) were mixed in monomer solution 1 (0.935 parts by mass) and stirred at room temperature to be uniformly dispersed. The obtained dispersion was filtered using a filter having a pore size of 5 μm, thereby obtaining QD dispersion 1 as a composition containing nanocrystals.

Examples 2 to 8, 10 and 40

QD dispersions 2 to 8, QD dispersion 10, and QD dispersion 13 were obtained in the same manner except that monomer solutions 2 to 8, monomer solution 10, and monomer solution 12 were used in place of monomer solution 1 in the method for producing QD dispersion 1, respectively.

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 particles B were used instead of luminescent particles a.

Example 11

QD dispersion 11 was obtained in the same manner as in the preparation method of QD dispersion 1 except that monomer solution 11 was used instead of monomer solution 1 and luminescent particles B were used instead of luminescent 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 particle C was used instead of luminescent particle 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 following table shows the content of monomer solutions 1 to 11 and luminescent particles a to C in QD dispersions 1 to 12 of examples 1 to 12 and QD dispersion C1 of comparative example 1. The numerical value is given in parts by mass.

TABLE 1

	Example 1	Example 2	Example 3	Example 4
					QD dispersions	1	2	3	4
Monomer solution 1	0.935
					Monomer solution 2		0.935
Monomer solution 3			0.935
					Monomer solution 4				0.935
Luminescent particles A	0.015	0.015	0.015	0.015

TABLE 2

	Example 5	Example 6	Example 7	Example 8
					QD dispersions	5	6	7	8
Monomer solution 5	0.935
					Monomer solution 6		0.935
Monomer solution 7			0.935
					Monomer solution 8				0.935
Luminescent particles A	0.015	0.015	0.015	0.015

TABLE 3

	Example 9	Example 10	Example 11	Example 12	Example 40	Comparative example 1
							QD dispersions	9	10	11	12	13	C1
Monomer solution
	4				0.935
Monomer solution 9								0.935					0.935
	Monomer solution 10		0.935
Monomer solution 11										0.935
	Monomer solution 12					0.935
Luminescent particles A									0.015			0.015	0.015
	Luminescent particles B	0.015		0.015
Luminescent particles C											0.015

Preparation of monomer solution containing initiator

(monomer solution B1)

In the method for producing the monomer solution 1, a monomer solution B1 containing a photopolymerization initiator was obtained in the same way except that 2 photopolymerization initiators were added in addition to the photopolymerizable monomers described above, and the mixture was stirred at 60 ℃ instead of room temperature. As 2 photopolymerization initiators, 0.3 parts by mass of "Omnirad TPO" manufactured by IGM Resin Co., ltd., and 0.2 parts by mass of "Omnirad 819" manufactured by IGM Resin Co., ltd were added.

(monomer solution B2-monomer solutions B11 and 13)

The same procedure was repeated except that the monomer solutions 2 to 11 were used instead of the monomer solution 1 in the preparation method of the monomer solution B1, to obtain the monomer solutions B2 to B11 and B13 containing the photopolymerization initiator.

(monomer solution B12)

In the production method of the monomer solution B1, a monomer solution B12 containing a photopolymerization initiator was obtained in the same way except that the monomer solution 2 was used instead of the monomer solution 1 and only 1 type of photopolymerization initiator was added instead of 2 types of photopolymerization initiator. As 1 kind of photopolymerization initiator, 0.5 parts by mass of "Omnirad TPO" manufactured by IGM Resin Co., ltd was added.

The contents of the monomer solutions B1 to B12 are shown in the following tables. The numerical values in the table are given in parts by mass.

TABLE 4

Monomer solution B	1	2	3	4
					Monomer solution 1	9.35
Monomer solution 2		9.35
					Monomer solution 3			9.35
Monomer solution 4				9.35
					Omnirad 819	0.2	0.2	0.2	0.2
TPO	0.3	0.3	0.3	0.3

TABLE 5

Monomer solution B	5	6	7	8
					Monomer solution 5	9.35
Monomer solution 6		9.35
					Monomer solution 7			9.35
Monomer solution 8				9.35
					Omnirad 819	0.2	0.2	0.2	0.2
TPO	0.3	0.3	0.3	0.3

TABLE 6

Monomer solution B	9	10	11	12	13
						Monomer solution 2				9.35
Monomer solution 9	9.35
						Monomer solution 10		9.35
Monomer solution 11			9.35
						Monomer solution 12					9.35
Omnirad 819	0.2	0.2	0.2		0.2
						TPO	0.3	0.3	0.3	0.5	0.3

Preparation of & lt & gtQD Dispersion B & gt

(QD Dispersion B1)

Luminescent particles a (0.015 parts by mass) were mixed in a monomer solution B1 (0.985 parts by mass) containing a photopolymerization initiator and stirred at room temperature to uniformly disperse them, thereby obtaining QD dispersion B1.

(QD Dispersion B2-QD Dispersion B8)

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

(QD Dispersion B9)

In the method for producing QD dispersion B1, QD dispersion B9 was obtained in the same manner except that monomer solution B9 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator, and luminescent particles B were used instead of luminescent particles a.

(QD Dispersion B10)

QD dispersion B10 was obtained in the same manner as in the preparation method of QD dispersion B1 except that monomer solution B10 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator.

(QD Dispersion B11)

In the method for producing QD dispersion B1, QD dispersion B11 was obtained in the same manner except that monomer solution B11 containing a photopolymerization initiator was used instead of monomer solution B1 containing a photopolymerization initiator, and luminescent particles B were used instead of luminescent particles a.

(QD Dispersion B12)

In the method for producing QD dispersion B1, QD dispersion B12 was obtained in the same manner except that the monomer solution B4 containing a photopolymerization initiator was used instead of the monomer solution B1 containing a photopolymerization initiator, and luminescent particles C were used instead of luminescent particles a.

(QD Dispersion B13)

QD dispersion B13 was obtained in the same manner as in the preparation method of QD dispersion B1 except that the monomer solution B12 containing a photopolymerization initiator was used instead of the 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 the monomer solution B13 containing a photopolymerization initiator was used instead of the monomer solution B1 containing a photopolymerization initiator.

(QD Dispersion BCl)

QD dispersion BC1 was obtained in the same manner as in the preparation method of QD dispersion B9 except that luminescent particles a were used instead of luminescent particles B.

The following table shows the content of QD dispersions B1 to B14 and QD dispersion BC1. The units in the table are parts by mass.

TABLE 7

QD dispersion B	1	2	3	4	5
						Monomer solution B1	0.985
Monomer solution B2		0.985
						Monomer solution B3		0.985
Monomer solution B4				0.985
						Monomer solution B5			0.985
Luminescent particles A	0.015	0.015	0.015	0.015	0.015

TABLE 8

QD dispersion B	6	7	8	9	10
						Monomer solution B6	0.985
Monomer solution B7		0.985
						Monomer solution B8		0.985
Monomer solution B9				0.985
						Monomer solution B10				0.985
Luminescent particles A	0.015	0.015	0.015		0.015
						Luminescent particles B			0.015

TABLE 9

QD dispersion B	11	12	13	14	Cl
						Monomer solution B4		0.985
Monomer solution B9					0.985
						Monomer solution B11	0.985
Monomer solution B12			0.985
						Monomer solution B13			0.985
Luminescent particles A			0.015	0.015	0.015
						Luminescent particles B	0.015
Luminescent particles C		0.015

Preparation of light-scattering particle Dispersion

(light-scattering particle Dispersion 1)

Titanium oxide particles (55 parts by mass, manufactured by Shimadzu corporation, "CR-60-2") were mixed with dicyclopentanyl methacrylate (45 parts by mass, manufactured by tokyo chemical industry Co., ltd.) as a photopolymerizable monomer. The average particle diameter (volume average diameter) of the titanium oxide particles was 300nm. Next, zirconia beads (diameter: 0.3 mm) were added to the obtained complex, and the dispersion treatment of the complex was performed by shaking for 2 hours using a paint conditioner. Thus, a light scattering particle dispersion 1 was obtained.

(light-scattering particle Dispersion 2)

Light-scattering particle dispersion 2 was obtained in the same manner as in the method for producing Light-scattering particle dispersion 1 except that Light ester L (co-polymer chemical company) was used instead of dicyclopentanyl methacrylate in the method for producing Light-scattering particle dispersion 1.

< preparation of QD ink >)

Example 13

Light scattering particle dispersion 1 (6 parts by mass) was mixed in QD dispersion B1 (94 parts by mass) and stirred at room temperature to uniformly disperse it. The obtained dispersion was filtered with a filter having a pore size of 5 μm, thereby obtaining a composition containing nanocrystals and QD ink 1 as an ink composition.

Examples 14 to 24 and 41

QD inks 2 to 12 and QD ink 14 were obtained in the same manner as in the method for producing QD ink 1 except that QD dispersions B2 to 12 and QD dispersion B14 were used instead of QD dispersion B1 in the method for producing QD ink 1 of example 13.

Example 25

QD ink 13 was obtained in the same manner as in the method for producing QD ink 1 in example 13, except that QD dispersion B13 was used instead of QD dispersion B1 and light scattering dispersion 2 was used instead of light scattering dispersion 1.

Comparative example 2

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 preparation method of QD ink 1 of example 13.

The following table shows the content 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. The numerical values in the table are given in parts by mass.

TABLE 10

	Example 13	Example 14	Example 15	Example 16	Example 17
						QD ink	1	2	3	4	5
QD dispersion B1	94
						QD dispersion B2		94
QD dispersion B3			94
						QD dispersion B4				94
QD dispersion B5					94
						Light-scattering particle dispersion 1	6	6	6	6	6

TABLE 11

	Example 18	Example 19	Example 20	Example 21	Example 22
						QD ink	6	7	8	9	10
QD dispersion B6	94
						QD dispersion B7		94
QD dispersion B8			94
						QD dispersion B9				94
QD dispersion B10					94
						Light-scattering particle dispersion 1	6	6	6	6	6

TABLE 12

	Example 23	Example 24	Example 25	Example 41	Comparative example 2
						QD ink	11	12	13	14	C1
QD dispersion B11	94
						QD dispersion B12		94
QD dispersion B13			94
						QD dispersion B14				94
QD Dispersion CB1					94
						Light-scattering particle dispersion 1	6	6		6	6
Light-scattering particle Dispersion 2			6

< fabrication of light conversion layer >)

Example 26

The QD ink 1 of example 13 thus obtained was applied onto a glass substrate (manufactured by corning corporation, "eaglxg") using a spin coater so that the film thickness after drying became 10 μm.

The obtained coating film was irradiated with 2000mJ/cm under a nitrogen atmosphere ² LED lamp of exposure of (a)Ultraviolet light with a wavelength of 365 nm. Thus, QD ink 1 of example 13 was cured, and a layer composed of the cured product of the ink composition was formed on a glass substrate, which was used as light conversion layer 1 of example 26.

Examples 27 to 38 and 42

The same procedure was repeated except that QD ink 2 to QD ink 13 in example 14 and QD ink 13 in example 25 and QD ink 14 in example 41 were used in place of QD ink 1 in example 13 in the production method of light conversion layer 1 in example 26, to produce light conversion layers 2 to 13 in example 38 and light conversion layer 14 in example 42 in example 27.

Comparative example 3

The light conversion layer C1 of comparative example 3 was produced in the same manner as in the production method of the light conversion layer 1 of example 26 except that the QD ink C1 of comparative example 2 was used instead of the QD ink 1 of example 13.

< evaluation >

[ Quantum yield (PLQY) retention ]

The quantum yields (PLQY) of QD dispersions 1 to 12 of example 1, QD dispersion 13 of example 40, and QD dispersion C1 of comparative example 1 were measured by an absolute PL quantum yield measuring device (manufactured by Bithomson photon Co., ltd. "Quanturus-QY"), and the quantum yield retention (a value obtained by dividing the quantum yield after 10 days of standing under the atmosphere after the preparation by the quantum yield immediately after the preparation) was calculated. The higher the quantum yield retention means the higher the stability of the luminescent particles to oxygen and water vapor.

[ dispersion stability ]

After 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 under the atmosphere, the presence or absence of precipitate was confirmed and evaluated according to the following criteria.

[ evaluation criterion ]

A: after 10 days, no precipitate was produced.

B: after 10 days, very little precipitate was produced. The precipitate is dissolved by shaking.

C: after 10 days, slightly more precipitate was generated. The precipitate remained even with shaking.

[ external Quantum efficiency retention of light conversion layer ]

External quantum efficiency 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 in the following manner, and the external quantum efficiency retention rate of the light conversion layer was calculated (a value obtained by dividing the external quantum efficiency after 10 days of formation of the light conversion layer by the external quantum efficiency immediately after formation of the light conversion layer).

A blue LED (peak emission wavelength 450nm; CCS Co., ltd.) was used as a surface emission light source, and a light conversion layer was provided on the light source with the glass substrate side as the lower side. The integrating sphere was connected to a radiospectrophotometer (manufactured by tsukamu electronics corporation, "MCPD-9800") and brought close to the light conversion layer provided on the blue LED. The blue LED was turned on in this state, and the quantum numbers of the excitation light and the luminescence (fluorescence) of the light conversion layer were measured to calculate the external quantum efficiency. The higher the external quantum efficiency retention means the higher the stability of the light conversion layer containing luminescent particles to oxygen and water vapor.

[ three-dimensional parameters ]

The following table shows the structural formulas of the compounds used as ligands that are located on the surface of the above luminescent nanocrystals.

TABLE 13

The structural formulas of the compounds used as monomers for preparing the QD dispersions and QD inks described above are shown in the following table.

TABLE 14

TABLE 15

The steric parameter MR is calculated using the following formula (C) for the above compound.

In the formula (C), n represents a refractive index, M represents a molecular weight, and d represents a density. The density and refractive index are values of 20℃or 25 ℃. The calculated stereo parameters MR are shown in the following table.

TABLE 16

< 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 were studied.

First, with respect to QD dispersion C1 of comparative example 1, the absolute value |Δmr| of the difference between the steric parameter MR of each monomer and the steric parameter MR of the ligand, and the weighted average |Δmr| of all |Δmr|, were calculated as follows _{Weighted average} . Further, the PLQY retention was measured for QD dispersion C1 of comparative example 1, and found to be 53.0%.

(1) |ΔMR| for the combination of Light ester L and oleic acid _PY

= | (MR of Light counter L) - (MR of oleic acid) |

＝|78.6－88.3|

＝9.7

(2) |ΔMR| when Light ester L is combined with oleylamine _PZ

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

＝|78.6－86.9|

＝8.3

(3) Light acrylate DCP-A in combination with oleic acid _QX

= | (Light acrylate DCP-a MR) - (oleic acid MR) |

＝|82.2－88.3|

＝6.1

(4) Light acrylate DCP-A in combination with oleylamine _QZ

= | (Light acrylate DCP-a MR) - (oleylamine MR) |

＝|82.2－86.9|

＝4.7

(5) 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

Wherein the coordination ratio of oleic acid and oleylamine coordinated to the surface of the luminescent nanocrystal was set to 0.5:0.5, calculating |ΔMR| _{Weighted average} 。

Next, the QD dispersions 1 to 12 of examples 1 to 12 and QD dispersion 13 of example 40 were also subjected to the same operation as in comparative example 1 to calculate |Δmr| and |Δmr| respectively _{Weighted average} And PLQY retention was measured. In each QD dispersion 1 to 12, 2 ligands were used, and the coordination ratio of each ligand was set to 0.5:0.5 to calculate |ΔMR| _{Weighted average} . In QD dispersion 12 of example 12, a ligand consisting of oleic acid and a ligand consisting of 3-aminopropyl triethoxysilane were coordinated to the surface of luminescent nanocrystals consisting of lead cesium tribromide crystals. Since 3-aminopropyl triethoxysilane coordinates to the surface of the luminescent nanocrystal to form a siloxane bond and cover the surface of the luminescent nanocrystal in a network, it is considered that exchange of oleic acid used as a ligand with a photopolymerizable monomer in the QD dispersion is suppressed as described below. From the above, in example 12, oleic acid alone was coordinated to the surface of the luminescent nanocrystal, that is, the coordination ratio of oleic acid was 1, and |Δmr| was calculated _{Weighted average} . The results are shown in the following table.

TABLE 17

1: oleylamine @ 2: oleic acid 3: n- (1-adamantyl) ethylenediamine

TABLE 18

1: oleylamine @ 2: oleic acid 3: n- (1-adamantyl) ethylenediamine

As shown in the above table, the maximum value of |ΔMR| of the QD dispersions of examples 1 to 12 and the QD dispersion of example 40 was 12 or more, and the weighted average |ΔMR| of all the |ΔMR| was equal to or greater than _{Weighted average} Is 12 or more. In contrast, the QD dispersion of comparative example 1 had a maximum value of |Δmr| much lower than 12, and |Δmr| _{Weighted average} Well below 12. The QD dispersions of examples 1 to 12 and the QD dispersion of example 40 were found to exhibit higher PLQY retention than the QD dispersion of comparative example 1.

The QD dispersions of examples 1 to 8, 10 and comparative example 1 contained luminescent particles having cationic oleylamine and anionic oleic acid coordinated thereto, whereas the QD dispersions of examples 9 and 11 contained luminescent particles having cationic N- (1-adamantyl) ethylenediamine and anionic oleic acid coordinated thereto. In the case of examples 9 and 11, in which N- (1-adamantyl) ethylenediamine was used instead of oleylamine and oleic acid as ligands, the PLQY retention of QD dispersion was also superior to comparative example 1. From the above, it is clear that the PLQY retention rate is high both when a compound having no cyclic structure is used as the ligand and a compound having a cyclic structure is used as the monomer, and when a compound having a cyclic structure is used as the ligand and a compound having no cyclic structure is used as the monomer. Further, according to the results of examples 1 to 5 and example 40, it was found that even if the cyclic structure was aromatic like aliphatic, a high PLQY was exhibited.

Further, as can be seen from the results of examples 1 to 12, |ΔMR| _{Weighted average} The larger the tends to increase PLQY retention.

Further, the presence or absence of an inorganic coating layer in the luminescent particles was investigated. The QD dispersion of example 12 is the same as the QD dispersion of example 4, except for the following: the luminescent nanocrystal has an inorganic coating layer containing Si on its surface, wherein 3-aminopropyl triethoxysilane is coordinated to the surface of the luminescent nanocrystal as a cationic ligand instead of oleylamine, and the ligand forms a siloxane bond. |ΔMR| in the QD dispersion of example 4 _{Weighted average} 24.8 versus 24.1 for the QD dispersion of example 12, 0.7 less. However, the PLQY retention in the QD dispersion of example 4 was 71.9, whereas the QD dispersion of example 12 was 75.8, 3.9 higher. From this result, it is considered that if the QD dispersion of example 12 is used, since an inorganic coating layer containing Si is formed on the surface of the luminescent nanocrystals, the luminescent nanocrystals are protected, and exchange of oleic acid and a photopolymerizable monomer is suppressed, so that the PLQY retention rate is increased.

< evaluation of QD ink >)

The maximum value of |Δmr| and |Δmr| were calculated for the QD inks of examples 13 to 25, example 41, and comparative example 2 obtained in the same manner as the QD dispersion _{Weighted average} . Maximum value of |Δmr| and |Δmr| _{Weighted average} The steric parameters MR of the dicyclopentanyl methacrylate and Light ester L used for preparing the Light scattering particle dispersions 1 to 2 were also calculated taking into consideration. Further, the dispersion stability of the QD ink was evaluated. The results are shown in the following table.

TABLE 19

As shown in the above table, it is clear that the maximum value of |ΔMR| of the QD inks of examples 13 to 25 and the QD ink of example 41 is 12 or more, and the weighted average |ΔMR| of all the |ΔMR| is equal to or greater than 12 _{Weighted average} Is 12 or more. In contrast to this,the QD ink of comparative example 2 had a maximum value of |Δmr| of 12 or more, but |Δmr| _{Weighted average} Well below 12. The QD inks of examples 13 to 25 were superior to the QD ink of comparative example 2 in dispersion stability. In particular, it is known that the value is |ΔMR| _{Weighted average} When the content is 20 or more, "A" is used, and excellent dispersion stability is exhibited.

< evaluation of light conversion layer >

Next, a light conversion layer was produced by the above method and evaluated. The results are shown in the following table.

TABLE 20

As shown in the above table, the external quantum efficiency retention of the light conversion layer C1 of comparative example 3 was 67.0% lower, whereas the light conversion layers 1 to 13 of examples 26 to 38 and the light conversion layer 14 of example 42 exhibited values higher than those of the light conversion layer C1 of comparative example 3.

From the results of QD dispersions 1 to 12 and QD dispersion 13 of examples 1 to 12, QD dispersion 13 of example 40, QD inks 1 to 13 of examples 13 to 25, and QD ink 14 of example 41, it was found that the above-described QD inks contain photopolymerizable monomers and luminescent particles having ligands on the surface of luminescent nanocrystals composed of metal halides and have |Δmr| _{Weighted average} A composition containing nanocrystals of 12 or more and |ΔMR| _{Weighted average} The nanocrystalline-containing composition of less than 12 is excellent in not only PLQY retention but also dispersion stability.

Further, the results of the light conversion layers 1 to 13 according to examples 26 to 38 and the light conversion layer 14 according to example 42 revealed that the light conversion layers contained |Δmr| in the examples _{Weighted average} A light conversion layer containing a cured product of a nanocrystalline-containing composition having a composition smaller than 12 contains |DeltaMR|in comparison with the light conversion layer _{Weighted average} The external quantum efficiency retention rate of the light conversion layer of the cured product of the composition containing nanocrystals of 12 or more is excellent. Accordingly, it is expected that the light emitting element having the light conversion layer formed of the composition containing nanocrystals of the present invention is excellent as wellExternal quantum efficiency retention of (2).

Symbol description

90: luminescent particles, inorganic coated luminescent particles, silica coated luminescent particles

91: inorganic coating layer, silica coating layer

910: luminescent particles and uncoated luminescent particles

911: nanocrystalline of

912: ligand layer

100: light-emitting element

200: EL light source unit

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 electrode

9: sealing layer

10: filling layer

11: protective layer

12: light conversion layer

13: upper base plate

14: EL layer

20: pixel unit

20a: 1 st pixel portion

20b: 2 nd pixel portion

20c: 3 rd pixel portion

21a: 1 st light scattering particle

21b: 2 nd light scattering particle

21c: 3 rd light scattering particle

22a: 1 st curing component

22b: 2 nd curing component

22c: 3 rd curing component

30: light shielding part

701: capacitor with a capacitor body

702: driving transistor

705: common electrode

706: signal line

707: scanning line

708: switching transistor

C1: signal line driving circuit

C2: scanning line driving circuit

And C3: control circuit

PE, R, G, B: pixel electrode

X: copolymer

XA: aggregate

x1: aliphatic polyamine chains

x2: hydrophobic organic segment

YA: core-shell silica nanoparticles

Z: a solution containing a raw material compound of semiconductor nanocrystals.

Claims

1. A composition comprising nanocrystals, characterized in that: light-emitting microparticles containing 1 or 2 or more photopolymerizable monomers and having 1 or 2 or more ligands on the surface of a light-emitting nanocrystal composed of 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, there are 1 or more combinations of photopolymerizable monomers and ligands satisfying the following formula (a),

a weighted average value |Δmr| of |Δmr| calculated in consideration of the content of each photopolymerizable monomer and the coordination ratio of each ligand on the surface of the luminescent nanocrystal in all combinations of each photopolymerizable monomer and each ligand contained in the nanocrystal-containing composition _{Weighted average} Satisfying the following (B),

|Δmr|= | (steric parameter MR of photopolymerizable monomer) - (steric parameter MR of ligand) |gtoreq 12 (a)

|ΔMR| _{Weighted average} ≥12(B)

Wherein the stereoscopic parameter MR is represented by the following formula (C),

2. The nanocrystal composition according to claim 1, wherein at least one of the photopolymerizable monomer or the ligand contains a compound having a cyclic structure in a combination of the photopolymerizable monomer and the ligand satisfying the formula (a).

3. The nanocrystal composition according to claim 2, wherein the compound having a cyclic structure comprises a cyclic structure represented by the following formulae (1-2) to (1-24),

4. The composition containing nanocrystals, according to any one of claims 1 to 3, wherein the luminescent microparticles have a ligand having a reactive group capable of forming a siloxane bond on the surface of the luminescent nanocrystals, and an inorganic coating layer containing Si is formed from the ligand.

5. The nanocrystal composition according to any one of claims 1 to 4, further comprising at least 1 or more of a photopolymerization initiator, a light scattering agent, and a dispersing agent.

6. An ink composition characterized in that: use of a nanocrystalline-containing composition according to any one of claims 1 to 3.

7. A light conversion layer, characterized by: a cured product comprising the ink composition according to claim 6.

8. A light emitting element characterized in that: a light conversion layer according to claim 7.