KR20220106047A - A quantum dot, a quantum dot dispersion, a light converting curable composition, electronic device, color filter, a light converting laminating unit and a display device - Google Patents

Abstract

The present invention provides a quantum dot having a ligand layer on a surface, wherein the ligand layer includes a compound having a specific chemical structure, a quantum dot dispersion comprising the quantum dot, and a light conversion ink composition. In addition, the quantum dot according to the present invention has excellent oxidation stability and reliability and thus can be effectively applied to various uses such as electronic devices, color filters, and light conversion laminated substrates.

Description

QUANTUM DOT, A QUANTUM DOT DISPERSION, A LIGHT CONVERTING CURABLE COMPOSITION, ELECTRONIC DEVICE, COLOR FILTER, A LIGHT CONVERTING LAMINATING UNIT AND A DISPLAY DEVICE}

The present invention relates to quantum dots, a quantum dot dispersion, a light conversion ink composition, an electronic device, a color filter, a light conversion laminated substrate, and an image display device.

Quantum dots have high luminescence and a narrow emission spectrum, can control the emission wavelength with one excitation wavelength, and have unique characteristics of a quantum dot that is stable against light. A lot of research has been done to use it in such an important application field.

These quantum dots are very sensitive to the state of the surface, and oxidation occurs from the surface depending on the dispersed solvent or the surrounding environment, resulting in a sharp decrease in luminous efficiency. For various applications of quantum dots, they must be dispersed in various solvents other than the organic solvent in which they were initially dispersed, or specific functional groups must be formed on the surface. There is this.

Many attempts have been made to overcome these problems, and various methods are currently being proposed. One of them is a ligand exchange method in which organic materials present on the surface of quantum dots are replaced with molecules having a desired functional group. This method is a method of substituting organic molecules with suitable organic molecules to apply the organic molecules present on the surface of the quantum dot, but has a disadvantage in causing a fatal problem in luminous efficiency because it directly affects the surface of the quantum dot.

Korean Patent Application Laid-Open No. 10-2018-0002716 and Korean Patent Registration No. 10-1628065 disclose quantum dots including ligands disposed on the surface, but the compatibility is low, the dispersibility is poor, and the stability and reliability are insufficient. , the light resistance is reduced over time, and the viscosity stability is not sufficient to solve the problems such as not suitable for the inkjet method.

Republic of Korea Patent Publication No. 10-2018-0002716 Republic of Korea Patent Registration No. 10-1628065

One object of the present invention is to provide a quantum dot excellent in optical properties, oxidation stability and reliability.

In addition, an object of the present invention is to provide a quantum dot dispersion comprising the quantum dots, excellent dispersibility and viscosity stability, and a light conversion ink composition comprising the quantum dot dispersion.

Another object of the present invention is to provide an electronic device including the quantum dots as a light emitting layer.

Another object of the present invention is to provide a color filter including a cured film formed by using the light conversion ink composition, a light conversion laminated substrate, and an image display device.

Another object of the present invention is to provide an image display device in which the electronic device is a quantum dot LED (QLED).

The present invention is a quantum dot having a ligand layer on the surface,

The ligand layer provides a quantum dot including a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

또는

이고,A is

or

ego,

R ₁ and R ₂ are each independently a C6 to C16 arylene group or a C5 to C16 heteroarylene group,

R ₃ and R ₄ are each independently a C6 to C16 aryl group or a C5 to C16 heteroaryl group,

Y is a C4 to C16 fused cyclic aromatic group,

,

,

,

,

,

,

또는

이며,B is a direct bond,

,

,

,

,

,

,

or

is,

C is -(CH ₂ ) _n1 -, -(OCH ₂ CH ₂ ) _n2 - or -(CH ₂ CH ₂ O) _n3 -,

n1 to n3 are each independently an integer of 0 to 20,

,

또는

이며,F is -COOH, -SH, -NH ₃ ,

,

or

is,

x and y are each independently an integer of 0-4.

In addition, the present invention provides a quantum dot dispersion comprising the quantum dots.

In addition, the present invention provides a light conversion ink composition comprising the quantum dot dispersion.

In addition, the present invention provides an electronic device including the quantum dots as a light emitting layer.

In addition, the present invention provides a color filter or a light conversion laminated substrate including a cured film formed using the light conversion ink composition.

In addition, the present invention provides an image display device including the color filter or the light conversion laminated substrate.

In addition, the present invention provides an image display device in which the electronic device is a quantum dot light emitting diode (QLED).

The quantum dot according to the present invention includes a compound represented by a specific chemical structure as a ligand layer, so that the surface of the quantum dot is protected, and thus, the quantum dot has excellent oxidative stability and thus has excellent luminescence properties and light retention. Accordingly, it can be usefully applied to a light emitting layer of an electronic device.

In addition, the quantum dots of the present invention have excellent compatibility with monomers and thus have excellent dispersion properties. When the photoconversion ink composition containing the quantum dots is used, the occurrence of defects such as inkjet nozzle clogging is suppressed, and process characteristics such as dryness and continuous jetting. This is excellent, improving the process yield and reducing the production cost by using a small amount.

Therefore, the quantum dots and the light conversion ink composition including the same provide an effect of improving all optical properties such as luminance, reliability and process properties, and thus can be effectively applied to various uses such as color filters and light conversion laminated substrates, Accordingly, it is possible to provide a high-quality image display device.

The present invention provides a quantum dot having a ligand layer on its surface, a quantum dot including a compound having a specific chemical structure in the ligand layer, and a quantum dot dispersion and a light conversion ink composition including the quantum dot. In addition, the quantum dots according to the present invention are excellent in oxidation stability and reliability, and thus can be effectively applied to various uses such as electronic devices, color filters, and light conversion laminated substrates.

In addition, the present invention provides an image display device including the color filter, the light conversion laminated substrate and/or an electronic device.

The electronic device, color filter, light conversion laminated substrate, and image display device of the present invention may be applied to a quantum dot light emitting diode (quantum dot LED, QLED) or to a quantum dot light emitting diode (QLED). .

As used herein, the term 'fused cyclic aromatic group' refers to an aromatic group having a ring sharing two or more adjacent carbon atoms.

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

< Quantum dots >

In the present invention, quantum dots may be used to emit light by a light source and generate light in the visible and infrared regions. A quantum dot is a material with a crystal structure of several nanometers, and may be composed of hundreds to thousands of atoms. Atoms form molecules, and molecules form aggregates of small molecules called clusters to form nanoparticles. Usually, when these nanoparticles have semiconductor characteristics, they are called quantum dots. The quantum dot of the present invention is not particularly limited as long as it conforms to this concept. When an object becomes smaller than nano size, the quantum confinement effect, which is a phenomenon in which the energy band gap of the object becomes larger, occurs. It emits energy corresponding to the gap and can emit light.

The quantum dot according to the present invention has a ligand layer on the surface, and the ligand layer is characterized in that it comprises a compound represented by the following formula (1). Accordingly, the quantum dot surface is protected and excellent in oxidation stability to prevent a decrease in quantum efficiency, thereby exhibiting excellent optical properties and improving reliability.

[Formula 1]

In Formula 1,

또는

이고,A is

or

ego,

R ₁ and R ₂ are each independently a C6 to C16 arylene group or a C5 to C16 heteroarylene group,

R ₃ and R ₄ are each independently a C6 to C16 aryl group or a C5 to C16 heteroaryl group,

Y is a C4 to C16 fused cyclic aromatic group,

,

,

,

,

,

,

또는

이며,B is a direct bond,

,

,

,

,

,

,

or

is,

C is -(CH ₂ ) _n1 -, -(OCH ₂ CH ₂ ) _n2 - or -(CH ₂ CH ₂ O) _n3 -,

n1 to n3 are each independently an integer of 0 to 20,

,

또는

이며,F is -COOH, -SH, -NH ₃ ,

,

or

is,

x and y are each independently an integer of 0-4.

In the present invention, the sum of x and y in Formula 1 may be 1 or more, and more preferably, the sum of x and y may be 4 or more. In this case, it is possible to provide a quantum dot dispersion having excellent dispersion stability due to excellent compatibility with the curable monomer and good dispersibility.

In one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by any one of Formulas 1-1 to 1-9 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In the present invention, the compound represented by Formula 1 may be coordinated to the surface of the quantum dot as an organic ligand to serve to stabilize the quantum dot.

Generally, the prepared quantum dots generally have a ligand layer on the surface, and immediately after the preparation, the ligand layer is oleic acid, lauric acid, 2-(2-methoxyethoxy)acetic acid, 2 -[2-(2-methoxyethoxy)ethoxy]acetic acid, succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl]ester, and the like. In this case, compared with the quantum dots of the present invention comprising the compound represented by Formula 1 as a ligand layer, the surface protection effect may be reduced due to non-binding defects on the surface of the quantum dots due to the weaker bonding force between the ligand layer and the quantum dots. have. In addition, in the case of oleic acid, it is well dispersed in saturated hydrocarbon solvents such as n-hexane, a highly volatile organic compound (VOC), and aromatic solvents such as chloroform and benzene, but solvents such as PGMEA or monomers (photopolymerizable compounds). ) has poor dispersibility.

The quantum dot according to the present invention includes the compound represented by Formula 1 in the ligand layer, so that the surface of the quantum dot is protected, so it can exhibit excellent oxidation stability compared to the conventional quantum dot, and has excellent dispersibility in the monomer. The effect of improving the optical characteristics appears.

In addition, the quantum dots of the present invention exhibit excellent dispersibility in not only aromatic solvents such as chloroform but also solvents such as PGMEA, and thus can be applied in the manufacture of QLED devices.

In some embodiments, the quantum dots according to the present invention include the compound represented by Formula 1 in the ligand layer, oleic acid, lauric acid, 2-(2-methoxyethoxy) ) acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl]ester, and the like may be further included.

The quantum dot is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation by light or electricity. For example, a group II-VI semiconductor compound; III-V semiconductor compounds; group IV-VI semiconductor compounds; Group IV element or a compound containing the same; And may be selected from the group consisting of a combination thereof, these may be used alone or in mixture of two or more.

For example, the II-VI semiconductor compound may include a binary compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; a triatomic compound selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

The group III-V semiconductor compound may include a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; a ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The present invention is not limited thereto.

The group IV-VI semiconductor compound may include a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and may be at least one selected from the group consisting of a quaternary compound selected from the group consisting of mixtures thereof, but is also not limited thereto.

The group IV element or a compound containing the same may include an element selected from the group consisting of Si, Ge, and mixtures thereof; and SiC, SiGe, and a di-element compound selected from the group consisting of mixtures thereof, but is not limited thereto.

Quantum dots have a homogeneous single structure; dual structures such as core-shell structures and gradient structures; Or they may have a mixed structure, and the quantum dots in the present invention are not particularly limited as long as they can emit light by stimulation by light.

According to an embodiment, the quantum dot has a core-shell structure, and the core includes InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, At least one selected from the group consisting of HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN, InAs and ZnO, wherein the shell is ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP , InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, may include one or more selected from the group consisting of SrSe and HgSe, preferably, InP / ZnS, InP / ZnSe , InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS, and InP/MnSe/ZnS, may include at least one selected from the group consisting of, but is not limited thereto.

In general, quantum dots may be manufactured by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process.

The quantum dots according to the present invention may be synthesized by a wet chemical process.

The wet chemical process is a method of growing particles by putting a precursor material in an organic solvent. When the crystal grows, the organic solvent naturally coordinates on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. It is possible to control the size growth of quantum dot particles through an easier and cheaper process than vapor deposition such as molecular beam epitaxy.

In the case of producing quantum dots by a wet chemical process, an organic ligand is used to prevent aggregation of quantum dots and to control the particle size of quantum dots to a nano level. As such an organic ligand, oleic acid may be generally used.

In one embodiment of the present invention, the oleic acid used in the manufacturing process of the quantum dots is replaced with the compound represented by Formula 1 through the ligand exchange method.

The ligand exchange is an original organic ligand, that is, a dispersion containing quantum dots having oleic acid, an organic ligand to be exchanged, that is, a compound represented by Formula 1 is added, and this is added at room temperature to 200° C. for 30 minutes to 3 hours. It can be carried out by stirring to obtain a quantum dot to which the compound represented by Formula 1 is bound.

If necessary, a process of isolating and purifying the quantum dots to which the compound represented by Formula 1 is bound may be additionally performed.

Quantum dots according to an embodiment of the present invention can be manufactured by an organic ligand exchange method under a simple stirring treatment at room temperature as described above, so there is an advantage that mass production is possible.

In addition, the quantum dot according to an embodiment of the present invention can maintain a quantum efficiency of about 85% or more compared to the initial quantum efficiency even after 15 days, so that it can be stably stored for a long period of time, so that it can be commercialized for various purposes.

< Quantum Dot Dispersion >

One embodiment of the present invention relates to a quantum dot dispersion. The quantum dot dispersion according to the present invention includes at least one selected from the aforementioned quantum dots, monomers, and solvents.

quantum dots

In the present invention, the quantum dots may be included in an amount of 10 to 95 parts by weight, preferably 20 to 90 parts by weight, more preferably 20 to 80 parts by weight based on 100 parts by weight of the total solid content of the quantum dot dispersion. When the quantum dots are included within the above range, it is possible to provide a quantum dot light conversion composition or a self-luminous photosensitive resin composition having excellent light emitting properties. When the quantum dots are included in less than the content range, optical characteristics may be deteriorated, and thus it may be difficult to implement a high-quality display device. In addition, when the content exceeds the above range, there are insufficient components for implementing curing or developability, and thus the productivity and product reliability of the post-production process of the display may be reduced due to lack of pattern formation or lack of curing degree of the coating film.

The monomer contained in the quantum dot dispersion of the present invention is a curable monomer for dispersion that serves to disperse the quantum dots.

The monomer may include a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₅ is a C ₁ -C ₂₀ alkylene group, a C ₁ -C ₂₀ phenylene group or a C ₃ -C ₁₀ cycloalkylene group, R ₆ and R ₇ are each independently hydrogen or a methyl group, and m is It is an integer from 1 to 15.

As used herein, a C ₃ -C ₁₀ cycloalkylene group refers to a simple or fused cyclic divalent hydrocarbon having 3 to 10 carbon atoms, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene. and the like, but are not limited thereto.

In the C ₁ -C ₂₀ alkylene group, C ₁ -C ₂₀ phenylene group and C ₃ -C ₁₀ cycloalkylene group, one or more hydrogens are C ₁ -C ₆ alkyl group, C ₂ -C ₆ Alkenyl group, C ₂ -C ₆ Alkynyl group, C ₃ -C ₁₀ Cycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyloxy group, C ₁ -C ₆ Halo Alkyl group, C ₁ -C ₆ Alkoxy group, C ₁ -C ₆ Thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano group , nitro, etc. may be substituted.

For example, as the compound represented by Formula 2, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, 2-hydroxy-3-methacrylpropyl acrylate, 1,9-bisacryloyl oxide cynonane, tripropylene glycol diacrylate, and the like, but is not limited thereto.

In the present invention, the monomer included in the quantum dot dispersion may include at least one compound represented by Formula 2 above.

When the compound represented by Formula 2 is used together with the quantum dot of the present invention having the compound represented by Formula 1 as a ligand layer, it has excellent compatibility with the ligand, thereby further improving dispersibility of the quantum dot.

The quantum dot dispersion of the present invention may further include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers as a dispersion monomer in addition to the compound represented by Formula 2, if necessary, among which, preferably A difunctional or higher functional monomer may be used.

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxyethyl acryl rate etc. are mentioned.

The type of the bifunctional monomer is not particularly limited, and for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate , neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. .

The type of the polyfunctional monomer is not particularly limited, and for example, trimethylolpropane tri(meth)acrylate, oxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa ( Meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

The dispersion monomer may be included in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight based on 100 parts by weight of the solid content of the total quantum dot dispersion.

If it is less than the above-mentioned c range, the dispersion properties may be deteriorated or the coating or jetting properties may be deteriorated due to the high viscosity of the dispersion. The optical properties may be degraded due to performance degradation.

The quantum dots according to the present invention can be dispersed using a solvent.

As said solvent, For example, alkylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, pentyl acetate (n-Pentyl acetate), chloroform, phenyl -Acetic acid ethyl ester, 3-phenyl-propionic acid methyl ester, 3-phenyl-propionic acid ethyl ester, 4-phenyl-butyric acid ethyl ester, 5-phenyl-pentanoic acid ethyl ester, 6-phenyl-hexanoic acid ethyl ester, 4-phenyl -Butyric acid propyl ester, 4-(4-chloro-phenyl)-butyric acid ethyl ester, 4-(3,4-dichloro-phenyl)-butyric acid ethyl ester, 3-cyclopenta-1,3-dienyl-propionic acid methyl ester , 4-cyclopenta-1,3-dienyl-butyric acid ethyl ester, 5-cyclopenta-1,3-dienyl-pentanoic acid ethyl ester, 6-cyclopenta-1,3-dienyl-hexanoic acid ethyl ester , 4-Cyclopenta-1,3-dienyl-butyric acid propyl ester, 3-furan-2-yl-propionic acid methyl ester, 4-furan-2-yl-butyric acid ethyl ester, 5-furan-2-yl-penta Noic acid ethyl ester, 6-furan-2-yl-hexanoic acid ethyl ester, 4-furan-2-yl-butyric acid propyl ester, furan-2-carboxylic acid propyl ester, furan-2-carboxylic acid butyl ester, 3 -Cyclopentyl-propionic acid methyl ester, 4-cyclopentyl-butyric acid ethyl ester, 5-cyclopentyl-pentanoic acid ethyl ester, 6-cyclopentyl-hexanoic acid ethyl ester, 4-cyclopentyl-butyric acid propyl ester, cyclopentanecarboxyl Acid isobutyl ester, cyclopentanecarboxylic acid pentyl ester, 3-(tetrahydro-furan-3-yl)-propionic acid methyl ester, 4-(tetrahydro-furan-3-yl)-butyric acid ethyl ester, 5-( Tetrahydro-furan-3-yl)-pentanoic acid ethyl ester, 6-(tetrahydro-furan-3-yl)-hexanoic acid ethyl ester, 4-(tetrahydro-furan-3-yl)-butyric acid propyl ester, Tetrahydro-furan-3-carboxylic acid propyl ester , Tetrahydro-furan-3-carboxylic acid butyl ester, 3-(tetrahydro-furan-2-yl)-propionic acid methyl ester, 4-(tetrahydro-furan-2-yl)-butyric acid ethyl ester, 5- (Tetrahydro-furan-2-yl)-pentanoic acid ethyl ester, 6-(tetrahydro-furan-2-yl)-hexanoic acid ethyl ester, 4-(tetrahydro-furan-2-yl)-butyric acid propyl ester , Tetrahydro-furan-2-carboxylic acid 2-ethyl-hexyl ester, cyclohexyl-acetic acid ethyl ester, 3-cyclohexyl-propionic acid methyl ester, 4-cyclohexyl-butyric acid ethyl ester, 5-cyclohexyl-pentanoic acid Ethyl ester, 6-cyclohexyl-hexanoic acid ethyl ester, 4-cyclohexyl-butyric acid propyl ester, cyclohexanecarboxylic acid propyl ester, cyclohexanecarboxylic acid hexyl ester, cyclohexyl-acetic acid allyl ester, 3-(tetrahydro -Pyran-2-yl)-propionic acid methyl ester, 4-(tetrahydro-pyran-2-yl)-butyric acid ethyl ester, 5-(tetrahydro-pyran-2-yl)-pentanoic acid ethyl ester, 6-( Tetrahydro-pyran-2-yl)-hexanoic acid ethyl ester, 4-(tetrahydro-pyran-2-yl)-butyric acid propyl ester, tetrahydro-pyran-2-carboxylic acid propyl ester, tetrahydro-pyran- 2-Carboxylic acid butyl ester, 3-(tetrahydro-pyran-3-yl)-propionic acid methyl ester, 4-(tetrahydro-pyran-3-yl)-butyric acid ethyl ester, 5-(tetrahydro-pyran- 2-yl)-Pentanoic acid ethyl ester, 6-(tetrahydro-pyran-3-yl)-hexanoic acid ethyl ester, 4-(tetrahydro-pyran-3-yl)-butyric acid propyl ester, tetrahydro-pyran- 3-carboxylic acid isobutyl ester, tetrahydro-pyran-3-carboxylic acid pentyl ester, 3-(tetrahydro-pyran-4-yl)-propionic acid methyl ester, 4-(tetrahydro-pyran-4-yl )-Butyric acid ethyl ester, 5-(tetrahydro-pyran-4-yl)-pentanoic acid ethyl ester, 6-(tetrahydro-pyran-4-yl)- hexanoic acid ethyl ester, 4-(tetrahydro-pyran-4-yl)-butyric acid propyl ester, tetrahydro-pyran-4-carboxylic acid butyl ester, tetrahydro-pyran-4-carboxylic acid propyl ester, etc. can be heard

Also, benzyl acetate ester, propionic acid phenethyl ester, propionic acid 3-phenyl-propyl ester, propionic acid 4-phenyl-butyl ester, butyric acid phenethyl ester, propionic acid 2-(4-chloro-phenyl)-ethyl ester, propionic acid 2-( 3,4-Dichloro-phenyl)-ethyl ester, acetic acid cyclopenta-1,3-dienylmethyl ester, propionic acid 2-cyclopenta-1,3-dienyl-ethyl ester, propionic acid 3-cyclopenta-1,3 -dienyl-propyl ester, propionic acid 4-cyclopenta-1,3-dienyl-butyl ester, butyric acid 2-cyclopenta-1,3-dienyl-ethyl ester, acetic acid furan-2-ylmethyl ester, propionic acid 2 -furan-2-yl-ethyl ester, propionic acid 3-furan-2-yl-propyl ester, propionic acid 4-furan-2-yl-butyl ester, butyric acid 2-furan-2-yl-ethyl ester, acetic acid cyclopentylmethyl Ester, propionic acid 2-cyclopentyl-ethyl ester, propionic acid 3-cyclopentyl-propyl ester, propionic acid 4-cyclopentyl-butyl ester, butyric acid 2-cyclopentyl-ethyl ester, acetic acid tetrahydro-furan-3-ylmethyl ester, Propionic acid 2-(tetrahydro-furan-3-yl)-ethyl ester, propionic acid 3-(tetrahydro-furan-3-yl)-propyl ester, propionic acid 4-(tetrahydro-furan-3-yl)-butyl ester , Butyric acid 2-(tetrahydro-furan-3-yl)-ethyl ester, acetic acid tetrahydro-furan-2-ylmethyl ester, propionic acid 2-(tetrahydro-furan-2-yl)-ethyl ester, propionic acid 3- (Tetrahydro-furan-2-yl)-propyl ester, propionic acid 4-(tetrahydro-furan-2-yl)-butyl ester, butyric acid 2-(tetrahydro-furan-2-yl)-ethyl ester, acetic acid cyclo Hexylmethyl ester, propionic acid 2-cyclohexyl-ethyl ester, propionic acid 3-cyclohexyl-propyl ester, propionic acid 4-cyclohexyl-butyl ester, butyric acid 2-cyclohexyl-ethyl ester, but-3-enoic acid cyclohexylmethyl ester Ster, Acetic acid tetrahydro-pyran-2-ylmethyl ester, propionic acid 2-(tetrahydro-pyran-2-yl)-ethyl ester, propionic acid 3-(tetrahydro-pyran-2-yl)-propyl ester, propionic acid 4-(Tetrahydro-pyran-2-yl)-butyl ester, butyric acid 2-(tetrahydro-pyran-2-yl)-ethyl ester, acetic acid tetrahydro-pyran-3-ylmethyl ester, propionic acid 2-(tetra Hydro-pyran-3-yl)-ethyl ester, propionic acid 3-(tetrahydro-pyran-2-yl)-propyl ester, propionic acid 4-(tetrahydro-pyran-3-yl)-butyl ester, butyric acid 2-( Tetrahydro-pyran-3-yl)-ethyl ester, acetic acid tetrahydro-pyran-4-ylmethyl ester, propionic acid 2-(tetrahydro-pyran-4-yl)-ethyl ester, propionic acid 3-(tetrahydro-pyran) -4-yl)-propyl ester, propionic acid 4-(tetrahydro-pyran-4-yl)-butyl ester, butyric acid 2-(tetrahydro-pyran-4-yl)-ethyl ester, and the like. In the present invention, the solvent may be used alone or may be used in combination with the above-mentioned monomers.

The solvent may be included in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the quantum dot dispersion, or a solvent-free type that does not contain a solvent. When the solvent is included in less than the above range, the dispersion characteristic is lowered, and the film formation characteristic by foreign substances may be deteriorated and the luminescent characteristic may be deteriorated. Since a decrease in the area may occur, it is preferable to satisfy the above range.

In the quantum dot (QD) dispersion, quantum dots can be dispersed as a single component of either a monomer or a solvent, or a quantum dot (QD) dispersion can be prepared by mixing a monomer and a solvent and dispersing the quantum dots through this. can

In the present invention, when a solvent and a monomer are mixed and used, the solvent may be included in an amount of 0.1 to 100 parts by weight based on the total weight ratio of the solvent and the monomer. More preferably, it may be included in an amount of 20 to 80 parts by weight. When included within the above range, dispersibility and viscosity stability are improved, so that storage stability is excellent, film-forming properties are excellent, so productivity can be improved, and a high-quality self-luminous display with excellent color gamut and luminance can be provided.

<Light Conversion Ink Composition>

The light conversion ink composition of the present invention includes the quantum dot dispersion described above.

In addition, it may further include one or more selected from scattering particles, a photopolymerizable compound, and a photopolymerization initiator, and, if necessary, may further include constituents such as additives known in the art.

In addition, as the light conversion ink composition of the present invention includes the quantum dot dispersion described above, it has excellent viscosity properties even without including a solvent, so it is suitably used for an inkjet process, but may further include a solvent of 10 ppm to 9000 ppm if necessary. have. In this case, the solvent included in the light conversion ink composition may be used without any particular limitation within the scope of the present invention as long as it can be used in the art.

Hereinafter, each component included in the light conversion ink composition of the present invention will be described in detail.

quantum dot dispersion

The quantum dot dispersion included in the light conversion ink composition of the present invention is applied as it is.

When the quantum dot dispersion is included in the light conversion ink composition of the present invention, it is possible to reduce the amount of outgas generated during the manufacture of the light conversion ink composition, and the prepared light conversion ink composition exhibits desired viscosity characteristics and excellent photoluminescence properties. have. In this aspect, the quantum dot dispersion in the light conversion ink composition of the present invention is preferably included in an amount of 10 to 90 wt%, preferably 20 to 80 wt%, based on the total light conversion ink composition.

scattering particles

The light conversion ink composition according to the present invention may include scattering particles.

The scattering particles may use a conventional inorganic material, and preferably may include a metal oxide having an average particle diameter of 30 to 1000 nm.

The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, It may be an oxide including one type of metal selected from the group consisting of Ce, Ta, In, and combinations thereof, but is not limited thereto.

Specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, MgO and One selected from the group consisting of combinations thereof is possible. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

When the light conversion ink composition according to the present invention includes scattering particles, it is preferable to increase the path of light spontaneously emitted from the quantum dots through the scattering particles, thereby increasing the overall light efficiency in the color filter or the light conversion laminated substrate.

Preferably, the scattering particles may have an average particle diameter of 30 to 1000 nm, preferably 100 to 500 nm. At this time, if the particle size is too small, a sufficient scattering effect of the light emitted from the quantum dots cannot be expected. use it

The scattering particles may be used in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the total light conversion ink composition. When the scattering particles are included within the above range, the effect of increasing the luminescence intensity can be maximized, which is preferable. When the scattering particles are included in less than the above range, it may be somewhat difficult to secure the desired luminescence intensity, and when it exceeds the above range, not only the effect of increasing the luminescence intensity is insufficient, but also the stability of the composition may be deteriorated, It is preferable to use it appropriately within the above range.

photopolymerizable compound

The photopolymerizable compound in the present invention is a compound capable of polymerization by the action of light and a photopolymerization initiator described later.

In one embodiment of the present invention, the photopolymerizable compound may include a compound represented by the formula (2).

[Formula 2]

In Formula 2,

R ₅ is a C ₁ -C ₂₀ alkylene group, a C ₁ -C ₂₀ phenylene group or a C ₃ -C ₁₀ cycloalkylene group, R ₆ and R ₇ are each independently hydrogen or a methyl group, and m is It is an integer from 1 to 15.

As used herein, a C ₃ -C ₁₀ cycloalkylene group refers to a simple or fused cyclic divalent hydrocarbon having 3 to 10 carbon atoms, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene. and the like, but are not limited thereto.

In the C ₁ -C ₂₀ alkylene group, C ₁ -C ₂₀ phenylene group and C ₃ -C ₁₀ cycloalkylene group, one or more hydrogens are C ₁ -C ₆ alkyl group, C ₂ -C ₆ Alkenyl group, C ₂ -C ₆ Alkynyl group, C ₃ -C ₁₀ Cycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyloxy group, C ₁ -C ₆ Halo Alkyl group, C ₁ -C ₆ Alkoxy group, C ₁ -C ₆ Thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano group , nitro, etc. may be substituted.

For example, as the compound represented by Formula 2, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, 2-hydroxy-3-methacrylpropyl acrylate, 1,9-bisacryloyl oxide cynonane, tripropylene glycol diacrylate, and the like, but is not limited thereto.

In the present invention, the monomer included in the quantum dot dispersion may include at least one compound represented by Formula 2 above.

The compound represented by Chemical Formula 2 exhibits low-viscosity characteristics to enable the realization of a low-viscosity light conversion ink composition. For example, when used together with the quantum dots of the present invention having the compound represented by Formula 1 as a ligand layer, the low-viscosity light has excellent compatibility with the ligand and further improves dispersibility of the quantum dots without a solvent. It may enable the implementation of a conversion ink composition. Accordingly, the light conversion ink composition according to the present invention can be effectively used to manufacture a color filter by an inkjet printing method.

In addition to the polymerizable compound represented by Formula 2, the light conversion ink composition of the present invention may further include a polymerizable compound commonly used in the art without departing from the object of the present invention. For example, a monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned, Among these, a bifunctional monomer is used preferably.

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxyethyl acryl rate, N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited, and for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene Glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

The type of the polyfunctional monomer is not particularly limited, and for example, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth) ) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

The photopolymerizable compound included in the light conversion ink composition of the present invention may include a compound of the same or different type from the monomer included in the quantum dot dispersion.

The photopolymerizable compound may be included in an amount of 1 to 45 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total light conversion ink composition. If the content is less than the above range, the photosensitivity may be lowered. On the contrary, if the content exceeds the above range, the adhesion of the quantum dot light conversion layer and the self-luminous photosensitive layer is insufficient, and the film strength is not sufficient, causing the coating film to float, resulting in production yield may lead to a decrease in

photopolymerization initiator

The photopolymerization initiator in the present invention is a compound for initiating polymerization of the above-described photopolymerizable compound, and is not particularly limited in the present invention, but acylphosphine-based, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, Benzoin-based, anthracene-based, anthraquinone-based, biimidazole-based compounds, etc. may be used, and these may be used alone or in combination of two or more.

For example, the benzophenone-based compound includes benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4, 4'-bis(diethyl amino) benzophenone and the like are possible.

Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylclioxylate, titanocene compounds and the like can be used.

The content of the photopolymerization initiator may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the total composition.

When the content of the photopolymerization initiator is within the above range, it is preferable because the light conversion ink composition tends to be highly sensitive to improve the strength of the pixel portion and smoothness on the surface of the pixel portion. In addition, when the content of the photopolymerization initiation auxiliary agent is within the above range, the sensitivity efficiency of the photoconversion ink composition is further increased, and the productivity of a color filter formed using the composition tends to be improved.

additive

The light conversion ink composition according to the present invention may further include known additives for various purposes. Such additives include, for example, fillers, other high molecular compounds, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like may be used in parallel. One or two or more of these additives may be used, and it is preferable to use them in an amount of 1 wt % or less in the total composition in consideration of light efficiency and the like.

Since the light conversion ink composition of the present invention has excellent optical properties, light resistance, and viscosity properties, it can be effectively applied when forming a cured film included in a color filter or a light conversion laminated base material. Therefore, the ink composition according to the present invention can be preferably used for manufacturing an image display device including a color filter or a light conversion laminated substrate.

<Electronic device>

According to an embodiment of the present invention, the quantum dots according to the present invention may be usefully applied to electronic devices such as light emitting diodes, organic light emitting diodes, sensors, imaging sensors, solar cells, and LCDs.

The electronic device according to the present invention may include the above-described quantum dots as a light emitting layer. For example, the quantum dots of the present invention may be included in a first electrode and a second electrode facing each other and a light emitting layer positioned between the first electrode and the second electrode.

The quantum dots used in the light emitting layer have a core-shell structure, and the cores are InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS. , HgSe, HgTe, GaN, GaP, GaAs, InGaN, InAs and at least one selected from the group consisting of ZnO, the shell is ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, may include at least one selected from the group consisting of SrSe and HgSe, preferably, InP / ZnS, InP / ZnSe, InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS and InP/MnSe/ZnS may include at least one selected from the group consisting of, but is not limited thereto.

As an example, a quantum dot light emitting diode (quantum dot LED, QLED) is an electroluminescence (EL) type device that emits light by electrically exciting quantum dots.

In the quantum dot light emitting diode (QLED), electrons and holes injected from both electrodes form excitons in the quantum dot emission layer, and light is emitted through radiative recombination of the excitons. Since it has the same operating principle as organic light-emitting diode (OLED), it is composed by replacing only the light-emitting layer with quantum dots instead of organic light-emitting materials in a multilayer device structure using the electron/hole injection layer and transport layer of conventional OLEDs as they are. can be

The manufacturing method of the quantum dot light emitting diode of the present invention is not particularly limited, and a method known in the art may be used.

For example, the method of manufacturing a quantum dot light emitting diode may be manufactured by sequentially stacking an anode, a cathode, an electron injection/transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

For another embodiment, the method for manufacturing a quantum dot light emitting diode may be manufactured by sequentially stacking a cathode, an electron injection transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode, and in another embodiment, a quantum dot light emitting diode The manufacturing method may be prepared by sequentially stacking an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron injection/transport layer, and a cathode.

In this case, the light emitting layer may include the above-described quantum dots.

< Cured film >

The present invention provides a cured film formed by using the light conversion ink composition, and the cured film may be included in a color filter or a light conversion laminated substrate.

<Light conversion laminated substrate>

The light conversion laminated substrate according to the present invention includes a cured product of the light conversion ink composition. Since the light conversion laminated substrate includes a light conversion ink composition that can be coated on a glass substrate, a solvent that does not correspond to a substance harmful to the human body can be used, thereby improving worker safety and product productivity.

The light conversion laminated substrate may include silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The light conversion laminated substrate may be formed by applying the light conversion ink composition and thermosetting.

<Color filter>

The color filter of the present invention is formed using the above-described light conversion ink composition.

The method for forming a coating film for forming the color filter of the present invention may use a method known in the art.

In one embodiment, the method of forming a coating film,

a) applying a light conversion ink composition to a substrate;

b) curing the obtained film by irradiating actinic light;

c) performing post-baking; may include.

The substrate may be a glass substrate or a polymer substrate, but is not limited thereto. As a glass substrate, especially soda-lime glass, barium or strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be used preferably. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide or polysulfone substrates.

At this time, the coating may be performed by a known wet coating method using an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet to obtain a desired thickness. .

Exposure is sensitized with light emitted from an exposure machine. In this case, the irradiated light may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The post-baking is performed to increase adhesion between the film and the substrate and the degree of curing, and may be performed, for example, through heat treatment at 80 to 250° C. for 10 to 120 minutes. The post-baking may be performed using an oven, a hot plate, or the like, like the pre-bake.

< Image display device >

The image display apparatus according to the present invention includes the above-described color filter, light conversion laminated substrate, and/or an electronic device.

The image display device of the present invention may be an image display device to which a quantum dot LED (QLED) is applied as an electronic device.

The image display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display for a digital camera display devices such as a device and a display device for car navigation, and the like, and a color display device is particularly suitable.

The image display device includes a configuration known to those skilled in the art, except for having the color filter or the light conversion laminated substrate, and may further include, that is, the present invention includes a color filter or a light It includes an image display device to which a conversion laminated substrate can be applied.

The image display device including the color filter according to the present invention may have excellent characteristics in color reproducibility, luminance, heat resistance, reliability, and the like.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.

Synthesis example

Synthesis Example 1: InP/ZnS core-shell quantum dot synthesis

0.05839 g of indium acetate, 0.12019 g of oleic acid, and 10 mL of 1-octadecene (ODE) were placed in a 3-neck flask. The flask was subjected to a degassing process for 30 minutes at 110° C. under 100 mTorr while stirring, and then heated to a temperature of 270° C. under an inert gas until the solution became transparent.

Prepare 0.025054 g of tris(trimethylsilyl)phosphine as a phosphorus (P) precursor, put it in 0.5 mL of 1-octadecene and 0.5 mL of tri-n-octylphosphine, stir it, and heat it to 270° C. under inert gas in the flask was quickly injected into After reacting for 1 hour, the reaction was terminated by rapid cooling. Then, when the temperature of the flask reached 100 °C, 10 mL of toluene was injected and transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using precipitation and redispersion methods. The purified InP core nanoparticles were dispersed in 1-octadecene and then stored.

3.669 g of zinc acetate, 20 mL of oleic acid, and 20 mL of 1-octadecene were put in a three-necked flask, and after degassing for 30 minutes at 110 °C and 100 mTorr while stirring, inert gas until the solution became transparent After heating to a temperature of 270 °C under

Add 0.6412 g of sulfur and 10 mL of tri-n-octylphosphine to a three-necked flask, heat to 80 °C while stirring in an inert gas atmosphere until the solution becomes transparent, and then cool to room temperature to obtain TOP:S-form S precursor solution got

In a separate three-necked flask, the prepared InP core nanoparticle solution was put, the temperature of the flask was adjusted to 300 °C, and 0.6 mL of the zinc precursor solution prepared in advance was quickly injected using a syringe. After that, 0.3 mL of the S precursor solution prepared in advance was injected into the flask at a rate of 2 mL/hr using a syringe pump. After the injection was completed, the reaction was further carried out for 3 hours, and the reaction was terminated by rapid cooling. When the temperature of the flask reached 100° C., 10 mL of toluene was injected, and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using precipitation and redispersion methods. The purified InP/ZnS core-shell structured nanoparticles were dispersed in n-chloroform and then stored. The solid content was adjusted to 10%. The maximum emission wavelength was 525 nm.

Synthesis Example 2: InP/ZnSe/ZnS core-shell quantum dot synthesis

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid, and 20 mL of 1-octadecene were placed in a reactor and heated to 120 °C under vacuum. After 1 hour, the atmosphere in the reactor was switched to nitrogen. After heating to 280° C., a mixed solution of 0.2 mmol (58 μl) of tris (trimethylsilyl) phosphine (TMS ₃ P) and 1.0 mL of trioctylphosphine was quickly injected and reacted for 0.5 minutes.

Then, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched to nitrogen and the temperature of the reactor was raised to 280°C. 2 mL of the previously synthesized InP core solution was added, and then 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled quickly to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP/ZnSe core-shell.

Then, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched to nitrogen and the temperature of the reactor was raised to 280°C. 2 mL of the previously synthesized InP core solution was added, followed by 4.8 mmol of sulfur (S/TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled quickly to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain quantum dots of InP/ZnSe/ZnS core-shell structure, which were then dispersed in chloroform. The solid content was adjusted to 10%. The maximum emission wavelength was 520 nm.

Synthesis Example 3: Synthesis of Ligand M1

THF 60mL, Pd ₂ (dba) ₃ 1.48g (1.61mmol), and (dicyclohexylphosphino)biphenyl 1.36g (3.87mmol) were put in a 4-neck flask equipped with a reflux condenser and stirred for 30 minutes. 4-bromo-4'-hydroxybiphenyl 16.08 g (64.6 mmol), N-Phenyl-1-naphthylamine 28.32 g (131.2 mmol), and LiN(SiMe ₃ ) ₂ 23.78 g (142 mmol) were dissolved in 140 mL of THF. After cooling under reflux for 3 days, the resultant was filtered using silica, washed with brine, and the organic layer was separated and dried over magnesium sulfate. After concentration, the ligand M1 was obtained by column purification. Light orange powder, 14.92 g (60%), LC-MS ([M+H] ⁺ ): 388.

Compound M1:

Synthesis Example 4: Synthesis of Ligand M2

Toluene 40mL and dioxane 40mL were put into a four-neck flask equipped with a reflux condenser, 10g (40.2mmol) of 4-bromo-4'-hydroxybiphenyl and 8.06g (48.2mmol) of carbazole were added and stirred in a nitrogen atmosphere. Pd ₂ (dba) ₃ 0.35 (0.382 mmol), and P(tBu) ₃ 0.077g (0.382mmol) was put into LiN(SiMe ₃ ) ₂ 14.8g (48.2mmol) was put. The reaction was carried out under reflux cooling at 80 °C for 2 days. After completion of the reaction, after lowering to room temperature, 20 mL of a 1M aqueous hydrochloric acid solution was added and stirred for 30 minutes. After neutralization with 10% aqueous sodium bicarbonate solution and washing with 100 mL of DI water twice, the organic layer was separated, dried over magnesium sulfate and concentrated, and then the ligand M2 was obtained by column purification. White powder, 6.6 g (50%), LC-MS ([M+H] ⁺ ):336.

Compound M2:

Synthesis Example 5: Synthesis of ligand M3

THF 60mL, Pd ₂ (dba) ₃ 1.48g (1.61mmol), and (dicyclohexylphosphino)biphenyl 1.36g (3.87mmol) were put in a 4-neck flask equipped with a reflux condenser and stirred for 30 minutes. 4-bromo-4'-hydroxyquaterphenyl 25.92 g (64.6 mmol), N-Phenyl-1-naphthylamine 28.32 g (131.2 mmol), and LiN(SiMe ₃ ) ₂ 23.78 g (142 mmol) were dissolved in 140 mL of THF. After cooling under reflux for 3 days, the resultant was filtered using silica, washed with brine, and the organic layer was separated and dried over magnesium sulfate. After concentration, the ligand M3 was obtained by column purification. Light orange powder, 14.92 g (60%), LC-MS ([M+H] ⁺ ): 401.05.

Compound M3:

Synthesis Example 6: Synthesis of ligand M4

Toluene 40mL and dioxane 40mL were put into a 4-neck flask equipped with a reflux condenser, 25.92g (64.6mmol) of 4-bromo-4'-hydroxyquaterphenyl and 8.06g (48.2mmol) of carbazole were added and stirred in a nitrogen atmosphere. Pd ₂ (dba) ₃ 0.35 (0.382 mmol), and P(tBu) ₃ 0.077g (0.382mmol) was put into LiN(SiMe ₃ ) ₂ 14.8g (48.2mmol) was put. The reaction was carried out under reflux cooling at 80 °C for 2 days. After completion of the reaction, after lowering to room temperature, 20 mL of a 1M aqueous hydrochloric acid solution was added and stirred for 30 minutes. After neutralization with 10% aqueous sodium bicarbonate solution and washing with 100 mL of DI water twice, the organic layer was separated, dried over magnesium sulfate and concentrated, and then the ligand M4 was obtained by column purification. As a white powder, 6.6 g (50%), LC-MS ([M+H] ⁺ ): 488.19.

Compound M4:

Synthesis Example 7: Synthesis of compound L1 (Formula 1-1)

Ligand M2 69g (177mmol), Mono-tert-butyl succinate 30.83g (177mmol), DMAP 100mg (0.8mmol) were added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the reaction was cooled to room temperature, filtered, neutralized with 10% aqueous sodium hydrogen carbonate solution, washed with 100 mL of DI water, and the organic layer was separated, dried over magnesium sulfate, and concentrated. 80 mL of dichloromethane was dissolved, 10 g of trifluoroacetic acid was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, neutralized with 10% aqueous sodium hydrogen carbonate solution, washed with 100 mL of DI water, the organic layer was separated, dried over magnesium sulfate, concentrated, and column purification was performed to obtain compound L1 (Formula 1-1). As a pale yellow solid, 51 g (59%), LC-MS([M+H] ⁺ ):488, ¹ H NMR (CDCl ₃ , 300 MHz): 7.10-7.51 (m, 13H), 6.45-6.81 (m) , 6H), 6.63 (t, 1H), and 2.67 (d, 4H).

: L1

: L1

Synthesis Example 8: Synthesis of compound L2 (Formula 1-2)

Ligand M1 69g (177mmol), 6-Mercaptohexanoic acid 26.24g (177mmol), DMAP 100mg (0.8mmol) was added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. Column purification was performed by dissolving in a small amount of chloroform to obtain compound L2 (Formula 1-2). Light yellow powder, 61 g (67%), LC-MS([M+H] ⁺ ): 518, ¹ H NMR (CDCl ₃ , 300 MHz): 7.10~7.51(m, 13H), 6.45~6.81 ( m, 6H), 6.61 (t, 1H), 2.58 (d, 2H), 2.24 (d, 2H), 1.30 to 1.60 (m, 6H).

:L2

:L2

Synthesis Example 9: Synthesis of compound L3 (Formula 1-3)

Ligand M2 59.3g (177mmol), Mono-tert-butyl succinate 30.83g (177mmol), DMAP 100mg (0.8mmol) were added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. 80 mL of dichloromethane was dissolved, 10 g of trifluoroacetic acid was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction was neutralized with a 10% aqueous sodium hydrogen carbonate solution, washed with 100 mL of DI water, the organic layer was separated, dried over magnesium sulfate, concentrated, and column purification was performed to obtain compound L3 (Formula 1-3). As a beige powder, 48 g (62%), LC-MS ([M+H] ⁺ ) : 436 ¹ H NMR (CDCl ₃ , 300 MHz): 8.05 (d, 2H), 7.51-8.01 (m, 14H) , 2.56(d, 2H).

:L3

:L3

Synthesis Example 10: Synthesis of compound L4 (Formula 1-4)

Ligand M2 70.8g (177mmol), 3-Mercaptohexanoic acid 26.24g (177mmol), DMAP 100mg (0.8mmol) was added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. Column purification was performed by dissolving in a small amount of chloroform to obtain compound L4 (Formula 1-4). Light beige powder, 56 g (68%), LC-MS: 466, LC-MS ([M+H] ⁺ ): 436 ¹ H NMR (CDCl ₃ , 300 MHz): 8.04 (d, 2H), 7.50 ∼8.00 (m, 14H), 2.56 (d, 2H), 2.22 (d, 2H), and 1.31∼1.61 (m, 6H).

:L4

:L4

Synthesis Example 11: Synthesis of compound L5 (Formula 1-5)

Ligand M3 70.18g (177mmol), 3-Mercaptopropionic acid 18.79g (177mmol), DMAP 100mg (0.8mmol) was added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. Column purification was performed by dissolving in a small amount of chloroform to obtain compound L5 (Formula 1-5). Light yellow powder, 65 g (58%), LC-MS([M+H] ⁺ ): 628.8, ¹ H NMR (CDCl ₃ , 300 MHz): 7.10~7.51(m, 21H), 6.45~6.81 ( m, 6H), 6.61 (t, 1H), 2.85 (d, 2H), 2.54 (d, 2H).

:L5

:L5

Synthesis Example 12: Synthesis of compound L6 (Formula 1-6)

Ligand M4 86.23g (177mmol), 3-Mercaptopropionic acid 18.79g (177mmol), DMAP 100mg (0.8mmol) were added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 6 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. Column purification was performed by dissolving in a small amount of chloroform to obtain compound L6 (Formula 1-6). Light beige powder, 56 g (68%), LC-MS ([M+H] ⁺ ):: 576.7, ¹ H NMR (CDCl ₃ , 300 MHz): 8.05 (d, 2H), 7.01-8.02 (m , 22H), 2.82 (d, 2H), and 2.51 (d, 2H).

: L6

: L6

Synthesis Example 13: Synthesis of the compound of Formula 1-7

Ligand M1 69g (177mmol), DL-Cysteine (Sigma-Aldrich) 21.45g (177mmol), DMAP 100mg (0.8mmol) was added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 12 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. It was dissolved in a small amount of chloroform and subjected to column purification to obtain a compound of Formula 1-7. It is a beige powder, 45 g (51%), LC-MS ([M+H] ⁺ ):492.

: L7

: L7

Synthesis Example 14: Synthesis of the compound of Formula 1-8

Ligand M4 86.23g (177mmol), 2-(sulfanylmethyl)succinic acid 29.06g (177mmol), DMAP 100mg (0.8mmol) were added to 100mL THF and stirred for 10 minutes. DIC 29.6g (177mmol) was added and reacted at room temperature in a nitrogen atmosphere for 48 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. It was dissolved in a small amount of chloroform and subjected to column purification to obtain a compound of Formula 1-8. As a beige powder, 35 g (31%), LC-MS ([M+H] ⁺ ): 634.

: L8

: L8

Synthesis Example 15: Synthesis of compounds of Formula 1-9

Ligand M2 59.3g (177mmol), DL-Cysteine (Sigma-Aldrich) 21.45g (177mmol), DMAP 100mg (0.8mmol) was added to 100mL THF and stirred for 10 minutes. DIC 22.3g (177mmol) was added and reacted at room temperature for 14 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, filtered, and concentrated under reduced pressure. It was dissolved in a small amount of chloroform and subjected to column purification to obtain a compound of Formula 1-9. It is a beige powder, 41 g (48%), LC-MS ([M+H] ⁺ ): 483.

: L9

: L9

Preparation Examples 1 to 21: Quantum dot dispersion preparation

Preparation Example 1: Quantum Dot Dispersion A-1

3.00 g of quantum dots of Synthesis Example 1 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, and 1.0 g of "Compound L1" was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then HDDA (1,6-Hexanediol diacrylate) was added and dispersed while heating to 80°C. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 524 nm.

Preparation Example 2: Quantum Dot Dispersion A-2

The quantum dots of Synthesis Example 1 were carried out in the same manner as in Example 1, except that “Compound L2” was used in 3.00 g.

The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 524 nm.

Preparation Example 3: Quantum Dot Dispersion A-3

The quantum dots of Synthesis Example 1 were carried out in the same manner as in Example 1, except that “Compound L3” was used in 3.00 g.

The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 525 nm.

Preparation Example 4: Quantum Dot Dispersion A-4

The quantum dots of Synthesis Example 1 were carried out in the same manner as in Preparation Example 1, except that “Compound L4” was used in 3.00 g.

The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 526 nm.

Preparation Example 5: Quantum Dot Dispersion A-5

3 g of quantum dots of Synthesis Example 2 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, and 1.0 g of "Compound L1" was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction mixture to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then HDDA was added and dispersed while heating to 80°C. The solid content was adjusted to 40%. The maximum emission wavelength was 521 nm.

Preparation Example 6: Quantum Dot Dispersion A-6

The same procedure as in Preparation Example 5 was performed, except that "Compound L3" was used instead of the ligand used in Preparation Example 5.

The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 520 nm.

Preparation Example 7: Quantum Dot Dispersion A-7

3.00 g of quantum dots of Synthesis Example 1 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, then 1.0 g of "Compound L1" was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction mixture to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then chloroform was added and dispersed while heating to 80°C. The solid content was adjusted to 5%. The maximum emission wavelength was 524 nm.

Preparation Example 8: Quantum Dot Dispersion A-8

Except that "Compound L2" was used in 3.00 g of the quantum dots of Synthesis Example 1, the same procedure as in Preparation Example 7 was carried out. The solid content was adjusted to 5% with chloroform. The maximum emission wavelength was 524 nm.

Preparation Example 9: Quantum Dot Dispersion A-9

Except that "Compound L3" was used in 3.00 g of the quantum dots of Synthesis Example 1, the same procedure as in Preparation Example 7 was carried out. The solid content was adjusted to 5% with chloroform. The maximum emission wavelength was 525 nm.

Preparation 10: quantum dot dispersion A-10

Except that "Compound L4" was used in 3.00 g of the quantum dots of Synthesis Example 1, the same procedure as in Preparation Example 7 was carried out. The solid content was adjusted to 5% with chloroform. The maximum emission wavelength was 526 nm.

Preparation Example 11: Quantum Dot Dispersion A-11

Except for using "Compound L5" in 3.00 g of the quantum dots of Synthesis Example 1, the same procedure as in Preparation Example 1 was carried out. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 523 nm.

Preparation 12: quantum dot dispersion A-12

The quantum dots of Synthesis Example 1 were carried out in the same manner as in Preparation Example 1, except that “Compound L6” was used in 3.00 g. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 523 nm.

Preparation 13: quantum dot dispersion A-13

The same procedure as in Preparation Example 5 was performed except that “Compound L5” was used instead of “Compound L1” used in Preparation Example 5. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 521 nm.

Preparation Example 14: Quantum Dot Dispersion A-14

The same procedure as in Preparation Example 5 was performed, except that “Compound L6” was used instead of “Compound L1” used in Preparation Example 5. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 522 nm.

Preparation 15: quantum dot dispersion A-15

It proceeded in the same manner as in Preparation Example 5, except that "Compound of Formula 1-7" was used instead of "Compound L1" used in Preparation Example 5. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 521 nm.

Preparation 16: quantum dot dispersion A-16

It proceeded in the same manner as in Preparation Example 5, except that "Compound of Formula 1-8" was used instead of "Compound L1" used in Preparation Example 5. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 523 nm.

Preparation 17: quantum dot dispersion A-17

It proceeded in the same manner as in Preparation Example 5, except that "Compound of Formula 1-9" was used instead of "Compound L1" used in Preparation Example 5. The solid content was adjusted to 40% with HDDA. The maximum emission wavelength was 521 nm.

Preparation 18: quantum dot dispersion A-18

3.00 g of quantum dots of Synthesis Example 1 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, then 1.0 g of “Compound L5” was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction mixture to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then chloroform was added and dispersed while heating to 80°C. The solid content was adjusted to 5%. The maximum emission wavelength was 525 nm.

Preparation 19: quantum dot dispersion A-19

3.00 g of quantum dots of Synthesis Example 1 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, then 1.0 g of “Compound L6” was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction mixture to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then chloroform was added and dispersed while heating to 80°C. The solid content was adjusted to 5%. The maximum emission wavelength was 526 nm.

Preparation 20: quantum dot dispersion A-20

3.00 g of quantum dots of Synthesis Example 1 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, then 1.0 g of “Compound L8” was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then chloroform was added and dispersed while heating to 80 °C. The solid content was adjusted to 5%. The maximum emission wavelength was 524 nm.

Preparation 21: quantum dot dispersion A-21

3.00 g of quantum dots of Synthesis Example 2 were placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse the quantum dots, then 1.0 g of “Compound L6” was added and reacted for one hour while heating to 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction mixture to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then chloroform was added and dispersed while heating to 80°C. The solid content was adjusted to 5%. The maximum emission wavelength was 522 nm.

Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2: Preparation of light conversion ink composition

The quantum dot dispersions of Preparation Examples A-1 to A-21 and the quantum dots of Synthesis Examples 1 and 2 were dispersed 50:50 with HDDA using the quantum dot dispersions of A-22 to A-23 below Table 1 and Tables A light conversion ink composition was prepared according to the components and contents of No. 2.

(weight%) Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 quantum dots
dispersion A-1 55 - - - - - - - - - A-2 - 50 - - - - - - - - A-3 - - 50 - - - - - - - A-4 - - - 50 - - - - - - A-5 - - - - 55 - - - - - A-6 - - - - - 60 - - - - A-9 - - - - - - 55 - - - A-10 - - - - - - - 50 - - A-11 - - - - - - - - 50 - A-12 - - - - - - - - - 50 A-13 - - - - - - - - - - A-14 - - - - - - - - - - A-15 - - - - - - - - - - A-16 - - - - - - - - - - A-17 - - - - - - - - - - A-18 - - - - - - - - - - A-19 - - - - - - - - - - A-20 - - - - - - - - - - A-21 - - - - - - - - - - A-22 - - - - - - - - - - A-23 - - - - - - - - - - photopolymerization
compound MN-1 39 41 42 42 37 32 32 42 42 37 scattering particles 5 8 5 3 5 5 10 5 5 10 light curing
initiator PI-1 One One 3 5 3 3 3 3 3 3

(weight%) Example comparative example 1-11 1-12 1-13 1-14 1-15 1-1 1-2 quantum dots
dispersion A-1 - - - - - - - A-2 - - - - - - - A-3 - - - - - - - A-4 - - - - - - - A-5 - - - - - - - A-6 - - - - - - - A-9 - - - - - - - A-10 - - - - - - - A-11 - - - - - - - A-12 - - - - - - - A-13 55 - - - - - - A-14 - 50 - - - - - A-15 - - 50 - - - - A-16 - - - 50 - - - A-17 - - - 50 - - A-18 - - - - - - - A-19 - - - - - - - A-20 - - - - - - - A-21 - - - - - - - A-22 - - - - - 50 - A-23 - - - - - - 50 photopolymerization
compound MN-1 41 44 44 37 44 44 44 scattering particles One 3 3 10 3 3 5 light curing
initiator PI-1 3 3 3 3 3 3 One

- A-1 to A-21: quantum dot dispersion of Preparation Examples 1 to 21

- A-22: Dispersion in which the quantum dots of Synthesis Example 1 were dispersed 50:50 with HDDA

- A-23: Dispersion in which the quantum dots of Synthesis Example 2 were dispersed 50:50 with HDDA

- MN-1: HDDA (1,6-Hexanediol diacrylate)

- Scattering particles: Scattering particles: TiO ₂ (Huntzmann, TR-88, particle size 220nm)

- PI-1: Irgacure OXE-01 (manufactured by BASF)

Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2: Preparation of light-emitting devices

Example 2-1

ITO is deposited on a glass substrate to form an anode, and PEDOT:PSS and Tris(4-carbazoyl-9-ylphenyl)amine (TCTA) are spin-coated thereon to form a hole transport layer. A light emitting layer is formed by spin coating the quantum dot dispersion A-18 according to Preparation Example 18 on the hole transport layer. AlQ3 is vacuum-deposited on the light emitting layer to form an electron transport layer. A light emitting device is manufactured by depositing Al on the electron transport layer to form a cathode.

Example 2-2

A light emitting device was manufactured in the same manner as in Example 2-1, except that the quantum dot dispersion A-19 according to Preparation Example 19 was used instead of the quantum dot dispersion according to Preparation Example 18.

Example 2-3

A light emitting device was manufactured in the same manner as in Example 2-1, except that the quantum dot dispersion A-20 according to Preparation Example 20 was used instead of the quantum dot dispersion according to Preparation Example 18.

Example 2-4

A light emitting device was manufactured in the same manner as in Example 2-1, except that the quantum dot dispersion A-21 according to Preparation Example 21 was used instead of the quantum dot dispersion according to Preparation Example 18.

Comparative Example 2-1

A light emitting device was manufactured in the same manner as in Example 2-1, except that the quantum dots prepared according to Synthesis Example 1 were used instead of the quantum dot dispersion according to Preparation Example 18.

Comparative Example 2-2

A light emitting device was manufactured in the same manner as in Example 2-1, except that the quantum dots prepared according to Synthesis Example 2 were used instead of the quantum dot dispersion according to Preparation Example 18.

Experimental example

(1) Preparation of light conversion coating layer and measurement of light conversion efficiency

Each of the photoconversion ink compositions prepared in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2 was applied on a 5cmХ5cm glass substrate by an inkjet method, and then g, h, and i lines were applied as an ultraviolet light source. After irradiation at 1000mJ/cm ² using a 1kW high-pressure mercury lamp containing all, the light conversion coating layer was prepared by heating in a heating oven at 180° C. for 30 minutes.

After placing the prepared light conversion coating layer on top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree Corporation), the light conversion efficiency was calculated using a luminance meter (CAS140CT Spectrometer, Instrument systems) using the following math It was measured using Equation 1, and the results are shown in Table 3 below.

[Equation 1]

(2) Viscosity stability evaluation

For the quantum dot dispersions used in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2, using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Co., Ltd.), the number of rotations was 20 rpm, The initial viscosity under the condition of a temperature of 30°C and the viscosity after storage for one month at a low temperature of 5°C were measured. Viscosity stability was evaluated by the rate of change of viscosity and is shown in Table 3 below.

<Evaluation criteria>

○: Viscosity change rate 105% or less

△: Viscosity change rate greater than 105% to 110% or less

×: Viscosity change rate exceeding 110%

(3) Dispersion particle size evaluation

The dispersed particle size of the quantum dot dispersion used in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2 was measured using ELSZ-2000ZS (manufactured by Otsuka Corporation), and the results are shown in Table 3 below. It was.

(4) Number of continuous jetting

After filling the photoconversion ink compositions of Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2 in Unijet's inkjet printing equipment, the temperature of the jetting head was fixed at 40° C., and then the ink was discharged for 1 minute for 30 minutes. The number of continuous jetting was evaluated by repeating the leaving until the nozzle was not discharged due to clogging of the nozzle of the jetting head, and the results are shown in Table 3 below.

(5) Film hardness

The degree of curing of the coating film prepared in the Experimental Example was measured at 150° C. using a hardness meter (HM500; manufactured by Fischer), and the surface hardness was evaluated based on the following criteria. The results are shown in Table 3 below.

<Evaluation criteria>

○: surface hardness of 50 or more

△: surface hardness less than 30 to 50

×: surface hardness less than 30

light conversion efficiency
(%) Viscosity stability dispersed particle size
(nm) Number of consecutive jets film hardness Example 1-1 32.0 ○ 6.4 more than 10 ○ 1-2 32.5 ○ 5.6 more than 10 ○ 1-3 33.0 ○ 6.2 more than 10 ○ 1-4 33.5 ○ 6.5 more than 10 ○ 1-5 34.6 ○ 6.4 more than 10 ○ 1-6 31.5 ○ 6 10 episodes ○ 1-7 31.0 ○ 6.4 more than 10 ○ 1-8 32.5 ○ 5.6 more than 10 ○ 1-9 32.1 ○ 6.2 more than 10 ○ 1-10 33.5 ○ 6.5 more than 10 ○ 1-11 32.4 ○ 6.4 10 episodes ○ 1-12 33.6 ○ 6 more than 10 ○ 1-13 32.0 ○ 6.4 more than 10 ○ 1-14 33.5 ○ 5.6 more than 10 ○ 1-15 34.0 ○ 6.2 more than 10 ○ comparative example 1-1 24.0 △ 24 not measurable x 1-2 23.1 x 32 1 time △

(6) light resistance

QE-2100 (Otsuka) measured the quantum efficiency at the initial stage of manufacturing the quantum dot dispersions of Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-2 and the absolute quantum efficiency after 7 days left in a blue LED light source at room temperature. was measured using

The results are shown in Table 4 below.

light fastness Initial QY (%) QY (%) after leaving for 7 days Δ QY (%) Example 1-1 88 77 88 1-2 90 79 88 1-3 89 81 91 1-4 90 76.5 85 1-5 88 81 92 1-6 86 75 87 1-7 88 79 90 1-8 86 81 94 1-9 87 82 94 1-10 86 78 91 1-11 89 78 88 1-12 84 78 93 1-13 86 76 88 1-14 85 73 86 1-15 87 76 87 comparative example 1-1 74 40 54 1-2 88 35 40

(7) Evaluation of external quantum efficiency, current efficiency and driving voltage

External quantum efficiency (EQE) while applying a voltage (0 V to 8 V) between the ITO electrode and the Al electrode of the light emitting device prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 , current efficiency and driving voltage were measured. The results are shown in Table 5 below.

External Quantum Efficiency (EQE) Current efficiency (Cd/A) Turn on Volate (5mA) Example 2-1 4.2 3.0 3.2 2-2 4.8 3.5 3.5 2-3 5.1 4.6 3.1 2-4 4.9 2.3 3.3 comparative example 2-1 1.9 0.65 5.5 2-2 2.0 1.3 6.0

Referring to Tables 3 and 4, the light conversion ink composition according to the present invention uses quantum dots into which a ligand compound represented by a specific chemical structure is introduced, thereby exhibiting superior light conversion efficiency compared to Comparative Examples 1 and 2 and at the same time more It was confirmed that a stable viscosity characteristic was exhibited. In addition, it was found that the quantum dot dispersions according to the present invention have excellent dispersibility, and the continuous jetting property of the light conversion ink composition of the present invention including the same can improve production efficiency.

For reference, according to the experimental example of Table 5, in the case of a light emitting device using a quantum dot dispersion containing a ligand on the surface of the present invention, compared to the light emitting device of Comparative Examples 2-1 to 2-2 that does not contain a ligand in the quantum dots, the outside It was found that the quantum efficiency and current efficiency were excellent, and the driving voltage performance was also improved.

Claims (16)

A quantum dot having a ligand layer on its surface, comprising:
Quantum dots comprising a compound represented by the following formula (1) in the ligand layer:
[Formula 1]

In Formula 1,
A is

or

ego,
R ₁ and R ₂ are each independently a C ₆ to C ₁₆ arylene group or a C ₅ to C ₁₆ heteroarylene group,
R ₃ and R ₄ are each independently a C ₆ to C ₁₆ aryl group or a C ₅ to C ₁₆ heteroaryl group,
Y is a C ₄ to C ₁₆ fused cyclic aromatic group,
B is a direct bond,

,

,

,

,

,

,

or

is,
C is -(CH ₂ ) _n1 -, -(OCH ₂ CH ₂ ) _n2 - or -(CH ₂ CH ₂ O) _n3 -,
n1 to n3 are each independently an integer of 0 to 20,
F is -COOH, -SH, -NH ₃ ,

,

or

is,
x and y are each independently an integer of 0-4. The quantum dot according to claim 1, wherein the ligand layer includes at least one selected from compounds represented by the following Chemical Formulas 1-1 to 1-9.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

The quantum dot according to claim 1, wherein the sum of x and y in Formula 1 is 4 or more. A quantum dot dispersion in which the quantum dots according to any one of claims 1 to 3 are dispersed including any one or more of a monomer or a solvent. The quantum dot dispersion according to claim 4, wherein the monomer comprises a compound represented by the following formula (2).
[Formula 2]

In Formula 2,
R ₅ is a C ₁ -C ₂₀ alkylene group, a C ₁ -C ₂₀ phenylene group, or a C ₃ -C ₁₀ cycloalkylene group,
R ₆ and R ₇ are each independently hydrogen or a methyl group,
m is an integer from 1 to 15; The method according to claim 5, The compound represented by Formula 2 is 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, 2-hydroxy-3-methacrylpropyl acrylate, 1,9-bisacryloyl oxide A quantum dot dispersion comprising at least one selected from cynonane and tripropylene glycol diacrylate. A light conversion ink composition comprising the quantum dot dispersion according to claim 4, further comprising any one or more selected from scattering particles, a photopolymerizable compound, and a photopolymerization initiator. The method according to claim 7, The scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, MgO, and a light conversion ink composition comprising at least one selected from the group consisting of combinations thereof. The method according to claim 7, 10ppm to 9000ppm of a solvent, or does not contain a solvent, the light conversion ink composition. An electronic device comprising the quantum dots of claim 1 as a light emitting layer. The electronic device according to claim 10, which is applied to a light emitting diode, an organic light emitting diode, a sensor, an imaging sensor, a solar cell or an LCD device. A color filter comprising a cured film formed using the light conversion ink composition according to claim 7. A light conversion laminated substrate comprising a cured film formed using the light conversion ink composition according to claim 7. An image display device comprising the color filter of claim 12 or the light conversion laminated substrate of claim 13 . An image display device comprising the electronic device of claim 10 . The image display device of claim 15 , wherein the electronic device comprises a quantum dot LED (QLED).