JP2021128342A - Light conversion curable composition, quantum dot light-emitting diode, quantum dot film, cured film formed using the composition and image display device including the cured film - Google Patents

Abstract

To provide a light conversion curable composition which is excellent in light conversion efficiency, coated film hardness and adhesion, and keeps excellent characteristics in an inkjet method.SOLUTION: There are a light conversion curable composition containing a quantum dot, an antioxidant, scattered particles, a photopolymerizable compound and a photopolymerizable initiator; a cured film formed using the same; a quantum dot light-emitting diode; and an image display device. The quantum dot has a ligand layer thereon, and the ligand layer contains a compound having a specific chemical structure. A light conversion curable composition is excellent in optical characteristics and reliability, and can be effectively applied to various applications such as a quantum dot film, a quantum dot light-emitting diode, a color filter and a light conversion laminated base material, and thereby can provide a high-quality image display device.SELECTED DRAWING: None

Description

The present invention relates to a photoconversion curable composition, a cured film formed using the same, a quantum dot light emitting diode including the cured film, and an image display device.

In an LCD (Liquid Crystal Display) television that uses a light emitting element (Light Emitting Diode, LED) as a backlight unit (Back Light Unit, BLU), the LED BLU is a part that actually emits light and is the most important part in the LCD television. one of.

As a method for forming a white LED BLU, a white LED BLU is usually formed by combining red (Red, R), green (Green, G), and blue (Blue, B) LED chips, or a blue LED. White is achieved by using a combination of a chip and a yellow (Yello) phosphor having a wide half-width light emitting wavelength.

However, when combining red, green, and blue LED chips, there is a problem that the manufacturing cost is high due to the number of LED chips and complicated processes, and when combining a blue LED chip with a yellow phosphor, green and red colors are used. The wavelength is not classified and the color purity is inferior, which causes a problem of deterioration in color reproducibility.

Recently, much research has been done on the use of quantum dots in applications such as biological imaging, energy conversion, and lighting (LED). The quantum dots have high luminescence and a narrow emission spectrum, the emission wavelength can be adjusted by one excitation wavelength, and the quantum dots have characteristics peculiar to the quantum dots that are stable with respect to light. However, such quantum dots are extremely sensitive to the state of the surface, and there is a problem that oxidation occurs from the surface due to the dispersed solvent and the surrounding environment, and eventually the luminous efficiency sharply decreases.

Many attempts have been made to overcome these problems, and various methods are currently being presented. One of them is a method of functional group substitution (ligand exchange) in which an organic substance existing on the surface of a quantum dot is replaced with a molecule having a desired functional group. This method replaces the organic molecules existing on the surface of the quantum dots with organic molecules suitable for trying to apply them, but it has a direct effect on the surface of the quantum dots, which is fatal to the luminous efficiency. It has the drawback of causing various problems.

Republic of Korea Published Patent No. 10-2018-0002716 and Republic of Korea Registered Patent No. 10-1628065 disclose for quantum dots containing ligands placed on the surface, but they have low compatibility and poor dispersibility. At present, problems such as insufficient stability and reliability, reduced light resistance over time, and insufficient viscosity stability have not been solved.

Further, in the Republic of Korea Registered Patent No. 10-1690624, a polymer resin layer in which a plurality of non-cadmium-based quantum dots are dispersed in a polymer resin and one or both sides are patterned; the polymer resin layer is formed on one surface. A first barrier film; and a second barrier film formed on the other surface of the polymer resin layer; the lower surface of the polymer resin layer is prism-patterned or lens-patterned. When the lower surface of the polymer resin layer is prism-patterned, the pitch of the prism pattern is 20 to 70 μm, the apex angle is 95 to 120 °, the cross section of the pattern is triangular, and the polymer resin. When the lower surface of the layer is a lens pattern, the pitch of the lens pattern is 20 to 70 μm, the pitch to height ratio is 4: 1 to 10: 1, and the cross section of the pattern is a semicircular optical sheet. However, since the structure is complicated by including a barrier layer, a base material layer, etc. in addition to the light emitting layer containing the quantum dots, the emission brightness of the quantum dots is lowered due to this, and the quantum. In order to prevent the problem that the dots are extinguished, the optical film is processed at a low process temperature, so that there is a problem in long-term reliability.

Republic of Korea Published Patent No. 10-2018-0002716 Republic of Korea Registered Patent No. 10-1690624

An object of the present invention is to provide a light conversion curable composition which is excellent in light conversion efficiency, coating film hardness and adhesion, and maintains excellent properties even in an inkjet method.

Another object of the present invention is to provide a photoconvertible curable composition having further improved viscosity stability and light resistance.

Furthermore, the present invention provides a cured film formed by using the photoconversion curable composition, a quantum dot light emitting diode (QLED) including the cured film, and an image display device. The purpose.

The present invention includes quantum dots, antioxidants, scattered particles, photopolymerizable compounds, and photopolymerizable initiators, the quantum dots having a ligand layer on the surface, and the ligand layer is represented by the following chemical formula 1. Provided is a photoconvertible curable composition containing the compound to be used.

(In the chemical formula 1,
A is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and the like. Alkanyl group with 2 to 30 carbon atoms, alkyl ester group with 2 to 30 carbon atoms, heteroaromatic hydrocarbon group with 4 to 30 carbon atoms, thioether group, thioester group with 1 to 30 carbon atoms, silyl group, or carbon number 1 to 30 silyl ester groups,
R ₁ and R ₂ are independently bonded, linear or branched alkylene groups having 1 to 30 carbon atoms, −OR ₁₁ −, −OC (= O) R ₁₂ −, − (OCH _2). CH ₂ ) _m − or − (OCH ₂ CH ₂ CH ₂ ) _l −
L ₁ and L ₂ are independently directly bonded, oxygen atoms, sulfur atoms, or -NH-, respectively.
D is an oxygen atom, a sulfur atom, or = NH,
X is a thiol group, a carboxyl group, an amine group, a phosphoric acid group, an imidazole group, or a tetrazole group.
R ₁₁ is a linear or branched alkylene group having 1 to 30 carbon atoms.
R ₁₂ is a linear or branched alkylene group having 4 to 30 carbon atoms.
m and l are independently integers of 1 to 150.

However, when A is a linear or branched alkyl group having 1 to 30, a cycloalkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, the above

The structure of the eggplant

It cannot be. )
Furthermore, the present invention provides an image display device including a cured film, a quantum dot light emitting diode, and the cured film formed by using the photoconversion curable composition.

The photoconvertible curable composition according to the present invention has high viscosity stability and is suitable for a continuous process by an inkjet method, and the coating film produced thereby exhibits an excellent effect of hardness and adhesion.

In addition, the quantum dots contained in the photoconvertible curable composition according to the present invention protect the surface of the quantum dots by containing a compound represented by a specific chemical formula structure as a ligand layer, and have oxidative stability and reliability. Excellent, prevents deterioration of quantum efficiency, and has excellent optical characteristics.

Therefore, in order to provide the effect of improving all the optical characteristics such as brightness, reliability, process characteristics, etc., the optical conversion curable composition includes a quantum dot film, a color filter, an optical conversion laminated substrate, and a quantum dot light emitting diode. It can be effectively applied to various applications such as, and thus a high-quality image display device can be provided.

The present invention relates to a photoconversion curable composition containing quantum dots, antioxidants, scattered particles, a photopolymerizable compound, and a photopolymerizable initiator, a cured film formed using the same, and a quantum dot containing the cured film. A light emitting diode (Quantum Dot Light-Emitting Diode, QLED) and an image display device are provided.

The photoconvertible curable composition of the present invention can prevent a decrease in quantum efficiency due to oxidation of the quantum dot surface by containing both a quantum dot containing the compound represented by Chemical Formula 1 as a ligand layer and an antioxidant. It exhibits excellent reliability and optical properties, and is characterized by further improved viscosity stability and light resistance.

Hereinafter, the configuration of the present invention will be described in detail.
<Light conversion curable composition>
The photoconvertible curable composition according to the present invention contains quantum dots, antioxidants, scattered particles, photopolymerizable compounds, photopolymerizable initiators, and is optionally selected from alkali-soluble resins and solvents. Can include one or more types.

The photoconversion curable composition may be a photoconversion ink composition or a photoconversion resin composition, and the photoconversion curable composition according to one embodiment of the present invention is a solvent from the viewpoint of continuous processability. It may be a solvent-free type that does not contain. The quantum dot ink composition has high dispersibility and viscosity stability, and can be suitably used for a continuous process by an inkjet method.

The method for producing the photoconvertible curable composition of the present invention is not particularly limited, and a method known in the art can be used.

Quantum dots Quantum dots may be those that emit light by themselves by a light source and are used to generate light in the visible and infrared regions. Quantum dots are substances having a crystal structure of several nanometers, and may be composed of hundreds to thousands of atoms. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. Normally, when these nanoparticles exhibit semiconductor characteristics, they are called quantum dots. .. The quantum dots of the present invention are not particularly limited as long as they conform to such a concept. When an object becomes smaller than nano size, the quantum constraint effect, which is a phenomenon in which the energy band gap (band gap) of the object increases, appears, and the quantum dots receive energy from the outside and reach an excited state. Then, the energy corresponding to the energy band gap is emitted by itself, and self-luminous can be performed.

The quantum dot has a ligand layer on the surface, and the ligand layer contains a compound represented by the following chemical formula 1. As a result, the surface of the quantum dots is protected, the oxidative stability is improved, the decrease in quantum efficiency is prevented, and the reliability can be improved.

In the chemical formula 1, A is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and 2 to 2 carbon atoms. 30 alkenyl groups, alkenyl groups with 2 to 30 carbon atoms, alkyl ester groups with 2 to 30 carbon atoms, heteroaromatic hydrocarbon groups with 4 to 30 carbon atoms, thioether groups, thioester groups with 1 to 30 carbon atoms, silyl It may be a group or a silyl ester group having 1 to 30 carbon atoms.

Further, in Formula 1, _{R 1} and _{R 2} are each independently a direct bond, a straight or branched chain alkylene group having 1 to 30 carbon atoms, _{-OR 11} -, or -OC (= O) It may be _{R 12} −, − (OCH ₂ CH ₂ ) _m −, or − (OCH ₂ CH ₂ CH ₂ ) _{l −.} The R ₁₁ may be a linear or branched alkylene group having 1 to 30 carbon atoms, and may preferably be a linear or branched alkylene group having 1 to 20 carbon atoms. .. The R ₁₂ may be a linear or branched alkylene group having 4 to 30 carbon atoms, or may preferably be a linear or branched alkylene group having 4 to 20 carbon atoms. ..

Further, m and l may be independently integers of 1 to 150, and preferably integers of 1 to 100.

Further, in the chemical formula 1, L ₁ and L ₂ may be directly bonded, an oxygen atom, a sulfur atom, or -NH-, respectively.

Further, in the chemical formula 1, D may be an oxygen atom, a sulfur atom, or = NH.

Further, in the chemical formula 1, X may be a thiol group, a carboxyl group, an amine group, a phosphoric acid group, an imidazole group, or a tetrazole group, preferably a thiol group, a carboxyl group, an amine group, or a phosphoric acid. It may be a group.

However, in the case of the chemical formula 1, A is a linear or branched alkyl group having 1 to 30, a cycloalkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.

The structure of the eggplant

It cannot be. If A is a linear or branched alkyl group having 1 to 30, a cycloalkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and said above.

The structure of the eggplant

If it corresponds to, there is a problem that the hardness of the coating film is reduced.
In one embodiment of the present invention, the compound represented by the chemical formula 1 may be a compound represented by any one of the following chemical formulas 1-1 to 1-51.

In the chemical formulas 1-10 to 1-13, n may be an integer of 1 to 150, preferably an integer of 1 to 100.

The compound represented by the chemical formula 1 of the present invention can play a role of stabilizing the quantum dots by coordinating and bonding to the surface of the quantum dots as an organic ligand. Generally, the produced quantum dots have a ligand layer on the surface, and the ligand layer immediately after production is oleic acid, lauric acid, 2- (2-methoxy). It may consist of ethoxy) acetic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, mono- [2- (2-methoxy-ethoxy) -ethyl] ester of succinic acid and the like. In this case, as compared with the quantum dots of the present invention containing the compound represented by the chemical formula 1 in the ligand layer, the weaker binding force between the ligand layer and the quantum dots causes a non-bonding defect on the surface of the quantum dots. The surface protection effect may be reduced. In the case of oleic acid, it disperses well in unsaturated hydrocarbon solvents such as n-hexane, which is a highly volatile compound (VOC), and aromatic solvents such as chloroform and benzene, but PGMEA. Dispersibility in solvents such as is poor.

The quantum dots according to the present invention can exhibit superior oxidative stability as compared with conventional quantum dots by containing the compound represented by the chemical formula 1 in the ligand layer to protect the surface of the quantum dots. Not only that, it has an excellent dispersibility in a solvent such as PGMEA and has an effect of improving optical characteristics.

In some examples, the quantum dots according to the present invention contain the compound represented by the chemical formula 1 in the ligand layer, whereby oleic acid, lauric acid, 2- (2- (2-). Further can include methoxyethoxy) acetic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, mono- [2- (2-methoxy-ethoxy) -ethyl] ester of succinic acid and the like.

When the ligand layer contains a metal compound as a ligand, the quantum dots according to the present invention may cause a problem that the dispersion stability of the photopolymerizable compound is impaired. Therefore, it is preferable that the quantum dots according to the present invention do not contain a metal compound as a ligand. Examples of the metal compound include, but are not limited to, metal organic salts, metal halides, hydrocarbyl metals, hydrocarbyl metal halides, or combinations thereof.

The quantum dots are not particularly limited as long as they are quantum dot particles that can emit light by stimulation with light or electricity. For example, II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; I-III-VI group semiconductor compounds; II-III-VI group semiconductor compounds; I-II-IV-VI group semiconductors. It can be selected from the group consisting of compounds; group IV elements or compounds containing them; and combinations thereof, and these can be used alone or in combination of two or more. For example, the group II-VI semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSte, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgTe, HgZnS, HgZnSe, HgZnSe, HgZnS. It may be selected from the group consisting of four elemental compounds selected from the group consisting of CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSte, HgZnSeS, HgZnSeTe, HgZnSte, and a mixture thereof, but is not limited thereto.

The Group III-V semiconductor compound is a two-element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A three-element compound selected from the group consisting of GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, It may be selected from the group consisting of four element compounds selected from the group consisting of GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It is not limited to.

The IV-VI group semiconductor compound is a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnPbSe, SnPbTe, and a mixture thereof; and one or more selected from a group consisting of a four-element compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and a mixture thereof. It may be, but it is also not limited to this.

The group I-III-VI semiconductor compound is a three-element compound selected from the group consisting of CuInS, CuInSe, CuInTe, CuGaS, CuGaSe, CuGaTe, AgInS, AgInSe, AgInTe, AgGaS, AgGaSe, AgGaTe, and mixtures thereof; And, but not limited to, one or more selected from the group consisting of four elemental compounds selected from the group consisting of CuInGaS, CuInGaSe, CuInSeS, CuGaSeS, AgInGaS, and mixtures thereof. ..

The II-III-VI group semiconductor compounds include ZnGaS, ZnAlS, ZnInS, ZnGaSe, ZnAlSe, ZnInSe, ZnGaTe, ZnAlTe, ZnInTe, ZnGaO, ZnAlO, ZnInO, HgGaS, HgAlS, HgInS, HgGaSe, HgGe , HgInTe, MgGaS, MgAlS, MgInS, MgGaSe, MgAlSe, MgInSe, and one or more selected from the three-element compounds selected from the group consisting of mixtures thereof, but is not limited thereto. No.

The II-III-VI group semiconductor compounds include ZnGaS, ZnAlS, ZnInS, ZnGaSe, ZnAlSe, ZnInSe, ZnGaTe, ZnAlTe, ZnInTe, ZnGaO, ZnAlO, ZnInO, HgGaS, HgAlS, HgInS, HgGaSe, HgGe , HgInTe, MgGaS, MgAlS, MgInS, MgGaSe, MgAlSe, MgInSe, and one or more selected from the three-element compounds selected from the group consisting of mixtures thereof, but is not limited thereto. No.

The group IV element or a compound containing the same is selected from the group consisting of Si, Ge, and a mixture thereof; and the group consisting of SiC, SiGe, and a mixture thereof. It may be selected from the group consisting of two elemental compounds.

Quantum dots may be a homogeneous single structure; a dual structure such as a core-shell structure and a gradient structure; or a mixed structure thereof, or the present invention. In the above, the type of the quantum dot is not particularly limited as long as it can emit light by stimulation with light.

According to one embodiment, the quantum dots have a core-shell structure, wherein the cores are InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS. , PbTe, AgInZnS, AgInGaS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN, InAs, and ZnO.

Further, in the core-shell structure, the shell is ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, GaS, InZnP, InGaP, InGaN, InZnSCdSe, PbS. , TiO, SrSe, and HgSe, including, but not limited to, one or more selected from the group.

According to one embodiment, the quantum dots of the core-shell structure are AgInGaS / GaS, InP / ZnS, InP / ZnSe, InP / GaP / ZnS, InP / ZnSe / ZnS, InP / ZnSeTe / ZnS, and InP / It can include, but is not limited to, one or more selected from the group consisting of MnSe / ZnS.

In general, quantum dots can be produced by a wet chemical process, a metalorganic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE).

The quantum dots according to the present invention can be synthesized by a wet chemical process.
The wet chemical step is a method in which a precursor substance is put into an organic solvent to grow particles. When the crystal grows, the organic solvent naturally coordinates with the surface of the quantum dot crystal and acts as a dispersant. Since the crystal growth is regulated, the growth of the size of the quantum dot particles can be controlled by a process that is easier and cheaper than the vapor phase vapor deposition method such as organic metal chemical vapor deposition or molecular beam epitaxy.

When quantum dots are produced by a wet chemical process, organic ligands are used to prevent quantum dot agglutination and control the particle size of the quantum dots to the nano level. As such an organic ligand, oleic acid can generally be used.

In one embodiment of the present invention, the oleic acid used in the process of producing the quantum dots is replaced by the compound represented by the chemical formula 1 by the ligand exchange method.

In the ligand exchange, the organic ligand to be exchanged, that is, the compound represented by Chemical Formula 1, is added to the dispersion liquid containing the original organic ligand, that is, the quantum dots having oleic acid, and this is added at room temperature to 200 ° C. It is carried out by stirring for 30 minutes to 3 hours to obtain quantum dots to which the compound represented by Chemical Formula 1 is bonded. If necessary, an additional step of separating and purifying the quantum dots to which the compound of Chemical Formula 1 is bonded may be performed.

As described above, the quantum dots according to the embodiment of the present invention have an advantage that they can be produced by an organic ligand exchange method under a simple stirring treatment at room temperature and can be mass-produced.

In addition, the quantum dots according to the embodiment of the present invention can maintain a quantum efficiency of about 90% or more of the initial quantum efficiency even after 15 days, can be stably stored for a long period of time, and are commercially available for various purposes. Can be converted.

As the quantum dots, it is preferable to manufacture and use a quantum dot dispersion liquid in which the quantum dots are uniformly dispersed. The quantum dot dispersion liquid contains the above-mentioned quantum dots, contains one or more of a photopolymerizable compound and a solvent, and specific matters concerning the photopolymerizable compound and the solvent will be described later.

The quantum dots may be contained in an amount of 1 to 75% by weight, preferably 3 to 70% by weight, more preferably 5 to 60% by weight, based on the total weight of the photoconvertible curable composition. When the quantum dots are included in the range, there are advantages that the luminous efficiency is excellent and the reliability of the light conversion coating layer produced by the light conversion curable composition is excellent.

Antioxidant The antioxidant acts to help prevent the quantum dots from oxidizing by reacting with oxygen radicals that may be generated during the process.

The antioxidant may contain one or more selected from phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants, and may remove or decompose all oxygen radicals and peroxides. It is possible to include both a phosphorus-based antioxidant and a phenol-based antioxidant from the viewpoint that the light resistance can be improved and the viscosity stability can be improved by preventing the quantum dots from aggregating. preferable.

In addition, the antioxidant may contain one or more selected from the compounds represented by the following chemical formulas 2-1 to 2-7.

In the chemical formula 2-1
R ₁₃ is an alkylene group having 1 to 10 carbon atoms.
R _{14 to} R ₂₅ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

In the chemical formula 2-2,
R _{26 to} R ₃₄ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

In the chemical formula 2-3,
R ₃₆ and R ₃₇ are alkylene groups having 1 to 10 carbon atoms.
R _{38 to} R ₄₁ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

In the chemical formula 2-4,
R _{42 to} R ₄₅ are alkylene groups having 1 to 10 carbon atoms.
R _{46 to} R ₅₃ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

In the chemical formula 2-5,
R _{55 to} R ₅₇ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms.

In the chemical formula 2-6,
R ₅₈ is − (OCH ₂ CH ₂ ) _k −, and k is an integer of 1 to 5.
R ₅₉ and R ₆₀ are independently alkylene groups having 1 to 10 carbon atoms.
R _{61 to} R ₆₈ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

In the chemical formula 2-7,
R ₆₉ is an alkylene group having 1 to 10 carbon atoms.
R _{70 to} R ₇₃ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.
R ₇₄ is an alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present invention, the antioxidant may include a compound represented by the chemical formula 2-1 and a compound represented by the chemical formula 2-5. In this case, the effect of improving the light resistance can be maximized, which is preferable.

The phosphorus-based antioxidant is, for example, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] Undecane, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyl) Oxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) Ditridecyl) phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl) -4-Hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , Tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6) -Di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-Di-t-Butylphenyl) [1,1-biphenyl] -4,4'diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl Esters, phosphonic acid and the like, preferably 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz. [D, f] [1,3,2] Dioxaphosfepine and diphenylisodecylphosphite can be used, but are not limited thereto.

The phenolic antioxidant is, for example, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy] -2. , 4,8,10-Tetraoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5, -trimethyl -2,4,6,-Tris (3'5'-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy) Phenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3 5-Tris (4-t-Butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-) t-Butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,4 -Bis [(octylthio) methyl] -O-cresol, 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl- [3-( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-) t-Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene, and tetrakis [methylene- 3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane and the like can be mentioned, preferably pentaerythritol tetrakis [3- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hi) Droxyphenyl) propionate], 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), octadecyl- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, And triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] can be used, but is not limited thereto.

The sulfur-based antioxidant is, for example, 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthiodipropionate, dimyristyl-). Examples thereof include 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate), and 2-mercaptobenzimidazole. Not limited to these.

In one embodiment of the present invention, as the antioxidant, a compound containing two or more selected from a phosphorus atom, a sulfur atom, and a phenol group in one molecule can be used, and as a specific example thereof, a compound can be used. 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] di Oxaphosphepine and 2,2-thio-diethylenebisthio) propionate], 2-mercaptobenzimidazole, dilauryl-3,3'-[3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], but is not limited to these.

The antioxidant is contained in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight, based on the total weight of the photoconvertible curable composition. When the antioxidant is included in the range, there is an advantage that the oxidation of the quantum dots can be effectively prevented during the process and the decrease in quantum efficiency can be minimized.

Scattered particles The scattered particles can use ordinary inorganic materials, and preferably contain a metal oxide having an average particle size of 30 to 1000 nm.

The metal oxides include 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, It may be, but is not limited to, an oxide containing one metal selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof.

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, materials surface-treated with compounds having unsaturated bonds, such as acrylates, can also be used.

When the quantum dot light conversion composition according to the present invention contains scattered particles, it increases the path of light spontaneously emitted from the quantum dots through the scattered particles to increase the overall light efficiency of the color filter. Is possible and preferable.

Preferably, the scattered particles can have an average particle size of 30 to 1000 nm, preferably those in the range of 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, and conversely, if the particle size is too large, it sinks in the composition or is uniform. Since the surface of the self-luminous layer of quality cannot be obtained, it is used after being appropriately adjusted within the above range.

The scattered particles are contained in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the photoconvertible curable composition. When the scattered particles are included in the range, there is an advantage that the overall light efficiency can be effectively improved.

Photopolymerizable compound The photopolymerizable compound acts to improve the dispersibility of quantum dots.

Examples of the photopolymerizable compound include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers, and a bifunctional or higher functional monomer can be preferably used.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl acrylate.

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

The type of the polyfunctional monomer is not particularly limited, and for example, trimethyl propantri (meth) acrylate, ethoxylated trimethylol propanthry (meth) acrylate, propoxylated trimethylol propanthry (meth) acrylate, and pentaerythritol tri. (Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate ) Acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

The content of the photopolymerizable compound is 10 to 90% by weight, preferably 25 to 85% by weight, based on the total weight of the photoconvertible curable composition. When the photopolymerizable compound is contained within the above range, it is preferable because the dispersibility characteristics of the quantum dots are good, the coating or jetting characteristics are excellent, and the optical characteristics and reliability are excellent.

Photopolymerization Initiator The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound described above, and is not particularly limited in the present invention, but has polymerization characteristics, start efficiency, absorption wavelength, availability, and price. From the above viewpoints, it is preferable to use one or more compounds selected from the group consisting of acetphenone-based compounds, benzophenone-based compounds, triazine-based compounds, oxime-based compounds, thioxanthone-based compounds, and benzoin-based compounds.

Specific examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, and pt. Examples thereof include −butyldichloroacetophenone, 4-chloroacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (methylthio) phenyl) -2-morpholinopropane-1-one and the like.

Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino). ) Benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3', 4'-dimethoxystyryl)-. 4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tolyl-4,6-bis (trichloromethyl) -s-triazine, 2-pipenyl-4,6-bis (trichloromethyl) -s-triazine, Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2-4-trichloromethyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. −On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl6- (2-methylbenzoyl) -9H-carbazole] -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-one-2-imine, N-acetyloxy-1- [9- (2-ethylhexyl) -6- (2,4,6-trimethylbenzoyl) -9H-benzo [i] carbazole-3-yl]- Examples thereof include 3- [1- (2,2,3,3-tetrafluoropropyloxy) phenyl] methaneimine.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

In addition to the above examples, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, acylphosphine compounds and the like can also be used as photopolymerization initiators.

The content of the photopolymerization initiator is 0.1 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the photoconvertible curable composition. When the photopolymerization initiator is contained within the above range, photopolymerization occurs sufficiently during exposure in the pattern forming step, and a decrease in transmittance due to the unreacted initiator remaining after photopolymerization can be prevented, which is preferable.

Alkali-soluble resin The alkali-soluble resin may be one or more selected from the group consisting of acrylic alkali-soluble resins and cardo-based alkali-soluble resins.

The acrylic alkali-soluble resin or the cardo-based alkali-soluble resin has a reactivity due to the action of light or heat, and acts to improve the dispersibility of quantum dots. The acrylic alkali-soluble resin or cardo-based alkali-soluble resin contained in the photoconversion curable composition of the present invention acts as a binder resin for quantum dots and can be used as a support for a photoconversion coating layer. There is no particular limitation.

When the photoconvertible curable composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin is 5 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the photoconvertible curable composition. Included in% by weight. When the alkali-soluble resin is contained within the above range, it is possible to prevent a decrease in the film thickness of the pixel portion and improve the dispersibility characteristics of the quantum dots, which is preferable.

Solvent As the solvent, a solvent usually used in the art can be used without particular limitation as long as it is effective in dissolving other components contained in the photoconvertible curable composition. As a specific example, the solvent may be used by selecting one or more from ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like. It is not limited.

Specifically, the ether solvent is ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene 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; and the like.

Specific examples of the acetate solvent include alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate;
Alkoxyalkyl acetates such as methoxybutyl acetate, methoxypentyl acetate, and n-pentyl acetate; and the like.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and the like.

Specific examples of the alcohol solvent include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like.

Specific examples of the ester solvent include cyclic esters such as γ-butyrolactone; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and the like.

Specific examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents can be used alone or in admixture of two or more.
When the photoconvertible curable composition of the present invention contains the solvent, the content of the solvent is 10 to 90% by weight, preferably 20 to 80% by weight, based on the total weight of the photoconvertible curable composition. , More preferably 30 to 70% by weight. When the solvent is contained within the above range, it is preferable because the dispersibility characteristics of the quantum dots are good, the coating or jetting characteristics are excellent, and the optical characteristics and reliability are excellent.

<Cured film>
The present invention provides a cured film formed using the light conversion curable composition, and the cured film may be a color filter, a light conversion laminated base material, or a quantum dot film.

Color filter As the pattern forming method for forming the color filter of the present invention, a method known in the art can be used.

In one embodiment, the pattern forming method is
a) The step of applying the quantum dot ink composition or the light conversion curable composition to the substrate, and
b) Pre-baking step to dry the solvent and
c) A step of applying a photomask on the obtained film and irradiating it with active light to cure the exposed part.
d) A step of performing a developing step of dissolving an unexposed portion using an alkaline aqueous solution, and
e) Can include drying and post-baking execution steps.

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

At this time, the coating is performed by a known wet method using a coating 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 so that a desired thickness can be obtained. It is done by the coating method.

Pre-baking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and the heating time in the prebake are appropriately selected according to the solvent used, and are carried out, for example, at a temperature of 80 to 150 ° C. for 1 to 30 minutes.

Further, the exposure performed after the prebaking is performed by an exposure device and exposed through a photomask to expose only the portion corresponding to the pattern. As the light to be irradiated at this time, for example, visible light, ultraviolet rays, X-rays, electron beams and the like can be used.

The developing step of dissolving the unexposed portion with the alkaline aqueous solution after exposure is performed for the purpose of removing the photosensitive resin composition of the unexposed portion of the unexposed portion, and a desired pattern is formed by this development. NS. As a developing solution suitable for development using this alkaline aqueous solution, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used. In particular, using an alkaline aqueous solution containing less than 1 to 3% by weight of carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc., in a temperature range of 10 to 50 ° C., preferably 20 to 40 ° C., a developer or ultrasonic cleaner. This can be done using a washing machine or the like.

Post-baking is performed in order to improve the adhesion between the patterned film and the substrate, and is performed, for example, by heat treatment at 80 to 250 ° C. for 10 to 120 minutes. Like pre-baking, post-baking can be performed using an oven, a hot plate, or the like.

Photo-conversion laminated base material The photo-conversion laminated base material according to the present invention contains a cured product of a photo-conversion curable composition. By containing a light conversion curable composition that can be coated on a glass base material, the light conversion laminated base material can use a solvent that does not correspond to a harmful substance to the human body, and improves the safety of workers and the productivity of products. Can be done.

The photoconversion laminated substrate may be silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be a polyether sulfone (PES) or a polycarbonate (polycarbonate,). PC) or the like.

The photoconversion laminated base material is formed by applying the photoconversion curable composition and thermosetting or photocuring.

Quantum dot film The quantum dot film according to the embodiment of the present invention can be produced by using the above-mentioned photoconversion curable composition.

The quantum dot film may additionally include a barrier layer on at least one surface of the quantum dot dispersion layer.

The barrier layer can have an oxygen permeability of 0.001 ^{cm 3} / m ^{2 · bar or less and a water permeability of 0.001 g / m 2} · day or less, for example, polyester, polycarbonate, polyolefin, cyclic. It can contain an olefin polymer or a polyimide.

The thickness of the quantum dot dispersion layer may be 10 μm to 100 μm, and the thickness of the barrier layer may be 50 μm to 70 μm.

The method for producing the quantum dot film of the present invention is not particularly limited, and a method known in the art can be used.

As an embodiment, a method for manufacturing a quantum dot film is
a) Steps to prepare the lower transparent base material and
b) The step of applying the photoconversion curable composition to the lower transparent substrate to form a thin film,
c) It can include a step of adhering an upper transparent base material on the thin film to produce a quantum dot film.

<Quantum dot light emitting diode>
The quantum dot light emitting diode (QLED) according to an embodiment of the present invention can include a cured film formed by using the above-mentioned photoconversion curable composition.

The quantum dot light emitting diode is an electroluminescence (EL) type device that electrically excites quantum dots to emit light.

In the quantum dot light emitting diode, electrons and holes injected from the electrodes on both sides form excitons in the quantum dot light emitting layer, and light is emitted by radiation recombination of the excitons. Since this has the same operating principle as an organic light-emitting diode (OLED), only the light emitting layer emits organic light in a multilayer element structure using the electron / hole injection layer and transport layer of an ordinary OLED as they are. It is constructed by substituting quantum dots instead of materials.

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

As one embodiment, the method for manufacturing a quantum dot light emitting diode can be manufactured by sequentially laminating an anode, a cathode, an electron injection / transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

As another embodiment, the method for manufacturing the quantum dot light emitting diode may be manufactured by sequentially laminating a cathode, an electron injection / transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode. As yet another embodiment, in the method for manufacturing a quantum dot light emitting diode, an anode, a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, an electron injection / transport layer, and a cathode are sequentially laminated. May be manufactured.

At this time, the light emitting layer can include a cured film formed by using the above-mentioned photoconversion curable composition.

<Image display device>
The image display device according to the present invention includes the above-mentioned cured film, that is, a color filter, a light conversion laminated base material, or a quantum dot film, and can include the above-mentioned quantum dot light emitting diode. Specifically, the image display device includes 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 mobile terminal such as a mobile phone, and the like. Examples include display devices such as digital camera display devices and car navigation display devices, and color display devices are particularly suitable.

The image display device includes, and may further include, configurations known to those skilled in the art of the present invention, except that it comprises the color filter or a light conversion laminated substrate, that is, the present invention. , Color filters, light conversion laminated substrates, or image display devices to which quantum dot films can be applied.

The image display device including the color filter according to the present invention can have excellent characteristics in color reproducibility, brightness, light resistance, reliability and the like.

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

<Example>
Synthesis Example 1: Synthesis of InP / ZnSe / ZnS core-shell quantum dots Indium acetate 0.4 mmol (0.058 g), palmitic acid 0.6 mmol (0.15 g), and 1-octadecene 20 mL of (octadecene) was 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 (TMS3P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 0.5 minutes.

Then, 2.4 mmol (0.448 g) of zinc acetate, 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, then 4.8 mmol of selenium (Se / TOP) in trioctylphosphine was added, and then the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled 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 (0.448 g) of zinc acetate, 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. After adding 2 mL of the previously synthesized InP core solution and then adding 4.8 mmol of sulfur (S / TOP) in trioctylphosphine, the final mixture was reacted for 2 hours. Ethanol is added to a reaction solution that has been rapidly cooled at room temperature, and the precipitate obtained by centrifugation is filtered under reduced pressure and then dried under reduced pressure to obtain quantum dots having an InP / ZnSe / ZnS core-shell structure, which are then converted to chloroform. Distributed. The solid content was adjusted to 10%. The maximum emission wavelength was 520 nm.

Production Examples 1-1 to 1-51 and Comparative Examples 1-1 to 1-8: Production of Quantum Dots Production Example 1-1: Ligand Substitution Reaction 1 (LE-1)
5 mL of the quantum dot solution obtained in Synthesis Example 1 was placed in a centrifuge tube, and 20 mL of ethanol was added for precipitation. The upper layer liquid is discarded by centrifugation, 3 mL of chloroform is added to the precipitate to disperse the quantum dots, and then 1.0 g of 2-Mercaptoethyl methyl glulate (Alfa Chemistry) represented by the following chemical formula 1-1 is added. It was put in and reacted for 1 hour while heating at 60 ° C. in a nitrogen atmosphere.

Next, 25 mL of n-hexane was added to the reaction product to precipitate quantum dots, and then centrifugation was performed to separate the precipitate to obtain a ligand-substituted quantum dot powder (LE-1). The maximum emission wavelength was 520 nm.

Production Example 1-2. Ligand substitution reaction 2 (LE-2)
The procedure was carried out in the same manner as in Production Example 1-1, except that allyl-mercaptooctanoate (ChemTik) represented by the following chemical formula 1-2 was used instead of the ligand used in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-3. Ligand substitution reaction 3 (LE-3)
Instead of the ligand used in Production Example 1-1, 4-Oxo-4- (prop-2-yn-1-ylamino) butanoic acid (Compi-Blocks Inc.) represented by the following chemical formula 1-3 was used. Except for the fact that it was used, the process proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 521 nm.

Production Example 1-4. Ligand substitution reaction 4 (LE-4)
Production Example 1-except that propionic acid represented by the following chemical formula 1-4, 3- (acetylthio)-, and carboxymethyl ester (Angene Chemical) were used instead of the ligand used in Production Example 1-1. It proceeded in the same manner as in 1. The maximum emission wavelength was 520 nm.

Production Example 1-5. Ligand substitution reaction 5 (LE-5)
Production Example 1-except that a Butanedioic acid represented by the following chemical formula 1-5, mono [2- (trimethylsilyl) ester] ester (ChemTik) was used instead of the ligand used in Production Example 1-1. It proceeded in the same manner as in 1. The maximum emission wavelength was 521 nm.

Production Example 1-6. Ligand substitution reaction 6 (LE-6)
The same as in Production Example 1-1, except that 2- (3-trihydroxysilropylcarbamoylamino) acetic acid (ChemTik) represented by the following chemical formula 1-6 was used instead of the ligand used in Production Example 1-1. I made it progress. The maximum emission wavelength was 521 nm.

Production Example 1-7. Ligand substitution reaction 7 (LE-7)
Same as in Production Example 1-1, except that 6-[(Cyclohexylcarbamoyl) amino] hexanoic acid (Ambed) represented by the following chemical formula 1-7 was used instead of the ligand used in Production Example 1-1. Proceeded to. The maximum emission wavelength was 522 nm.

Production Example 1-8. Ligand substitution reaction 8 (LE-8)
Same as Production Example 1-1, except that 6- (3-phenylureido) caproic acid (Ange Chemical) represented by the following chemical formula 1-8 was used instead of the ligand used in Production Example 1-1. Proceeded to. The maximum emission wavelength was 521 nm.

Production Example 1-9. Ligand substitution reaction 9 (LE-9)
Production Example 1-except that 3-[((benzylthio) carbonothioyl) thio] propionic acid (TCI) represented by the following chemical formula 1-9 was used instead of the ligand used in Production Example 1-1. It proceeded in the same manner as in 1. The maximum emission wavelength was 521 nm.

Production Example 1-10. Ligand substitution reaction 10 (LE-10)
With the exception of Production Example 1-1, except that SH-PEG-Silane (Biochemeg, MW600) represented by the following chemical formula 1-10 was used instead of the ligand used in Production Example 1-1. It proceeded in the same manner. The maximum emission wavelength was 520 nm.

Production Example 1-11. Ligand substitution reaction 11 (LE-11)
_{Production Example 1-1, except that Silane-PEG-NH 2} (Biochemeg, MW1K) represented by the following chemical formula 1-11 was used instead of the ligand used in Production Example 1-1. Proceeded in the same way as. The maximum emission wavelength was 520 nm.

Production Example 1-12. Ligand substitution reaction 12 (LE-12)
_{Production Example 1-1, except that Monoethoxysilane-PEG-NH 2} (Biochempeg, MW5K) represented by the following chemical formula 1-12 was used instead of the ligand used in Production Example 1-1. Proceeded in the same way as. The maximum emission wavelength was 522 nm.

Production Example 1-13. Ligand substitution reaction 13 (LE-13)
_{Production Example 1-except that Silane-PEG-NH 2} (Nanosoft Polymers, MW1K) represented by the following chemical formula 1-13 was used instead of the ligand used in Production Example 1-1. It proceeded in the same manner as in 1. The maximum emission wavelength was 522 nm.

Production Example 1-14. Ligand substitution reaction 14 (LE-14)
The procedure was carried out in the same manner as in Production Example 1-1, except that N- (benzyloxycarbonyl) aminomethylphosphonic acid (Chemspace) represented by the following chemical formula 1-14 was used instead of the ligand used in Production Example 1-1. rice field. The maximum emission wavelength was 523 nm.

Production Example 1-15. Ligand substitution reaction 15 (LE-15)
Similar to Production Example 1-1, except that N-Fmoc-1-aminomethylphosphonic acid (BOC Sciences) represented by the following chemical formula 1-15 was used instead of the ligand used in Production Example 1-1. I made it progress. The maximum emission wavelength was 523 nm.

Production Example 1-16. Ligand substitution reaction 16 (LE-16)
Production Example 1-1, except that 2- (2'-acetoxypropionic acid) propionic acid (Aurora Fine Chemicals) represented by the following chemical formula 1-16 was used instead of the ligand used in Production Example 1-1. Proceeded in the same way as. The maximum emission wavelength was 522 nm.

Production Example 1-17. Ligand substitution reaction 17 (LE-17)
Proceed in the same manner as in Production Example 1-1, except that 5-methoxycarbonyl-4-oxopentanoic acid (ChemTik) represented by the following chemical formula 1-17 was used instead of the ligand used in Production Example 1-1. I let you. The maximum emission wavelength was 522 nm.

Production Example 1-18. Ligand substitution reaction 18 (LE-18)
Instead of the ligand used in Production Example 1-1, 4-oxo-1,7-heptanedionic acid, monomethyl ester (self-synthesized; Synthetic Communications, 1983, vol. 13, # 3) represented by the following chemical formula 1-18. , P.243-254), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 523 nm.

Production Example 1-19. Ligand substitution reaction 19 (LE-19)
Except that 2- (2-methoxy-2-oxoacetic acido) acetic acid (Debye Scientific Co., Ltd) represented by the following chemical formula 1-19 was used instead of the ligand used in Production Example 1-1. The process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-20. Ligand substitution reaction 20 (LE-20)
Instead of the ligand used in Production Example 1-1, methyl-2- (4-imidazolyl) ethylamide (self-synthesis; Nucleosides, nucleosides and nucleic acids, 2005, vol.24, #) represented by the following chemical formula 1-20. The process was carried out in the same manner as in Production Example 1-1, except that 9, p.1333-1343) was used. The maximum emission wavelength was 521 nm.

Production Example 1-21. Ligand substitution reaction 21 (LE-21)
Instead of the ligand used in Production Example 1-1, 8-methoxy-6-oxo-octanoic acid represented by the following chemical formula 1-21 (self-synthesis; Journal of the American Chemical Society, 1955, vol.77, p. The process was carried out in the same manner as in Production Example 1-1, except that .2534) was used. The maximum emission wavelength was 521 nm.

Production Example 1-22. Ligand substitution reaction 22 (LE-22)
Production Example 1 except that 3- (2-methoxy-ethylcarbamoyl sulfanyl) -propionic acid (Angene International Limited) represented by the following chemical formula 1-22 was used instead of the ligand used in Production Example 1-1. It proceeded in the same manner as -1. The maximum emission wavelength was 522 nm.

Production Example 1-23. Ligand substitution reaction 23 (LE-23)
The process was carried out in the same manner as in Production Example 1-1, except that instead of the ligand used in Production Example 1-1, an acetic acid (BOC Sciences) represented by the following chemical formula 1-23 was used. .. The maximum emission wavelength was 523 nm.

Production Example 1-24. Ligand substitution reaction 24 (LE-24)
Instead of the ligand used in Production Example 1-1, a methylcarbamimidoylmercapto-acetic acid represented by the following chemical formula 1-24 (self-synthesis; Acta Chemica Scandinavica (1947), 1967, vol.21, p.843-848; CAS). The process was carried out in the same manner as in Production Example 1-1, except that No. 16321-22-4) was used. The maximum emission wavelength was 521 nm.

Production Example 1-25. Ligand substitution reaction 25 (LE-25)
Instead of the ligand used in Production Example 1-1, an acetic acid (self-synthesized; Organic and Biomolecular Chemistry, 2012, vol.10, # 5, p.) Represented by the following chemical formula 1-25. The process was carried out in the same manner as in Production Example 1-1, except that 978-987; CAS No. 16974-45-1) was used. The maximum emission wavelength was 522 nm.

Production Example 1-26. Ligand substitution reaction 26 (LE-26)
Instead of the ligand used in Production Example 1-1, 2- [2- (1 (3) H-imidazol-4-yl) -ethyl] -1-methyl-isothiourea represented by the following chemical formula 1-26 ( The process was carried out in the same manner as in Production Example 1-1, except that (Angene Chemical) was used. The maximum emission wavelength was 522 nm.

Production Example 1-27. Ligand substitution reaction 27 (LE-27)
Instead of the ligand used in Production Example 1-1, 2- (allyloxy) ethyl3-mercaptopropanoate represented by the following chemical formula 1-27 (Synthesis itself; J. Med. Chem. 2019, 62, 2, 699-726) Was used, and the process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 521 nm.

Production Example 1-28. Ligand substitution reaction 28 (LE-28)
Instead of the ligand used in Production Example 1-1, 2- (2- (allyloxy) ethoxy) ethyl3-mercaptopropanoate (self-synthesized; J. Med. Chem. 2019, 62, 2) represented by the following chemical formula 1-28. , 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 521 nm.

Production Example 1-29. Ligand substitution reaction 29 (LE-29)
Instead of the ligand used in Production Example 1-1, 2- (2- (2- (allyloxy) ethoxy) ethyl3-mercaptopropanoate (self-synthesized; J. Med. Chem.) Represented by the following chemical formula 1-29. It proceeded in the same manner as in Production Example 1-1 except that 2019, 62, 2, 699-726) was used. The maximum emission wavelength was 522 nm.

Production Example 1-30. Ligand substitution reaction 30 (LE-30)
Instead of the ligand used in Production Example 1-1, 3,6,9,12-tetraoxapentadec-14-enyl3-mercaptopropanoate (synthesized by itself; J. Med. Chem. 2019, 62) represented by the following chemical formula 1-30. , 2, 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-31. Ligand substitution reaction 31 (LE-31)
Instead of the ligand used in Production Example 1-1, 2- (vinyloxy) ethyl3-mercaptopropanoate represented by the following chemical formula 1-31 (Synthesis itself; J. Med. Chem. 2019, 62, 2, 699-726) Was used, and the process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 520 nm.

Production Example 1-32. Ligand substitution reaction 32 (LE-32)
Instead of the ligand used in Production Example 1-1, 2- (2- (vinyloxy) ethoxy) ethyl3-mercaptopropanoate (self-synthesized; J. Med. Chem. 2019, 62, 2) represented by the following chemical formula 1-32. , 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-33. Ligand substitution reaction 33 (LE-33)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxyoctadec-17-enyl3-mercaptopropanoate (self-synthesized; J. Med. Chem. 2019) represented by the following chemical formula 1-33. , 62, 2, 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-34. Ligand substitution reaction 34 (LE-34)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxaheptadec-16-enyl3-mercaptopropanoate (synthesized by itself; J. Med. Chem. 2019) represented by the following chemical formula 1-34. , 62, 2, 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-35. Ligand substitution reaction 35 (LE-35)
Instead of the ligand used in Production Example 1-1, 3-mercapto-N- (3,6,9,12-tetraoxapentadec-14-enyl) propanamide (synthesized by itself; J. et al.) Represented by the following chemical formula 1-35. The process was carried out in the same manner as in Production Example 1-1, except that Med. Chem. 2019, 62, 2, 699-726) was used. The maximum emission wavelength was 522 nm.

Production Example 1-36. Ligand substitution reaction 36 (LE-36)
Instead of the ligand used in Production Example 1-1, 3-mercapto-N- (3,6,9,12,15-pentaoxaoctadec-17-enyl) propanamide (synthesized by itself; The process was carried out in the same manner as in Production Example 1-1, except that J. Med. Chem. 2019, 62, 2, 699-726) was used. The maximum emission wavelength was 522 nm.

Production Example 1-37. Ligand substitution reaction 37 (LE-37)
Instead of the ligand used in Production Example 1-1, 3- (3- (3- (allyloxy) ropoxy) ropoxy) ropyl3-mercaptopropanoate (synthesized by itself; J. Med. Chem. It proceeded in the same manner as in Production Example 1-1 except that 2019, 62, 2, 699-726) was used. The maximum emission wavelength was 522 nm.

Production Example 1-38. Ligand substitution reaction 38 (LE-38)
Instead of the ligand used in Production Example 1-1, 4,8,12,16-tetraoxanonedec-18-enyl3-mercaptopropanoate (synthesized by itself; J. Med. Chem. 2019, 62) represented by the following chemical formula 1-38. , 2, 699-726), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-39. Ligand substitution reaction 39 (LE-39)
Instead of the ligand used in Production Example 1-1, 2- (2- (allyloxy) ethoxy) ethyl3-amipopropanoate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-39 was used. Except, the process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 520 nm.

Production Example 1-40. Ligand substitution reaction 40 (LE-40)
Instead of the ligand used in Production Example 1-1, 2- (2- (vinyloxy) ethoxy) ethyl3-amipopropanoate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-40 was used. Except, the process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 520 nm.

Production Example 1-41. Ligand substitution reaction 41 (LE-41)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxyoctadec-17-enyl2-aminoacetylate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-41 was used. It proceeded in the same manner as in Production Example 1-1 except that it was used. The maximum emission wavelength was 522 nm.

Production Example 1-42. Ligand substitution reaction 42 (LE-42)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxaheptadec-16-enyl2-aminoacetylate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-42 was used. It proceeded in the same manner as in Production Example 1-1 except that it was used. The maximum emission wavelength was 522 nm.

Production Example 1-43. Ligand substitution reaction 43 (LE-43)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxaheptadec-16-enyl3-aminopropanoate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-43 was used. It proceeded in the same manner as in Production Example 1-1 except that it was used. The maximum emission wavelength was 522 nm.

Production Example 1-44. Ligand substitution reaction 44 (LE-44)
Instead of the ligand used in Production Example 1-1, 3,6,9,12,15-pentaoxyoctadec-17-enyl3-aminopropanoate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-44 was used. It proceeded in the same manner as in Production Example 1-1 except that it was used. The maximum emission wavelength was 522 nm.

Production Example 1-45. Ligand substitution reaction 45 (LE-45)
Instead of the ligand used in Production Example 1-1, 3-amino-N- (3,6,9,12,15-pentaoxaoctadec-17-enyl) propanamide represented by the following chemical formula 1-45 (synthesis itself; The process was carried out in the same manner as in Production Example 1-1, except that Tetrahedron76 (2020) 131127) was used. The maximum emission wavelength was 522 nm.

Production Example 1-46. Ligand substitution reaction 46 (LE-46)
Instead of the ligand used in Production Example 1-1, 4,8,12,16-tetraoxanonedec-18-enyl3-aminopropanoate (self-synthesized; Tetrahedron76 (2020) 131127) represented by the following chemical formula 1-46 was used. Except for the above, the process was carried out in the same manner as in Production Example 1-1. The maximum emission wavelength was 522 nm.

Production Example 1-47. Ligand substitution reaction 47 (LE-47)
Instead of the ligand used in Production Example 1-1, S-2- (2-methoxyethoxy) ethyl3-mercaptoponethioate (synthesized by itself; J. Med. Chem. 2019, 62, 2, 2) represented by the following chemical formula 1-47. It proceeded in the same manner as in Production Example 1-1 except that 699-726) was used. The maximum emission wavelength was 521 nm.

Production Example 1-48. Ligand substitution reaction 48 (LE-48)
Instead of the ligand used in Production Example 1-1, S-2,5,8,11-tetraoxtridecan-13-yl3-mercaptoponethioate (self-synthesized; Bulletin of the Chemical Society of Japan) represented by the following chemical formula 1-48. , 1982, vol.55, # 7, p.2303-2304), and proceeded in the same manner as in Production Example 1-1. The maximum emission wavelength was 521 nm.

Production Example 1-49. Ligand substitution reaction 49 (LE-49)
Instead of the ligand used in Production Example 1-1, S-2,5,8,11,14-pentaoxadecan-16-yl3-mercaptoponethioate (self-synthesis; Bulletin of the Chemical Society) represented by the following chemical formula 1-49. It proceeded in the same manner as in Production Example 1-1 except that of Japan, 1982, vol.55, # 7, p.2303-2304) was used. The maximum emission wavelength was 522 nm.

Production Example 1-50. Ligand substitution reaction 50 (LE-50)
Instead of the ligand used in Production Example 1-1, S-5,8,11-trioxa-2-thriatridecan-13-yl3-mercaptopropanethioate (self-synthesized; Bulletin of the Chemical Society) represented by the following chemical formula 1-50. It proceeded in the same manner as in Production Example 1-1 except that of Japan, 1982, vol.55, # 7, p.2303-2304) was used. The maximum emission wavelength was 522 nm.

Production Example 1-51. Ligand substitution reaction 51 (LE-51)
Instead of the ligand used in Production Example 1-1, S-5,8,11,14-tellaoxa-2-thiahexadecan-16-yl3-mercaptoponethioate (self-synthesized; Bulletin of the) represented by the following chemical formula 1-51. The procedure was the same as in Production Example 1-1, except that Chemical Society of Japan, 1982, vol.55, # 7, p.2303-2304) was used. The maximum emission wavelength was 522 nm.

Comparative Production Example 1-1: Preparation of InP / ZnSe / ZnS core-shell quantum dots (1P) in which the ligand exchange reaction has not been performed Quantum dot powder (1P) from the quantum dot solution of Synthesis Example 1 in which oleic acid is bonded to the surface. Got

Comparative Production Example 1-2: Ligand Substitution Reaction 52 (LE-52)
The process was carried out in the same manner as in Production Example 1-1, except that 8-Phynicotropic acid (Alfa Aesar) represented by the following chemical formula 3-1 was used instead of the ligand used in Production Example 1-1.

Comparative Production Example 1-3: Ligand Substitution Reaction 53 (LE-53)
Proceed in the same manner as in Production Example 1-1, except that 6-cyclohexyl-hexanoic acid (BOC Sequence) represented by the following chemical formula 3-2 was used instead of the ligand used in Production Example 1-1. rice field.

Comparative Production Example 1-4: Ligand Substitution Reaction 54 (LE-54)
Same as Production Example 1-1 except that mPEG-AA (Creative PEG Works, MW350) represented by the following chemical formula 3-3 was used instead of the ligand used in Production Example 1-1. Proceeded to.

Comparative Production Example 1-5: Ligand Substitution Reaction 55 (LE-55)
The procedure was carried out in the same manner as in Production Example 1-1, except that the adipic acid monomethyl ester (manufactured by Sigma-Aldrich) represented by the following chemical formula 3-4 was used instead of the ligand used in Production Example 1-1.

Comparative Production Example 1-6: Ligand Substitution Reaction 56 (LE-56)
The procedure was carried out in the same manner as in Production Example 1-1, except that the malonic acid monophenyl ester represented by the following chemical formula 3-5 was used instead of the ligand used in Production Example 1-1.

Comparative Production Example 1-7: Ligand Substitution Reaction 57 (LE-57)
Proceeding in the same manner as in Production Example 1-1, except that N-phenyl-succinamic acid (Compi-Blocks) represented by the following chemical formula 3-6 was used instead of the ligand used in Production Example 1-1. I let you.

Comparative Production Example 1-8: Ligand Substitution Reaction 58 (LE-58)
Proceeding in the same manner as in Production Example 1-1, except that 3- (cyclohexylcarbamoyl) propionic acid (Ange Chemical) represented by the following chemical formula 3-7 was used instead of the ligand used in Production Example 1-1. I let you.

Production Examples 2-1 to 2-9 and Comparative Production Examples 2-1 to 2-2: Production of Quantum Dot Dispersion Liquid A quantum dot dispersion liquid was produced according to the components and contents in Table 1 below.

-LE-27 to LE-41: Quantum dot powder according to Production Examples 1-27 to 1-41-P1: Quantum dot powder according to Comparative Production Example 1-1-LE-54: Quantum dot powder according to Comparative Production Example 1-4 -M-1: 1,4-Butanediol diacrylate (BDDA)
-M-2: 1,6-Hexanediol dialurate (HDDA)
-M-3: Pentaeritric triacrylate (PETA)
Examples 1 to 17 and Comparative Examples 1 to 11: Preparation of photoconvertible curable composition A photoconversion curable composition was produced according to the components and contents of Tables 2 and 3 below.

-A-1 to A-9: Quantum dot dispersion according to Production Examples 2-1 to 2-9 -a-1 to a-2: Quantum dot dispersion according to Comparative Production Examples 2-1 to 2-2 -MN- 1: ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
-MN-2: Pentaerythritol triacrylate-PI-1: Irgacure OXE-01 (manufactured by BASF)
-Scattered particles: TiO ₂ (manufactured by Huntsman, TR-88, particle size 220 nm)
-O-1: Irganox 1010 (phenolic antioxidant, manufactured by BASF)
-O-2: Sumilizer GP (phenolic and phosphorus-based antioxidants, manufactured by Sumitomo Chemical Co., Ltd.)
-O-3: Irganox 1035 (phenolic and sulfur-based antioxidants, manufactured by BASF)
-O-4: Sumilizer BBM-S (phenolic antioxidant, manufactured by Sumitomo Chemical Co., Ltd.)
-O-5: 135A (Phosphorus-based antioxidant, manufactured by ADEKA)
-O-6: AO-50 (phenolic antioxidant, ADEKA manufactured)
-O-7: Irganox245 (phenolic antioxidant, manufactured by BASF)
Experimental Example (1) Viscosity Stability Evaluation The photoconvertible curable composition according to Examples 1 to 17 and Comparative Examples 1 to 11 was used with an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Co., Ltd.). The initial viscosity, the viscosity after storage at room temperature for 1 month, and the viscosity after storage at 40 ° C. for 2 weeks were measured under the conditions of a rotation speed of 20 rpm and a temperature of 30 ° C., respectively. From the viscosity change rate calculated by this, the viscosity stability was evaluated according to the following evaluation criteria, and the results are shown in Table 4 below.

<Evaluation criteria for viscosity stability>
◯: Viscosity change rate 105% or less Δ: Viscosity change rate 105% excess 110% or less ×: Viscosity change rate 110% excess

As shown in the results of Table 4, it can be confirmed that the photoconvertible curable compositions of Examples 1 to 17 of the present application are excellent in viscosity stability at room temperature and 40 ° C. It was confirmed that the quantum dot dispersions of Comparative Examples 1 to 11 had a very low viscosity stability, and in particular, in the case of Comparative Examples 1 to 9 containing no antioxidant, the viscosity stability at 40 ° C. was lowered. can do.

(2) Production of Light Conversion Coating Layer and Evaluation of Light Conversion Efficiency After applying the light conversion curable compositions of Examples 1 to 17 and Comparative Examples 1 to 11 on a glass substrate of 5 cm × 5 cm by an inkjet method, ultraviolet rays are emitted. A 1 kW high-pressure mercury lamp containing all g, h, and i rays as a light source was used to ^{irradiate at 1000 mJ / cm 2} , and then heated in a heating oven at 180 ° C. for 30 minutes to produce a light conversion coating layer. After placing the manufactured light conversion coating layer on top of a blue light source (XLamp XR-E LED, Royal blue450, Cree), a brightness measuring instrument (CAS140CT Spectrometer, Instrument systems) and the following formula The optical conversion efficiency was measured and calculated using No. 1, and the results are shown in Table 5 below. The higher the light conversion efficiency (%), the better the brightness can be obtained.

(3) Evaluation of Number of Continuous Jettings After filling the light conversion curable compositions of Examples 1 to 17 and Comparative Examples 1 to 11 in an inkjet printing facility manufactured by Unijet, the temperature of the jetting head was fixed at 40 ° C. After that, after ejecting the ink for 1 minute, the ink was left to stand once for 30 minutes, and the number of continuous jettings was evaluated by repeating the process until the ink was not ejected due to the nozzle clogging of the jetting head, and the results are shown in Table 4 below. As the number of continuous jettings increases, excellent characteristics can be obtained in the continuous inkjet process.

(4) Evaluation of coating film hardness The degree of curing of the manufactured photoconversion coating layer was measured at a high temperature of 150 ° C. using a hardness tester (HM500; Fisher's product), and the coating film hardness was evaluated according to the following evaluation criteria. .. The results are shown in Table 4 below.

<Evaluation criteria for coating film hardness>
◯: Surface hardness 50 or more and Δ: Surface hardness 30 or more and less than 50 ×: Surface hardness less than 30 (5) Light resistance evaluation The manufactured light conversion coating layer is a blue light source (XLamp XR-E LED, Royal blue450, Cree). After being left to stand for 24 hours, the maintenance rate (%) with respect to the initial light conversion efficiency was confirmed to evaluate the light resistance. The results are shown in Table 4 below.

As shown in the results of Table 5, it can be confirmed that the photoconversion coating layer according to Examples 1 to 17 containing the antioxidant exhibits excellent light resistance. In particular, it can be confirmed that the photoconversion coating layer according to Examples 10 to 17 containing all of the phosphorus-based antioxidant and the phenol-based antioxidant is further excellent in light resistance.

On the other hand, in the cases of Comparative Examples 1 to 11 containing no antioxidant, it can be confirmed that the light resistance is lowered. In particular, in the cases of Comparative Examples 10 and 11 using quantum dots not containing the compound represented by Chemical Formula 1 as a ligand, it can be confirmed that the light resistance is remarkably lowered.

As described above, when both the quantum dot containing the compound represented by the chemical formula 1 as a ligand and the antioxidant are used on the surface, the surface of the quantum dot is protected, the oxidation stability is excellent, and the decrease in quantum efficiency is prevented. It was confirmed that reliability such as viscosity stability and light resistance was improved.

Claims (18)

Includes quantum dots, antioxidants, scattered particles, photopolymerizable compounds and photopolymerizable initiators,
The quantum dots have a ligand layer on the surface and
A photoconvertible curable composition in which the ligand layer contains a compound represented by the following chemical formula 1.

(In the chemical formula 1,
A is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and the like. Alkanyl group with 2 to 30 carbon atoms, alkyl ester group with 2 to 30 carbon atoms, heteroaromatic hydrocarbon group with 4 to 30 carbon atoms, thioether group, thioester group with 1 to 30 carbon atoms, silyl group, or carbon number 1 to 30 silyl ester groups,
R ₁ and R ₂ are independently bonded, linear or branched alkylene groups having 1 to 30 carbon atoms, −OR ₁₁ −, −OC (= O) R ₁₂ −, − (OCH _2). CH ₂ ) _m − or − (OCH ₂ CH ₂ CH ₂ ) _l −
L ₁ and L ₂ are independently directly bonded, oxygen atoms, sulfur atoms, or -NH-, respectively.
D is an oxygen atom, a sulfur atom, or = NH,
X is a thiol group, a carboxyl group, an amine group, a phosphoric acid group, an imidazole group, or a tetrazole group.
R ₁₁ is a linear or branched alkylene group having 1 to 30 carbon atoms.
R ₁₂ is a linear or branched alkylene group having 4 to 30 carbon atoms.
m and l are independently integers of 1 to 150.
However, when A is a linear or branched alkyl group having 1 to 30, a cycloalkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, the above

The structure of the eggplant

It cannot be. ) The photoconvertible curable composition according to claim 1, wherein the ligand layer contains one or more selected from the compounds represented by the following chemical formulas 1-1 to 1-51.

(In the chemical formulas 1-10 to 1-13, n is an integer of 1 to 150.)

The ligand layer consists of oleic acid, lauric acid, 2- (2-methoxyethoxy) acetic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, and mono- [2- (2-methoxyethoxy) ethoxy] acetic acid. The photoconvertible curable composition according to claim 1, further comprising one or more selected from the group consisting of 2- (2-methoxy-ethoxy) -ethyl] esters. The photoconvertible curable composition according to claim 1, wherein the antioxidant comprises one or more selected from a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant. The photoconvertible curable composition according to claim 4, wherein the antioxidant contains a phosphorus-based antioxidant and a phenol-based antioxidant. The photoconvertible curable composition according to claim 4, wherein the antioxidant comprises one or more selected from the compounds represented by the following chemical formulas 2-1 to 2-7.

(In the above chemical formula 2-1
R ₁₃ is an alkylene group having 1 to 10 carbon atoms.
R _{14 to} R ₂₅ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. )

(In the chemical formula 2-2,
R _{26 to} R ₃₄ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. )

(In the chemical formula 2-3,
R ₃₆ and R ₃₇ are alkylene groups having 1 to 10 carbon atoms.
R _{38 to} R ₄₁ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. )

(In the chemical formula 2-4,
R _{42 to} R ₄₅ are alkylene groups having 1 to 10 carbon atoms.
R _{46 to} R ₅₃ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. )

(In the chemical formula 2-5,
R _{55 to} R ₅₇ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms. )

(In the chemical formula 2-6,
R ₅₈ is − (OCH ₂ CH ₂ ) _k −, and k is an integer of 1 to 5.
R ₅₉ and R ₆₀ are independently alkylene groups having 1 to 10 carbon atoms.
R _{61 to} R ₆₈ are independently substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. )

(In the chemical formula 2-7,
R ₆₉ is an alkylene group having 1 to 10 carbon atoms.
R _{70 to} R ₇₃ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.
R ₇₄ is an alkyl group having 1 to 30 carbon atoms. ) The photoconvertible curable composition according to claim 6, wherein the antioxidant comprises a compound represented by the chemical formula 2-1 and a compound represented by the chemical formula 2-5. The photoconvertible curable composition according to claim 1, wherein the quantum dots have a core-shell structure including a core and a shell covering the core. The cores are InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, AgInGaS, HgS, HgSe, HgS. The photoconvertible curable composition according to claim 8, which comprises one or more of InGaN, InAs, and ZnO. The shell is among ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, GaS, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, SrSe, and HgSe. The photoconvertible curable composition according to claim 8, which comprises one or more of the above. The quantum dot is one selected from the group consisting of AgInGaS / GaS, InP / ZnS, InP / ZnSe, InP / GaP / ZnS, InP / ZnSe / ZnS, InP / ZnSeTe / ZnS, and InP / MnSe / ZnS. The photoconvertible curable composition according to claim 1, which comprises the above. The photoconvertible curable composition according to claim 1, further comprising an alkali-soluble resin. The light conversion curable composition according to claim 1, wherein the light conversion curable composition is a light conversion ink composition or a photo conversion resin composition. With respect to the total weight of the photoconvertible curable composition
The quantum dots 1 to 75% by weight;
0.1 to 20% by weight of the antioxidant;
1 to 20% by weight of the scattered particles;
The photoconvertible curable composition according to claim 1, which comprises 10 to 90% by weight of the photopolymerizable compound; and 0.1 to 20% by weight of the photopolymerization initiator. A cured film formed by using the photoconvertible curable composition according to any one of claims 1 to 14. The cured film according to claim 15, wherein the cured film is a color filter, a light conversion laminated base material, or a quantum dot film. The quantum dot light emitting diode (QLED) including the cured film according to claim 15. An image display device including the cured film according to claim 15.