KR20230160086A - Quantum dot, method of modifyng quantum dot, curable composition, cured layer using the composition, color filter including the cured layer and display device including the color filter - Google Patents

Abstract

It consists of a core portion and a shell portion surrounding the core portion, wherein the shell portion is doped with an element having a valence of +3, using a modified quantum dot, the modification method, a curable composition containing the modified quantum dot, and the curable composition. A manufactured cured film, a color filter including the cured film, and a display device including the color filter are provided.

Description

Quantum dots, quantum dot modification method, curable composition containing the quantum dots, a cured film manufactured using the composition, a color filter containing the cured film, and a display device containing the color filter {QUANTUM DOT, METHOD OF MODIFYNG QUANTUM DOT, CURABLE COMPOSITION, CURED LAYER USING THE COMPOSITION, COLOR FILTER INCLUDING THE CURED LAYER AND DISPLAY DEVICE INCLUDING THE COLOR FILTER}

This description relates to quantum dots, a method of modifying quantum dots, a curable composition containing the quantum dots, a cured film manufactured using the composition, a color filter containing the cured film, and a display device containing the color filter.

In the case of general quantum dots, the solvent in which they are dispersed is limited due to their hydrophobic surface characteristics, and as a result, it is true that they face many difficulties in introducing them into polar systems such as binders or curable monomers.

For example, even in the case of quantum dot ink compositions that are being actively studied, at the initial stage, they were dispersed in solvents used in curable compositions with relatively low polarity and high hydrophobicity. For this reason, it was difficult to include more than 20% by weight of quantum dots relative to the total amount of the composition, making it impossible to increase the luminous efficiency of the ink beyond a certain level, and even if additional quantum dots were added and dispersed to increase luminous efficiency, ink-jetting was not possible. This possible point also exceeded the range, so fairness could not be satisfied.

In addition, in order to achieve a viscosity range that allows ink-jetting, a method of lowering the ink solid content by including more than 50% by weight of solvent relative to the total amount of the composition has been used, and this method also has somewhat satisfactory results in terms of viscosity. However, during ink-jetting, there are problems such as nozzle drying due to solvent volatilization, nozzle clogging, and single film thickness decrease over time after ink-jetting, and the thickness deviation after curing is severe. It has the disadvantage of being difficult to apply to actual processes.

Therefore, the solvent-free type of quantum dot ink that does not contain a solvent is the most desirable form to apply in actual processes, and the current technology for applying quantum dots themselves to solvent-type compositions is evaluated to have reached a certain limit.

In order to develop a solvent-free curable composition, it must be possible to control dispersibility through surface modification of quantum dots with hydrophobic characteristics, and the final composition must be able to satisfy ink-jetting fairness. In solvent-free curable compositions containing a high content of quantum dots, which have emerged to reduce nozzle drying due to solvent volatilization and to reduce single film thickness variation over time, 'efficiency of quantum dots', which is the main light-emitting element, and 'ligand for surface modification thereof' ' and 'composition design of the composition' are important factors that determine the dispersibility, thermal curing degree, and light curing degree of the final manufactured composition.

Quantum dots are surface-treated with inorganic components of the core and shell and organic ligands, making them hydrophobic, and have different emission wavelengths depending on their inorganic composition and size. Quantum dot single-film specimens (cured films) for displays must achieve high efficiency, and to this end, development of a quantum dot synthesis method that changes the inorganic composition of core/shell quantum dots is currently actively underway.

One embodiment is intended to provide modified quantum dots that are capable of shifting to long wavelengths and have a minimized organic matter (impurity) content on the surface of the quantum dots.

Another embodiment is to provide a method of modifying quantum dots so that a shift to a longer wavelength is possible and the organic matter (impurity) content on the surface of the quantum dots is minimized.

Another embodiment is to provide a curable composition containing the modified quantum dots or the quantum dots modified by the quantum dot modification method.

Another embodiment is to provide a cured film manufactured using the curable composition.

Another embodiment is to provide a color filter including the cured film.

Another embodiment is to provide a display device including the color filter.

One embodiment provides a quantum dot consisting of a core portion and a shell portion surrounding the core portion, and the shell portion is doped with an element having a valence of +3.

The element having a valence of +3 may include yttrium (Y), scandium (Sc), a lanthanide group element, an actinide group element, or a combination thereof.

The shell portion may be a single layer or a multi-layer, the single layer may be a ZnS layer, and the multi-layer may include a ZnS layer at the outermost portion.

The shell portion may also be doped with an element with a valence of +2.

The element with the valence +2 may include Zn.

The element with a valence of +3 may be included in an amount equal to or greater than that of the element with a valence of +2.

Another embodiment includes a first step of preparing quantum dots consisting of a core portion and a shell portion surrounding the core portion and not doped with any element, and a second step of adding an ionic bond-containing additive represented by the following formula (1) to the quantum dots. A quantum dot reforming method including the following steps is provided.

[Formula 1]

MX ₃

In Formula 1,

M is an element with valence +3,

X is a halide element.

The element having a valence of +3 may include yttrium (Y), scandium (Sc), a lanthanide group element, an actinide group element, or a combination thereof.

The shell portion may be a single layer or a multi-layer, the single layer may be a ZnS layer, and the multi-layer may include a ZnS layer at the outermost portion.

The additive may further include an ionic compound represented by the following formula (2).

[Formula 2]

M'X ₃

In Formula 2,

M’ is an element with valence +2,

X is a halide element.

The element with the valence +2 may include Zn.

The ionic compound represented by Formula 1 may be added in an amount equal to or greater than that of the ionic compound represented by Formula 2.

The ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are contained in equal weight, and an additive containing the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 It may be included in an amount of 4% by weight or less based on the total amount of the quantum dots of the first step and the additives of the second step.

The ionic bond represented by Formula 1 is included in a greater weight than the ionic bond represented by Formula 2, and the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are 2:1 to 2:1. It may be included in a weight ratio of 3:1.

Another embodiment is (A) the quantum dots or quantum dots modified by the above modification method; (B) photopolymerizable monomer; and (C) a light diffuser.

The curable composition may be a solvent-free curable composition.

The solvent-free curable composition includes 3 to 50 wt% of the quantum dots, based on the total amount of the solvent-free curable composition; 30% to 95% by weight of the photopolymerizable monomer; And it may include 1% to 20% by weight of the light diffuser.

The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

The curable composition may further include a polymerization initiator, a polymerization inhibitor, or a combination thereof.

The curable composition may further include a solvent.

The curable composition includes 1% to 40% by weight of the quantum dots, based on the total weight of the curable composition; 1% to 20% by weight of the photopolymerizable monomer; It may include 1% to 20% by weight of the light diffuser and 40% to 80% by weight of the solvent.

The curable composition includes malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or, it may further include a combination thereof.

Another embodiment provides a cured film manufactured using the curable composition.

Another embodiment provides a color filter including the cured film.

Another embodiment provides a display device including the color filter.

Details of other aspects of the invention are included in the detailed description below.

In quantum dots with a core-shell structure, by doping the outermost part of the shell with an element with a valence of +3, a long wavelength shift can be easily achieved, and the content of impurities (organic substances) present in the outermost part of the quantum dot is minimized. Optical characteristics can be improved. In addition, the viscosity of the curable composition containing the quantum dots can be easily adjusted even if the quantum dots are contained in a high content, thereby improving ink dispersibility.

Figure 1 is a diagram showing a structure in which yttrium (Y) is doped in the outermost part constituting a quantum dot of a core-shell structure according to an embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, “alkyl group” refers to a C1 to C20 alkyl group, “alkenyl group” refers to a C2 to C20 alkenyl group, and “cycloalkenyl group” refers to a C3 to C20 cycloalkenyl group. , “Heterocycloalkenyl group” refers to a C3 to C20 heterocycloalkenyl group, “aryl group” refers to a C6 to C20 aryl group, “arylalkyl group” refers to a C6 to C20 arylalkyl group, and “alkylene group” means a C1 to C20 alkylene group, “arylene group” means a C6 to C20 arylene group, “alkylarylene group” means a C6 to C20 alkylarylene group, and “heteroarylene group” means a C3 to C20 heteroarylene group. It means an arylene group, and “alkoxylene group” means a C1 to C20 alkoxylene group.

Unless otherwise specified herein, “substitution” means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, “hetero” means that at least one hetero atom of N, O, S, and P is included in the chemical formula.

Also, unless otherwise specified in the specification, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid.” "It means that both are possible.

Unless otherwise specified herein, “combination” means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

Additionally, unless otherwise specified in the specification, “*” refers to a portion connected to the same or different atom or chemical formula.

Most of the quantum dot surface modification materials so far have been compounds containing thiol groups or carboxyl groups at the terminals, and to date, the surface modification materials have been passivated to quantum dots to surface modify the quantum dots and then used in curable compositions. However, the present inventors wondered whether the limit had been reached in improving the viscosity or optical properties of a curable composition having such a composition, and asked whether it would be possible to surface modify quantum dots in a completely different direction than before. As a result of reviewing the research from various angles and conducting experiment after experiment, we deviated from the conventional surface modification method of improving the polarity, heat resistance, and dispersibility of the surface of quantum dots, and used an element with a valence of +3 as a catalyst. By doping the outermost part of the shell that constitutes the quantum dots, it was possible to control the wavelength of the quantum dots, which is one of the important optical properties. That is, quantum dots according to one embodiment are capable of shifting to long wavelengths, which is advantageous for wavelength control. In addition, in the case of a solvent-free curable composition containing a high content of quantum dots, the viscosity at room temperature increases and the ink-dispersibility at room temperature is greatly reduced. According to one embodiment, the solvent-free curable composition containing quantum dots is as described above. Even if quantum dots are included in a high content, the viscosity at room temperature is low, which can improve ink dispersibility at room temperature.

In other words, the present inventors used a catalyst containing an element with a valence of +3 to induce a bond between the 'element ion with a valence of +3' and the 'shell of the quantum dot (specifically, ZnS)' on the surface of the quantum dot, thereby forming the quantum dot. Quantum dots that enable wavelength control were developed and the present invention was completed.

Hereinafter, each component constituting the curable composition containing quantum dots according to one embodiment will be described in detail.

quantum dot

One embodiment provides a quantum dot consisting of a core portion and a shell portion surrounding the core portion, and the shell portion is doped with an element having a valence of +3.

Optical properties, half width, wavelength, and optical efficiency are the main physical properties that change depending on the surface modification of quantum dots. However, the wavelength, which is the basic physical property of quantum dots, does not change significantly even before and after surface modification, so the wavelength of quantum dots cannot be adjusted only through surface modification of quantum dots. Assuming that it was difficult, an attempt was made to control the wavelength by changing the composition of the composition containing the surface-modified quantum dots. However, according to one embodiment, a catalyst having a trivalent ion such as yttrium(III) is used to easily induce (Y ³⁺ )-shell (ZnS) bonding on the quantum dot surface, thereby controlling the wavelength. Provides possible quantum dots, and further provides a curable composition containing the quantum dots.

For example, the element having a valence of +3 may include yttrium (Y), scandium (Sc), a lanthanide group element, an actinide group element, or a combination thereof. The lanthanide group elements refer to elements with atomic numbers 57 (La) to 71 (Lu) on the periodic table, and the actinium group elements refer to elements with atomic numbers 89 (Ac) to 103 (Lr) in the periodic table. means.

For example, the shell part may be a single layer or a multi-layer. If the shell part is a single layer, the outermost part may be a ZnS layer. If the shell part is a multi-layer, the outermost part may be a ZnS layer.

For example, the shell portion may be doped with an element with a valence of +2 in addition to the element with a valence of +3.

For example, the element whose valence is +2 may include Zn, but is not necessarily limited thereto.

For example, the element with a valence of +3 may be included in a content (concentration) equal to or greater than that of the element with a valence of +2. In this case, the wavelength of the quantum dot can be controlled so that the wavelength shift occurs more easily toward a longer wavelength, and the amount of impurities (organic substances) on the surface of the quantum dot can also be reduced.

Meanwhile, according to another embodiment, a method for modifying the quantum dots is provided. The quantum dot modification method includes a first step of preparing quantum dots consisting of a core portion and a shell portion surrounding the core portion and not doped with any element, and a second step of adding an ionic bond-containing additive represented by the following formula (1) to the quantum dots. Includes steps.

[Formula 1]

MX ₃

In Formula 1,

M is an element with valence +3,

X is a halide element.

M, the element with a valence of +3, may be as described above.

The shell portion of the quantum dot may be a single layer or a multi-layer, and the details for each case may also be the same as described above.

For example, the additive may further include an ionic compound represented by the following formula (2).

[Formula 2]

M'X ₃

In Formula 2,

M’ is an element with valence +2,

X is a halide element.

M’, the element with a valence of +2, may be as described above.

For example, the ionic compound represented by Formula 1 may be added in a weight equal to or greater than that of the ionic compound represented by Formula 2. In this case, the wavelength of the quantum dot can be controlled so that the wavelength shift occurs more easily toward a longer wavelength, and the amount of impurities (organic substances) on the surface of the quantum dot can also be reduced.

For example, the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are included in equal weight, and include the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2. The additive may be included in an amount of 4% by weight or less compared to the total amount of the quantum dots of the first step and the additives of the second step. When the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are included in the same amount, the relative content of the additive relative to the total amount of the quantum dots of the first step and the additive of the second step increases. It is difficult to shift the wavelength of the quantum dot toward a longer wavelength, and the content of residual organic matter (impurities) on the surface of the quantum dot increases, so the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 should be included in the same amount. In this case, it may be preferable that the additive is included in an amount of 4% by weight or less compared to the total amount of the quantum dots of the first step and the additives of the second step.

For example, the ionic bond represented by Formula 1 is included in a greater weight than the ionic bond represented by Formula 2, and the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are 2: It may be included in a weight ratio of 1 to 3:1. When the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are contained in different amounts, the ionic bond represented by Formula 1 has a greater weight than the ionic bond represented by Formula 2. Its inclusion is desirable in terms of long-wavelength shift of the quantum dots and minimizing residual organic matter on the surface of the quantum dots. Specifically, when the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are included in a weight ratio of 2:1 to 3:1, more specifically, the ionic bond represented by Formula 1 and the formula When the ionic compound represented by 2 is included in a weight ratio of 3:1, the wavelength of the quantum dot can be controlled so that the wavelength shift occurs more easily toward a longer wavelength, and the amount of impurities (organic substances) on the surface of the quantum dot can also be reduced. there is.

For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots are present in an amount of 3% by weight to 60% by weight, such as 5% by weight to 60% by weight, such as 10% by weight to 60% by weight, such as 20% by weight. It may be included in 50% by weight. When the quantum dots are included within the above range, high light retention rate and light efficiency can be achieved even after curing.

For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the quantum dots may be included in an amount of 1% to 40% by weight, for example, 3% to 30% by weight, based on the total amount of the curable composition. When the quantum dots are included within the above range, the light conversion rate is excellent and pattern characteristics and development characteristics are not impaired, so excellent processability can be achieved.

For example, the quantum dots absorb light in a wavelength range of 360 nm to 780 nm, for example, 400 nm to 780 nm, and emit fluorescence in a wavelength range of 500 nm to 700 nm, for example, 500 nm to 580 nm, or emit fluorescence in a wavelength range of 600 nm to 680 nm. You can. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ _em ) of 500 nm to 680 nm.

The quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dot has a half width in the above range, color purity is high, which has the effect of increasing color reproduction rate when used as a color material in a color filter.

The quantum dots may each independently be an organic material, an inorganic material, or a hybrid of an organic material and an inorganic material.

The quantum dots may each independently consist of a core and a shell surrounding the core, and the core and shell each independently consist of a core made of group II-IV, group III-V, etc., core/shell, core/first shell/ It may have a structure such as a second shell, an alloy, or an alloy/shell, but is not limited thereto.

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. , but is not necessarily limited to this. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnSeS, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto. .

In one embodiment, as interest in the environment has recently greatly increased worldwide and regulations on toxic substances have been strengthened, a light-emitting material with a cadmium-based core may be used instead of a light-emitting material, which has a somewhat low quantum yield but is environmentally friendly. Non-cadmium-based light emitting materials (InP/ZnS, InP/ZnSe/ZnS, InP/ZnSeS/ZnS, etc.) were used, but are not necessarily limited thereto.

In the case of the quantum dots of the core/shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

For example, the quantum dots may each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may each independently have an average particle diameter of 10 nm to 15 nm. The green quantum dots may each independently have an average particle diameter of 5 nm to 8 nm.

Meanwhile, for the dispersion stability of the quantum dots, the curable composition according to one embodiment may further include a dispersant. The dispersant helps the light conversion material such as quantum dots to be uniformly dispersed within the curable composition, and nonionic, anionic, or cationic dispersants can all be used. Specifically, polyalkylene glycol or its esters, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide. Adducts, alkyl amines, etc. can be used, and these can be used alone or in a mixture of two or more types. The dispersant may be used in an amount of 0.1% to 100% by weight, for example, 10% to 20% by weight, based on the solid content of the light conversion material such as quantum dots.

photopolymerizable monomer

The curable composition according to one embodiment includes a photopolymerizable monomer, and the photopolymerizable monomer may have a carbon-carbon double bond at its terminal.

The photopolymerizable monomer having a carbon-carbon double bond at the terminal may be included in an amount of 30% to 95% by weight, for example, 40% to 90% by weight, based on the total amount of the solvent-free curable composition. When the content of the photopolymerizable monomer having a carbon-carbon double bond at the terminal is within the above range, it is possible to manufacture a solvent-free curable composition having a viscosity capable of ink jetting. In addition, the quantum dots in the prepared solvent-free curable composition have excellent dispersibility. , optical characteristics can also be improved.

For example, the photopolymerizable monomer having a carbon-carbon double bond at the terminal may have a molecular weight of 170 g/mol to 1,000 g/mol. When the molecular weight of the photopolymerizable monomer having a carbon-carbon double bond at the terminal is within the above range, it can be advantageous for ink-jetting because it does not impair the optical properties of the quantum dots and does not increase the viscosity of the composition.

For example, the photopolymerizable monomer having a carbon-carbon double bond at the terminal may be represented by the following formula (6), but is not necessarily limited thereto.

[Formula 6]

In Formula 6 above,

R ⁶ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ⁶ and L ⁸ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

L ⁷ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*).

For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following formula 6-1 or 6-2, but is not necessarily limited thereto.

[Formula 6-1]

[Formula 6-2]

For example, photopolymerizable monomers having a carbon-carbon double bond at the terminal include, in addition to the compounds represented by Formula 6-1 or Formula 6-2, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate , dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, It may further include propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

In addition, in addition to the photopolymerizable monomer having a carbon-carbon double bond at the terminal, it may further include a monomer commonly used in conventional thermosetting or photocuring compositions, for example, the monomer may be bis[1-ethyl(3-ox). [cetanyl)] It may further include oxetane-based compounds such as methyl ether.

In addition, when the curable composition includes a solvent, the photopolymerizable monomer may be included in an amount of 1% to 20% by weight, 1% to 15% by weight, such as 5% to 15% by weight, based on the total amount of the curable composition. there is. When the photopolymerizable monomer is included within the above range, the optical properties of the quantum dots can be improved.

light diffuser

The curable composition according to one embodiment may further include a light diffuser.

For example, the light diffuser may include barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), or a combination thereof.

The light diffuser reflects light that is not absorbed by the quantum dots and allows the quantum dots to reabsorb the reflected light. That is, the light diffuser can increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

The light diffuser may have an average particle diameter (D ₅₀ ) of 150 nm to 250 nm, specifically 180 nm to 230 nm. When the average particle diameter of the light diffuser is within the above range, a better light diffusion effect can be achieved and light conversion efficiency can be increased.

The light diffuser may be included in an amount of 1% to 20% by weight, such as 2% to 15% by weight, such as 3% to 10% by weight, based on the total amount of the curable composition. If the light diffuser is included in less than 1% by weight based on the total amount of the curable composition, it is difficult to expect an effect of improving light conversion efficiency due to the use of the light diffuser, and if it is included in more than 20% by weight, there is a problem of quantum dot precipitation. There is a risk that this may occur.

polymerization initiator

The curable composition according to one embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, for example, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and aminoketone-based compounds. etc. may be used, but are not necessarily limited thereto.

Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 Examples include '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be mentioned.

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

Examples of the triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 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-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4 -bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. .

Examples of the oxime-based compounds include O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used. Specific examples of the O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butane-1-oneoxime- O-acetate, etc. can be mentioned.

Examples of the aminoketone-based compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1), etc.

In addition to the above compounds, the photopolymerization initiator may include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, and biimidazole-based compounds.

The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.

Examples of the thermal polymerization initiator include peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, and methyl ethyl ketone peroxide. Oxides, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azo-bis(isobutyronitrile), t-butyl perbenzo ate, etc., and 2,2'-azobis-2-methylpropionitrile, etc., but are not necessarily limited thereto, and any one widely known in the art can be used.

The polymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 1% to 4% by weight, based on the total amount of the curable composition. When the polymerization initiator is included within the above range, curing occurs sufficiently during exposure or heat curing to obtain excellent reliability, and a decrease in transmittance due to unreacted initiator can be prevented, thereby preventing a decrease in the optical properties of quantum dots.

binder resin

The curable composition according to one embodiment may further include a binder resin.

The binder resin may include an acrylic resin, a cardo-based resin, an epoxy resin, or a combination thereof.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing one or more acrylic repeating units.

Specific examples of the acrylic binder resin include polybenzyl methacrylate, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/ Examples include, but are not limited to, 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and these can be used alone or in combination of two types. The above can also be used in combination.

The weight average molecular weight of the acrylic resin may be 5,000 g/mol to 15,000 g/mol.　When the weight average molecular weight of the acrylic resin is within the above range, it has excellent adhesion to the substrate, good physical and chemical properties, and appropriate viscosity.

The acid value of the acrylic resin may be 80 mgKOH/g to 130 mgKOH/g. When the acid value of the acrylic resin is within the above range, the resolution of the pixel pattern is excellent.

The cardo-based resin can be used in a typical curable resin (or photosensitive resin) composition, for example, the one shown in Korean Patent Publication No. 10-2018-0067243 can be used, but is not limited thereto.

The cardo-based resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic acid dianhydride, Anhydride compounds such as rylene tetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic acid anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

The weight average molecular weight of the cardo-based resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. If the weight average molecular weight of the cardo-based resin is within the above range, a pattern can be easily formed without residue when manufacturing a cured film, there is no loss of film thickness when developing a solvent-type curable composition, and a good pattern can be obtained.

When the binder resin is a cardo-based resin, the curable composition containing it, especially the photosensitive resin composition, has excellent developability, has good sensitivity during photocuring, and has excellent fine pattern formation.

The epoxy resin is a monomer or oligomer that can be polymerized by heat, and may include compounds having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

The epoxy resin may include, but is not limited to, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.

As commercial products of these compounds, bisphenyl epoxy resins include YX4000, YX4000H, YL6121H, YL6640, and YL6677 from Yukashell Epoxy Co., Ltd.; Cresol novolak-type epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Yukashell Epoxy Co., Ltd. )'s Epicoat 180S75; Bisphenol A type epoxy resins include Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 from Yukashell Epoxy Co., Ltd.; Bisphenol F-type epoxy resins include Epicoat 807 and 834 from Yukashell Epoxy Co., Ltd.; Phenolic noblock-type epoxy resins include Epicoat 152, 154, and 157H65 from Yukashell Epoxy Co., Ltd. and EPPN 201 and 202 from Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CY175, CY177 and CY179 from CIBA-GEIGY A.G., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from U.C.C., and Shodine 509 from Showa Denko Co., Ltd. , Araldite CY-182, CY-192 and CY-184 from CIBA-GEIGY A.G., Epicron 200 and 400 from Dainipbon Ink Kogyo Co., Ltd., and Epicot 871 and 872 from Yukashell Epoxy Co., Ltd. and EP1032H60, ED-5661 and ED-5662 from Celanese Coatings Co., Ltd.; Aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yukashell Epoxy Co., Ltd., Eporite 100MF from Kyoesha Yushi Chemical Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd. You can.

For example, when the curable composition according to one embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5% by weight to 10% by weight, for example, 1% by weight to 5% by weight, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the binder resin may be included in an amount of 1% to 30% by weight, for example, 3% to 20% by weight, based on the total amount of the curable composition. In this case, it is excellent and can improve pattern characteristics, heat resistance, and chemical resistance.

Other additives

To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

The polymerization inhibitor may include a hydroquinone-based compound, a catechol-based compound, or a combination thereof, but is not necessarily limited thereto. As the curable composition according to one embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, room temperature crosslinking can be prevented during exposure to light after printing (coating) the curable composition.

For example, the hydroquinone-based compound, catechol-based compound, or combinations thereof include hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyroga Roll, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O') aluminum (Tris(N-hydroxy-N -nitrosophenylamineto-O,O')aluminium) or a combination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the form of the dispersion is 0.001% by weight to 3% by weight, for example, 0.01% by weight to 2% by weight, based on the total amount of the curable composition. It can be included as a percentage. When the polymerization inhibitor is included within the above range, it is possible to solve the problem of aging at room temperature and prevent deterioration of sensitivity and surface peeling.

In addition, the curable composition according to one embodiment includes malonic acid to improve heat resistance and reliability; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or it may further include a combination thereof.

For example, the curable composition according to one embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, carboxyl group, methacryloxy group, isocyanate group, or epoxy group to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, and γ glycidoxy propyl. Trimethoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be used, and these can be used alone or in combination of two or more.

The silane-based coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the curable composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the curable composition may further include a surfactant, such as a fluorine-based surfactant, if necessary, to improve coating properties and prevent defects, that is, to improve leveling performance.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mol to 10,000 g/mol, and specifically, may have a weight average molecular weight of 6,000 g/mol to 10,000 g/mol. Additionally, the fluorine-based surfactant may have a surface tension of 18 mN/m to 23 mN/m (measured in 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). If the weight average molecular weight and surface tension of the fluorine-based surfactant are within the above range, leveling performance can be further improved, stains can be prevented during high speed coating, and there are fewer film defects due to less bubble generation. , gives excellent properties to slit coating, a high-speed coating method.

Examples of the fluorine-based surfactants include BM-1000 ^® and BM-1100 ^® from BM Chemie; Mecha pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , etc. from Dai Nippon Inki Chemicals Co., Ltd.; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® , etc. from Sumitomo 3M Co., Ltd.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® , etc.; Toray Silicone Co., Ltd.'s SH-28PA ^® , Dong-190 ^® , Dong-193 ^® , SZ-6032 ^® , SF-8428 ^® , etc.; Fluorine-based surfactants commercially available under names such as F-482, F-484, F-478, and F-554 from DIC Co., Ltd. can be used.

Additionally, the curable composition according to one embodiment may use a silicone-based surfactant along with the fluorine-based surfactant described above. Specific examples of the silicone-based surfactant include TSF400, TSF401, TSF410, and TSF4440 manufactured by Toshiba Silicone, but are not limited thereto.

Surfactants including the fluorine-based surfactant may be included in an amount of 0.01 parts by weight to 5 parts by weight, for example, 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant is contained within the above range, the occurrence of foreign substances in the sprayed composition is reduced.

Additionally, a certain amount of other additives such as antioxidants may be added to the curable composition according to one embodiment within a range that does not impair the physical properties.

menstruum

Meanwhile, the curable composition according to one embodiment may further include a solvent.

The solvent includes, for example, alcohols such as methanol and ethanol; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Alternatively, there are compounds of keto acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. Examples include ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., but are not limited thereto.

For example, the solvent may include glycol ethers such as ethylene glycol monoethyl ether and ethylene diglycol methyl ethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; It is preferable to use alcohols such as ethanol or a combination thereof.

For example, the solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrroli It may be a polar solvent including dine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The solvent may be included in an amount of 40% to 80% by weight, for example, 45% to 80% by weight, based on the total amount of the curable composition. When the solvent is included within the above range, the solvent-type curable composition has an appropriate viscosity and can have excellent coating properties during large-area coating using spin coating and slit.

Another embodiment provides the curable composition, for example, a cured film manufactured using the curable composition, a color filter including the cured film, and a display device including the color filter.

One of the methods for producing the cured film includes forming a pattern by applying the curable composition on a substrate using an inkjet spraying method (S1); and curing the pattern (S2).

(S1) Step of forming a pattern

The curable composition is preferably applied to the substrate at a thickness of 0.5 to 20 ㎛ by inkjet dispersion. The inkjet spraying can form a pattern by spraying only a single color per nozzle and spraying repeatedly according to the number of colors required. To reduce the process, the pattern can be formed by spraying the required number of colors simultaneously through each inkjet nozzle. It can also be formed.

(S2) Curing step

Pixels can be obtained by curing the obtained pattern. At this time, as a curing method, either a thermal curing process or a photo curing process can be applied. The thermal curing process is preferably performed by heating to a temperature of 100°C or higher, more preferably by heating to 100°C to 300°C, and more preferably by heating to 160°C to 250°C. You can. The photocuring process irradiates active rays such as UV light of 190 nm to 450 nm, for example, 200 nm to 500 nm. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

Another method of manufacturing the cured film is to manufacture the cured film using the lithography method using the curable composition, and the manufacturing method is as follows.

(1) Application and film formation stage

The curable composition is applied to a desired thickness, for example, 2㎛ to 10㎛, using a method such as spin or slit coating, roll coating, screen printing, or applicator method on a substrate that has undergone a predetermined pretreatment. Afterwards, the solvent is removed by heating at a temperature of 70°C to 90°C for 1 to 10 minutes to form a coating film.

(2) exposure step

In order to form the necessary pattern on the obtained coating film, a mask of a predetermined shape is interposed, and then actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, are irradiated. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

The exposure amount varies depending on the type, mixing amount, and dry film thickness of each component of the curable composition, but is, for example, 500 mJ/cm ² or less (based on a 365 nm sensor) when using a high-pressure mercury lamp.

(3) Development stage

Following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed parts remaining to form an image pattern. That is, when developing with an alkaline developer, the unexposed portion is dissolved and an image color filter pattern is formed.

(4) Post-processing step

The image pattern obtained by the above phenomenon can be cured by heating again or irradiating with actinic rays, etc., in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc.

Hereinafter, preferred embodiments of the present invention will be described. However, the following example is only a preferred example of the present invention, and the present invention is not limited by the following example.

(Manufacture of surface modified quantum dots)

Manufacturing Example 1

A magnetic bar is placed in a three-neck round bottom flask, and red quantum dot dispersion solution (InP/ZnSeS/ZnS, Hansol Chemical; quantum dot solid content: 26.5% by weight) is added. YCl ₃ (additive) is added here in an amount of 4% by weight based on the total amount of the quantum dots and additives, and stirred in a nitrogen atmosphere at 80-90°C. After completion of the reaction, cool to room temperature (23°C) and then add the quantum dot reaction solution to cyclohexane to prevent precipitation. The precipitate and cyclohexane are separated through centrifugation, and the precipitate is sufficiently dried in a vacuum oven for one day to obtain surface-modified red quantum dots.

Production example 2

Instead of YCl ₃ , a mixture of ZnCl ₂ and YCl ₃ in a weight ratio of 1:1 (1% by weight of ZnCl ₂ + 1% by weight of YCl ₃ ) was added as an additive, and the input content was also controlled to 2% by weight instead of 4% by weight. Except for this, it was the same as Preparation Example 1.

Production example 3

Instead of YCl ₃ , a mixture of ZnCl ₂ and YCl ₃ in a weight ratio of 1:2 (1% by weight of ZnCl ₂ + 2% by weight of YCl ₃ ) was added as an additive, and the input content was also controlled to 3% by weight instead of 4% by weight. Except for this, it was the same as Preparation Example 1.

Production example 4

Preparation Example 1 was repeated, except that instead of YCl ₃ , a mixture of ZnCl ₂ and YCl ₃ in a weight ratio of 1:3 (1% by weight of ZnCl ₂ + ₃ % by weight of YCl 3) was added as an additive.

Production example 5

Preparation Example 1 was the same as in Preparation Example 1, except that instead of YCl ₃ , a mixture of ZnCl ₂ and YCl ₃ in a weight ratio of 1:1 (2% by weight of ZnCl ₂ + 2% by weight of YCl ₃ ) was added as an additive.

Production example 6

Preparation Example 1 was the same as in Preparation Example 1, except that ZnCl ₂ was added as an additive instead of YCl ₃ .

(Preparation of curable composition)

Based on the following components, curable compositions according to Examples 1 to 5 and Reference Example 1 were prepared.

(A) Quantum dots

(A-1) Surface-modified red quantum dots prepared from Preparation Example 1 above

(A-2) Surface-modified red quantum dots prepared from Preparation Example 2 above

(A-3) Surface-modified red quantum dots prepared from Preparation Example 3 above

(A-4) Surface-modified red quantum dots prepared from Preparation Example 4 above

(A-5) Surface-modified red quantum dots prepared from Preparation Example 5 above

(A-6) Surface-modified red quantum dots prepared from Preparation Example 6 above

(B) Polymerizable compounds

Compound represented by the following formula 6-2 (1,6-Hexanediol diacrylate, Miwon Special Chemicals)

[Formula 6-2]

(C) Photopolymerization initiator

TPO-L (Polynetron Co., Ltd.)

(D) Light diffuser

Titanium dioxide dispersion (rutile type TiO ₂ ; D50 (180 nm), solid content 50% by weight, Iridos Co., Ltd.)

(E) Polymerization inhibitor

Methylhydroquinone (TOKYO CHEMICAL)

Examples 1 to 5 and Reference Example 1

Specifically, the surface-modified red quantum dots and the polymerizable compound are mixed and stirred for 12 hours. Add polymerization inhibitor here and stir for 5 minutes. Next, if necessary, add a photoinitiator and then add a light diffuser.

(For example, in the case of Example 1, 41 g of surface-modified red quantum dots and 41 g of a polymerizable compound represented by Chemical Formula 6-2 were mixed and stirred to prepare a green quantum dot dispersion, and then mixed with Chemical Formula 6-2. Add 10.95 g of another curable monomer represented by number 2 and 0.05 g of polymerization inhibitor and stir for 5 minutes, then add 3 g of photoinitiator and 4 g of light diffuser and stir to prepare a curable composition.)

The specific composition is shown in Table 1 below.

(Unit: weight%) (A) Quantum dots (B) polymerizability
compound (E) polymerization
prohibition (C) Photoinitiator (D) Light diffuser (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) Example 1 41 - - - - - 51.95 0.05 3 4 Example 2 - 41 - - - - 51.95 0.05 3 4 Example 3 - - 41 - - - 51.95 0.05 3 4 Example 4 - - - 41 - - 51.95 0.05 3 4 Example 5 - - - - 41 - 51.95 0.05 3 4 Reference example 1 - - - - - 41 51.95 0.05 3 4

Evaluation 1: Evaluation of wavelength, residual organic matter, Y and Zn content (concentration) of surface-modified quantum dots

Quantum dots according to Preparation Examples 1 to 6 were measured using a QE-2100 quantum efficiency meter (Otsuka Electronics) to measure the range of emission occurring at an excitation wavelength of 450 nm and the wavelength at which the peak with maximum intensity appears, and surface modification was performed. The quantum dots were measured up to 600°C at a temperature increase rate of 10°C/min using TGA (thermal decomposition meter, TA Instrument, SDT-650) to evaluate the residual organic content (concentration) on the surface of the quantum dots. In addition, the content (concentration) of Y and Zn doped in the quantum dots after surface modification was measured using ICP-OES (Inductively Coupled Plasma Emission Spectrometer, Agilent 5100SVDV) after nitric acid reaction treatment at 180°C for 2 hours, and the results are as follows. It is shown in Table 2.

Wavelength (nm) Residual organic matter (%) Y(%) Zn(%) Manufacturing Example 1 637.4 21.4 0.84 - Production example 2 637.6 23.1 1.54 1.46 Production example 3 637.8 22.8 3.2 1.69 Production example 4 638.0 20.6 4.4 2.38 Production example 5 637.4 23.4 3.8 2.57 Production example 6 637.3 25.0 - 4.3

From Table 2, it can be seen that the quantum dots according to Preparation Examples 1 to 5 can easily move the wavelength of the quantum dots toward a longer wavelength compared to the quantum dots according to Preparation Example 6, and the residual organic matter content on the surface of the quantum dots is not large.

Evaluation 2: Outgas evaluation of curable composition

Outgassing properties were evaluated for each of the curable compositions according to Examples 1 to 5 and Reference Example 1, and the results are shown in Table 3 below.

(Outgas generation evaluation method)

Single-film specimens made from the curable compositions of Examples 1 to 5 and Reference Example 1 are weighed and placed in an HS vial, and then sealed with a cap. Headspace GC (Shimdzu, GC2010 plus Series) collected the gases at 180°C for 30 minutes to measure the amount of outgassed, and the results are shown in Table 3 below.

Outgas (Area, %) Example 1 7.20 × 10 ⁶ Example 2 7.11 × 10 ⁶ Example 3 7.03 × 10 ⁶ Example 4 6.77 × 10 ⁶ Example 5 7.08 × 10 ⁶ Reference example 1 7.49 × 10 ⁶

From Table 2, it can be seen that the curable composition according to Examples 1 to 5 has a relatively low outgassing amount compared to the curable composition according to Reference Example 1.

The present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art will be able to form other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

Claims (25)

It consists of a core portion and a shell portion surrounding the core portion,
The shell portion is a quantum dot doped with an element with a valence of +3.
According to paragraph 1,
The element having a valence of +3 is a quantum dot including yttrium (Y), scandium (Sc), a lanthanide group element, an actinium group element, or a combination thereof.
According to paragraph 1,
The shell portion is single layer or multilayer,
The single layer is a ZnS layer,
The multilayer is a quantum dot including a ZnS layer in the outermost part.
According to paragraph 1,
The shell portion is a quantum dot doped with an element with a valence of +2.
According to clause 4,
The element whose valence is +2 is a quantum dot containing Zn.
According to clause 4,
Quantum dots in which the element with a valence of +3 is contained in an amount equal to or greater than that of the element with a valence of +2.
A first step of preparing quantum dots consisting of a core portion and a shell portion surrounding the core portion and not doped with any element, and
A second step of adding an ionic bond-containing additive represented by the following formula (1) to the quantum dots:
Quantum dot modification method comprising:
[Formula 1]
MX ₃
In Formula 1,
M is an element with valence +3,
X is a halide element.
In clause 7,
The quantum dot reforming method wherein the element having a valence of +3 includes yttrium (Y), scandium (Sc), a lanthanide group element, an actinium group element, or a combination thereof.
In clause 7,
The shell portion is single layer or multilayer,
The single layer is a ZnS layer,
A quantum dot modification method wherein the multilayer includes a ZnS layer at the outermost part.
In clause 7,
The quantum dot modification method further comprises an ionic compound represented by the following formula (2):
[Formula 2]
M'X ₃
In Formula 2,
M' is an element with valence +2,
X is a halide element.
According to clause 10,
Quantum dot reforming method wherein the element having a valence of +2 includes Zn.
According to clause 10,
A curable composition in which the ionic bond represented by Formula 1 is added in an amount equal to or greater than that of the ionic bond represented by Formula 2.
According to clause 12,
The ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are contained in equal weight,
Quantum dot reforming method wherein the additive containing the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 is included in an amount of 4% by weight or less based on the total amount of the quantum dots of the first step and the additives of the second step.
According to clause 12,
The ionic bond represented by Formula 1 is included in a greater weight than the ionic bond represented by Formula 2,
A method for modifying quantum dots, wherein the ionic bond represented by Formula 1 and the ionic bond represented by Formula 2 are included in a weight ratio of 2:1 to 3:1.
(A) the quantum dot of any one of claims 1 to 6 or the quantum dot modified by the Gabil method of any one of claims 7 to 14;
(B) photopolymerizable monomer; and
(C) Light diffuser
A curable composition comprising.
According to clause 15,
The curable composition is a solvent-free curable composition.
According to clause 16,
The solvent-free curable composition is, relative to the total amount of the solvent-free curable composition,
3% to 50% by weight of the quantum dots;
30% to 95% by weight of the photopolymerizable monomer; and
1% to 20% by weight of the light diffuser
A solvent-free curable composition comprising a.
According to clause 15,
The light diffuser is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
According to clause 15,
The curable composition further includes a polymerization initiator, a polymerization inhibitor, or a combination thereof.
According to clause 15,
The curable composition further includes a solvent.
According to clause 20,
The curable composition includes 1% to 40% by weight of the quantum dots, based on the total weight of the curable composition; 1% to 20% by weight of the photopolymerizable monomer; A curable composition comprising 1% to 20% by weight of the light diffuser and 40% to 80% by weight of the solvent.
According to clause 15,
The curable composition includes malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or a curable composition further comprising a combination thereof.
A cured film manufactured using the curable composition according to any one of claims 15 to 22.
A color filter comprising the cured film of claim 23.
A display device comprising the color filter of claim 24.