KR20240004019A - Curable composition, cured layer using the composition, color filter including the cured layer and display device including the color filter - Google Patents

Abstract

(A) Quantum dots; (B) a light diffuser containing a hydrophilic group on the surface; and (C) a curable composition including an additive capable of reacting with the hydrophilic group, a cured film manufactured using the curable composition, a color filter including the cured film, and a display device including the color filter.

Description

A curable composition, a cured film manufactured using the composition, a color filter comprising the cured film, and a display device comprising the color filter {CURABLE COMPOSITION, CURED LAYER USING THE COMPOSITION, COLOR FILTER INCLUDING THE CURED LAYER AND DISPLAY DEVICE INCLUDING THE COLOR FILTER}

This description relates to a curable composition, a cured film manufactured using the composition, a color filter comprising the cured film, and a display device comprising 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 the case of solvent-free curable compositions (quantum dot ink compositions), there are several problems such as clogging and discharge failure due to nozzle drying due to volatility, single film thickness reduction due to volatilization of the ink composition jetted within the pattern partition pixels, and storage stability is poor. There is also a problem. In the case of existing quantum dot ink compositions, in order to improve the storage stability, polymerization inhibitors, etc. are added to lower the reactivity between the components included in the composition, the content of the initiator is controlled, the functional group in the polymerizable compound is modified, etc. Although various methods have been tried, the storage stability of the solvent-free curable composition containing quantum dots has not yet been significantly improved.

One embodiment is to provide a curable composition with excellent storage stability.

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 includes (A) quantum dots; (B) a light diffuser containing a hydrophilic group on the surface; and (C) an additive capable of reacting with the hydrophilic group.

The hydrophilic group may be a carboxyl group.

The additive may be capable of forming an ionic bond, hydrogen bond, or coordination bond with the hydrophilic group.

The additive may include water, amine compounds, polyol compounds, or combinations thereof.

The amine compound may include primary amine, secondary amine, tertiary amine, or a combination thereof.

The amine compound may include a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

The polyol compound may be represented by the following formula (2).

[Formula 2]

In Formula 2,

L ² and L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, provided that L ² and L ³ are not a single bond at the same time.

The additive may be included in an amount of 0.05% by weight to 0.5% by weight based on the total amount of the curable composition.

The curable composition may further include a polymerizable compound.

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

The solvent-free curable composition is, relative to the total amount of the solvent-free curable composition,

5% to 60% by weight of the quantum dots; 1% to 10% by weight of the light diffuser; 0.05% to 0.5% by weight of the additive; And it may include 38% by weight to 90% by weight of the polymerizable compound.

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 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.

By including additives capable of reacting with hydrophilic groups in the curable composition containing quantum dots, problems such as lowering of dispersibility and thickening of the curable composition containing quantum dots and sedimentation of the light diffuser are solved, ultimately improving the storage stability of the curable composition containing quantum dots. You can.

Figure 1 is a diagram showing the reaction between a quantum dot (QD) and a hydrophilic group (carboxyl group) on the surface of a light diffuser (TiO ₂ ).
Figure 2 shows that the additive that can react with the hydrophilic group hydrogen bonds with the hydrophilic group (carboxyl group) on the surface of the light diffuser (TiO ₂ ), thereby blocking the reaction between the quantum dots (QD) and the hydrophilic group (carboxyl group) on the surface of the light diffuser (TiO ₂ ). This is a picture that shows. (In Figure 2, R ¹ and R ² may each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and n and m may each independently be an integer of 0 to 20. there is.)
Figure 3 is a photograph of the curable composition prepared according to Comparative Example 1, and after 24 hours at 45°C, precipitation of the light diffuser occurred and phase separation occurred.
Figure 4 is a photograph of the curable composition prepared according to Example 1, and after 24 hours at 45°C, no precipitation of the light diffuser occurred and no phase separation phenomenon was observed.

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.

The curable composition containing quantum dots is manufactured by mixing a quantum dot dispersion and a dispersion of a light diffuser (TiO _2, etc.). After mixing, when maintained at the process temperature (45°C) during ink-jetting, which is a relatively high temperature compared to room temperature, the above The light diffuser reacts with the surface of the quantum dots, thereby lowering the dispersibility of the quantum dots, which causes foreign matter to be generated during single film coating of the composition, and phase separation between the curable compositions due to increased precipitation of the light diffuser, which causes the nozzle to dry during ink-jetting. Problems such as clogging may occur.

Accordingly, after experiencing countless trials and errors while trying a wide variety of methods to solve the above problems, the present inventors effectively solved the above problems by adding some additives capable of reacting with hydrophilic groups into the composition of the curable composition containing quantum dots. After confirming that improvements could be made, the present invention was completed.

The curable composition containing quantum dots according to the present invention includes a light diffuser containing a hydrophilic group on the surface and an additive capable of reacting with the hydrophilic group on the surface of the light diffuser, thereby causing a decrease in dispersibility and thickening of the curable composition containing quantum dots. By solving the problem of sedimentation, etc., it is possible to ultimately improve the storage stability of the curable composition containing quantum dots.

Generally, in order to improve the dispersibility of a curable composition containing quantum dots, the length of the quantum dot surface modification material is adjusted, thiol-based additives or polymer binders are additionally used, or high-sensitivity initiators or multifunctional monomers are additionally used. Considering that none of the technologies have been able to significantly improve the storage stability of the curable composition containing quantum dots, the present invention solves problems that the prior art could not solve, and the level of the invention can be said to be very high.

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

quantum dot

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.

For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots may be included in an amount of 5% by weight to 60% by weight, such as 10% by weight to 55% by weight, such as 15% by weight to 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.

To date, curable compositions (inks) containing quantum dots have been developed to specialize in thiol-based binders or monomers with good compatibility with quantum dots, and are even being commercialized. The quantum dots may be quantum dots that have not been surface modified, or may be quantum dots that have been surface modified with the thiol-based binder or monomer.

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, 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/ZeSe/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.

light diffuser

The curable composition according to one embodiment includes a light diffuser, specifically a light diffuser containing a hydrophilic group on the surface.

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, but is not necessarily limited thereto. As a light diffuser containing a hydrophilic group on the surface, any nanoparticle that can function as a scatterer can be used.

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 hydrophilic group on the surface of the light diffuser may be, for example, a carboxyl group, but is not necessarily limited thereto.

The hydrophilic group on the surface of the light diffuser may cause mutual reactions such as ionic bonding, hydrogen bonding, or coordination bonding with additives described later, and as a result, the hydrophilic group does not react with the surface of the quantum dot described above, thereby reducing the dispersibility of the quantum dot. It can be prevented from deteriorating. In the absence of the additive, some of the hydrophilic groups on the surface of the light diffuser react directly with the surface of the quantum dot, thereby lowering the dispersibility of the quantum dot, causing precipitation/sedimentation of the light diffuser and resulting phase separation phenomenon. According to one embodiment, the above-described problem can be easily solved because the additive is included as an essential component.

The light diffuser may be included in an amount of 1% to 20% by weight, such as 1% to 15% by weight, such as 1% 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.

Additives that can react with hydrophilic groups

The curable composition according to one embodiment includes an additive capable of reacting with the hydrophilic group on the surface of the above-described light diffuser.

For example, the additive may include water, an amine compound, a polyol compound, or a combination thereof, but is not necessarily limited thereto.

For example, the amine compound may include ammonia, primary amine, secondary amine, tertiary amine, or a combination thereof.

For example, the amine compound may include a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1,

L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.

For example, the polyol compound may be represented by the following formula (2).

[Formula 2]

In Formula 2,

L ² and L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, provided that L ² and L ³ are not a single bond at the same time.

For example, the polyol compound may be represented by the following Chemical Formula 2-1 or Chemical Formula 2-2, but is not necessarily limited thereto.

[Formula 2-1]

[Formula 2-2]

In Formula 2-1,

L ⁴ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

In Formula 2-2,

L ⁴ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

n and m are each independently integers from 0 to 20.

For example, the additive may be included in an amount of 0.05% by weight to 0.5% by weight based on the total amount of the curable composition. When the additive is contained in an amount of less than 0.05% by weight based on the total amount of the curable composition, it is difficult to effectively prevent the reaction between the quantum dot surface and the light diffuser, and when the additive is contained in an amount greater than 0.5% by weight based on the total amount of the curable composition, the light diffuser This may be undesirable because the relative content may decrease, which may lower the optical properties of the curable composition.

polymerizable compound

The curable composition according to one embodiment may further include a polymerizable compound.

For example, the polymerizable compound may have a carbon-carbon double bond at the terminal.

The polymerizable compound having a carbon-carbon double bond at the terminal may be included in an amount of 38% to 90% by weight, for example, 39% to 89% by weight, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound 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 polymerizable compound 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 polymerizable compound 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 polymerizable compound 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 ⁷ and L ⁹ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

L ⁸ 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, polymerizable compounds 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 polymerizable compound 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 polymerizable compound 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 polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved.

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 the 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 producing a cured film, there is no loss of film thickness when developing the 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 %. 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 may include organic solvents such as 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 heat 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 quantum dots)

Place a magnetic bar in a three-neck round bottom flask, and add green quantum dot dispersion solution (InP/ZnSe/ZnS, Hansol Chemical; quantum dot solid content 23% by weight). Here, a surface modification material is added according to the composition in Table 1 below, and stirred at 80°C in a nitrogen atmosphere. 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 green quantum dots.

(Preparation of curable composition)

Based on the following components, curable compositions according to Examples 1 to 18, Comparative Example 1, and Comparative Example 2 were prepared.

(A) Quantum dots

(A-1) Green quantum dot (InP/ZnSe/ZnS, Hansol Chemical)

(A-2) Red quantum dot (InP/ZnSe/ZnS, Hansol Chemical)

(B) Light diffuser containing a carboxyl group on the surface

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

(C) Additives

(C-1) Water (deionized water; DIW)

(C-2) Butanediol (SIGMA-ALDRICH)

(SIGMA-ALDRICH)(C-3)

(SIGMA-ALDRICH)

(C-4) Propylamine (SIGMA-ALDRICH)

(C-5) Diethylamine (SIGMA-ALDRICH)

(C-6) Triethylamine (SIGMA-ALDRICH)

(D) Polymerizable compounds

Compound represented by the following formula 6-2 (M200, Miwon Chemical Co., Ltd.)

[Formula 6-2]

(E) Photopolymerization initiator

TPO-L (Polynetron Co., Ltd.)

(F) Polymerization inhibitor

Methylhydroquinone (TOKYO CHEMICAL)

Examples 1 to 17, Comparative Example 1 and Comparative Example 2

Specifically, the quantum dots and the polymerizable compound are mixed and stirred for 12 hours. Add polymerization inhibitor here and stir for 5 minutes. Next, after adding the photopolymerization initiator, the light diffuser and additives are added.

(For example, in the case of Example 1, 41 g of green quantum dots and 41 g of a polymerizable compound represented by Formula 6-2 were mixed and stirred to prepare a green quantum dot dispersion, and then mixed with 41 g of the compound represented by Formula 6-2 as a polymerizable compound. 5.5 g to 5.95 g of another polymerizable compound and 1 g of a polymerization inhibitor were added and stirred for 5 minutes, and then 3 g of a photopolymerization initiator, 8 g of a light diffuser, and 0.05 g to 0.5 g of an additive were added and stirred to form a curable composition (ink). manufactures.)

The specific composition is shown in Table 1 and Table 2 below.

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 quantum dot (A-1) 41 41 41 41 41 41 41 41 41 41 (A-2) - - - - - - - - - - polymerizable compound 46.95 46.9 46.8 46.5 46.5 46.5 46.5 46.5 46.5 47 Polymerization inhibitor One One One One One One One One One One photopolymerization initiator 3 3 3 3 3 3 3 3 3 3 light diffuser 8 8 8 8 8 8 8 8 8 8 additive (C-1) 0.05 0.1 0.2 0.5 - - - - - - (C-2) - - - - 0.5 - - - - - (C-3) - - - - - 0.5 - - - - (C-4) - - - - - - 0.5 - - - (C-5) - - - - - - - 0.5 - - (C-6) - - - - - - - - 0.5 -

(Unit: weight%) Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative Example 2 quantum dot (A-1) - - - - - - - - - (A-2) 41 41 41 41 41 41 41 41 41 polymerizable compounds 46.95 46.9 46.8 46.5 46.5 46.5 46.5 46.5 47 Polymerization inhibitor One One One One One One One One One photopolymerization initiator 3 3 3 3 3 3 3 3 3 light diffuser 8 8 8 8 8 8 8 8 8 additive (C-1) 0.05 0.1 0.2 - - - - - - (C-2) - - - 0.5 - - - - - (C-3) - - - - 0.5 - - - - (C-4) - - - - - 0.5 - - - (C-5) - - - - - - 0.5 - - (C-6) - - - - - - - 0.5 -

Evaluation: Evaluation of sedimentation stability and particle size dispersion of the curable composition

After preparing the curable compositions according to Examples 1 to 17, Comparative Examples 1 and 2, they were left at 45°C for 7 days to check the sedimentation state and particle size (D50) of the composition, and the results were are shown in Tables 3 and 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Day 0
(Room temperature) sedimentation state OK OK OK OK OK OK OK OK OK OK Particle size (D50) 185.2 183.6 162.1 164.7 173.6 174.5 165.1 180.5 164.2 188.8 Day 1
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK NG Particle size (D50) 193.2 176.4 171.2 164 193.4 178.1 163.5 188.1 182.1 191.5 Day 3
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK NG Particle size (D50) 206.5 178.3 165.1 155.3 199.5 171.3 167.6 185.2 184.2 252.8 Day 5
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK NG Particle size (D50) 205.1 178.4 168.1 161.5 193.7 175.2 170.2 190.1 181.9 216.2 Day 7
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK NG Particle size (D50) 179.2 185.5 162 150.8 189.8 178.9 168.5 186.2 180.7 239.5

(OK: Phase separation is not observed with the naked eye, NG: Phase separation is observed with the naked eye)

Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative Example 2 Day 0
(Room temperature) sedimentation state OK OK OK OK OK OK OK OK OK Particle size (D50) 187.3 185.5 185.5 177.9 186.1 180.1 180.9 185.6 180.6 Day 3
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK Particle size (D50) 181.3 181.3 183.4 192.4 187.7 186.5 185.3 180.2 217.5 Day 5
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK Particle size (D50) 195.6 187.2 189.7 186.6 182.3 185.2 190.2 179.5 211.8 Day 7
(45℃) sedimentation state OK OK OK OK OK OK OK OK OK Particle size (D50) 182.5 178.3 183.7 175.2 185.1 190.2 186.3 186.1 202.7

(OK: Phase separation is not observed with the naked eye, NG: Phase separation is observed with the naked eye)

From Tables 3 and 4, it can be seen that the curable compositions according to Examples 1 to 17 maintain excellent sedimentation stability and particle size dispersibility for 7 days compared to the curable compositions according to Comparative Examples 1 and 2. You can.

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 (18)

(A) Quantum dots;
(B) a light diffuser containing a hydrophilic group on the surface; and
(C) Additives capable of reacting with the hydrophilic group
A curable composition comprising.
According to paragraph 1,
A curable composition in which the hydrophilic group is a carboxyl group.
According to paragraph 1,
The additive is a curable composition capable of ionic bonding, hydrogen bonding, or coordination bonding with the hydrophilic group.
According to paragraph 1,
A curable composition wherein the additive includes water, an amine compound, a polyol compound, or a combination thereof.
According to paragraph 4,
The curable composition wherein the amine compound includes primary amine, secondary amine, tertiary amine, or a combination thereof.
According to paragraph 4,
The amine compound is a curable composition comprising a repeating unit represented by the following formula (1):
[Formula 1]

In Formula 1,
L ¹ is a substituted or unsubstituted C1 to C20 alkylene group.
According to paragraph 4,
The polyol compound is a curable composition represented by the following formula (2):
[Formula 2]

In Formula 2,
L ² and L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, provided that L ² and L ³ are not a single bond at the same time.
According to paragraph 1,
The additive is included in an amount of 0.05% by weight to 0.5% by weight based on the total amount of the curable composition.
According to paragraph 1,
The curable composition further includes a polymerizable compound.
According to clause 9,
The curable composition is a solvent-free curable composition.
According to clause 10,
The solvent-free curable composition is, relative to the total amount of the solvent-free curable composition,
5% to 60% by weight of the quantum dots;
1% to 10% by weight of the light diffuser;
0.05% to 0.5% by weight of the additive; and
38% to 90% by weight of the polymerizable compound
A solvent-free curable composition comprising a.
According to paragraph 1,
The light diffuser is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
According to paragraph 1,
The curable composition further includes a polymerization initiator, a polymerization inhibitor, or a combination thereof.
According to paragraph 1,
The curable composition further includes a solvent.
According to paragraph 1,
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 1 to 15.
A color filter comprising the cured film of claim 16.
A display device including the color filter of claim 17.