WO2024147426A1 - Curable composition, cured film produced using composition, color filter including cured film and display device including color filter - Google Patents

Abstract

Provided are: a curable composition comprising (A) quantum dots and (B) a polymerizable compound which comprises a compound represented by a specific chemical formula; a cured film produced 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.

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 being introduced 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, so it was not possible 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 gave 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), due to the nature of containing an excessive amount of polymerizable compounds, clogging and discharge defects due to nozzle drying due to volatility, and single film thickness reduction due to volatilization of the ink composition jetted within the pattern partition pixels etc. becomes a problem. Therefore, efforts are being made from various angles to improve the optical properties of solvent-free curable compositions. In order to improve the optical properties of a solvent-free curable composition, a method of increasing the content of inorganic materials is generally used, but the problem is that as the content of inorganic materials increases, the reflectance increases. In other words, the problems of improving optical properties and reducing reflectance of solvent-free curable compositions are in a trade-off relationship, and the need for technology that can improve both properties simultaneously (improving optical properties and reducing reflectance) is growing.

One embodiment is to provide a curable composition that can simultaneously improve optical properties and reduce reflectance.

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; and (B) a polymerizable compound including a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L ¹ is a divalent linking group containing a sulfur atom, but does not include a disulfide (*-SS-*) linking structure,

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 C3 to C20 cycloalkylene group,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The L ¹ may be represented by any one of the following formulas L-1 to formula L-4.

[Formula L-1]

[Formula L-2]

[Formula L-3]

[Formula L-4]

In Formula L-1 to Formula L-4,

L ⁴ to L ⁸ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The compound represented by Formula 1 may have a refractive index greater than 1.455.

The compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The polymerizable compound may further include a compound having a different structure from the compound represented by Formula 1.

A compound having a structure different from the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

L ⁹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*),

L ¹⁰ and L ¹¹ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The compound represented by Formula 2 may have a refractive index of 1.455 or less.

The compound represented by Formula 1 and the compound having a structure different from the compound represented by Formula 1 may be included in a weight ratio of 1:9 to 9:1.

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

The solvent-free curable composition includes 5 to 60 wt% of the quantum dots, based on the total amount of the solvent-free curable composition; And it may include 40% by weight to 95% by weight of the polymerizable compound.

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

The light diffuser may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, 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 polymerizable compound; And it may include 40% by weight 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.

The cured film may have a diffuse reflectance of 50% to 55%.

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 a di(meth)acrylate compound containing sulfur in a curable composition containing quantum dots, the optical properties of the curable composition containing quantum dots can be improved while simultaneously reducing reflectance.

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 among 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.

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

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

polymerizable compound

The curable composition containing quantum dots according to one embodiment includes a sulfur-containing di(meth)acrylate compound having a high refractive index as a polymerizable compound, so that the high refractive characteristics of the sulfur-containing di(meth)acrylate compound are the optical properties of the curable composition. This leads to an improvement effect, and furthermore, when the curable composition is thermally cured, a thiol-ene addition reaction is induced, thereby promoting hardening of the surface of the cured film of the curable composition, thereby satisfying the reflectance reduction effect at the same time.

The sulfur-containing di(meth)acrylate compound may be represented by the following formula (1).

[Formula 1]

In Formula 1,

L ¹ is a divalent linking group containing a sulfur atom, but does not include a disulfide (*-SS-*) linking structure,

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 C3 to C20 cycloalkylene group,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The green quantum dot-containing curable composition has the disadvantage of having a relatively low absorption rate (abs.) and luminous efficiency (EQE) compared to the red quantum dot-containing curable composition, and having a reflectance that is nearly twice as high. Therefore, the technical challenge of improving the brightness of the green quantum dot pixels in the panel and further improving the brightness of the front side by reducing external light reflection has not yet been solved.

The present inventors have clearly addressed the above problems, conducted related research for a long time and experienced hundreds of trials and errors to improve the optical properties and reduce the reflectance of the curable composition containing green quantum dots, and polymerized the compound represented by Formula 1 above. The above technical problem was solved by applying it as a chemical compound.

In general, the main method used to improve the optical properties of curable compositions containing green quantum dots was to increase the content of inorganic substances, and conversely, the main method used to reduce the reflectance of the curable compositions containing green quantum dots was to increase the content of inorganic substances. Since improving optical properties and reducing reflectance are opposite physical properties, that is, they are in a trade-off relationship, it was very difficult to achieve both properties at the same time.

According to one embodiment, the sulfur-containing di(meth)acrylate compound represented by Formula 1 is applied as a polymerizable compound to a curable composition composition to improve optical properties and reflectance in a curable composition containing green quantum dots in addition to a curable composition containing red quantum dots. The reduction effect can be achieved simultaneously.

Specifically, the improvement in optical properties is due to the high refractive index of the compound represented by Formula 1. For example, the compound represented by Formula 1 may have a refractive index of more than 1.455, for example, more than 1.455 and less than 1.7. Since the compound represented by Formula 1 has a high refractive index in the above range, it is included as a polymerizable compound. The optical properties of a curable composition containing quantum dots can be greatly improved.

Furthermore, the reflectance reduction effect is achieved by thermally curing the curable composition according to one embodiment, when the compound represented by Chemical Formula 1 used as the polymerizable compound is thermally decomposed to reveal a thiol group, and the (meth)acrylate group is formed by this thiol group. The thiol-ene reaction between the carbon-carbon double bond and the thiol group is easily induced (see the reaction formula below), promoting surface curing of the thermosetting single film of the curable composition according to one embodiment, ultimately increasing the reflectance of the cured film, especially The diffuse reflectance can be greatly reduced. For example, the diffuse reflectance of the cured film can be reduced to 55% or less, for example, 50% to 55%.

[Reaction formula]

In Formula 1, when L ¹ includes a disulfide (*-SS-*) linking structure or when L ² or L ³ includes an arylene group as a linking group, the refractive index of the compound is lowered, which is disadvantageous in terms of improving optical properties. In addition, it is undesirable because the thiol-ene reaction does not occur smoothly and the effect of reducing reflectance is halved.

For example, L ¹ may be represented by any one of the following formulas L-1 to L-4.

[Formula L-1]

[Formula L-2]

[Formula L-3]

[Formula L-4]

In Formula L-1 to Formula L-4,

L ⁴ to L ⁸ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

When the L ¹ linking group of Formula 1 has the above structure, it can be very advantageous to simultaneously improve optical properties and reduce reflectance (diffuse reflectance) of the curable composition according to one embodiment.

For example, the compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-3, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

For example, the polymerizable compound may further include a compound having a different structure from the compound represented by Formula 1. That is, the polymerizable compound may include the compound represented by Formula 1 and other compounds having a different structure.

For example, a compound having a structure different from the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

L ⁹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*),

L ¹⁰ and L ¹¹ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The curable composition according to one embodiment may further include the compound represented by Formula 2 as a polymerizable compound together with the compound represented by Formula 1 having a high refractive index, or the compound represented by Formula 1 may be used alone. As in the case of use, the effect of improving the optical properties of the curable composition and reducing the reflectance can be achieved at the same time.

For example, the compound represented by Formula 2 may have a refractive index of 1.455 or less. If the compound represented by Formula 2 has a refractive index of more than 1.455, it is advantageous for improving optical properties, but may be disadvantageous in terms of reducing reflectance.

For example, the compound represented by Formula 1 and the compound having a different structure from the compound represented by Formula 1 (e.g., the compound represented by Formula 2, etc.) have a weight ratio of 1:9 to 9:1, for example, 5:5 to 5:5. It may be included in a weight ratio of 9:1.

For example, the compound represented by Formula 1 may be included in a larger amount than a compound having a different structure from the compound represented by Formula 1 (for example, the compound represented by Formula 2, etc.).

For example, a compound represented by Formula 1 and a compound having a different structure from the compound represented by Formula 1 (for example, a compound represented by Formula 2, etc.) may be included in a weight ratio of 6:4 to 9:1.

When the compound represented by Formula 1 is contained in a greater amount than the compound having a different structure from the compound represented by Formula 1 (e.g., the compound represented by Formula 2, etc.), for example, at a weight ratio of 6:4 to 9:1, The curing rate of the curable composition according to one embodiment is increased, thereby maximizing simultaneous improvement of the two effects of improving optical properties and reducing reflectance.

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

[Formula 2-1]

[Formula 2-2]

For example, compounds having a different structure from the compound represented by Formula 1 include, in addition to the compounds represented by Formula 2-1 and Formula 2-2, 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, monomers commonly used in conventional thermosetting or photocuring compositions may be further used. For example, the monomer may be an oxetane-based monomer such as bis[1-ethyl(3-oxetanyl)]methyl ether. It may further include compounds, etc.

The polymerizable compound may be included in an amount of 40% to 95% by weight, for example, 50% to 90% by weight, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound is within the above range, it is possible to manufacture a solvent-free curable composition having a viscosity capable of ink jetting. Additionally, the quantum dots in the prepared solvent-free curable composition can have excellent dispersibility, thereby improving optical properties. It can be.

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

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.

quantum dot

For example, the quantum dots may have a maximum fluorescence emission wavelength 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 are present in an amount of 5% by weight to 60% by weight, such as 10% by weight to 60% by weight, such as 20% by weight to 60% by weight, such as 30% 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% by weight to 40% by weight, for example, 3% by weight 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, the color purity is high, which has the effect of increasing the 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.

For example, the quantum dots may be surface-modified with a ligand having a polar group, for example, a ligand having high affinity for the polymerizable compound. In the case of surface-modified quantum dots as described above, it is very easy to manufacture high-concentration or highly concentrated quantum dot dispersions (improvement of the dispersibility of quantum dots in polymerizable compounds), which can have a significant impact on improving light efficiency, especially in the implementation of solvent-free curable compositions. It can be advantageous.

For example, the ligand having the polar group may have a structure with high affinity to the chemical structure of the polymerizable compound.

For example, the ligand having the polar group may be represented by any one of the compounds represented by the following formulas A to Q, but is not necessarily limited thereto.

[Formula A]

[Formula B]

[Formula C]

[Formula D]

(In the above formula D, m1 is an integer from 0 to 10.)

[Formula E]

[Formula F]

[Formula G]

[Formula H]

[Formula I]

[Formula J]

[Formula K]

[Formula L]

[Formula M]

[Formula N]

[Formula O]

[Formula P]

[Formula Q]

When using the above-mentioned ligand, the surface modification of the quantum dots is easier, and when the quantum dots surface-modified with the above-mentioned ligand are added to the above-mentioned polymerizable compound and stirred, a very transparent dispersion can be obtained, which indicates that the surface modification of the quantum dots is very good. It becomes a standard for confirmation.

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 it is 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 novolak-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 Dainippon 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 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 included 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; Or there are compounds of keto acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, 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. At this time, the cured film may have a diffuse reflectance of 50% to 55% as described above.

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 been pretreated. 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 400 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 for example, when using a high-pressure mercury lamp, it is 500 mJ/cm ² or less (based on a 365 nm sensor).

(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.

Preparation of polymerizable compounds

Manufacturing Example 1

Add 20g of 2,2-thiodiethanol to the flask and sufficiently dissolve in 400mL of dichloromethane. Add 32.6 g of acryloyl chloride here and stir in a nitrogen atmosphere. 36.4 g of Trimethylamine was injected drop-wise at 0°C for 1 hour, then stirred for 2 hours and the reaction was terminated. After adding 200mL of dichloromethane and 500mL of water and extracting, separate the dichloromethane layer, add diluted hydrochloric acid, and repeat extraction three times. Separate the dichloromethane layer, add MgSO ₄ and stir for 5 minutes. After filtering, the filtrate is concentrated. After column purification, concentration and vacuum drying are performed to prepare a compound (refractive index: 1.495) represented by the following formula 1-1.

[Formula 1-1]

Production example 2

Put 20g of 3,6-dithia-1,8-octanediol into a flask and sufficiently dissolve in 200mL of dichloromethane and 200mL of ethanol. Add 21.8 g of acryloyl chloride here and stir in a nitrogen atmosphere. At 0°C, 24.4 g of Trimethylamine was injected drop-wise for 1 hour, then stirred for 2 hours and the reaction was terminated. After adding 200mL of dichloromethane and 500mL of water and extracting, separate the dichloromethane layer, add diluted hydrochloric acid, and repeat extraction three times. Separate the dichloromethane layer, add MgSO ₄ and stir for 5 minutes. After filtering, the filtrate is concentrated. After column purification, concentration and vacuum drying are performed to prepare a compound (refractive index: 1.529) represented by the following formula 1-2.

[Formula 1-2]

Production example 3

Add 20g of 1,4-dithiane-2,5-diol to 300mL of ethanol and 200mL of dichloromethane and stir. Add 26g of acryloyl chloride here and stir in a nitrogen atmosphere. 29.2 g of Trimethylamine was injected drop-wise at 0°C for 1 hour, then stirred for 2 hours and the reaction was terminated. After adding 200mL of dichloromethane and 500mL of water and extracting, separate the dichloromethane layer, add diluted hydrochloric acid, and repeat extraction three times. Separate the dichloromethane layer, add MgSO ₄ and stir for 5 minutes. After filtering, the filtrate is concentrated. After column purification, concentration and vacuum drying are performed to prepare a compound (refractive index: 1.680) represented by the following formula 1-3.

[Formula 1-3]

Production example 4

Dissolve 100g of 1,6-hexanediol in 100ml of toluene and react with 135g of acrylic acid and 8.2g of methanesulfonic acid at 120°C for 5 hours to prepare a compound (refractive index: 1.455) represented by the following formula 2-2.

[Formula 2-2]

Comparative Manufacturing Example 1

Sufficiently dissolve 20 g of Bis(2-hydroxyethyl) disulfide in 300 mL of ethanol and 150 mL of methylene chloride. Add 25.7 g of acryloyl chloride here and stir for 10 minutes. 28.8 g of Triethylamine was slowly injected drop-wise at 0°C, and after stirring for 5 hours, the reaction was terminated, and 250 mL of methylene chloride and 300 mL of water were added and extracted. The organic layer was separated and extracted three additional times with a diluted aqueous hydrochloric acid solution. Separate the dichloromethane layer, add MgSO ₄ and stir for 5 minutes. After filtering, the filtrate is concentrated. After column purification, concentration and vacuum drying are performed to prepare a compound represented by the following formula C-1 (refractive index: 1.517).

[Formula C-1]

Comparative Manufacturing Example 2

Sufficiently dissolve 20g of 1,4-benzene dithiol in 200mL of methylene chloride. Add 22.5 g of 2-chloroethyl acrylate and stir for 10 minutes, then slowly inject 17 g of triethylamine drop-wise at 0°C, and terminate the reaction after stirring for 12 hours. After adding 300mL of methylene chloride and 300mL of water and extracting, separate the organic layer, add diluted hydrochloric acid solution, and repeat extraction three times. Separate the dichloromethane layer, add MgSO ₄ and stir for 5 minutes. After filtering, the filtrate is concentrated. After column purification, concentration and vacuum drying are performed to prepare a compound represented by the following formula C-2 (refractive index: 1.556).

[Formula C-2]

Preparation of surface-modified quantum dot dispersion

Production example 5

A magnetic bar is placed in a three-neck round bottom flask, and green quantum dot dispersion solution (InP/ZnSe/ZnS, Hansol Chemical; quantum dot solid content 23% by weight) is added to each. A compound (ligand) represented by the following formula Q is added here, 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. Separate the precipitate and cyclohexane through centrifugation, and dry the precipitate in a vacuum oven for 24 hours to obtain surface-modified quantum dots.

The surface-modified green quantum dots were stirred in a polymerizable compound for 12 hours to obtain a surface-modified quantum dot dispersion (QD solid content: 23% by weight).

(*Synthesis of compound represented by chemical formula Q: Place 100g of PH-4 (Han Nong Chemical) in a two-necked round bottom flask and sufficiently dissolve in 300mL of THF. Add 15.4g of NaOH and 100mL of water at 0℃, and then obtain a clear solution. Sufficiently dissolve 73 g of para-toluene sulfonic chloride in 100 mL of THF and slowly inject it for 1 hour, then stir at room temperature for 12 hours. After adding methylene chloride and stirring, saturated NaHCO ₃ solution was added, the solvent was removed, and 50 g of the obtained dried material was placed in a two-neck round bottom flask and thoroughly stirred in 300 mL of ethanol. Afterwards, add 27 g of Thiourea and reflux at 80°C for 12 hours. Then, add an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water and stir for 5 more hours. After stirring, add an aqueous hydrochloric acid solution and extract and titrate. , moisture removal, and solvent removal are carried out sequentially and dried in a vacuum oven for 24 hours to obtain a compound represented by the following formula Q.)

[Formula Q]

(Preparation of curable composition)

Examples 1 to 7 and Comparative Examples 1 to 3

Curable compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were prepared with the compositions shown in Tables 1 and 2 below using the components mentioned below.

Specifically, the quantum dot dispersion is weighed and diluted by mixing with a polymerizable compound, and then a polymerization inhibitor is added and stirred for 5 minutes. Next, after adding the photoinitiator, add the light diffuser. Thereafter, the crude solution is stirred for 1 hour to prepare a curable composition.

(A) Quantum dots

Surface-modified green quantum dot dispersion prepared from Preparation Example 5

(B) Polymerizable compounds

(B-1) Compound of Preparation Example 1

(B-2) Compound of Preparation Example 2

(B-3) Compound of Preparation Example 3

(B-4) Compound of Preparation Example 4

(B-5) Compound of Comparative Preparation Example 1

(B-6) Compound of Comparative Preparation Example 2

(C) Photopolymerization initiator

TPO-L (Polynetron Co., Ltd.)

(D) Light diffuser

Titanium dioxide dispersion (TiO ₂ solid content 20% by weight, average particle diameter: 200nm, Dito Technology Co., Ltd.)

(E) Polymerization inhibitor

Methylhydroquinone (TOKYO CHEMICAL)

(Unit: weight%)

		Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
(A) Quantum dot dispersion		42	42	42	42	42	42	42
(B) Polymerizable compounds	(B-1)	10.58	20.7	31.28	41.4	46	-	-
	(B-2)	-	-	-	-	-	41.4	-
	(B-3)	-	-	-	-	-	-	41.4
	(B-4)	35.42	25.3	14.72	4.6	-	4.6	4.6
	(B-5)	-	-	-	-	-	-	-
	(B-6)	-	-	-	-	-	-	-
	(B-7)	-	-	-	-	-	-	-
(C) Photopolymerization initiator		3	3	3	3	3	3	3
(D) Light diffuser		8	8	8	8	8	8	8
(E) Polymerization inhibitor		One	One	One	One	One	One	One
Sum		100	100	100	100	100	100	100

(Unit: weight%)

		Comparative Example 1	Comparative Example 2	Comparative Example 3
(A) Quantum dot dispersion		42	42	42
(B) Polymerizable compounds	(B-1)	-	-	-
	(B-2)	-	-	-
	(B-3)	-	-	-
	(B-4)	4.6	4.6	46
	(B-5)	-	-	-
	(B-6)	41.4	-	-
	(B-7)	-	41.4	-
(C) Photopolymerization initiator		3	3	3
(D) Light diffuser		8	8	8
(E) Polymerization inhibitor		One	One	One
Sum		100	100	100

Evaluation: Evaluation of optical properties and diffuse reflectance of curable composition

For each of the curable compositions according to Examples 1 to 7 and Comparative Examples 1 to 3, the quantum efficiency (EQE) after exposure and the diffuse reflectance (SCE) after curing were measured using a spectrophotometer (Konica Minolta, CM-3600A). It was measured using and the results are shown in Table 3 below.

	Quantum efficiency after exposure (%)	Diffuse reflectance after curing (%)
Example 1	32.2	54.7
Example 2	32.9	53.6
Example 3	33.1	53.6
Example 4	33.6	52.5
Example 5	31.9	55.8
Example 6	33.5	52.5
Example 7	34.0	52.1
Comparative Example 1	31.5	56.1
Comparative Example 2	30.8	57.3
Comparative Example 3	31.7	56.1

From Table 3, compared to the curable compositions according to Comparative Examples 1 to 3, the curable compositions according to Examples 1 to 7 have higher quantum efficiency after exposure, resulting in improved optical properties, and at the same time, the diffuse reflectance after curing Since this is low, it can be confirmed that it also has the effect of reducing reflectance.

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 (19)

1. (A) Quantum dots; and

   (B) a polymerizable compound containing a compound represented by the following formula (1)

   A curable composition comprising:

   [Formula 1]

   

   In Formula 1,

   L ¹ is a divalent linking group containing a sulfur atom, but does not include a disulfide (*-SS-*) linking structure,

   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 C3 to C20 cycloalkylene group,

   R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
2. According to paragraph 1,

   Wherein L ¹ is a curable composition represented by any one of the following formulas L-1 to L-4:

   [Formula L-1]

   

   [Formula L-2]

   

   [Formula L-3]

   

   [Formula L-4]

   

   In Formula L-1 to Formula L-4,

   L ⁴ to L ⁸ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
3. According to paragraph 1,

   The compound represented by Formula 1 is a curable composition having a refractive index of more than 1.455.
4. According to paragraph 1,

   The compound represented by Formula 1 is a curable composition represented by any one of the following Formulas 1-1 to 1-3.

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   
5. According to paragraph 1,

   The curable composition wherein the polymerizable compound further includes a compound having a different structure from the compound represented by Formula 1.
6. According to clause 5,

   A compound having a structure different from the compound represented by Formula 1 is a curable composition represented by Formula 2 below.

   [Formula 2]

   

   In Formula 2,

   L ⁹ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*),

   L ¹⁰ and L ¹¹ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

   R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
7. According to clause 6,

   The compound represented by Formula 2 is a curable composition having a refractive index of 1.455 or less.
8. According to clause 5,

   A curable composition comprising the compound represented by Formula 1 and a compound having a structure different from the compound represented by Formula 1 in a weight ratio of 1:9 to 9:1.
9. According to paragraph 1,

   The curable composition is a solvent-free curable composition.
10. According to clause 9,

    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; and

    40% to 95% by weight of the polymerizable compound

    A solvent-free curable composition comprising a.
11. According to paragraph 1,

    The curable composition further includes a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.
12. According to clause 11,

    The light diffuser is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
13. According to paragraph 1,

    The curable composition further includes a solvent.
14. According to clause 13,

    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 polymerizable compound; and 40% to 80% by weight of the solvent.
15. 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.
16. A cured film manufactured using the curable composition according to any one of claims 1 to 15.
17. According to clause 16,

    The cured film is a cured film having a diffuse reflectance of 50% to 55%.
18. A color filter comprising the cured film of claim 16.
19. A display device including the color filter of claim 18.