TWI833040B - Quantum dot, curable composition comprising the same, cured layer using the composition, and color filter including the cured layer - Google Patents

Abstract

Provided are a quantum dot surface-modified with a compound represented by Chemical Formula 1, a curable composition including the quantum dot, a cured layer, and a color filter.

Description

Quantum dots, curable compositions including the same, cured layers using the compositions, and color filters including the cured layers

[Cross-reference to related applications]

This application claims the priority and rights of Korean Patent Application No. 10-2019-0127123, which was filed with the Korean Intellectual Property Office on October 14, 2019. The entire content of the Korean patent application is incorporated into this case for reference. .

The present disclosure relates to a quantum dot, a curable composition including the same, a cured layer using the composition, and a color filter including the cured layer.

In the case of general quantum dots, the solvents in which quantum dots are dispersed are limited due to their hydrophobic surface properties. Therefore, it is difficult to introduce them into polar systems such as adhesives or curable monomers.

For example, even where quantum dot ink compositions are actively studied, the polarity is relatively low in the initial step, and it may be dispersed in a solvent for a curable composition with high hydrophobicity. Therefore, since it is difficult to contain 20% by weight or more of quantum dots based on the total amount of the composition, the optical efficiency of the ink cannot be increased beyond a certain level. Although quantum dots are additionally added and dispersed to improve light efficiency, the viscosity will exceed the range capable of inkjet (12 centipoise), and therefore handleability may not be satisfied.

To obtain a viscosity range capable of jetting, a method of reducing the solids content of the ink by dissolving 50% or more of the solvent based on the total weight of the composition also provides somewhat satisfactory results in terms of viscosity . However, in terms of viscosity, it can be considered a satisfactory result, but may become worse due to drying of the nozzle due to solvent evaporation, clogging of the nozzle and reduction of the monolayer over time after spraying, and difficulty in controlling the curing thickness deviation after. Therefore, it is difficult to apply it to actual manufacturing processes.

Therefore, solvent-free quantum dot inks that do not contain solvents are the most desirable form for practical process applications. Current technologies for applying quantum dots themselves to solvent-based compositions are now somewhat limited.

As reported so far, in the case of the most desirable solvent-based compositions to be applied in practical processes, quantum dots that are not surface modified (e.g., ligand substituted) have, based on the total amount of the solvent-based composition, Content of 20% to 25% by weight. Therefore, it is difficult to improve the optical efficiency and absorbance due to viscosity limitations. At the same time, attempts have been made to reduce the quantum dot content and increase the light diffusing agent (scatterer) content in other improvement approaches, but this has also failed to solve the precipitation problem and low light efficiency.

One embodiment provides a quantum dot that is surface-modified with a compound having an excellent passivation effect and therefore has improved light efficiency.

Another embodiment provides a curable composition containing quantum dots.

Another embodiment provides a cured layer produced using the curable composition.

Another embodiment provides a color filter including the solidified layer.

One embodiment provides a quantum dot surface-modified with a compound represented by Chemical Formula 1.

[Chemical formula 1]

In Chemical Formula 1, R ¹ is a carboxyl group, *-P(=O)(OH) ₂ or a thiol group, and R ² is "unsubstituted or substituted by vinyl, allyl, epoxy, (methyl ) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group substituted C1 to C20 alkyl group", "unsubstituted or vinyl, allyl, epoxy group, (meth)acrylate group, C1 to C20 alkoxy substituted by C1 to C10 alkyl or C6 to C12 aryl", "unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl "C6 to C20 aryl group substituted by C6 to C12 aryl group" or "unsubstituted or substituted by vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C12 Aryl-substituted C6 to C20 aryloxy group", or "represented by Chemical Formula 1A", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ is "substituted or unsubstituted vinyl group", "unsubstituted or vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 Alkyl or C6 to C12 aryl substituted C1 to C20 alkyl" or "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl or C6 to C12 aryl-substituted C2 to C20 alkenyl", and L ¹ is "C1 to C20 alkylene unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "C3 to C20 cycloalkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "from Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2 "One of the expressions", [Chemical Formula 1B-1-1] [Chemical formula 1B-1-2] [Chemical formula 1B-2-1] [Chemical formula 1B-2-2] [Chemical formula 1B-3-1]

[Chemical formula 1B-3-2]

[Chemical formula 1B-5-2] [Chemical formula 1B-6-1] [Chemical formula 1B-6-2] [Chemical formula 1B-7-1] [Chemical formula 1B-7-2] Wherein, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b are independently a hydrogen atom or a carboxyl group, and R ^c is O, S, NH, C1 to C20 alkylene group, C1 to C20 Alkylamino group or C2 to C20 allylamine group, L ² is a single bond, *-C(=O)O-* or *-S-*, and L ³ is composed of Chemical Formula 1C-1 or Chemical Formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , m is an integer from 1 to 20, and n is an integer from 1 or 2.

The compound represented by Chemical Formula 1 may be represented by Chemical Formula 2.

[Chemical formula 2]

In Chemical Formula 2, R ² may be "C1 to C20 that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl, or C6 to C12 aryl. "Alkyl", "C1 to C20 alkoxy that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl group that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl" or "unsubstituted or [ Chemical formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl or C6 to C12 aryl substituted C1 to C20 alkyl" or "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl-substituted C2 to C20 alkenyl group", and L ¹ can be "C1 to C20 alkylene group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group ” or “C3 to C20 cycloalkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group” or “can be represented by Chemical Formula 1B-1-1, Chemical Formula 1B-2 -1. Expressed by one of Chemical Formula 1B-3-1, Chemical Formula 1B-4-1, Chemical Formula 1B-5-1, Chemical Formula 1B-6-1 and Chemical Formula 1B-7-1", [Chemical Formula 1B-1- 1] [Chemical formula 1B-2-1] [Chemical formula 1B-3-1] [Chemical formula 1B-4-1] [Chemical formula 1B-5-1] [Chemical formula 1B-6-1] [Chemical formula 1B-7-1] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, L ² can be a single bond, *-C(=O)O-* or *-S-*, and L ³ can be composed of chemical formula 1C-1 or chemical formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ may be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl, and m can be an integer from 1 to 20.

In Chemical Formula 2, R ² may be "a C1 to C20 alkyl group that is unsubstituted or substituted by a C1 to C10 alkyl group or a C6 to C12 aryl group", "a C1 to C20 alkyl group that is unsubstituted or substituted by a C1 to C10 alkyl group or a C6 to C12 aryl group" Aryl-substituted C1 to C20 alkoxy", "unsubstituted or C6 to C20 aryl substituted by C1 to C10 alkyl or C6 to C12 aryl" or "unsubstituted or C1 to C10 alkyl or C6 to C12 aryl-substituted C6 to C20 aryloxy group", L ¹ can be "unsubstituted C1 to C20 alkylene group" or "unsubstituted C3 to C20 cycloalkylene group", L ² can be Single bond, *-C(=O)O-* or *-S-*, and L ³ can be represented by Chemical Formula 1C-1 or Chemical Formula 1C-2, [Chemical Formula 1C-1] [Chemical formula 1C-2] Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ may be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl, and m can be an integer from 1 to 20.

The compound represented by Chemical Formula 1 may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-8.

[Chemical formula 2-1]

[Chemical formula 2-2]

[Chemical formula 2-3]

[Chemical formula 2-4]

[Chemical formula 2-5]

[Chemical formula 2-6]

[Chemical formula 2-7]

[Chemical formula 2-8]

In Chemical Formula 1, R ¹ may be a carboxyl group or a thiol group, and R ² may be a C1 to C20 alkane that is unsubstituted or substituted by a vinyl group, an allyl group, an epoxy group or a (meth)acrylate group. group", "C1 to C20 alkoxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", "unsubstituted or substituted by vinyl, allyl, C6 to C20 aryl substituted by epoxy or (meth)acrylate" or "C6 to C20 aryl unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate. Oxygen group", or may be "represented by Chemical Formula 1A", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate", and L ¹ may be "unsubstituted or substituted by C1 to C20 alkylene substituted by vinyl, allyl, epoxy or (meth)acrylate" or "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylic acid "Ester group-substituted C3 to C20 cycloalkyl group" may be "represented by one of Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2 " , [Chemical Formula 1B-1-1] [Chemical formula 1B-1-2] [Chemical formula 1B-2-1] [Chemical formula 1B-2-2] [Chemical formula 1B-3-1] [Chemical formula 1B-3-2] [Chemical formula 1B-4-1] [Chemical formula 1B-4-2] [Chemical formula 1B-5-1] [Chemical formula 1B-5-2] [Chemical formula 1B-6-1] [Chemical formula 1B-6-2] [Chemical formula 1B-7-1] [Chemical formula 1B-7-2] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, L ² can be a single bond, *-C(=O)O-* or *-S-*, and L ³ can be composed of chemical formula 1C-1 or chemical formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ may be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl group, m may be an integer from 1 to 20, and n may be an integer of 1 or 2.

The compound represented by Chemical Formula 1 may be represented by Chemical Formula 3.

[Chemical formula 3]

In Chemical Formula 3, R ⁴ may be "a C1 to C20 alkyl group that is unsubstituted or substituted by a vinyl group, an allyl group, an epoxy group or a (meth)acrylate group", "an unsubstituted or substituted by a vinyl group" , Allyl, epoxy or (meth)acrylate group substituted C1 to C20 alkoxy group", "Unsubstituted or vinyl, allyl, epoxy or (meth)acrylate group Substituted C6 to C20 aryloxy group" or "C6 to C20 aryloxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", or "can be represented by Chemical Formula 1A" , [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", R ⁵ can be a carboxyl or thiol group, L ⁶ and L ⁷ can be independently substituted or unsubstituted C1 to C20 alkylene group, and L ⁸ can be a single bond, *-S-*, *-C(=O)-* or *-OC(= O)-*, L ⁹ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and m may be an integer from 1 to 20.

The compound represented by Chemical Formula 1 may be represented by Chemical Formula 4.

[Chemical formula 4]

In Chemical Formula 4, R ⁴ may be "a C1 to C20 alkyl group that is unsubstituted or substituted by a vinyl group, an allyl group, an epoxy group or a (meth)acrylate group", "an unsubstituted or substituted by a vinyl group" , Allyl, epoxy or (meth)acrylate group substituted C1 to C20 alkoxy group", "Unsubstituted or vinyl, allyl, epoxy or (meth)acrylate group Substituted C6 to C20 aryloxy group" or "C6 to C20 aryloxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", or may be "represented by Chemical Formula 1A ", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", L ⁶ and L ⁷ may independently be substituted Or unsubstituted C1 to C20 alkylene group, L ⁸ can be a single bond, *-S-*, *-C(=O)-* or *-OC(=O)-*, L ⁹ can be a single bond The bond is either a substituted or unsubstituted C1 to C20 alkylene group, and L ¹⁰ may be composed of Chemical Formula 1B-1-1, Chemical Formula 1B-2-1, Chemical Formula 1B-3-1, Chemical Formula 1B-4-1, One of Chemical Formula 1B-5-1, Chemical Formula 1B-6-1 and Chemical Formula 1B-7-1 represents, [Chemical Formula 1B-1-1] [Chemical formula 1B-2-1] [Chemical formula 1B-3-1] [Chemical formula 1B-4-1] [Chemical formula 1B-5-1] [Chemical formula 1B-6-1] [Chemical formula 1B-7-1] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, and m may be an integer from 1 to 20.

The compound represented by Chemical Formula 1 may be represented by one of Chemical Formula 3-1 to Chemical Formula 3-6.

[Chemical formula 3-1]

[Chemical formula 3-2]

[Chemical formula 3-3]

[Chemical formula 3-4]

[Chemical formula 3-5]

[Chemical formula 3-6]

The compound represented by Chemical Formula 1 may be represented by Chemical Formula 4-1.

[Chemical formula 4-1]

The quantum dots may have a maximum fluorescence emission wavelength at 500 nanometers to 680 nanometers.

Another embodiment provides a solvent-free curable composition including quantum dots and a polymerizable monomer having a carbon-carbon double bond at the terminus.

The polymerizable monomer in the solvent-free curable composition may have a molecular weight of 220 g/mol to 1,000 g/mol.

The polymerizable monomer in the solvent-free curable composition may be represented by Chemical Formula 5.

[Chemical formula 5]

In Chemical Formula 5, R ¹⁰¹ and R ¹⁰² may be independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁰¹ and L ¹⁰³ may be independently a substituted or unsubstituted C1 to C10 alkyl group. Alkyl group, and L ¹⁰² may be substituted or unsubstituted C1 to C10 alkyl or ether group (*-O-*).

The solvent-free curable composition may include 1% to 60% by weight of quantum dots and 40% to 99% by weight of polymerizable monomers.

The solvent-free curable composition may further include a polymerization initiator, a light diffusing agent, or a combination thereof.

Another embodiment provides a solvent-based curable composition including quantum dots, a binder resin and a solvent.

The solvent-based curable composition may include 1 to 40% by weight of quantum dots; 1 to 30% by weight of a binder resin; and the balance of solvent.

The solvent-based curable composition may further include a polymerizable monomer, a polymerization initiator, a light diffusing agent, or a combination thereof.

Another embodiment provides a cured layer produced using the curable composition.

Another embodiment provides a color filter including a cured layer.

Other embodiments of the invention are included in the following detailed description.

One embodiment provides a quantum dot surface-modified with a specific ligand, and the specific ligand has a very good passivation effect on the quantum dots, and compared with traditional quantum dots, the surface-modified Quantum dots can be readily applied to both solvent-based and solvent-free curable compositions to improve handleability, and can greatly increase the optical efficiency of cured layers produced using the compositions. In addition, the curable composition including quantum dots according to embodiments has improved storage stability and heat resistance.

Embodiments of the invention are explained in detail below. However, these embodiments are exemplary and the present invention is not limited thereto, and the present invention is defined by the scope of the patent application.

As used herein, when no definition is otherwise provided, "alkyl" refers to C1 to C20 alkyl, "alkenyl" refers to C2 to C20 alkenyl, "cycloalkenyl" refers to C3 to C20 cycloalkenyl, "Heterocycloalkenyl" refers to C3 to C20 heterocyclic alkenyl, "aryl" refers to C6 to C20 aryl, "arylalkyl" refers to C6 to C20 arylalkyl, and "alkylene" is Refers to C1 to C20 alkylene group, "arylene group" refers to C6 to C20 aryl group, "alkyl aryl group" refers to C6 to C20 alkyl aryl group, "heteroaryl group" refers to C3 to C20 aryl group Heteroaryl, and "alkoxy" refers to C1 to C20 alkoxy.

As used herein, when no specific definition is otherwise provided, "substituted" means that at least one hydrogen atom is replaced by a substituent selected from: halogen atom (F, Cl, Br or I), hydroxyl group, C1 to C20 alkane Oxygen group, nitro group, cyano group, amine group, imine group, azido group, amidine group, hydrazine group, hydrazone group, carbonyl group, aminomethane 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, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl or combinations thereof.

As used herein, when no specific definition is otherwise provided, "hetero" refers to the inclusion of at least one heteroatom of N, O, S, and P in the chemical formula.

As used herein, when no specific definition is otherwise provided, "(meth)acrylate" refers to both "acrylate" and "methacrylate" and "(meth)acrylic" refers to "acrylic" and "methacrylic acid".

As used herein, when no specific definition is otherwise provided, the term "combination" refers to mixing or copolymerization.

As used herein, when a definition is not otherwise provided, when a chemical bond is not drawn where it should be given in a chemical formula, a hydrogen atom is bonded at that position.

As used herein, Cardo-based resin refers to a resin containing at least one functional group selected from Chemical Formula 6-1 to Chemical Formula 6-11 in the skeleton of the resin.

Furthermore, in this specification, when no definition is otherwise provided, "*" refers to a point connected to the same or different atoms or chemical formulas.

Due to the hydrophobic surface properties, general quantum dots are limitedly dispersed in a few solvents, so there are many difficulties when introducing quantum dots into polar systems such as binder resins, curable monomers, etc.

For example, even quantum dot-containing curable compositions that have been actively studied still have relatively low polarity in the initial steps and are prepared by dispersing quantum dots only in curable compositions with high hydrophobicity. Therefore, it is difficult to include a high content of quantum dots of 20% by weight or more based on the total composition, and therefore, the light efficiency of the curable composition cannot be improved to a predetermined level or higher, and in order to improve the light efficiency, even if the quantum dots are If the dots are excessively added and dispersed, the viscosity of the composition (12 centipoise) will also exceed the viscosity range that can be inkjet, and therefore the handleability may not be met.

Additionally, to achieve a viscosity range within which inkjet can be performed, a method has been used that includes a solvent in an amount greater than or equal to 50% by weight relative to the total curable composition to reduce the solids content of the curable composition, which can It brings excellent viscosity, but has the disadvantages of nozzle drying, nozzle clogging due to solvent evaporation, single film reduction over time after inkjet, and severe thickness changes after curing, and is therefore difficult to apply in actual processes.

Therefore, considering that solvent-free compositions that do not contain solvents are the development direction suitable for practical processes, curable compositions containing quantum dots have limitations in the application of current quantum dots themselves.

As reported so far, since quantum dots that have not been surface modified (e.g., ligand substituted) are included in a small amount of 20% to 25% by weight based on the curable composition, it is difficult to improve the optical efficiency due to viscosity limitations. and absorption rate. In addition, another way to improve is to reduce the content of quantum dots and increase the content of light diffusing agents such as _TiO2 , which cannot improve the precipitation problem or low light efficiency.

Traditional solvent-based curable compositions containing quantum dots may cause nozzle clogging due to drying of the solvent in the nozzle during the inkjet process as described above, failure to maintain target pixel thickness due to evaporation of ink in the inkjet pixel, and therefore Inkjet processability is not guaranteed.

Furthermore, in order to form a layer with a predetermined thickness by post-baking (or otherwise thermal curing) after forming a thin film in the pixel, pinning points should be formed by jetting a large amount of ink at a position well above the height of the pixel ( The maximum height at which the bubbles do not collapse), which is practically impossible, and furthermore, the processable solvent should have a surface tension close to 40 dynes/cm, which is rarely possible.

Most ligands used for surface modification of quantum dots usually have thiol groups, but as mentioned above, quantum dots surface modified with thiol group-containing ligands have low dispersibility and poor The inkjet process, and most importantly, considering the demand for optical properties in the market, has reached its limits.

Therefore, the inventors have long studied and invented the surface modification of quantum dots using functional groups that do not include thiol groups or include carbon-carbon double bonds or epoxy groups. Even if they have thiol groups, they will still be Prevent the deterioration of the optical properties of quantum dots, and at the same time greatly improve the storage stability and heat resistance of curable compositions containing quantum dots.

For example, the ligand may be represented by Chemical Formula 1.

[Chemical formula 1]

In Chemical Formula 1, R ¹ is a carboxyl group, *-P(=O)(OH) ₂ or a thiol group, and R ² is "unsubstituted or substituted by vinyl, allyl, epoxy, (methyl ) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group substituted C1 to C20 alkyl group", "unsubstituted or vinyl, allyl, epoxy group, (meth)acrylate group, C1 to C20 alkoxy substituted by C1 to C10 alkyl or C6 to C12 aryl", "unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl "C6 to C20 aryl group substituted by C6 to C12 aryl group" or "unsubstituted or substituted by vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C12 Aryl-substituted C6 to C20 aryloxy group", or "represented by Chemical Formula 1A", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ is "substituted or unsubstituted vinyl group", "unsubstituted or vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 Alkyl or C6 to C12 aryl substituted C1 to C20 alkyl" or "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl or C6 to C12 aryl-substituted C2 to C20 alkenyl", and L ¹ is "C1 to C20 alkylene unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "C3 to C20 cycloalkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "can be from Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2 "One of the expressions", [Chemical Formula 1B-1-1] [Chemical formula 1B-1-2] [Chemical formula 1B-2-1] [Chemical formula 1B-2-2] [Chemical formula 1B-3-1] [Chemical formula 1B-3-2] [Chemical formula 1B-4-1] [Chemical formula 1B-4-2] [Chemical formula 1B-5-1] [Chemical formula 1B-5-2] [Chemical formula 1B-6-1] [Chemical formula 1B-6-2] [Chemical formula 1B-7-1] [Chemical formula 1B-7-2] Wherein, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b are independently a hydrogen atom or a carboxyl group, and R ^c is O, S, NH, C1 to C20 alkylene group, C1 to C20 Alkylamino group or C2 to C20 allylamine group, L ² is a single bond, *-C(=O)O-* or *-S-*, and L ³ is composed of Chemical Formula 1C-1 or Chemical Formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , m is an integer from 1 to 20, and n is an integer from 1 or 2.

In L ² , *-C(=O)O-* may have a different attachment order than *-O(C=O)-*, and the carbonyl group of *-C(=O)O-* may be attached to L ¹ linker, and the ether group can be attached to the L ³ linker.

For example, the compound represented by Chemical Formula 1 may be represented by Chemical Formula 2.

[Chemical formula 2]

In Chemical Formula 2, R ² may be "C1 to C20 that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl, or C6 to C12 aryl. "Alkyl", "C1 to C20 alkoxy that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl group that is unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl" or "unsubstituted or [ Chemical formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl or C6 to C12 aryl substituted C1 to C20 alkyl" or "unsubstituted or vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl-substituted C2 to C20 alkenyl group", and L ¹ can be "C1 to C20 alkylene group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group ” or “C3 to C20 cycloalkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group” or “can be represented by Chemical Formula 1B-1-1, Chemical Formula 1B-2 -1. Expressed by one of Chemical Formula 1B-3-1, Chemical Formula 1B-4-1, Chemical Formula 1B-5-1, Chemical Formula 1B-6-1 and Chemical Formula 1B-7-1", [Chemical Formula 1B-1- 1] [Chemical formula 1B-2-1] [Chemical formula 1B-3-1] [Chemical formula 1B-4-1] [Chemical formula 1B-5-1] [Chemical formula 1B-6-1] [Chemical formula 1B-7-1] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, L ² can be a single bond, *-C(=O)O-* or *-S-*, and L ³ can be composed of chemical formula 1C-1 or chemical formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ may be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl, and m can be an integer from 1 to 20.

The compound represented by Chemical Formula 1, specifically the compound represented by Chemical Formula 2, is a ligand having a completely different structure from a thiol-based compound generally used as a conventional surface modification material for quantum dots, and when using such a When the surface of quantum dots is modified by a bit body, the surface-modified quantum dots can greatly improve the light efficiency of the cured layer produced using a composition containing quantum dots, and further improve the storage stability and heat resistance of the composition.

In Chemical Formula 2, R ² may be "a C1 to C20 alkyl group that is unsubstituted or substituted by a C1 to C10 alkyl group or a C6 to C12 aryl group", "a C1 to C20 alkyl group that is unsubstituted or substituted by a C1 to C10 alkyl group or a C6 to C12 aryl group" Aryl-substituted C1 to C20 alkoxy", "unsubstituted or C6 to C20 aryl substituted by C1 to C10 alkyl or C6 to C12 aryl" or "unsubstituted or C1 to C10 alkyl or C6 to C12 aryl-substituted C6 to C20 aryloxy group", L ¹ can be "unsubstituted C1 to C20 alkylene group" or "unsubstituted C3 to C20 cycloalkylene group", L ² can be Single bond, *-C(=O)O-* or *-S-*, and L ³ can be represented by Chemical Formula 1C-1 or Chemical Formula 1C-2,

[Chemical formula 1C-1]

[Chemical formula 1C-2]

Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ can be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ can be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl, and m can be an integer from 1 to 20.

On the other hand, the compound represented by Chemical Formula 1 may be a compound not represented by Chemical Formula 2, wherein (in Chemical Formula 1) R ¹ may be a carboxyl group or a thiol group, and R ² may be unsubstituted or vinyl. , C1 to C20 alkyl group substituted by allyl, epoxy or (meth)acrylate group", "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group "C1 to C20 alkoxy group", "C6 to C20 aryl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", "unsubstituted or substituted by vinyl group" , allyl, epoxy or (meth)acrylate group substituted C6 to C20 aryloxy group", or "can be represented by Chemical Formula 1A", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate", and L ¹ may be "unsubstituted or substituted by C1 to C20 alkylene substituted by vinyl, allyl, epoxy or (meth)acrylate" or "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylic acid "Ester group-substituted C3 to C20 cycloalkyl group" or "can be represented by one of Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2 " , [Chemical Formula 1B-1-1] [Chemical formula 1B-1-2] [Chemical formula 1B-2-1] [Chemical formula 1B-2-2] [Chemical formula 1B-3-1] [Chemical formula 1B-3-2] [Chemical formula 1B-4-1] [Chemical formula 1B-4-2] [Chemical formula 1B-5-1] [Chemical formula 1B-5-2] [Chemical formula 1B-6-1] [Chemical formula 1B-6-2] [Chemical formula 1B-7-1] [Chemical formula 1B-7-2] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, L ² can be a single bond, *-C(=O)O-* or *-S-*, and L ³ can be composed of chemical formula 1C-1 or chemical formula 1C-2 represents, [Chemical Formula 1C-1] [Chemical formula 1C-2] Among them, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ may be a substituted or unsubstituted C1 to C20 alkylene group. Alkyl group, m may be an integer from 1 to 20, and n may be an integer of 1 or 2.

For example, the compound represented by Chemical Formula 1 may be represented by Chemical Formula 3 or Chemical Formula 4.

[Chemical formula 3]

[Chemical formula 4]

In Chemical Formula 3, R ⁴ may be "a C1 to C20 alkyl group that is unsubstituted or substituted by a vinyl group, an allyl group, an epoxy group or a (meth)acrylate group", "an unsubstituted or substituted by a vinyl group" , Allyl, epoxy or (meth)acrylate group substituted C1 to C20 alkoxy group", "Unsubstituted or vinyl, allyl, epoxy or (meth)acrylate group Substituted C6 to C20 aryloxy group" or "C6 to C20 aryloxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", or "can be represented by Chemical Formula 1A" , [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", R ⁵ can be a carboxyl or thiol group, L ⁶ and L ⁷ can be independently substituted or unsubstituted C1 to C20 alkylene group, and L ⁸ can be a single bond, *-S-*, *-C(=O)-* or *-OC(= O)-*, L ⁹ may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and m may be an integer from 1 to 20, and [Chemical Formula 4] Among them, in Chemical Formula 4, R ⁴ may be "C1 to C20 alkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", "unsubstituted or substituted by C1 to C20 alkoxy substituted by vinyl, allyl, epoxy or (meth)acrylate", "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylic acid "C6 to C20 aryloxy group substituted by ester group" or "C6 to C20 aryloxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", or "can be represented by Chemical Formula 1A represents", [Chemical Formula 1A] Wherein, in Chemical Formula 1A, R ³ may be "substituted or unsubstituted vinyl", "C1 unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group to C20 alkyl" or "C2 to C20 alkenyl that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", L ⁶ and L ⁷ may independently be substituted Or unsubstituted C1 to C20 alkylene group, L ⁸ can be a single bond, *-S-*, *-C(=O)-* or *-OC(=O)-*, L ⁹ can be a single bond The bond is either a substituted or unsubstituted C1 to C20 alkylene group, and L ¹⁰ may be composed of Chemical Formula 1B-1-1, Chemical Formula 1B-2-1, Chemical Formula 1B-3-1, Chemical Formula 1B-4-1, One of Chemical Formula 1B-5-1, Chemical Formula 1B-6-1 and Chemical Formula 1B-7-1 represents, [Chemical Formula 1B-1-1] [Chemical formula 1B-2-1] [Chemical formula 1B-3-1] [Chemical formula 1B-4-1] [Chemical formula 1B-5-1] [Chemical formula 1B-6-1] [Chemical formula 1B-7-1] Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b can be independently a hydrogen atom or a carboxyl group, and R ^c can be O, S, NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, and m may be an integer from 1 to 20.

The compound represented by Chemical Formula 1 may have a weight average molecular weight of less than or equal to 1000 g/mol, such as 200 g/mol to 1000 g/mol. When the weight average molecular weight of the compound represented by Chemical Formula 1 is within the above range, the viscosity of the curable composition including quantum dots surface-modified with the compound can be kept low, which may be advantageous for inkjet.

For example, Chemical Formula 1 may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-8, Chemical Formula 3-1 to Chemical Formula 3-6, and Chemical Formula 4-1, but is not necessarily limited thereto.

[Chemical formula 2-1]

[Chemical formula 2-2]

[Chemical formula 2-3]

[Chemical formula 2-4]

[Chemical formula 2-5]

[Chemical formula 2-6]

[Chemical formula 2-7]

[Chemical formula 2-8]

[Chemical formula 3-1]

[Chemical formula 3-2]

[Chemical formula 3-3]

[Chemical formula 3-4]

[Chemical formula 3-5]

[Chemical formula 3-6]

[Chemical formula 4-1]

For example, quantum dots can have a maximum fluorescence emission wavelength at 500 nanometers to 680 nanometers.

A curable composition according to another embodiment includes quantum dots surface-modified with the compound represented by Chemical Formula 1.

To this point, curable compositions (inks) containing quantum dots have been developed toward specialized monomers having good compatibility with quantum dots and, in addition, have been commercialized.

On the other hand, due to the general and widely used polymerizable monomers and vinyl monomers (including vinyl monomers, acrylate monomers, methacrylate monomers, etc., including monofunctional monomers or polyethylene monomers), Functional monomers) have low compatibility with quantum dots and are limited in the dispersibility of quantum dots, so effectively applying them to various developments of curable compositions containing quantum dots is essentially difficult. Most importantly, -olefinic monomers do not exhibit high concentration quantum dot dispersibility and are therefore difficult to apply to curable compositions containing quantum dots.

Due to these disadvantages, curable compositions containing quantum dots have been developed with compositions containing a considerable amount (greater than or equal to 50% by weight) of solvent, but when the solvent content is increased, inkjet processability may deteriorate. Therefore, there is an increasing demand for solvent-free curable compositions to satisfy inkjet processability.

The present invention provides a solvent-free curable composition, which is increasingly in demand, and performs surface modification by using a polymerizable monomer including a compound having a carbon-carbon double bond at the terminal and a compound represented by Chemical Formula 1. dots, even in solvent-free systems, the affinity of quantum dots to curable compositions can be improved to achieve high-concentration dispersibility and even passivation effects of quantum dots without damaging the natural optical properties of quantum dots.

Each component constituting the solvent-free curable composition is explained in detail below. quantum dots

The quantum dots contained in the solvent-free curable composition include quantum dots surface-modified with the compound represented by Chemical Formula 1.

For example, quantum dots absorb light in the wavelength region of 360 nanometers to 780 nanometers, such as 400 nanometers to 780 nanometers, and in the wavelength region of 500 nanometers to 700 nanometers, such as 500 nanometers to 580 nanometers. Emit fluorescence or emit fluorescence in the wavelength region of 600 nanometers to 680 nanometers. That is, the quantum dots may have a maximum fluorescence emission wavelength (λ _em ) at 500 nm to 680 nm.

Quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, such as 20 nm to 50 nm. When the quantum dots have a full width at half maximum (FWHM) in the stated range, when used as color materials in color filters, color reproducibility is increased due to high color purity.

Quantum dots can be independently organic materials, inorganic materials, or a mixture (mixture) of organic materials and inorganic materials.

Quantum dots can independently be composed of a core and a shell surrounding the core, and the core and the shell can independently have a core, core/shell, core/first shell/second shell composed of II-IV groups, III-V groups, etc. , alloy, alloy/shell, etc. structure, but not limited to this.

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

In the embodiment, since global environmental concerns have greatly increased recently and regulations on toxic materials have been tightened, a non-cadmium-based luminescent material (InP/ZnS) that is slightly lower in quantum efficiency (quantum yield) but is environmentally friendly is used , InP/ZnSe/ZnS, etc.) to replace the luminescent material with a cadmium core, but it is not necessarily limited to this.

In the case of core/shell structured quantum dots, the overall size (average particle diameter) including the shell may be 1 nm to 15 nm, such as 5 nm to 15 nm.

For example, quantum dots may independently include red quantum dots, green quantum dots, or combinations thereof. Red quantum dots can independently have an average particle size of 10 to 15 nanometers. Green quantum dots can independently have an average particle size of 5 to 8 nanometers.

On the other hand, in order to achieve dispersion stability of quantum dots, the solvent-free curable composition according to embodiments may further include a dispersant. The dispersant contributes to the uniform dispersion of the light conversion material, such as quantum dots, in the solvent-free curable composition, and may include a nonionic, anionic, or cationic dispersant. Specifically, the dispersant can be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate ester, sulfonate salt, carboxylate ester, carboxylates, alkylamide alkylene oxide addition products, alkylamines, etc., and they may be used alone or in a mixture of two or more. The dispersant may be used in an amount of 0.1% to 100% by weight, such as 10% to 20% by weight, based on the solids content of the light conversion material (eg quantum dots).

Quantum dots surface-modified with Chemical Formula 1 or Chemical Formula 2 may be included in an amount of 1 to 60% by weight, for example, 3 to 50% by weight based on the total amount of the solvent-free curable composition. When surface-modified quantum dots within the above range are included, the light conversion rate can be improved, and the pattern characteristics and development characteristics are not disturbed, so that it can have excellent handleability. Polymerizable monomers with carbon-carbon double bonds at the termini

The monomer having a carbon-carbon double bond at the terminal should be included in an amount of 40 to 99% by weight, such as 50 to 97% by weight, based on the total amount of the solvent-free curable composition. When a monomer having a carbon-carbon double bond at the terminal is included within the range, a solvent-free curable composition having a viscosity capable of inkjet can be prepared, and the quantum of the solvent-free curable composition prepared The dots may have improved dispersion, thereby improving optical properties.

For example, a monomer with a carbon-carbon double bond at the terminus may have a molecular weight of 220 g/mol to 1,000 g/mol. When the monomer having a carbon-carbon double bond at the terminus has a molecular weight within the stated range, inkjet can be advantageously performed because it does not increase the viscosity of the composition and does not hinder the optical properties of the quantum dots.

For example, a monomer having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 5, but is not necessarily limited thereto.

[Chemical formula 5]

In Chemical Formula 5, R ¹⁰¹ and R ¹⁰² may independently be a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁰¹ and L ¹⁰³ may independently be a substituted or unsubstituted C1 to C10 alkyl group. Alkyl group, and L ¹⁰² may be substituted or unsubstituted C1 to C10 alkyl or ether group (*-O-*).

For example, a monomer having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 5-1 or 5-2, but is not necessarily limited thereto.

[Chemical formula 5-1]

[Chemical formula 5-2]

For example, in addition to the compound of the above-mentioned Chemical Formula 5-1 or Chemical Formula 5-2, the monomer having a carbon-carbon double bond at the terminal may further include ethylene glycol diacrylate, triethylene glycol diacrylate, 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, phenolic epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethyl Acrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate or combinations thereof.

In addition, common monomers of conventional thermosetting or photocurable compositions may be further included together with monomers having carbon-carbon double bonds at the terminals. For example, the monomer further includes oxetane-based compounds, such as bis[1-ethyl(3-oxetanyl)]methyl ether and the like. polymerization initiator

The solvent-free curable composition according to embodiments may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

Photopolymerization initiators are commonly used initiators for photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and oxime compounds. , aminoketone compounds, etc., but are not necessarily limited thereto.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tertiary butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-( 4-(Methylthio)phenyl)-2-morpholinylpropan-1-one, 2-phenylmethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan- 1-Keto etc.

Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, diacrylate Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylamino Benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

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

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

Examples of the triazine-based compound may be 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(trichloro Methyl)-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-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol 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 compound may be an O-acyl oxime-based compound, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1 -(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl- α-Oxylamino-1-phenylpropan-1-one, etc. Specific examples of the O-acyl oxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4- base-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4- Phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1-one oxime-O-ethyl Acid ester, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, etc.

Examples of the aminoketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 and the like.

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

The photopolymerization initiator may be used with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and subsequently transmitting its energy.

Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Examples of thermal polymerization initiators may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-butyl peroxide, peroxide Cyclohexane oxide, methyl ethyl ketone peroxide, hydroperoxides (such as tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azobis( isobutyronitrile), tert-butyl perbenzoate, etc., such as 2,2'-azobis-2-methylpropionitrile, but it is not necessarily limited thereto, and those commonly known in the art can be used. Any kind.

The polymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 1% to 4% by weight, based on the total amount of the solvent-free curable composition. When the polymerization initiator is included within the range, excellent reliability can be obtained due to sufficient curing during exposure or thermal curing, and transmittance deterioration due to the non-reactive initiator is prevented, thereby preventing quantum dots optical properties deteriorate. Light diffusing agent (or light diffusing agent dispersion)

The solvent-free curable composition according to embodiments may further include a light diffusing agent.

For example, the light diffusing agent may include barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), titanium dioxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), or combinations thereof.

The light diffusing agent can reflect the unabsorbed light in the quantum dots and allow the quantum dots to absorb the reflected light again. That is, the light diffusing agent can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

The light diffusing agent may have an average particle diameter (D ₅₀ ) of 150 nm to 250 nm, and specifically 180 nm to 230 nm. When the average particle size of the light diffusing agent is within the above range, it can have better light diffusing effect and improve light conversion efficiency.

The light diffusing agent may be included in an amount of 1 to 20% by weight, such as 5 to 10% by weight, based on the total amount of the solvent-free curable composition. When the light diffusing agent is included in an amount of less than 1% by weight based on the total amount of the solvent-free curable composition, it is difficult to expect a light conversion efficiency improvement effect due to the use of the light diffusing agent, whereas when the light diffusing agent is included in an amount of more than 20% by weight When using a diffusing agent, there is a possibility that the quantum dots may precipitate. Other additives

In order to achieve improved stability and dispersion of quantum dots, the solvent-free curable composition according to embodiments 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. When the solvent-free curable composition according to the embodiment further includes a hydroquinone-based compound, a catechol-based compound, or a combination thereof, room temperature cross-linking during exposure after coating of the solvent-free curable composition can be prevented.

For example, the hydroquinone-based compound, the catechol-based compound or a combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone , 2,5-bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, tert-butyl Catechol, 4-methoxycatechol, gallicol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitroso Phenylamino-O,O')aluminum or combinations thereof, but need not be limited thereto.

The hydroquinone-based compound, the catechol-based compound, or a combination thereof can be used in the form of a dispersion. The polymerization inhibitor in the form of a dispersion may be included in an amount of 0.001% to 3% by weight, such as 0.1% to 2% by weight, based on the total amount of the solvent-free curable composition. When the polymerization inhibitor is included within the above range, the lapse of time at room temperature can be solved, and at the same time, sensitivity deterioration and surface delamination phenomena can be prevented.

In addition, the solvent-free curable composition according to the embodiment may further include malonic acid; 3-amino-1,2-propanediol; silane coupling agent; leveling agent; fluorine-based surfactant; or a combination thereof, to Improve heat resistance and reliability.

For example, the solvent-free curable composition according to the embodiment may further include a silane-based coupling agent having reactive substituents such as vinyl, carboxyl, methacryloxy, isocyanate, epoxy, etc. to improve coupling with Close contact characteristics of the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacrylooxypropyltrimethoxysilane, vinyltriacetyloxysilane, vinyltrimethoxysilane, and γ-isocyanate. Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc., and these coupling agents can be used alone or in combination with two or more used in mixture form.

The silane-based coupling agent can be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solvent-free curable composition. When the silane-based coupling agent is included within the above range, close contact properties, storage capacity, etc. are improved.

In addition, the solvent-free curable composition may optionally further contain a surfactant (such as a fluorine-based surfactant) to improve coating properties and suppress the occurrence of spots, that is, to improve leveling performance.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 to 10,000 g/mol, and specifically 6,000 to 10,000 g/mol. In addition, the fluorine-based surfactant can have a surface tension of 18 mN/m to 23 mN/m (measured in a 0.1% polyethylene glycol monomethylether acetate (PGMEA) solution) ). When the fluorine-based surfactant has a weight average molecular weight and a surface tension within the above range, the leveling efficiency can be further improved, and when slit coating is applied as high-speed coating, excellent characteristics can be provided. This is because Film defects can be produced less frequently by preventing spotting and suppressing vapor generation during high-speed coating.

Examples of fluorine-based surfactants can be BM-1000 ^® and BM-1100 ^® (BM Chemie Inc.); MEGAFACE F 142D ^® , F 172 ^® , F 173 ^® and F 183 ^® (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135 ^® , FULORAD FC-170C ^® , FULORAD FC-430 ^® and Florad FC-431 ^® (Sumitomo 3M Co., Ltd.); SURFLON S-112 ^® , SURFLON S-113 ^® , SURFLON S-131 ^® , Saffron S-141 ^® and Saffron S-145 ^® (ASAHI Glass Co., Ltd.); and SH-28PA ^® , SH-190 ® , SH-193 ^® , SZ- 6032 ^® and SF-8428 ^® etc. (Toray Silicone Co., Ltd.); F-482, F-484, F from Dainippon Ink Co., Ltd. (DIC Co., Ltd.) -478, F-554, etc.

In addition, in addition to the fluorine-based surfactant, the solvent-free curable composition according to the embodiment may further include a silicone-based surfactant. Specific examples of silicone surfactants include TSF400, TSF401, TSF410, TSF4440, etc. from Toshiba Silicone Co., Ltd., but are not limited thereto.

The surfactant may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight based on 100 parts by weight of the solvent-free curable composition. When the surfactant is included within the above range, foreign matter is less generated in the sprayed composition.

In addition, unless the properties are deteriorated, the solvent-free curable composition according to the embodiment may further include a predetermined amount of other additives, such as antioxidants, stabilizers, and the like.

For example, in addition to the above solvent-free curable composition, the curable composition may provide a solvent-based curable composition including quantum dots surface-modified by Chemical Formula 1 or Chemical Formula 2, a binder resin, and a solvent. Herein, based on the total amount of the solvent-based curable composition, 1 to 40% by weight of surface-modified quantum dots may be included. It may be advantageous in terms of handleability when surface-modified quantum dots are included in the stated content range based on the total amount of the solvent-based curable composition.

Below, each component constituting the solvent-based curable composition is explained in detail. adhesive resin

The adhesive resin may include acrylic resin, Cardo resin, epoxy resin, or combinations thereof.

The acrylic resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer may be an ethylenically unsaturated monomer including at least one carboxyl group, and examples of the monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumarate Diacids or combinations thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight (for example, 10% to 40% by weight) based on the total amount of the acrylic adhesive resin.

The second ethylenically unsaturated monomer can be an aromatic vinyl compound, such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether, etc.; an unsaturated carboxylate compound, such as (methane Methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzene (meth)acrylate Methyl ester, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; unsaturated aminoalkyl carboxylate compounds, such as 2-aminoethyl (meth)acrylate, (methyl) 2-Dimethylaminoethyl acrylate, etc.; Carboxylic acid vinyl ester compounds, such as vinyl acetate, vinyl benzoate, etc.; Unsaturated carboxylic acid glycidyl ester compounds, such as (meth)glycidyl acrylate, etc. Ethylene cyanide compounds, such as (meth)acrylonitrile, etc.; Unsaturated amide compounds, such as (meth)acrylamide, etc.; etc., and the second ethylenically unsaturated monomer can be used alone or with Use as a mixture of two or more.

Specific examples of the acrylic adhesive resin may be polybenzyl methacrylate, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer , (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer etc., but are not limited thereto, and these may be used alone or in a mixture of two or more.

The weight average molecular weight of the acrylic adhesive resin may be 5,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the acrylic adhesive resin is within the range, close contact properties with the substrate and physical and chemical properties are improved, and the viscosity is appropriate.

The Cardo-based resin may include repeating units represented by Chemical Formula 6.

[Chemical formula 6]

In Chemical Formula 6, R ³¹ and R ³² may be independently a hydrogen atom or a substituted or unsubstituted (meth)acryloxyalkyl group, and R ³³ and R ³⁴ may be independently a hydrogen atom, a halogen atom or Substituted or unsubstituted C1 to C20 alkyl, and Z ¹ can be a single bond, O, CO, SO ₂ , CR ³⁵ R ³⁶ , SiR ³⁷ R ³⁸ (wherein, R ³⁵ to R ³⁸ can be independently hydrogen Atom is either a substituted or unsubstituted C1 to C20 alkyl group) or one of the linking groups represented by Chemical Formula 6-1 to Chemical Formula 6-11, [Chemical Formula 6-1]

[Chemical formula 6-2]

In Chemical Formula 6-5, R ^e may be a hydrogen atom, ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or phenyl group.

[Chemical formula 6-6]

[Chemical formula 6-7]

[Chemical formula 6-8]

[Chemical formula 6-9]

[Chemical formula 6-10]

[Chemical formula 6-11] ^Z2 can be an anhydride moiety, and t1 and t2 can independently be an integer from 0 to 4.

The weight average molecular weight of the Cardo-based adhesive resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the Cardo-based binder resin is within the range, a satisfactory pattern can be formed without residues during production of the cured layer and without loss during development of the solvent-based curable composition. film thickness.

The Cardo-based adhesive resin may include a functional group represented by Chemical Formula 7 at at least one of both terminals.

[Chemical Formula 7]

In Chemical Formula 7, Z ³ may be represented by Chemical Formula 7-1 to Chemical Formula 7-7.

[Chemical formula 7-1]

In Chemical Formula 7-1, R ^f and R ^g may independently be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group.

[Chemical formula 7-2]

[Chemical formula 7-3]

[Chemical formula 7-4]

[Chemical formula 7-5]

In Chemical Formula 7-5, R ^h may be O, S, NH, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamino group, or C2 to C20 alkenylamine group.

[Chemical formula 7-6]

[Chemical formula 7-7]

Cardo-based resin can be prepared, for example, by mixing at least two of the following compounds: a fluorene-containing compound, such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; an acid anhydride compound, such as Pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, Tetrahydrofuran tetracarboxylic dianhydride and tetrahydrophthalic anhydride; glycol compounds, such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds, such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzene Methanol; solvent compounds, such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds, such as triphenylphosphine, etc.; and amine or ammonium salt compounds, such as tetramethylammonium chloride, tetraethyl Ammonium bromide, benzyldiethylamine, triethylamine, tributylamine or benzyltriethylammonium chloride.

When the binder resin is a Cardo-based resin, the solvent-based curable composition including the Cardo-based resin, especially the photosensitive resin composition, has excellent developability and sensitivity during photocuring and therefore has fine Pattern forming ability.

The acid value of the acrylic resin may range from 80 mg KOH/g to 130 mg KOH/g. When the acid value of the acrylic resin is within the above range, excellent pixel resolution can be obtained.

The epoxy resin may be a thermally polymerizable monomer or oligomer, and may include compounds having carbon-carbon unsaturated bonds and carbon-carbon ring bonds.

Epoxy resins may further include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin and aliphatic polyglycidyl ether, but are not necessarily limited thereto.

As the commercially available product of the compound, it can be biphenyl epoxy resin, such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 of Yuka Shell Epoxy Co., Ltd.; cresol novolac Epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 from Nippon Kayaku Co. Ltd. and Yoka Shell Epoxy Co., Ltd. EPIKOTE 180S75, etc.; Bisphenol A epoxy resin, such as EPIKOTE 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 of Youjia Shell Epoxy Co., Ltd.; Bisphenol F Epoxy resins, such as Eucalyptus Shell Epoxy Co., Ltd.'s Epicot 807 and 834; phenol novolac epoxy resins, such as Eucalyptus Shell Epoxy Co., Ltd.'s Epicoat 152, 154 or 157H65 and Nippon Chemical Co., Ltd. EPPN 201, 202; cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 of CIBA-GEIGY A.G Corp., ERL-4234, ERL-4299, ERL- 4221 and ERL-4206, Showdyne 509 from Showa Denko K.K., Araldite CY-182, CY-192 and CY-184 from Ciba-Geigy A.G. EPICLON 200 and 400 from Dainippon Ink & Chemicals Inc., EPIKOTE 871 and 872 from Youjia Shell Epoxy Co., Ltd. and EP1032H60, Celanese Paint Company Celanese Coating Corporation's ED-5661 and ED-5662; aliphatic polyglycidyl ethers, such as Epicot 190P and 191P from Yujia Shell Epoxy Co., Ltd., Kyoeisha Yushi Kagaku Oleochemical Industry Co., Ltd. EPOLITE 100MF from Kogyo Co., Ltd., EPIOL TMP from Nihon Yushi K. K., etc.

The binder resin may be included in an amount of 1 to 30% by weight based on the total amount of the solvent-based curable composition. Solvent

Solvents may include, for example, alcohols, such as methanol, ethanol, etc.; glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; cellosolve acetate, such as methyl cellosolve acetate, Ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; carbitol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethyl carbitol, etc. Glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate. Esters, etc.; 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, 2-Heptanone, etc.; Saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; Lactic acid esters, such as methyl lactate, ethyl lactate, etc.; Alkyl glycolate Esters, such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl acetate, etc. Methyl oxyacetate, ethoxyethyl acetate, etc.; Alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; Alkyl 3-alkoxypropionate Esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-hydroxypropionic acid alkyl esters, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate , ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-hydroxy-2-methylpropionic acid alkyl ester, such as 2-hydroxy -Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionate, such as 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate , 2-hydroxy-3-methylmethyl butyrate, etc.; or ketoacid ester, such as ethyl pyruvate, etc., and in addition, it can be N-methylformamide, N,N-dimethylformamide , N-methylformaniline, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyltrisoxide, benzyl ethyl ether, dihexyl Ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid Diethyl acid, γ-butyrolactone, ethyl carbonate, propyl carbonate, phenyl cellosolve acetate, etc., but are not limited to these.

For example, the solvent may be expected to be a glycol ether, such as ethylene glycol monoethyl ether, ethylene glycol methyl ethyl ether, etc.; a glycol alkyl ether acetate, such as ethyl cellosolve acetate, etc.; an ester, such as propionic acid 2-hydroxyethyl ester, etc.; carbitol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.; alcohols, such as ethanol etc. or a combination thereof.

For example, the solvent may be a polar solvent, including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, 2- Butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone or combinations thereof.

Based on the total amount of the solvent-based curable composition, the balance, such as 30 to 80 wt%, such as 35 to 70 wt% of the solvent, may be included. When the solvent is within the range, the solvent-based curable composition has an appropriate viscosity and therefore has excellent coating properties when being coated in a large area by spin coating and slot coating.

For example, in addition to the above components, the solvent-based curable composition may further include one or more of the aforementioned polymerizable monomers having carbon-carbon double bonds at the terminals, polymerization initiators, light diffusing agents and other additives. , and its specific composition or amount is the same as above.

For example, the solvent-based curable composition may be a photosensitive resin composition. In this case, the solvent-type curable composition may include a photopolymerization initiator as a polymerization initiator.

Another embodiment provides a cured layer manufactured using the solvent-free curable composition and the solvent-based curable composition, a color filter including the cured layer, and a display device including the color filter.

One method of producing the cured layer may include: coating the above-mentioned solvent-free curable composition and solvent-based curable composition on a substrate using an inkjet jetting method to form a pattern (S1); and curing the pattern (S2). (S1) Form a pattern

It is desirable to apply the solvent-free curable composition to a substrate by an inkjet spraying method to a thickness of 0.5 microns to 20 microns. The inkjet spraying method can form a pattern by each nozzle spraying a single color and thus repeating the spraying a number of times equal to the required number of colors, but the pattern can be formed by each inkjet nozzle spraying the required number of colors simultaneously, to reduce the manufacturing process. (S2) Curing

The obtained pattern is cured to obtain pixels. Here, the curing method may be a thermal curing or light curing process. The thermal curing process may be performed at greater than or equal to 100°C, desirably in the range of 100°C to 300°C, and more desirably in the range of 160°C to 250°C. The photocuring process may include irradiating actinic rays, such as ultraviolet rays with a wavelength of 190 nanometers to 450 nanometers, such as 200 nanometers to 500 nanometers. Irradiation is performed by using light sources such as mercury lamps, metal halide lamps, argon lasers with low pressure, high pressure or ultra-high pressure. X-rays, electron beams, etc. can also be used as needed.

Other methods of producing the cured layer may include using the aforementioned solvent-free curable composition and solvent-based curable composition to produce the cured layer by the following photolithography method. (1) Coating and film formation

The aforementioned curable composition is coated on a substrate subjected to predetermined pretreatment using a spin coating or slit coating method, a roller coating method, a screen printing method, a coater method, etc. to have a desired thickness, for example, between 2 Thicknesses in the micron to 10 micron range. The coated substrate is then heated at a temperature of 70°C to 90°C for 1 minute to 10 minutes to remove the solvent and form a film. (2) Exposure

After placing a mask with a predetermined shape, the resulting film is irradiated with actinic rays such as UV rays of 190 to 450 nanometers, such as 200 to 500 nanometers, to form a desired pattern. The irradiation is performed using light sources such as mercury lamps, metal halide lamps, argon lasers with low pressure, high pressure or ultra-high pressure. X-rays, electron beams, etc. can also be used as needed.

When using a high-pressure mercury lamp, the exposure process uses a light dose of, for example, 500 mJ/cm2 or less (using a 365 nm sensor). However, the light dose may vary depending on the type of each component of the curable composition, their combination ratio, and dry film thickness. (3) Development

After the exposure process, the exposed film is developed using an alkaline aqueous solution to form an image pattern by dissolving and removing excess parts except the exposed parts. In other words, when developed using an alkaline developing solution, the unexposed areas are dissolved and an image color filter pattern is formed. (4) Post-processing

The developed image pattern can be cured by heating again or by irradiating it with actinic rays, etc. to achieve excellent qualities in terms of heat resistance, light resistance, close contact properties, crack resistance, chemical resistance, high strength, storage stability, etc. .

In the following, the invention is explained in more detail with reference to examples. However, these examples should not be construed in any sense as limiting the scope of the invention. (Ligand synthesis) Synthesis example 1

400 grams of polyoxyethylene monomethyl ether (MPEG-400, Hannong Chemicals Inc.) and 100 grams of succinic anhydride were put together, and then heated to 100°C and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature (23°C) to obtain 500 g of the final product represented by Chemical Formula 2-1.

[Chemical formula 2-1] Synthesis example 2

According to the same method as Synthesis Example 1 except that 270 grams of polyoxyethylene phenyl ether (PH-4, Hannon Chemical Company) was used instead of 400 grams of polyoxyethylene monomethyl ether (MPEG-400, Hannon Chemical Company) 370 g of the final product represented by Chemical Formula 2-2 was obtained.

[Chemical formula 2-2] Synthesis example 3

384 g of the final product represented by Chemical Formula 2-3 was obtained according to the same method as Synthesis Example 2, except that 114 g of glutaric anhydride was used instead of 100 g of succinic anhydride.

[Chemical formula 2-3] Synthesis example 4

270 grams of polyoxyethylene phenyl ether (PH-4, Hannon Chemical Company) and 152 grams of tetrahydrophthalic anhydride were put together, and then heated to 100°C and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature (23°C) to obtain 422 g of the final product represented by Chemical Formula 2-4.

[Chemical formula 2-4] Synthesis example 5

934 grams of polyoxyethylene styrenated phenyl ether (TSP-150, Hannon Chemical Company), 100 grams of succinic anhydride and 500 grams of toluene were put together, and then heated to 100°C and reacted for 24 hours. When the reaction was completed, toluene was removed to obtain 1000 g of the final product represented by Chemical Formula 2-5.

[Chemical formula 2-5] Synthesis example 6

620 g of polyoxyethylene styrenated phenyl ether was obtained according to the same method as Synthesis Example 5, except that 520 g of polyoxyethylene cumyl phenyl ether (DCP-3016, Hannon Chemical Co., Ltd.) was used instead of 934 g of polyoxyethylene styrenated phenyl ether. The final product represented by Chemical Formula 2-6.

[Chemical formula 2-6] Synthesis Example 7

At 0°C, slowly inject 191 g of p-toluenesulfonyl chloride and 150 ml of tetrahydrofuran (THF) into 400 g of polyoxyethylene monomethyl ether (MPEG-400, Hannon Chemical Company), 44 g of NaOH, and 500 ml of tetrahydrofuran. (THF) and 100 ml of distilled water. 30 minutes after injection, the resulting mixture was stirred at room temperature (23°C) for 12 hours. When the reaction is complete, the resultant is purified by extraction, neutralization and concentration, and then fully dried in a vacuum oven. The resulting product was placed in a flask and dissolved in ethanol under a nitrogen atmosphere. Subsequently, 4 equivalents of thiourea were added thereto, and then stirred at 100°C for 12 hours. A dilute solution of NaOH was additionally added thereto, and the mixture was further stirred for 5 hours. When the reaction was completed, the resultant was washed several times with distilled water and dilute hydrochloric acid solution, extracted and neutralized, and then sufficiently dried in a vacuum oven to finally obtain the compound represented by Chemical Formula A.

[Chemical formula A]

444 g of the compound represented by Chemical Formula A, 72 g of acrylic acid, 10 g of triethylamine and 300 g of THF were put together, and then reacted at 50° C. for 12 hours, and diluted with excess methylene chloride. Subsequently, the diluted result was neutralized with a 5% HCl aqueous solution to obtain an organic layer alone, and the organic layer was concentrated under reduced pressure to obtain 500 g of the final product represented by Chemical Formula 2-7.

[Chemical formula 2-7] Synthesis example 8

Except that 270 g of polyoxyethylene phenyl ether (PH-4, Hannon Chemical Co., Ltd.) was used instead of 400 g of polyoxyethylene monomethyl ether, 340 g was obtained according to the same method as Synthesis Example 7, represented by Chemical Formula 2-8 the final product.

[Chemical formula 2-8] Synthesis example 9

270 grams of polyoxyethylene phenyl ether (PH-4, Hannon Chemical Company) and 140 grams of allyl succinic anhydride were put together, and then heated to 100°C and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 410 g of the final product represented by Chemical Formula 3-1.

[Chemical formula 3-1] Synthesis example 10

130 g of 2-hydroxyethyl methacrylate, 100 g of succinic anhydride and 0.1 g of MEHQ were put together, and then heated to 70°C and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 230 g of the final product represented by Chemical Formula 3-2.

[Chemical formula 3-2] Synthesis Example 11

At 0°C, 191 g of p-toluenesulfonyl chloride and 150 ml of THF were slowly injected into 600 g of polyoxyethylene monoallyl ether (APEG-1000, Hannon Chemical Company), 44 g of NaOH, 500 ml of THF and 100 ml of THF. mixed solution of distilled water. 30 minutes after injection, the resulting mixture was cooled to room temperature (23°C) and stirred for 12 hours. When the reaction is complete, the resultant is purified by extraction, neutralization and concentration, and then fully dried in a vacuum oven. The resulting product was placed in a flask and dissolved in ethanol under a nitrogen atmosphere. Then, 4 equivalents of thiourea were added thereto, and then stirred at 100°C for 12 hours. To this was additionally added a dilute solution of NaOH, and then stirred for 5 hours. When the reaction was completed, the resultant was washed and extracted with distilled water and dilute hydrochloric acid solution, and sufficiently dried in a vacuum oven to obtain 580 g of the final product represented by Chemical Formula 3-3.

[Chemical formula 3-3] Synthesis example 12

600 grams of polyoxyethylene monoallyl ether (APEG-1000, Hannon Chemical Company) and 100 grams of succinic anhydride were put together, and then heated to 100°C and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 700 g of the final product represented by Chemical Formula 3-4.

[Chemical formula 3-4] Synthesis example 13

500 g of the compound represented by Chemical Formula 3-3 according to Synthesis Example 11, 72 g of acrylic acid, 10 g of triethylamine and 300 g of THF were put together, and then reacted at 50° C. for 12 hours, with an excess of dichloride Methane is diluted. Subsequently, neutralization was performed using a 5% HCl aqueous solution to obtain an organic layer alone, and the organic layer was concentrated under reduced pressure to obtain 500 g of the final product represented by Chemical Formula 3-5.

[Chemical formula 3-5] Synthesis Example 14

Mix 600 grams of polyoxyethylene monoallyl ether (APEG-1000, Hannong Chemical Company), 124 grams of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 500 grams of toluene and 60 grams of triethylamine were put together, and then heated to 100°C and reacted for 24 hours. When the reaction was completed, the resultant was neutralized with a 5% HCl solution to remove toluene, and then 700 g of the final product represented by Chemical Formula 4-1 was obtained.

[Chemical formula 4-1] Comparative synthesis example 1

Put 10 grams of 2-mercapto-1-ethanol, 13.3 grams of 2-2-(2-methoxyethoxy)ethoxyacetic acid and 2.1 grams of p-toluenesulfonic acid monohydrate into a 2-neck round-bottomed flask. , and then dissolved in 300 ml of cyclohexane. After tightening the Dean Stark to the injection hole, attach the condenser to it. After the solution was refluxed for 8 hours, the reaction was completed. (Check the final amount of water collected in Dean Stark). The reactants were transferred to a separatory funnel, extracted, neutralized to remove the solvent, and dried in a vacuum oven to obtain the final product represented by Chemical Formula C-1.

[Chemical formula C-1] (Preparation of dispersion of quantum dots surface-modified with ligand) Preparation Example 1

The magnetic rod was placed into a 3-neck round-bottomed round flask, and the quantum dot-CHA (cyclohexyl acetate) solution (solid content: 26% to 27% by weight) was weighed and added thereto. . A ligand represented by Chemical Formula 2-1 is added thereto.

The mixture was mixed thoroughly for 1 minute and then stirred at 80°C under a nitrogen atmosphere. When the reaction was completed, the result was cooled to room temperature, and the quantum dot reaction solution was added to cyclohexane to obtain a precipitate. Separate the precipitated quantum dot powder from cyclohexane by centrifugation. The clear solution was decanted and discarded, and the precipitate was then fully dried in a vacuum oven for one day to obtain surface-modified quantum dots.

The surface-modified quantum dots were stirred together with the monomer represented by Chemical Formula 5-2 (1,6-hexanediol diacrylate; Miwon Commercial Co., Ltd.) for 12 hours. , to obtain surface-modified quantum dot dispersions.

[Chemical formula 5-2] Preparation Example 2

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-2 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 3

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-3 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 4

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-4 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 5

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-5 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 6

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-6 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 7

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-7 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 8

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 2-8 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 9

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 3-1 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 10

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 3-2 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 11

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 3-3 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 12

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 3-4 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 13

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 3-5 was used instead of the ligand represented by Chemical Formula 2-1. Preparation Example 14

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula 4-1 was used instead of the ligand represented by Chemical Formula 2-1. Comparative Preparation Example 1

A surface-modified quantum dot dispersion was obtained according to the same method as Preparation Example 1, except that the ligand represented by Chemical Formula C-1 was used instead of the ligand represented by Chemical Formula 2-1. Evaluation 1 : Dispersibility

The particle size of each quantum dot dispersion according to Preparation Examples 1 to 14 and Comparative Preparation Example 1 was measured three times by using a particle size analyzer to obtain an average particle size, and the results are shown in Tables 1 and 2.

(Table 1) Particle size (nm) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 D50 11.4 11.5 11.4 11.3 11.0 10.8 10.9 11.0 (Table 2) Particle size (nm) Preparation Example 9 Preparation Example 10 Preparation Example 11 Preparation Example 12 Preparation Example 13 Preparation Example 14 Comparative Preparation Example 1 D50 11.0 11.1 10.7 10.8 11.0 11.8 15.0

Referring to Tables 1 and 2, each of the quantum dot dispersions according to Preparation Examples 1 to 14 exhibits a narrow particle distribution, which indicates that the quantum dots are well dispersed in high boiling point and high surface tension solvents, but according to comparison The quantum dot dispersion of Preparation Example 1 exhibits a broad particle distribution, which indicates that the quantum dots are not well dispersed in high boiling point and high surface tension solvents.

(Preparation of solvent-free curable composition)

Example 1

The dispersion obtained in Preparation Example 1 was weighed, and then mixed and diluted with the monomer represented by Chemical Formula 5-2, and a polymerization inhibitor (methylhydroquinone, Tokyo Chemical Industry Co., Ltd. ( Tokyo Chemical Industry Co., Ltd.)), and then stirred for 5 minutes. Subsequently, a photoinitiator (TPO-L, Polynetron) was injected thereto, and a light diffusing agent (TiO ₂ (solid content: 50% by weight)) was added thereto; Ditto Technologies ( Ditto Technology)). The overall dispersion was stirred for 1 hour to prepare a solvent-free curable composition. Based on the total amount of the solvent-free curable composition, it contains 40% by weight of quantum dots, 48% by weight of the monomer represented by Chemical Formula 3-2, 1% by weight of polymerization inhibitor, and 3% by weight of photoinitiator. and 8% by weight of light diffusing agent.

Example 2

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 2 was used instead of the dispersion obtained in Preparation Example 1.

Example 3

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 3 was used instead of the dispersion obtained in Preparation Example 1. Example 4

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 4 was used instead of the dispersion obtained in Preparation Example 1. Example 5

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 5 was used instead of the dispersion obtained in Preparation Example 1. Example 6

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 6 was used instead of the dispersion obtained in Preparation Example 1. Example 7

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 7 was used instead of the dispersion obtained in Preparation Example 1. Example 8

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 8 was used instead of the dispersion obtained in Preparation Example 1. Example 9

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 9 was used instead of the dispersion obtained in Preparation Example 1. Example 10

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 10 was used instead of the dispersion obtained in Preparation Example 1. Example 11

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 11 was used instead of the dispersion obtained in Preparation Example 1. Example 12

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 12 was used instead of the dispersion obtained in Preparation Example 1. Example 13

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 13 was used instead of the dispersion obtained in Preparation Example 1. Example 14

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Preparation Example 14 was used instead of the dispersion obtained in Preparation Example 1. Comparative example 1

A solvent-free curable composition was prepared according to the same method as Example 1, except that the dispersion obtained in Comparative Preparation Example 1 was used instead of the dispersion obtained in Preparation Example 1. Evaluation 2 : Evaluation of optical characteristics

Each of Examples 1 to 14 and Comparative Example 1 was coated using a spin coater (800 rpm, 5 seconds, Opticoat MS-A150, Mikasa Co., Ltd.). A solvent-free curable composition was coated on yellow photoresist (YPR) to a thickness of 15 microns and exposed using a 395 nm ultraviolet (UV) exposure machine at 5000 millijoules under a nitrogen atmosphere ( 83℃, 10 seconds). Subsequently, each 2 cm × 2 cm single film sample was loaded into an integrating sphere device (QE-2100, Otsuka Electronics, Co., Ltd.), and the light conversion rate was measured. Thereafter, the loaded single film sample was dried in a nitrogen atmosphere drying oven at 180° C. for 30 minutes, and then the light retention rate after exposure and before drying was measured, and the measurement results are shown in Table 3.

(table 3) Light conversion rate (%) Light retention rate (%) Maximum emission wavelength (nm) Example 1 26.0 88 544 Example 2 29.9 99 545 Example 3 29.5 99 545 Example 4 30.0 95 543 Example 5 28.5 89 543 Example 6 32.2 97 543 Example 7 31.6 93 535 Example 8 31.9 92 535 Example 9 31.1 96 542 Example 10 27.5 95 544 Example 11 32.0 90 541 Example 12 31.0 90 542 Example 13 26.9 94 543 Example 14 28.2 94 542 Comparative example 1 22.8 91 543

From Table 3, it can be seen that the solvent-free curable composition according to the Example exhibits improved optical properties. (Preparation of solvent-based curable composition) Example 15

Each solvent-type curable composition (photosensitive resin composition) was prepared using corresponding amounts of the following components.

Specifically, the photopolymerization initiator was dissolved in the solvent, and the solution was sufficiently stirred at room temperature for 2 hours. Subsequently, the binder resin was added together with the quantum dot dispersion and dispersant (TEGO D685, manufactured by Evonik Corp.) of Preparation Example 1, and the resulting mixture was heated again at room temperature. Stirred for 2 hours. Then, a light diffusing agent and a fluorine-based surfactant were added thereto, and then stirred at room temperature for 1 hour, and the product therein was filtered three times to remove impurities and prepare a photosensitive resin composition. 1) Quantum dot dispersion: Preparation Example 1 2) Binder resin: 25 wt% Cardo-based binder resin (TSR-TA01, TAKOMA) 3) Polymerizable monomer: 5.4 wt% Pentaerythritol hexamethacrylate (DPHA, Nippon Chemical Co., Ltd.) 4) Photopolymerization initiator: 0.7% by weight of diphenyl (2,4,6-trimethylbenzyl)phosphine oxide (TPO, Sigma-Aldrich Corporation) 5) Solvent: 39 wt% dimethyl adipate 6) Light diffuser: 39 wt% titanium dioxide dispersion (TiO ₂ solids content: 20 wt%, Average particle size: 200 nm, Ditu Technology Co., Ltd.) 7) Other additives: 0.9% by weight fluorine-based surfactant (F-554, Dainippon Ink Chemical Co., Ltd.) Example 16

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 2 was used instead of the dispersion obtained in Preparation Example 1. Example 17

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 3 was used instead of the dispersion obtained in Preparation Example 1. Example 18

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 4 was used instead of the dispersion obtained in Preparation Example 1. Example 19

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 5 was used instead of the dispersion obtained in Preparation Example 1. Example 20

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 6 was used instead of the dispersion obtained in Preparation Example 1. Example 21

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 7 was used instead of the dispersion obtained in Preparation Example 1. Example 22

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 8 was used instead of the dispersion obtained in Preparation Example 1. Example 23

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 9 was used instead of the dispersion obtained in Preparation Example 1. Example 24

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 10 was used instead of the dispersion obtained in Preparation Example 1. Example 25

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 11 was used instead of the dispersion obtained in Preparation Example 1. Example 26

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 12 was used instead of the dispersion obtained in Preparation Example 1. Example 27

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 13 was used instead of the dispersion obtained in Preparation Example 1. Example 28

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Preparation Example 14 was used instead of the dispersion obtained in Preparation Example 1. Comparative example 2

A solvent-type curable composition was prepared according to the same method as Example 15, except that the dispersion obtained in Comparative Preparation Example 1 was used instead of the dispersion obtained in Preparation Example 1. Evaluation 3 : Light conversion rate and light retention rate of quantum dots

The curable compositions according to Examples 15 to 28 and Comparative Example 2 were respectively coated on a single surface of the glass substrate to 6 micron thick and then dried on a hot plate at 80°C for 1 minute to obtain a film. Then, after irradiation with UV light at a power of 100 mJ/cm2, post-baking (POB) was performed for 30 minutes in a convection cleaning oven (Jongro) at 180°C. The light conversion rate was measured using an exposure machine (ghi broadband, Ushio Inc.), and the results are shown in Tables 4 and 5.

(Table 4) (Unit: %) Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Initial light conversion rate 23.5 27.0 26.7 27.0 25.9 29.3 28.4 28.9 Light conversion rate after executing POB once 23.0 26.5 26.2 26.5 25.4 28.9 27.8 28.3

(Table 5) (Unit: %) Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Comparative example 2 Initial light conversion rate 28.0 24.6 29.0 28.2 23.9 25.3 22.0 Light conversion rate after executing POB once 27.4 24.1 28.4 27.6 23.6 24.8 20.0

As shown in Tables 4 and 5, the solvent-based curable composition prepared by using the surface-modified quantum dots according to the embodiments showed little deterioration in light conversion efficiency due to the color filter process, and thus showed high Light retention.

While the present invention has been described in connection with exemplary embodiments which are presently considered practical, it is to be understood that the invention is not limited to the disclosed embodiments, but is instead intended to cover all embodiments within the spirit and scope of the appended claims. Various modifications and equivalent arrangements. Therefore, it should be understood that the above-described embodiments are exemplary and do not limit the invention in any way.

without

without

Claims (20)

A quantum dot surface-modified with a compound represented by Chemical Formula 1:

Wherein, in Chemical Formula 1, R ¹ is a carboxyl group, *-P(=O)(OH) ₂ or a thiol group, and R ² is "unsubstituted or substituted by vinyl group, allyl group, epoxy group, ( Meth)acrylate group, C1 to C10 alkyl group or C6 to C20 aryl group substituted by C6 to C12 aryl group", "unsubstituted or vinyl, allyl, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C20 aryloxy group substituted by C6 to C12 aryl group", or "represented by Chemical Formula 1A",

Wherein, in Chemical Formula 1A, R ³ is "C1 to C1 to C10 alkyl group which is unsubstituted or substituted by vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group. C20 alkyl" or "C2 to C20 alkenyl unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl", And L ¹ is "C1 to C20 alkylene group that is not substituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "unsubstituted or substituted by vinyl, allyl , epoxy or (meth)acrylate group-substituted C3 to C20 cycloalkyl group" or "represented by one of Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2",

[Chemical formula 1B-2-2]

[Chemical formula 1B-6-1]

[Chemical formula 1B-7-2]

Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b are independently hydrogen atoms or carboxyl groups, and R ^c is O, S, NH, C1 to C20 alkylene group, C1 to C20 Alkylamino or C2 to C20 allylamine, L ² is a single bond, *-C(=O)O-* or *-S-*, and L ³ consists of Chemical Formula 1C-1 or Chemical Formula 1C-2 express,

Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , m is an integer from 1 to 20, and n is an integer from 1 or 2. The quantum dot as claimed in claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 2:

Among them, in Chemical Formula 2, R ² is "a C1 to C20 alkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", "unsubstituted or substituted by vinyl group, allyl, epoxy, (meth)acrylate group, C1 to C10 alkyl or C6 to C12 aryl substituted C1 to C20 alkoxy group", "unsubstituted or vinyl, allyl group, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C20 aryl group substituted by C6 to C12 aryl group" or "unsubstituted or vinyl, allyl, epoxy group , (meth)acrylate group, C1 to C10 alkyl group or C6 to C20 aryloxy group substituted by C6 to C12 aryl group", or "represented by Chemical Formula 1A",

Wherein, in Chemical Formula 1A, R ³ is "C1 to C1 to C10 alkyl group which is unsubstituted or substituted by vinyl group, allyl group, epoxy group, (meth)acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group. C20 alkyl" or "C2 to C20 alkenyl unsubstituted or substituted by vinyl, allyl, epoxy, (meth)acrylate, C1 to C10 alkyl or C6 to C12 aryl", And L ¹ is "C1 to C20 alkylene group that is not substituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "unsubstituted or substituted by vinyl, allyl , C3 to C20 cycloalkyl group substituted by epoxy group or (meth)acrylate group" or "from Chemical Formula 1B-1-1, Chemical Formula 1B-2-1, Chemical Formula 1B-3-1, Chemical Formula 1B-4 -1. Expressed by one of Chemical Formula 1B-5-1, Chemical Formula 1B-6-1 and Chemical Formula 1B-7-1",

[Chemical formula 1B-7-1]

Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b are independently hydrogen atoms or carboxyl groups, and R ^c is O, S, NH, C1 to C20 alkylene group, C1 to C20 Alkylamino or C2 to C20 allylamine, L ² is a single bond, *-C(=O)O-* or *-S-*, and L ³ is composed of Chemical Formula 1C-1 or Chemical Formula 1C-2 express,

Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , and m is an integer from 1 to 20. The quantum dot as claimed in claim 2, wherein, in Chemical Formula 2, R ² is "a C1 to C20 alkoxy group that is unsubstituted or substituted by a C1 to C10 alkyl group or a C6 to C12 aryl group", "unsubstituted "C6 to C20 aryl group substituted or substituted by C1 to C10 alkyl group or C6 to C12 aryl group" or "C6 to C20 aryloxy group unsubstituted or substituted by C1 to C10 alkyl group or C6 to C12 aryl group" , L ¹ is "unsubstituted C1 to C20 alkylene group" or "unsubstituted C3 to C20 cycloalkylene group", L ² is a single bond, *-C(=O)O-* or *- S-*, and ^L3 is represented by Chemical Formula 1C-1 or Chemical Formula 1C-2,

Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , and m is an integer from 1 to 20. The quantum dot of claim 1, wherein the compound represented by Chemical Formula 1 is represented by one of Chemical Formula 2-2 to Chemical Formula 2-6 and Chemical Formula 2-8:

The quantum dot as claimed in claim 1, wherein in Chemical Formula 1, R ¹ is a carboxyl group or a thiol group, and R ² is "unsubstituted or vinyl, allyl, epoxy or (methyl)""C1 to C20 alkyl group substituted by acrylate group", "C1 to C20 alkoxy group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group", "unsubstituted or "C6 to C20 aryl substituted by vinyl, allyl, epoxy or (meth)acrylate" or "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate""C6 to C20 aryloxy group substituted by acrylate group", or "represented by Chemical Formula 1A",

Wherein, in Chemical Formula 1A, R ³ is "a C1 to C20 alkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "unsubstituted or substituted by vinyl C2 to C20 alkenyl substituted by vinyl, allyl, epoxy or (meth)acrylate", and L ¹ is "unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate ) acrylate group-substituted C1 to C20 alkylene group" or "C3 to C20 cycloalkylene group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or " Represented by one of Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2", [Chemical Formula 1B-1-1]

[Chemical formula 1B-3-1]

[Chemical formula 1B-6-2]

Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-2, R ^a and R ^b are independently hydrogen atoms or carboxyl groups, and R ^c is O, S, NH, C1 to C20 alkylene group, C1 to C20 Alkylamino or C2 to C20 allylamine, L ² is a single bond, *-C(=O)O-* or *-S-*, and L ³ is composed of Chemical Formula 1C-1 or Chemical Formula 1C-2 express,

Wherein, in Chemical Formula 1C-1 and Chemical Formula 1C-2, L ⁴ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group. , m is an integer from 1 to 20, and n is an integer from 1 or 2. The quantum dot as claimed in claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 3:

Wherein, in Chemical Formula 3, R ⁴ is represented by Chemical Formula 1A, [Chemical Formula 1A]

Wherein, in Chemical Formula 1A, R ³ is "a C1 to C20 alkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "unsubstituted or substituted by vinyl "C2 to C20 alkenyl group substituted by alkyl, allyl, epoxy or (meth)acrylate", R ⁵ is a carboxyl or thiol group, L ⁶ and L ⁷ are independently substituted or unsubstituted C1 to C20 alkylene group, L ⁸ is a single bond, *-S-* or *-OC(=O)-*, L ⁹ is substituted or unsubstituted C1 to C20 alkylene group, and m is 1 An integer up to 20. The quantum dot as claimed in claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 4:

Wherein, in Chemical Formula 4, R ⁴ is represented by Chemical Formula 1A, [Chemical Formula 1A]

Wherein, in Chemical Formula 1A, R ³ is "a C1 to C20 alkyl group that is unsubstituted or substituted by vinyl, allyl, epoxy or (meth)acrylate group" or "unsubstituted or substituted by vinyl "C2 to C20 alkenyl group substituted by alkyl, allyl, epoxy or (meth)acrylate group", L ⁶ and L ⁷ are independently substituted or unsubstituted C1 to C20 alkylene group, L ⁸ is a single bond, *-S-* or *-OC(=O)-*, L ⁹ is a substituted or unsubstituted C1 to C20 alkylene group, and L ¹⁰ is composed of Chemical Formula 1B-1-1, Chemical Formula Represents one of 1B-2-1, Chemical Formula 1B-3-1, Chemical Formula 1B-4-1, Chemical Formula 1B-5-1, Chemical Formula 1B-6-1, and Chemical Formula 1B-7-1,

[Chemical formula 1B-2-1]

[Chemical formula 1B-5-1]

Among them, in Chemical Formula 1B-1-1 to Chemical Formula 1B-7-1, R ^a and R ^b are independently a carboxyl group, *-P(=O)(OH) ₂ or a thiol group, and R ^c is O, S , NH, C1 to C20 alkylene group, C1 to C20 alkylamino group or C2 to C20 allylamine group, and m is an integer from 1 to 20. The quantum dot of claim 1, wherein the compound represented by Chemical Formula 1 is represented by one of Chemical Formula 3-1 to Chemical Formula 3-6:

Wherein, in Chemical Formula 3-6, n is an integer from 1 to 20. The quantum dot as claimed in claim 1, wherein the compound represented by Chemical Formula 1 is represented by Chemical Formula 4-1:

Wherein, in Chemical Formula 4-1, n is an integer from 1 to 20. The quantum dot of claim 1, wherein the quantum dot has a maximum fluorescence emission wavelength between 500 nanometers and 680 nanometers. A solvent-free curable composition includes the quantum dot as described in claim 1; and a polymerizable monomer having a carbon-carbon double bond at the end. The solvent-free curable composition of claim 11, wherein the polymerizable monomer has a molecular weight of 220 g/mol to 1,000 g/mol. The solvent-free curable composition as claimed in claim 11, wherein the polymerizable monomer is represented by Chemical Formula 5:

Wherein, in Chemical Formula 5, R ¹⁰¹ and R ¹⁰² are independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁰¹ and L ¹⁰³ are independently a substituted or unsubstituted C1 to C10 alkyl group. Alkyl, and L ¹⁰² is substituted or unsubstituted C1 to C10 alkyl or ether group (*-O-*). The solvent-free curable composition according to claim 11, comprising: 1 to 60 wt% of the quantum dots, and 40 to 99 wt% of the polymerizable monomer. The solvent-free curable composition as claimed in claim 11 further includes a polymerization initiator, a light diffusing agent or a combination thereof. A solvent-based curable composition includes: the quantum dots described in claim 1; a binder resin; and a solvent. The solvent-based curable composition according to claim 16, comprising 1 to 40% by weight of the quantum dots; 1 to 30% by weight of the binder resin; and the balance of the solvent. The solvent-based curable composition as described in claim 16, further including Contains polymerizable monomers, polymerization initiators, light diffusing agents or combinations thereof. A cured layer produced using the solvent-free curable composition as described in claim 11 or the solvent-based curable composition as described in claim 16. A color filter including the cured layer described in claim 19.