CN114096640A

CN114096640A - Quantum dot, curable composition including the same, cured layer using the composition, and color filter including the cured layer

Info

Publication number: CN114096640A
Application number: CN202080048120.2A
Authority: CN
Inventors: 姜龙熙; 金钟基; 林知泫; 金东俊; 金美善; 朴民志; 李范珍; 李仁宰; 崔美贞
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2019-10-14
Filing date: 2020-09-18
Publication date: 2022-02-25
Anticipated expiration: 2040-09-18
Also published as: WO2021075741A1; CN114096640B; KR102648364B1; TW202116720A; KR102609622B1; KR20210044044A; TWI833040B; KR20230169894A

Abstract

Provided are a quantum dot, a curable composition including the quantum dot, a cured layer, and a color filter.

Description

Quantum dot, curable composition including the same, cured layer using the composition, and color filter including the cured layer

Technical Field

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.

Background

In the case of a general quantum dot, a solvent in which the quantum dot is dispersed is limited due to a surface property having hydrophobicity. Therefore, it is difficult to incorporate it into polar systems such as adhesives or curable monomers.

For example, even in the case of actively studying the quantum dot ink composition, the polarity is relatively low in the initial step, and it can be dispersed in a solvent for a curable composition having high hydrophobicity. Therefore, it is difficult to include 20 wt% or more than 20 wt% of quantum dots based on the total amount of the composition, and thus the light efficiency of the ink cannot be improved beyond a certain level. Although quantum dots are additionally added and dispersed to improve light efficiency, the viscosity exceeds the range (12 centipoise (cPs)) capable of Ink jetting (Ink-jetting), and thus may not satisfy the processability.

To obtain a viscosity range capable of ink jetting, a method of reducing the solid content of the ink by dissolving 50% by weight or more than 50% by weight of a solvent based on the total amount of the composition, which also provides a slightly satisfactory result in terms of viscosity. However, it may be considered as a satisfactory result in terms of viscosity, but nozzle drying due to solvent evaporation at the time of jetting (jetting), nozzle clogging, and monolayer reduction with the passage of time after jetting (jetting) may become worse, and it is difficult to control thickness deviation after curing. Therefore, it is difficult to apply it to an actual process.

Therefore, solvent-free quantum dot inks that do not contain solvents are the most desirable form for practical manufacturing processes. Current techniques for applying quantum dots per se to solvent-based compositions are now somewhat limited.

As reported so far, in the case of the most desirable solvent-based composition to be applied to an actual process, the quantum dots that are not surface-modified (e.g., ligand-substituted) have a content of 20 to 25 wt% based on the total amount of the solvent-based composition. Therefore, it is difficult to improve light efficiency and absorption rate due to viscosity limitation. Meanwhile, attempts have been made to reduce the quantum dot content and increase the content of a light diffuser (scatterer) in other improvement approaches, but this also fails to solve the precipitation problem and the low light efficiency problem.

Disclosure of Invention

Technical problem

An embodiment is to provide a quantum dot that is surface-modified with a compound having an excellent passivation effect, and thus has improved light efficiency.

Another embodiment is to provide a quantum dot containing curable composition.

Another embodiment is to provide a cured layer produced using the curable composition.

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

Technical solution

One embodiment provides a quantum dot surface-modified with a compound represented by chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

R¹is a carboxyl group, — P (═ O) (OH)₂Or a thiol group, and

R²is "C1 to C20 alkyl which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", or "C6 to C20 aryloxy which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", or "represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³is "substituted or unsubstituted vinyl", "not substitutedC1 to C20 alkyl which is substituted or unsubstituted with vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl "or C2 to C20 alkenyl which is unsubstituted or substituted with vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", and

L¹is "C1 to C20 alkylene which is unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate" or "C3 to C20 cycloalkylene which is unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate" or "represented by one of chemical formulae 1B-1-1 to 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-2,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

R^cis O, S, NH, C1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 allylamino,

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁴is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer of 1 to 20, and

n is an integer of 1 or 2.

The compound represented by chemical formula 1 may be represented by chemical formula 2.

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

R²c1 to C20 alkyl which may be "unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which may be unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl"," C6 to C20 aryl which is unsubstituted or substituted with vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl "or" C6 to C20 aryloxy which is unsubstituted or substituted with vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl ", or" may be represented by chemical formula 1A ",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³may be a "substituted or unsubstituted vinyl group", "C1 to C20 alkyl group which is unsubstituted or substituted with a vinyl group, allyl group, epoxy group, (meth) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group" or a "C2 to C20 alkenyl group which is unsubstituted or substituted with a vinyl group, allyl group, epoxy group, (meth) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group", and

L¹may be a "C1 to C20 alkylene group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group" or a "C3 to C20 cycloalkylene group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group" or "may be represented by one of 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 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

R^ccan be O, S, NH, C1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 allylamino,

L²may be a single bond, — C (═ O) O —, or — -S —, and

L³may be represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁴a C1 to C20 alkylene group which may be a single bond or substituted or unsubstituted,

L⁵may be a substituted or unsubstituted C1 to C20 alkylene group, and

m may be an integer of 1 to 20.

In chemical formula 2, R²May be "C1 to C20 alkyl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl" or "C6 to C20 aryloxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl",

L¹may be an "unsubstituted C1 to C20 alkylene" or an "unsubstituted C3 to C20 cycloalkylene",

L²may be a single bond, — C (═ O) O —, or — -S —, and

L³may be represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵may be a substituted or unsubstituted C1 to C20 alkylene group, and

m may be an integer of 1 to 20.

The compound represented by chemical formula 1 may be represented by one of chemical formulas 2-1 to 2-8.

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

In the chemical formulaIn 1, R¹May be a carboxyl group or a thiol group, and

R²may be "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³may be a "substituted or unsubstituted vinyl group", "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C2 to C20 alkenyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", and

L¹may be a "C1 to C20 alkylene group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or a "C3 to C20 cycloalkylene group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-2,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

L²may be a single bond, — C (═ O) O —, or — -S —, and

L³may be represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁴c1 to C which may be a single bond or substituted or unsubstitutedA C20 alkylene group, the alkylene group,

L⁵may be a substituted or unsubstituted C1 to C20 alkylene group,

m may be an integer of 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 the chemical formula 3, the first and second,

R⁴may be "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "may be represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³may be "substituted or unsubstituted vinyl", "C1 to C20 alkyl unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate" or "C2 to C20 alkenyl unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate",

R⁵it may be a carboxyl group or a thiol group,

L⁶and L⁷May independently be a substituted or unsubstituted C1 to C20 alkylene group,

L⁸(may be)a single bond, — S-, — C (═ O) -, or — OC (═ O) -,

L⁹may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and

m may be an integer of 1 to 20.

The compound represented by chemical formula 1 may be represented by chemical formula 4.

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

R⁴may be "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

L⁸may be a single bond, -S, -C (═ O) -, or-OC (═ O) -,

L¹⁰can be represented by one of 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 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

R^cmay be O, S, NH, C1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 allylamino, and

m may be an integer of 1 to 20.

The compound represented by chemical formula 1 may be represented by one of chemical formulas 3-1 to 3-6.

[ chemical formula 3-1]

[ chemical formula 3-2]

[ chemical formulas 3-3]

[ chemical formulas 3-4]

[ chemical formulas 3-5]

[ chemical formulas 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 (nm) to 680 nm.

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

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

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

[ chemical formula 5]

In the chemical formula 5, the first and second organic solvents,

R¹⁰¹and R¹⁰²May independently be a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L¹⁰¹and L¹⁰³May independently be a substituted or unsubstituted C1 to C10 alkylene group, and

L¹⁰²may be a substituted or unsubstituted C1 to C10 alkylene or ether group (— O-).

The solvent-free curable composition may include 1 to 60 wt% of the quantum dot and 40 to 99 wt% of the polymerizable monomer.

The solvent-free curable composition may further comprise a polymerization initiator, a light diffuser, or a combination thereof.

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

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

The solvent-based curable composition may further comprise a polymerizable monomer, a polymerization initiator, a light diffuser, 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 present invention are included in the detailed description below.

Beneficial effect

An embodiment provides a quantum dot surface-modified with a specific ligand, and the specific ligand has a very good passivation effect on the quantum dot, and the surface-modified quantum dot can be easily applied to both a solvent-based curable composition and a solvent-free curable composition to improve processibility, and can greatly improve light efficiency of a cured layer produced using the composition, compared to conventional quantum dots. In addition, the curable composition including the quantum dot according to the embodiment has improved storage stability and heat resistance.

Detailed Description

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto, and the invention is defined by the scope of the claims.

As used herein, when a definition is not 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 heterocycloalkenyl, "aryl" refers to C6 to C20 aryl, "arylalkyl" refers to C6 to C20 arylalkyl, "alkylene" refers to C1 to C20 alkylene, "arylene" refers to C6 to C20 arylene, "alkylarylene" refers to C6 to C20 alkylarylene, "heteroarylene" refers to C3 to C20 heteroarylene, and "alkyleneoxy" refers to C1 to C20 alkyleneoxy.

As used herein, "substituted," when a specific definition is not otherwise provided, means that at least one hydrogen atom is replaced with a substituent selected from the group consisting of: a halogen atom (F, Cl, Br, or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imine group, an azide group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

As used herein, "hetero", when a specific definition is not otherwise provided, means that at least one heteroatom of N, O, S and P is included in the chemical formula.

As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid", when a specific definition is not otherwise provided.

As used herein, the term "combination" refers to mixing or copolymerization when specific definitions are not otherwise provided.

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

As used herein, a cardol resin refers to a resin comprising at least one functional group selected from chemical formulas 6-1 to 6-11 in a backbone (backbone) of the resin.

In addition, in the present specification, "+" refers to a point connected to the same or different atom or chemical formula, when no definition is otherwise provided.

Due to the hydrophobic surface characteristics, quantum dots are generally limitedly dispersed in a small number of solvents, and thus there are many difficulties in introducing quantum dots into a polar system such as a binder resin, a curable monomer, and the like.

For example, even a curable composition containing quantum dots, which has been actively studied, has relatively low polarity (polarity) in an initial step, and is prepared by dispersing quantum dots only in a curable composition having high hydrophobicity. It is difficult to include a high content of quantum dots of 20 wt% or more than 20 wt% based on the total composition, and therefore, the light efficiency of the curable composition cannot be improved at a predetermined level or more, and even if the quantum dots are excessively added and dispersed, the viscosity (12 centipoise (cPs)) of the composition exceeds the viscosity range capable of Ink-jetting (Ink-jetting) for improving the light efficiency, and thus the processability may not be satisfied.

Further, in order to achieve a viscosity range capable of performing ink jetting, a method has been used which includes a solvent at a content of 50 wt% or more with respect to the total curable composition to reduce the solid content of the curable composition, which may result in excellent viscosity, but has disadvantages of drying of nozzles due to volatilization of the solvent, nozzle clogging, reduction of a single film with the passage of time after ink jetting, and severe thickness variation after curing, and thus is difficult to apply to a practical process.

Therefore, the curable composition containing quantum dots has a limitation in application of the current quantum dots themselves, considering that a solvent-free composition containing no solvent is a development direction suitable for practical processes.

It has been reported so far that it is difficult to improve light efficiency and absorption rate due to the limitation of viscosity since quantum dots not surface-modified (e.g., ligand-substituted) are contained in a small amount of 20 to 25 wt% based on the curable composition. In addition, another improved approach is to reduce the content of quantum dots and increase, for example, TiO₂The method of the content of the light diffusing agent, which also cannot improve the precipitation problem or the low light efficiency.

Conventional solvent-based curable compositions containing quantum dots may cause nozzle clogging due to drying of the solvent in the nozzle during ink jetting as described above, fail to maintain a target pixel thickness due to evaporation of the ink in the inkjet pixel, and thus fail to ensure inkjet processability.

Furthermore, in order to form a layer having a predetermined thickness by post baking (or otherwise thermally curing) after forming a thin film in a pixel, a pinning (pinning) point (maximum height at which bubbles do not collapse) should be formed by jetting a large amount of ink at a position far higher than the height of the pixel, which is practically impossible, and furthermore, a processable solvent should have a surface tension of approximately 40 dyne/cm (dyne/cm), which is rarely likely to occur.

Most of ligands used for surface modification of quantum dots generally have a thiol group, but as described above, quantum dots surface-modified with thiol group-containing ligands have low dispersibility and poor inkjet processes, and most importantly, have reached the limit in consideration of the demand for optical characteristics in the market.

Accordingly, the present inventors have studied for a long time and found that the surface modification of quantum dots using a functional group not including a thiol group or including a carbon-carbon double bond or an epoxy group, even if it has a thiol group, thereby preventing the optical characteristics of the quantum dots from being deteriorated and simultaneously greatly improving the storage stability and heat resistance of the curable composition containing the quantum dots.

For example, the ligand may be represented by chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

R¹is a carboxyl group, — P (═ O) (OH)₂Or a thiol group, and

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³is "a substituted or unsubstituted vinyl group", "a C1 to C20 alkyl group which is unsubstituted or substituted by a vinyl group, allyl group, epoxy group, (meth) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group" or "a C2 to C20 alkenyl group which is unsubstituted or substituted by a vinyl group, allyl group, epoxy group, (meth) acrylate group, C1 to C10 alkyl group or C6 to C12 aryl group", and

L¹is "C1 to C20 alkylene group unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate group" or "C3 to C20 cycloalkylene group unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate group" or "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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-2,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer of 1 to 20, and

n is an integer of 1 or 2.

At L²In the formula, the carbonyl group of-C (═ O) O —) may have a different order of attachment from that of-O (C ═ O) -, and the carbonyl group of-C (═ O) O —) may be attached to L¹A linking group, and an ether group may be linked to L³A linking group.

For example, the compound represented by chemical formula 1 may be represented by chemical formula 2.

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

R²may be "C1 to C20 alkyl which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", or "C6 to C20 aryloxy which is unsubstituted or substituted by vinyl, allyl, epoxy, (meth) acrylate, C1 to C10 alkyl or C6 to C12 aryl", or "may be represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

[ 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

L²may be a single bond, — C (═ O) O —, or — -S —, and

L³may be represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵may be a substituted or unsubstituted C1 to C20 alkylene group, and

m may be an integer of 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 thiol-based compounds, which are generally used as conventional surface modification materials for quantum dots, and when the quantum dots are surface-modified with such ligands, the surface-modified quantum dots can greatly improve the light efficiency of a 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, R²May be "C1 to C20 alkyl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl" or "C6 to C20 aryloxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", L1¹May be "unsubstituted C1 to C20 alkylene" or "unsubstituted C3 to C20 cycloalkylene", L²May be a single bond, — C (═ O) O —, or —, S —, and L³Can be composed ofChemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁴c1 to C20 alkylene which may be single bond or substituted or unsubstituted, L⁵May be a substituted or unsubstituted C1 to C20 alkylene group, and m may be an integer of 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) R¹May be a carboxyl or thiol group, R²May be "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "may be represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³may be "substituted or unsubstituted vinyl", "C1 to C20 alkyl unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate groups" or "unsubstituted or substituted with vinylAllyl, epoxy or (meth) acrylate substituted C2 to C20 alkenyl ", and

L¹may be a "C1 to C20 alkylene group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or a "C3 to C20 cycloalkylene group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-2,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

R^cmay be O, S, NHC1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 allylamino,

L²may be a single bond, — C (═ O) O —, or — -S —, and

L³may be represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵may be a substituted or unsubstituted C1 to C20 alkylene group,

m may be an integer of 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 the chemical formula 3, the first and second,

R⁴may be "C1 to C20 alkyl which is unsubstituted or substituted by vinyl, allyl, epoxy or (meth) acrylate groups", "unsubstituted or substituted by vinyl, allyl, epoxy or (meth) acrylate groupsAn ester group-substituted C1 to C20 alkoxy group, a "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or a "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "may be represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R⁵it may be a carboxyl group or a thiol group,

L⁸may be a single bond, -S, -C (═ O) -, or-OC (═ O) -,

m may be an integer from 1 to 20, and

[ chemical formula 4]

Wherein, in chemical formula 4,

R⁴may be "C1 to C20 alkyl which is unsubstituted or substituted by vinyl, allyl, epoxy or (meth) acrylate", "C1 to C20 alkoxy which is unsubstituted or substituted by vinyl, allyl, epoxy or (meth) acrylate", "unsubstituted or substituted by vinyl, allyl, epoxy or (meth) acrylateA (meth) acrylate group-substituted C6 to C20 aryl group "or" a C6 to C20 aryloxy group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group ", or" may be represented by chemical formula 1A ",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

L⁸may be a single bond, -S, -C (═ O) -, or-OC (═ O) -,

[ 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bMay independently be a hydrogen atom or a carboxyl group,

m may be an integer of 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/mole, for example, 200 g/mole to 1000 g/mole. 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 the quantum dot surface-modified with the compound may 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 formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

[ chemical formula 3-1]

[ chemical formula 3-2]

[ chemical formulas 3-3]

[ chemical formulas 3-4]

[ chemical formulas 3-5]

[ chemical formulas 3-6]

[ chemical formula 4-1]

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

A curable composition according to another embodiment includes a quantum dot surface-modified with a compound represented by chemical formula 1.

Up to now, curable compositions (inks) comprising quantum dots have been developed towards specialized monomers with good compatibility with quantum dots, and, in addition, have been commercialized.

On the other hand, since a generally and widely used polymerizable monomer, an-ene (-ene) based monomer (including a vinyl based monomer, an acrylate based monomer, a methacrylate based monomer, etc., which includes a monofunctional monomer or a polyfunctional monomer) has low compatibility with the quantum dot and is limited in dispersibility of the quantum dot, it is substantially difficult to effectively apply it to various developments of a curable composition containing the quantum dot. Most importantly, the-ene-based monomers do not exhibit high concentration quantum dot dispersibility and thus are difficult to apply to quantum dot-containing curable compositions.

Due to these disadvantages, a curable composition containing quantum dots has been developed to have a composition containing a considerable amount (50 wt% or more) of a solvent, but inkjet (Ink) processability may be deteriorated when the solvent content is increased. Therefore, in order to satisfy inkjet (Ink jetting) processability, there is an increasing demand for solvent-free curable compositions.

The present invention provides a solvent-free curable composition in which demand is increasing, and by using a polymerizable monomer including a compound having a carbon-carbon double bond at a terminal and a quantum dot surface-modified with a compound represented by chemical formula 1, the affinity of the quantum dot for the curable composition can be improved even in a solvent-free system to achieve high-concentration dispersibility and even passivation (deactivation) effect of the quantum dot, while not damaging the natural optical characteristics of the quantum dot.

Hereinafter, each component constituting the solvent-free curable composition is described in detail.

Quantum dots

The quantum dot included in the solvent-free curable composition includes a quantum dot surface-modified with a compound represented by chemical formula 1.

For example, the quantum dot absorbs light in a wavelength region of 360 nm to 780 nm, e.g., 400 nm to 780 nm, and emits fluorescent light in a wavelength region of 500 nm to 700 nm, e.g., 500 nm to 580 nm or emits fluorescent light in a wavelength region of 600 nm to 680 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (λ) at 500 nm to 680 nm_em)。

The quantum dots can 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 dot has a full width at half maximum (FWHM) of the range, color reproducibility increases due to high color purity when used as a color material in a color filter.

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

The quantum dot may be independently composed of a core and a shell surrounding the core, and the core and the shell may independently have a structure of a core, a core/shell, a core/first shell/second shell, an alloy/shell, etc., composed of groups II-IV, III-V, etc., but is not limited thereto.

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 is not necessarily limited thereto. 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 the attention to the environment has been greatly increased worldwide recently and the control of toxic materials has been strengthened, a non-cadmium-based light emitting material (InP/ZnS, InP/ZnSe/ZnS, etc.) having a cadmium-based core, which is slightly low in quantum efficiency (quantum yield), but is environmentally friendly, is used instead of the light emitting material having a cadmium-based core, but is not necessarily limited thereto.

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

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

On the other hand, to achieve dispersion stability of the quantum dots, the solvent-free curable composition according to the embodiment may further include a dispersant. The dispersant contributes to uniform dispersibility of the light conversion material such as quantum dots in the solvent-free curable composition, and may include a nonionic dispersant, an anionic dispersant, or a cationic dispersant. Specifically, the dispersant may be polyalkylene glycol or an ester thereof, polyalkylene oxide, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonic acid ester, carboxylic acid salt, alkylamide alkylene oxide addition product, alkylamine, or the like, and it 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 wt%, for example, 10 to 20 wt%, based on the solid content of the light conversion material (e.g., quantum dot).

The quantum dot surface-modified with chemical formula 1 or chemical formula 2 may be included in an amount of 1 to 60 wt%, for example, 3 to 50 wt%, based on the total amount of the solvent-free curable composition. When the surface-modified quantum dot is included in the range, the light conversion rate may be improved, and the pattern characteristic and the developing characteristic are not disturbed, so that it may have excellent processability.

Polymerizable monomer having carbon-carbon double bond at terminal

The monomer having a carbon-carbon double bond at the terminal should be contained in an amount of 40 to 99 wt%, for example, 50 to 97 wt%, based on the total amount of the solvent-free curable composition. When the monomer having a carbon-carbon double bond at the terminal is included in the range, a solvent-free curable composition having a viscosity capable of ink jetting may be prepared, and the quantum dots in the prepared solvent-free curable composition may have improved dispersibility, thereby improving optical characteristics.

For example, the monomer having a carbon-carbon double bond at the terminal may have a molecular weight of 220 g/mole (g/mol) to 1,000 g/mole. When the monomer having a carbon-carbon double bond at the terminal has a molecular weight within the range, ink jetting can be advantageously performed because it does not increase the viscosity of the composition and does not hinder the optical characteristics of the quantum dot.

For example, the 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 the chemical formula 5, the first and second organic solvents,

For example, the 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, the monomer having a carbon-carbon double bond at the terminal may include ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

Further, a monomer commonly used for conventional thermosetting or photocurable compositions may be further contained together with a monomer having a carbon-carbon double bond at the terminal. For example, the monomer also includes oxetane compounds such as bis [ 1-ethyl (3-oxetanyl) ] methyl ether and the like.

Polymerization initiator

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

The photopolymerization initiator is an initiator commonly used for photosensitive resin compositions, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and amino ketone-based compounds, but not necessarily limited thereto.

Examples of the acetophenone-based compound may be 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone, and the like.

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

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl 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 (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4, 6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (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 and the like.

Examples of the oxime-based compound may be O-acyloxime-based compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione, 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone, O-ethoxycarbonyl- α -oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyloxime-based compound may be 1, 2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-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) -octan-1-one oxime-O-acetate, 1- (4-phenylthiophenyl) -butane-1-one oxime-O-acetate, and the like.

Examples of the amino ketone compound include 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (2-Benzyl-2-dimethyllamino-1- (4-morpholinophenyl) -butanone-1), and the like.

The photopolymerization initiator may further contain a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a bisimidazole-based compound, and the like, in addition to the above-mentioned compounds.

The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then 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 the thermal polymerization initiator may be peroxides, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-sec-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2-azo-bis (isobutyronitrile), tert-butyl perbenzoate, and the like, such as 2,2' -azobis-2-methylpropionitrile, but are not necessarily limited thereto, and any one known in the art may be used.

The polymerization initiator may be included in an amount of 0.1 to 5 wt%, for example, 1 to 4 wt%, based on the total amount of the solvent-free curable composition. When the polymerization initiator is included within the range, excellent reliability may be obtained due to sufficient curing during exposure or thermal curing, and deterioration of transmittance due to a non-reactive initiator is prevented, thereby preventing deterioration of optical characteristics of the quantum dot.

Light diffusing agent (or light diffusing agent dispersion)

The solvent-free curable composition according to the embodiment may further include a light diffuser.

For example, the light diffuser may include barium sulfate (BaSO)₄) Calcium carbonate (CaCO)₃) Titanium dioxide (TiO)₂) Zirconium oxide (ZrO)₂) Or a combination thereof.

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

The light diffuser may have an average particle diameter (D) of 150 to 250 nm, and specifically 180 to 230 nm₅₀). When the average particle diameter of the light diffuser is within the range, it may have a better light diffusing effect and improve light conversion efficiency.

The light diffuser may be included in an amount of 1 to 20 wt%, for example, 5 to 10 wt%, based on the total amount of the solvent-free curable composition. When the light diffusing agent is contained in an amount of less than 1 wt% based on the total amount of the solvent-free curable composition, it is difficult to expect the light conversion efficiency improving effect due to the use of the light diffusing agent, whereas when the light diffusing agent is contained in an amount of more than 20 wt%, there is a possibility that the quantum dot may be precipitated.

Other additives

To achieve stability and dispersion improvement of the quantum dots, the solvent-free curable composition according to the embodiment may further include a polymerization inhibitor.

The polymerization inhibitor may include hydroquinone-based compounds, catechol-based compounds, 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 crosslinking during exposure after coating the solvent-free curable composition may be prevented.

For example, the hydroquinone-based compound, the catechol-based compound, or the combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, tributylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 5-bis (1, 1-dimethylbutyl) hydroquinone, 2, 5-bis (1,1,3, 3-tetramethylbutyl) hydroquinone, catechol, tert-butylcatechol, 4-methoxycatechol, gallophenol, 2, 6-di-tert-butyl-4-methylphenol, 2-naphthol, Tris (N-hydroxy-N-nitrosophenylamino-O, O ') aluminum (Tris (N-hydroxy-N-nitrosophenylamino-O, O') aluminum), or a combination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, the catechol-based compound, or a combination thereof may be used in the form of a dispersion. The polymerization inhibitor may be included in the form of a dispersion in an amount of 0.001 to 3% by weight, for example, 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 range, the time lapse at room temperature can be solved, and at the same time, the sensitivity deterioration and the surface delamination phenomenon can be prevented.

Further, the solvent-free curable composition according to the embodiment may further include malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; a leveling agent; a 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 a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, or the like, to improve the close contact property with the substrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta-epoxycyclohexyl) ethyltrimethoxysilane, etc., and these coupling agents may be used alone or in a mixture of two or more.

The silane-based coupling agent may 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 contained within the range, the close contact property, the storage ability, and the like are improved.

In addition, the solvent-free curable composition may optionally further comprise a surfactant (e.g., a fluorine-based surfactant) to improve coating properties and suppress the generation of spots, i.e., to improve leveling (leveling) performance.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mole to 10,000 g/mole, and specifically 6,000 g/mole to 10,000 g/mole. In addition, the fluorine-based surfactant may have a surface tension of 18 milli-newtons per meter (mN/m) to 23 milli-newtons per meter (measured in a 0.1% Polyethylene Glycol Monomethyl Ether Acetate (PGMEA) solution). When the fluorine-based surfactant has a weight average molecular weight and a surface tension within the ranges, leveling performance may be further improved, and when slit coating (slit coating) is applied as high speed coating (high speed coating), excellent characteristics may be provided, since film defects may be less generated by preventing generation of spots and suppressing generation of vapor during high speed coating.

An example of the fluorine-based surfactant may be

And

(BM Chemie Inc.)); meijia Method (MEGAFACE) F

F

F

And F

(Dainippon Ink chemical Co., Ltd. (Dainippon Ink Kagaku Kogyo Co., Ltd.)); florade (FULORAD)

Florad

Florad

And Florad

(Sumitomo 3M Co., Ltd.); shafulon (SURFLON)

Shafulong (a medicine for treating diabetes)

Shafulong (a medicine for treating diabetes)

Shafulong (a medicine for treating diabetes)

And saflufon

(Asahi Glass Co., Ltd.); and

and

etc. (Toray Silicone co., Ltd.)); f-482, F-484, F-478, F-554, and the like, available from Dainippon ink chemical Co., Ltd.

Further, the solvent-free curable composition according to the embodiment may further include a silicone-based surfactant in addition to the fluorine-based surfactant. Specific examples of the silicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440, and the like, of Toshiba silicone co.

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 contained in the range, foreign substances are less generated in the sprayed composition.

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

For example, 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, in addition to the above solvent-free curable composition. Herein, the surface-modified quantum dots may be included in an amount of 1 to 40% by weight, based on the total amount of the solvent-type curable composition. When the surface-modified quantum dots are included in the content range based on the total amount of the solvent-type curable composition, it may be advantageous in terms of handleability.

Hereinafter, each component constituting the solvent-type curable composition is described in detail.

Adhesive resin

The adhesive resin may include an acrylic resin, a cardo resin, an epoxy resin, or a combination 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 comprising 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, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt% (e.g., 10 to 40 wt%), based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α -methylstyrene, vinyltoluene, vinylbenzyl methyl ether, or the like; unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and the like; unsaturated aminoalkyl carboxylate compounds such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and the like; vinyl carboxylate compounds such as vinyl acetate, vinyl benzoate and the like; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate and the like; vinyl cyanide compounds such as (meth) acrylonitrile and the like; unsaturated amide compounds such as (meth) acrylamide and the like; and the like, and the second ethylenically unsaturated monomer may be used alone or in a mixture of two or more.

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

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

The carduo resin may include a repeating unit represented by chemical formula 6.

[ chemical formula 6]

In the chemical formula 6, the first and second,

R³¹and R³²May independently be a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R³³and R³⁴May independently be a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

Z¹can be a single bond, O, CO, SO₂、CR³⁵R³⁶、SiR³⁷R³⁸(wherein, R³⁵To R³⁸May be independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by chemical formula 6-1 to chemical formula 6-11,

[ chemical formula 6-1]

[ chemical formula 6-2]

[ chemical formula 6-3]

[ chemical formulas 6-4]

[ chemical formulas 6-5]

In the chemical formula 6-5,

R^acan be hydrogen atom, ethyl, C₂H₄Cl、C₂H₄OH、CH₂CH＝CH₂Or a phenyl group.

[ chemical formulas 6-6]

[ chemical formulas 6 to 7]

[ chemical formulas 6 to 8]

[ chemical formulas 6 to 9]

[ chemical formulas 6 to 10]

[ chemical formulas 6 to 11]

Z²Can be an anhydride moiety, and

t1 and t2 may independently be integers from 0 to 4.

The weight average molecular weight of the cardol multi-component binder resin may be 500 g/mole to 50,000 g/mole, for example 1,000 g/mole to 30,000 g/mole. When the weight average molecular weight of the carden multisystem binder resin is within the range, a satisfactory pattern can be formed without residue during production of the cured layer and without loss of film thickness during development of the solvent-type curable composition.

The carduon-series adhesive resin may include a functional group represented by chemical formula 7 at least one of both ends.

[ chemical formula 7]

In the chemical formula 7, the first and second,

Z³may be represented by chemical formula 7-1 to chemical formula 7-7.

[ chemical formula 7-1]

In chemical formula 7-1, R^fAnd R^gAnd may be independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.

[ chemical formula 7-2]

[ chemical formulas 7-3]

[ chemical formulas 7-4]

[ chemical formulas 7-5]

In chemical formula 7-5, R^hMay be O, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.

[ chemical formulae 7 to 6]

[ chemical formulae 7 to 7]

Cardol resins can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds such as 9, 9-bis (4-oxacyclopropylmethoxyphenyl) fluorene; acid anhydride compounds such as pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic 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 benzyl alcohol; solvent-based compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidinone; phosphorus compounds such as triphenylphosphine, etc.; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.

When the binder resin is a cardmultisine resin, a solvent-type curable composition, particularly a photosensitive resin composition, comprising the cardmultisine resin has excellent developability and sensitivity during photocuring and thus has fine pattern formation ability.

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

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

The epoxy resin may further include bisphenol a epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether, but is not necessarily limited thereto.

As commercially available products of the compounds, there may be mentioned bisphenyl Epoxy resins, 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., (Nostoc corporation, Japan), and Epicot (EPIKOTE)180S75 from Eja shell epoxy Co., Ltd.); bisphenol a epoxy resins such as epicocote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 by yu jia shell epoxy limited; bisphenol F epoxy resins such as epidett 807 and 834 from yu jia shell epoxy limited; phenol novolac epoxy resins, such as EPPN 152, 154 or 157H65 from yu jia shell epoxy and EPPN 201, 202 from japan chemicals co; cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 from Ciba-Geigy A.GCorp., Inc., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from Ciba-Geigy A.G, Showa Denko 509 from U.C.C., El-Dode (Showdyne)509 from Showa Denko K.K, Elida (Araldite) CY-182, CY-192 and CY-184 from Ciba-Geigy A.G, Epicotin (EPICLON)200 and 400 from Daippon Ink chemical Co., Ltd., Eicotin Ex-Piercol (EPOTE) 871 and 400 from Euik shell epoxy Co., Ltd., EP H351032, and EP H60, Sairansys paint GmbH 62 and Gmb-5661 from Yu-Geigy Corporation; aliphatic polyglycidyl ethers such as epidett 190P and 191P by yu jia shell epoxy limited, EPOLITE (EPOLITE)100MF by Kyoeisha Yushi Kagaku Kogyo co., Ltd.), epotmp by japan fats & oils company (Nihon Yushi K.K), and the like.

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

Solvent(s)

The solvent may, for example, include alcohols, such as methanol, ethanol, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether and the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; 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, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactates such as methyl lactate, ethyl lactate, and the like; alkyl glycolates such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-hydroxypropionates such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and the like; alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methyl butyrate, and the like; or ketoacid esters such as ethyl pyruvate, etc., and further, may be N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate (phenyl cellosolve acetate), etc., but is not limited thereto.

For example, the solvent may desirably be a glycol ether, such as ethylene glycol monoethyl ether, or the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; alcohols, such as ethanol, and the like, or combinations 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 a combination thereof.

The balance, e.g., 30 to 80 wt%, e.g., 35 to 70 wt%, of the solvent may be included based on the total amount of the solvent-based curable composition. When the solvent is in the range, the solvent-based curable composition has an appropriate viscosity, and thus may have excellent coating properties when coated in a large area by spin coating and slit coating.

For example, the solvent-type curable composition may further contain one or more of the aforementioned polymerizable monomer having a carbon-carbon double bond at the terminal, polymerization initiator, light diffuser and other additives in addition to the above-mentioned components, and the specific composition or amount thereof is the same as described 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 above solvent-free curable composition and solvent-based curable composition, a color filter including the cured layer, and a display device including the color filter.

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

(S1) Pattern formation

It may be desirable to coat the solvent-free curable composition on the substrate to 0.5 to 20 micrometers in an inkjet spray method. The inkjet ejection method may form a pattern by ejecting a single color per nozzle and thus repeatedly ejecting as many times as the required number of colors, but a pattern may be formed by simultaneously ejecting the required number of colors per inkjet nozzle to reduce the process.

(S2) curing

The obtained pattern is cured to obtain pixels. Herein, the curing method may be a thermal curing or photo curing process. The thermal curing process may be performed at greater than or equal to 100 ℃, desirably in the range of 100 ℃ to 300 ℃, and more desirably in the range of 160 ℃ to 250 ℃. The photo-curing process may include irradiating actinic rays, such as ultraviolet rays of 190 nm to 450 nm, such as 200 nm to 500 nm. The irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, etc. may be used as necessary.

Other methods of producing a cured layer may include producing a cured layer by the following photolithography method using the aforementioned solvent-free curable composition and solvent-based curable composition.

(1) Coating and film formation

The aforementioned curable composition is coated on a substrate subjected to a predetermined pretreatment to have a desired thickness, for example, a thickness in the range of 2 to 10 μm, using a spin coating or slit coating method, a roll coating method, a screen printing method, a coater method, or the like. Then, the coated substrate is heated at a temperature of 70 ℃ to 90 ℃ for 1 minute to 10 minutes to remove the solvent and form a film.

(2) Exposure method

After the mask having a predetermined shape is set, the resulting film is irradiated with actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm to form a desired pattern. The irradiation is performed using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, etc. may be used as necessary.

When a high-pressure mercury lamp is used, the exposure process uses, for example, 500 mJ/cm²) Or a light dose of less than 500 mj/cm (using a 365 nm sensor). However, the light dose may vary depending on the kind of each component of the curable composition, the combination ratio thereof, and the dry film thickness.

(3) Development

After the exposure process, the exposed film is developed by dissolving and removing an unnecessary portion except for the exposed portion using an alkaline aqueous solution to form an image pattern. In other words, when developed using an alkaline developing solution, the unexposed area is dissolved and an image color filter pattern is formed.

(4) Post-treatment

The developed image pattern may be cured again by heating or irradiation with actinic rays or the like to achieve excellent qualities in terms of heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, storage stability and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.

(ligand Synthesis)

Synthesis example 1

400 g of Polyoxyethylene monomethyl ether (MPEG-400, Hannon Chemicals Inc.) and 100 g of succinic anhydride (succinic anhydride) were put together and then heated to 100 ℃ and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature (23 ℃) to obtain 500 g of a final product represented by chemical formula 2-1.

[ chemical formula 1-1]

Synthesis example 2

370 g of a final product represented by chemical formula 2-2 was obtained in the same manner as in Synthesis example 1, except that 270 g of Polyoxyethylene phenyl ether (Polyoxylene monomethylether) (PH-4, Hannong chemical Co., Ltd.) was used in place of 400 g of Polyoxyethylene monomethyl ether (MPEG-400, Hannong chemical Co., Ltd.).

[ 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 synthetic example 2, except that 114 g of glutaric anhydride (glutamic anhydride) was used instead of 100 g of succinic anhydride (succinic anhydride).

[ chemical formulas 2-3]

Synthesis example 4

270 g of Polyoxyethylene phenyl ether (PH-4, Han nong chemical Co.) and 152 g of tetrahydrophthalic anhydride (tetrahydrophthalic anhydride) were put together, and then heated to 100 ℃ and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature (23 ℃) to obtain 422 g of a final product represented by chemical formulas 2 to 4.

[ chemical formulas 2-4]

Synthesis example 5

934 g of Polyoxyethylene styrenated phenyl ether (TSP-150, Hannong chemical Co.), 100 g of succinic anhydride (succinic anhydride) and 500 g of toluene (toluene) were put together, and then heated to 100 ℃ and reacted for 24 hours. When the reaction was completed, toluene was removed to obtain 1000 g of a final product represented by chemical formula 2-5.

[ chemical formulas 2 to 5]

Synthesis example 6

620 g of a final product represented by chemical formula 2-6 was obtained according to the same method as in Synthesis example 5, except that 520 g of Polyoxyethylene cumyl phenyl ether (Polyoxylene cumyl phenyl ether) (DCP-3016, Han nong chemical Co., Ltd.) was used instead of 934 g of Polyoxyethylene styrenated phenyl ether (Polyoxylene styrenated phenyl ether).

[ chemical formulas 2 to 6]

Synthesis example 7

191 g of p-toluenesulfonyl chloride (p-toluenesulfonic chloride) and 150 ml of Tetrahydrofuran (THF) were slowly injected into a mixed solution of 400 g of Polyoxyethylene monomethyl ether (MPEG-400, Han chemical Co., Ltd.), 44 g of NaOH, 500 ml of Tetrahydrofuran (THF) and 100 ml of distilled water at 0 ℃. After 30 minutes of injection, the resulting mixture was stirred at room temperature (23 ℃) for 12 hours. When the reaction is completed, the resultant is purified through extraction, neutralization and concentration processes, and then sufficiently 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 (thiourea) were added thereto, and then stirred at 100 ℃ for 12 hours. To this was added an additional NaOH diluted solution and stirred for a further 5 hours. When the reaction was completed, the resultant was washed several times with distilled water and a dilute hydrochloric acid solution, extracted and neutralized, and then sufficiently dried in a vacuum oven to finally obtain a compound represented by chemical formula a.

[ chemical formula A ]

444 g of the compound represented by the formula A, 72 g of acrylic acid (acrylic acid), 10 g of triethylamine (triethylamine) and 300 g of THF were put together and then reacted at 50 ℃ for 12 hours, and diluted with an excess of dichloromethane (dichloromethane). Subsequently, the diluted resultant was neutralized with 5% aqueous HCl solution to separately obtain an organic layer, and the organic layer was concentrated under reduced pressure to obtain 500 g of a final product represented by chemical formulas 2 to 7.

[ chemical formulae 2 to 7]

Synthesis example 8

340 g of final products represented by chemical formulas 2 to 8 were obtained according to the same method as in synthetic example 7, except that 270 g of Polyoxyethylene phenyl ether (Polyoxylene phenyl ether) (PH-4, Han nong chemical Co., Ltd.) was used instead of 400 g of Polyoxyethylene monomethyl ether (Polyoxylene monomethylether).

[ chemical formulas 2 to 8]

Synthesis example 9

270 g of Polyoxyethylene phenyl ether (PH-4, Han nong chemical Co.) and 140 g of allyl succinic anhydride (allyl succinic anhydride) were put together, and then heated to 100 ℃ and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 410 g of a final product represented by chemical formula 3-1.

[ chemical formula 3-1]

Synthesis example 10

130 g of 2-Hydroxyethyl methacrylate (2-hydroxyethane), 100 g of succinic anhydride (succinic anhydride) and 0.1 g of MEHQ were put together, and then heated to 70 ℃ and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 230 g of a final product represented by chemical formula 3-2.

[ chemical formula 3-2]

Synthesis example 11

191 g of p-toluenesulfonyl chloride (p-toluenesulfonic chloride) and 150 ml of THF were slowly injected into a mixed solution of 600 g of Polyoxyethylene Monoallyl Ether (Polyoxylene Monoallyl Ether) (APEG-1000, Henron chemical Co., Ltd.), 44 g of NaOH, 500 ml of THF and 100 ml of distilled water at 0 ℃. After 30 minutes of injection, the resulting mixture was cooled to room temperature (23 ℃) and stirred for 12 hours. When the reaction is completed, the resultant is purified through extraction, neutralization and concentration processes, and then sufficiently 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 (thiourea) were added thereto, and then stirred at 100 ℃ for 12 hours. To this was added an additional NaOH diluted solution, and then stirred for 5 hours. When the reaction was completed, the resultant was washed and extracted with distilled water and a dilute hydrochloric acid solution, and sufficiently dried in a vacuum oven to obtain 580 g of a final product represented by chemical formula 3-3.

[ chemical formulas 3-3]

Synthesis example 12

600 g of Polyoxyethylene Monoallyl Ether (Polyoxylene Monoallyl Ether) (APEG-1000, Han chemical Co.) and 100 g of succinic anhydride (succinic anhydride) were put together, and then heated to 100 ℃ and reacted for 12 hours. When the reaction was completed, the resultant was cooled to room temperature to obtain 700 g of a final product represented by chemical formula 3-4.

[ chemical formulas 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 (acrylic acid), 10 g of triethylamine (triethylamine) and 300 g of THF were put together and then reacted at 50 ℃ for 12 hours and diluted with an excess of dichloromethane (dichloridedimethane). Subsequently, neutralization was performed using 5% aqueous HCl solution to separately obtain an organic layer, and the organic layer was concentrated under reduced pressure to obtain 500 g of a final product represented by chemical formula 3-5.

[ chemical formulas 3-5]

Synthesis example 14

600 g of Polyoxyethylene Monoallyl Ether (Polyoxylene Monoallyl Ether) (APEG-1000, Han chemical Co.), 124 g of Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicylo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride), 500 g of toluene (toluene) and 60 g of triethyleneamine (triethyleneamine) were put together, and then heated to 100 ℃ 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 a final product represented by chemical formula 4-1 was obtained.

[ chemical formula 4-1]

Comparative Synthesis example 1

10 g of 2-mercapto-1-ethanol (2-mercapto-1-ethanol), 13.3 g of 2-2- (2-methoxyethoxy) ethoxyacetic acid (2-2- (2-methoxyethoxy) ethoxyacetic acid) and 2.1 g of p-toluenesulfonic acid monohydrate (p-toluenesulfonic acid monohydrate) were placed in a 2-neck round-bottom flask, respectively, and then dissolved in 300 ml of cyclohexane (cyclohexane). After dean stark was fastened to the injection hole, a condenser (condensor) was attached thereto. After the solution was refluxed for 8 hours, the reaction was complete. (check the final amount of water collected in dean stark). The reaction was transferred to a separatory funnel (separation funnel), extracted (extraction), neutralized to remove the solvent, and dried in a vacuum oven to obtain a final product represented by chemical formula C-1.

[ chemical formula C-1]

(preparation of a Dispersion of Quantum dots surface-modified with ligands)

Preparation example 1

A magnetic rod was placed in a 3-neck round-bottom round flask, and a quantum dot-CHA (cyclohexyl acetate) solution (solid content: 26 wt% to 27 wt%) was weighed and added thereto. To which a ligand represented by chemical formula 2-1 is added.

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

The surface-modified quantum dot was stirred with a monomer (1,6-hexanediol diacrylate) represented by chemical formula 5-2, Miwon Commercial Co., Ltd.) for 12 hours to obtain a surface-modified quantum dot dispersion.

[ 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

Surface-modified quantum dot dispersions were 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

Surface-modified quantum dot dispersions were 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 of the quantum dot dispersions according to preparation examples 1 to 14 and comparative preparation example 1 was measured three times with a Particle Size Analyzer (Particle Size Analyzer) by using a Micro Particle Size Analyzer (Micro 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 exhibited a narrow particle distribution, which indicates that the quantum dots are well dispersed in a high boiling point and high surface tension solvent, but the quantum dot dispersion according to comparative preparation example 1 exhibited a wide particle distribution, which indicates that the quantum dots are not well dispersed in a high boiling point and high surface tension solvent.

(preparation of solvent-free curable composition)

Example 1

The dispersion obtained in preparation example 1 was weighed, and then mixed with a monomer represented by Chemical formula 5-2 and diluted, and a polymerization inhibitor (methyl hydroquinone, Tokyo Chemical Industry co., Ltd.) was added thereto, and then stirred for 5 minutes. Subsequently, a photoinitiator (TPO-L, polynetron) was injected thereinto, and a light diffuser (TiO) was added thereto₂(solid content: 50% by weight); di graphics Technology, inc (Ditto Technology)). The overall dispersion was stirred for 1 hour to prepare a solvent-free curable composition. The composition comprises 40 wt% of quantum dots, 48 wt% of a monomer represented by chemical formula 3-2, 1 wt% of a polymerization inhibitor, 3 wt% of a photoinitiator, and 8 wt% of a light diffuser, based on the total amount of the solvent-free curable composition.

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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 the solvent-free curable compositions according to examples 1 to 14 and comparative example 1 was coated to a thickness of 15 μm on a Yellow Photoresist (YPR) using a spin coater (800 revolutions per minute (rpm), 5 seconds, oppoki kott (optical) MS-a150, sank limited (Mikasa co., Ltd.), and exposed to 5000 millijoules (mJ) with a 395 nm Ultraviolet (UV) exposure machine under a nitrogen atmosphere (83 ℃, 10 seconds). Subsequently, a single film sample of 2 centimeters by 2 centimeters (cm) each was loaded in an integrating sphere device (QE-2100, tsukamur Electronics, Ltd.) and the light conversion rate was measured. Thereafter, the loaded single film sample was dried at 180 ℃ for 30 minutes in a nitrogen atmosphere drying oven, and then the light retention after exposure before drying was measured, and the measurement results are shown in table 3.

(Table 3)

	Light conversion Rate (%)	Light holding ratio (%)	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 compositions according to the examples exhibited improved optical characteristics.

(preparation of solvent-type curable composition)

Example 15

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

Specifically, a photopolymerization initiator was dissolved in a solvent, and the solution was sufficiently stirred at room temperature for 2 hours. Subsequently, a binder resin was added together with the quantum dot dispersion of preparation example 1, a dispersant (digo (TEGO) D685, made by winning inc (Evonik Corp.), and the resulting mixture was stirred again at room temperature 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 thereof was filtered three times to remove impurities and prepare a photosensitive resin composition.

1) Quantum dot dispersion: preparation example 1

2) Binder resin: 25% by weight of Casino multisystem adhesive resin (TSR-TA01, Takema (TAKOMA))

3) Polymerizable monomers: 5.4% by weight of pentaerythritol hexamethylacrylate (DPHA, Nippon Kayaku Co., Ltd.)

4) Photopolymerization initiator: 0.7 wt% of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (TPO, Sigma-Aldrich Corporation)

5) Solvent: 39% by weight dimethyl adipate (dimethyl adipate)

6) Light diffusing agent: 39% by weight of a titanium dioxide dispersion (TiO)₂Solid content: 20 wt%, average particle diameter: 200 nm, Dituo Technique Co Ltd

7) Other additives: 0.9% by weight of a 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 in 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 coated to a thickness of 6 μm on a single surface of a glass substrate using a spin coater (150 revolutions per minute (rpm), opu kott (optical) MS-a150, chimpanzee (Mikasa) ltd), respectively, and then dried on a hot plate (hot-plate) of a hot-plate (hot-plate) at 80 ℃ for 1 minute to obtain a film. Then, the power consumption (power) was 100 mJ/cm²) After the ultraviolet irradiation, the light conversion rate was measured with an exposure machine (ghi broadband, Ushio Inc.) by performing post-baking (POB) in a convection cleaning oven (Jongro) at 180 ℃ for 30 minutes, and the results are shown in tables 4 and 5.

(Table 4)

(unit:%)

(Table 5)

(unit:%)

As shown in tables 4 and 5, the solvent-type curable composition prepared by using the surface-modified quantum dot according to the example exhibited small deterioration of light conversion rate due to the color filtering process, and thus exhibited high light retention rate.

While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, it should be understood that the above-described embodiments are exemplary, and are not to be construed as limiting the invention in any way.

Claims

1. A quantum dot surface-modified with a compound represented by chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1,

R¹is a carboxyl group, — P (═ O) (OH)₂Or a thiol group, and

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

[ 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 formulas 1B-1-1 to 1B-7-2,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer of 1 to 20, and

n is an integer of 1 or 2.

2. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by chemical formula 2:

[ chemical formula 2]

Wherein, in chemical formula 2,

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

L¹is "C1 to C20 alkylene group unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate group" or "C3 to C20 cycloalkylene group unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate group" or "represented by one of 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 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group, and

m is an integer of 1 to 20.

3. The quantum dot of claim 1, wherein

Wherein, in chemical formula 2,

R²is "C1 to C20 alkyl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C1 to C20 alkoxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl", "C6 to C20 aryl which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl" or "C6 to C20 aryloxy which is unsubstituted or substituted by C1 to C10 alkyl or C6 to C12 aryl",

L¹is "unsubstituted C1 to C20 alkylene" or "unsubstituted C3 to C20 cycloalkylene",

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group, and

m is an integer of 1 to 20.

4. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by one of chemical formulae 2-1 to 2-8:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

[ chemical formulas 2 to 6]

[ chemical formulae 2 to 7]

[ chemical formulas 2 to 8]

5. The quantum dot of claim 1, wherein

In the chemical formula 1, the first and second,

R¹is a carboxyl or thiol group, and

R²is "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³is "substituted or unsubstituted vinyl", "not substitutedA C1 to C20 alkyl group substituted or not with a vinyl, allyl, epoxy or (meth) acrylate group "or a" C2 to C20 alkenyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group ", and

[ 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 formulas 1B-1-1 to 1B-7-2,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

L²is a single bond, — C (═ O) O —, or — -S —, and

L³represented by chemical formula 1C-1 or chemical formula 1C-2,

[ chemical formula 1C-1]

[ chemical formula 1C-2]

Wherein, in chemical formula 1C-1 or chemical formula 1C-2,

L⁵is a substituted or unsubstituted C1 to C20 alkylene group,

m is an integer of 1 to 20, and

n is an integer of 1 or 2.

6. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by chemical formula 3:

[ chemical formula 3]

Wherein, in chemical formula 3,

R⁴is "unsubstituted orA C1 to C20 alkyl group substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group, a C1 to C20 alkoxy group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group, a C6 to C20 aryl group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group, or a C6 to C20 aryloxy group unsubstituted or substituted with a vinyl group, allyl group, epoxy group or (meth) acrylate group, or represented by chemical formula 1A,

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

R³is "substituted or unsubstituted vinyl", "C1 to C20 alkyl unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate" or "C2 to C20 alkenyl unsubstituted or substituted with vinyl, allyl, epoxy or (meth) acrylate",

R⁵is a carboxyl group or a thiol group, and,

L⁶and L⁷Independently a substituted or unsubstituted C1 to C20 alkylene,

L⁸is a single bond, -S, -C (═ O) -, or-OC (═ O) -,

L⁹is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and

m is an integer of 1 to 20.

7. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by chemical formula 4:

[ chemical formula 4]

Wherein, in chemical formula 4,

R⁴is "C1 to C20 alkyl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C1 to C20 alkoxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", "C6 to C20 aryl group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group" or "C6 to C20 aryloxy group unsubstituted or substituted with a vinyl, allyl, epoxy or (meth) acrylate group", or "represented by chemical formula 1A",

[ chemical formula 1A ]

Wherein, in chemical formula 1A,

L⁶and L⁷Independently a substituted or unsubstituted C1 to C20 alkylene,

L⁸is a single bond, -S, -C (═ O) -, or-OC (═ O) -,

L¹⁰is represented by one of 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 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]

Wherein, in chemical formulas 1B-1-1 to 1B-7-1,

R^aand R^bIndependently a hydrogen atom or a carboxyl group,

R^cis O, S, NH, C1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 allylamino, and

m is an integer of 1 to 20.

8. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by one of chemical formulae 3-1 to 3-6:

[ chemical formula 3-1]

[ chemical formula 3-2]

[ chemical formulas 3-3]

[ chemical formulas 3-4]

[ chemical formulas 3-5]

[ chemical formulas 3-6]

9. The quantum dot of claim 1, wherein the compound represented by chemical formula 1 is represented by chemical formula 4-1:

[ chemical formula 4-1]

10. The quantum dot of claim 1, wherein the quantum dot has a maximum fluorescence emission wavelength at 500 to 680 nanometers.

11. A solvent-free curable composition comprising

The quantum dot of claim 1; and

a polymerizable monomer having a carbon-carbon double bond at a terminal.

12. The solvent-free curable composition of claim 11, wherein the polymerizable monomer has a molecular weight of 220 g/mole to 1,000 g/mole.

13. The solvent-free curable composition according to claim 11, wherein the polymerizable monomer is represented by chemical formula 5:

[ chemical formula 5]

Wherein, in chemical formula 5,

R¹⁰¹and R¹⁰²Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L¹⁰¹and L¹⁰³Independently is a substituted or unsubstituted C1 to C10 alkylene group, and

L¹⁰²is a substituted or unsubstituted C1 to C10 alkylene or ether (— O-).

14. The solvent-free curable composition of claim 11, comprising:

1 to 60% by weight of the quantum dots, and

40 to 99 weight percent of the polymerizable monomer.

15. The solvent-free curable composition of claim 11, further comprising a polymerization initiator, a light diffuser, or a combination thereof.

16. A solvent-borne curable composition comprising:

the quantum dot of claim 1;

a binder resin; and

a solvent.

17. The solvent-borne curable composition of claim 16, comprising

1 to 40 weight percent of the quantum dots;

1 to 30% by weight of the binder resin; and

the balance of the solvent.

18. The solvent-borne curable composition according to claim 16, further comprising a polymerizable monomer, a polymerization initiator, a light diffuser, or a combination thereof.

19. A cured layer produced using the solvent-free curable composition of claim 11 or the solvent-based curable composition of claim 16.

20. A color filter comprising the cured layer of claim 19.