KR102360988B1 - Curable composition including quantum dot, resin layer using the same and display device - Google Patents

Abstract

[화학식 2]

(상기 화학식에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) quantum dots; (B) binder resin; (C) a polymerizable compound comprising a first polymerizable compound and a second polymerizable compound; and (D) a solvent, wherein the first polymerizable compound is represented by the following Chemical Formula 1-2, the second polymerizable compound is represented by the following Chemical Formula 2, and the first polymerizable compound and the second polymerizable compound A curable composition in which the compound is contained in a weight ratio of 5:1 to 1:1, a resin film prepared using the curable composition, and a display device including the resin film are provided.
[Formula 1-2]

[Formula 2]

(In the above formula, each substituent is as defined in the specification.)

Description

Curable composition containing quantum dots, resin film and display device using the same {CURABLE COMPOSITION INCLUDING QUANTUM DOT, RESIN LAYER USING THE SAME AND DISPLAY DEVICE}

The present disclosure relates to a curable composition containing quantum dots, a resin film using the same, and a display device including the resin film.

The color filter is used for liquid crystal display devices, optical filters of cameras, etc., and is manufactured by coating fine areas colored with three or more colors on a solid-state imaging device or a transparent substrate. Such a colored thin film may be generally formed by a dyeing method, a printing method, a pigment dispersion method, an inkjet method, and the like.

In the dyeing method, an image with a dyeing base such as natural photosensitive resin such as gelatin, amine-modified polyvinyl alcohol, or amine-modified acrylic resin is formed on a substrate in advance, and then dyed with a dye such as a direct dye to form a colored thin film. In the case of the dyeing method, the clarity and dispersibility of commonly used dyes and resins themselves are good, but there are disadvantages in that light resistance, moisture resistance and heat resistance are inferior.

In the printing method, a colored thin film is formed by printing using an ink in which a pigment is dispersed in a thermosetting or photocurable resin, and then curing with heat or light. In the case of the dyeing method, the material cost can be reduced compared to other methods, but there is a disadvantage in that it is difficult to form a highly precise and detailed image.

The pigment dispersion method is a method of forming a colored thin film by repeating a series of processes of coating, exposing, developing, and thermally curing a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method has advantages in that heat resistance and durability can be improved and the thickness of the film can be maintained uniformly. In addition, the implementation of the fine pattern is excellent and the manufacturing method is relatively easy, so it is universally employed. For example, in Korean Patent Publication No. 1992-7002502, Korean Patent Publication No. 1994-0005617, Korean Patent Publication No. 1995-0011163, Korean Patent Publication No. 1995-7000359, etc., the preparation of a colored photosensitive resin composition using a pigment dispersion method A method is being proposed.

However, the method requires a process of coating, exposing, developing, and curing each of red (R), green (G) and blue (B) to form a pixel, so the manufacturing process is very long and the control factor between the processes is very long. As the number increases, it is difficult to manage the yield.

In order to overcome this problem, various new process methods have been used to replace the conventional pigment dispersion method, and a representative one is the inkjet printing method. In the inkjet printing method, a light blocking layer such as a black matrix is formed on a glass substrate and ink is injected into the pixel space. In the inkjet printing method, since separate processes such as coating, exposure, and development are unnecessary in manufacturing the color filter, materials required for the process can be reduced and the process can be simplified.

When a color filter is manufactured using the inkjet ink as described above, it is common to use a mixture of two or more types of pigments in order to secure required color characteristics. In particular, in a red filter, a dicytopyrrolopyrrole-based red pigment, for example, C.I. Pigment Red 254 is mainly used. In addition, as a toning pigment, an anthraquinone-based red pigment, for example, C.I. Pigment Red 177 may be added, or an isoindolinone-based yellow pigment such as C.I. It is common to add Pigment Yellow 139. Optionally other yellow and orange pigments, for example C.I. Pigment Yellow 138, C.I Pigment Yellow 150, C.I. Pigment Orange 38, etc. may be added. The above pigments have excellent color characteristics, light resistance and heat resistance, and have been commonly used as a material for color filters. However, as the use of LCD color filters has recently expanded, the level of required properties is increasing day by day. Therefore, in order to improve color characteristics such as brightness and color purity when transmitted, research on atomizing and finely dispersing the pigments is being conducted, but in fact, there is a limit to the expression of color characteristics of a color filter only with the combination of these pigments.

One embodiment is to provide a curable composition containing quantum dots that can prevent reduction in luminance while minimizing cure shrinkage during thermal processing.

Another embodiment is to provide a resin film prepared using the curable composition.

Another embodiment is to provide a display device including the resin film.

One embodiment is (A) quantum dots; (B) binder resin; (C) a polymerizable compound comprising a first polymerizable compound and a second polymerizable compound; and (D) a solvent, wherein the first polymerizable compound is represented by the following Chemical Formula 1-2, the second polymerizable compound is represented by the following Chemical Formula 2, and the first polymerizable compound and the second polymerizable compound The compound provides a curable composition included in a weight ratio of 5:1 to 1:1.

[Formula 1-2]

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delete

[Formula 2]

In Formula 1-2 and Formula 2,

R ¹ is represented by the following formula (3),

R ² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ to L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[Formula 3]

In Formula 3,

R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The first polymerizable compound and the second polymerizable compound may be included in a weight ratio of 3:1 to 1:1.

The quantum dot may be a quantum dot that absorbs light of 360 nm to 780 nm and emits fluorescence at 500 nm to 700 nm.

The quantum dots may include green quantum dots and red quantum dots.

The quantum dots may be included in an amount of 1 wt% to 40 wt% based on the total amount of the curable composition.

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

The binder resin may have a weight average molecular weight of 500 g/mol to 50,000 g/mol.

The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, 2-butoxyethanol , N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The curable composition may further include a diffusing agent.

The dispersing agent may be included in an amount of 0.1 wt% to 20 wt% based on the total amount of the curable composition.

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

The curable composition may further include a thiol-based additive.

The thiol-based additive may include at least two or more functional groups represented by the following Chemical Formula 4 at the terminal thereof.

[Formula 4]

In Formula 4,

L ¹³ and L ¹⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted It is a C2 to C20 heteroarylene group.

The curable composition includes 1 wt% to 40 wt% of the quantum dots, 1 wt% to 40 wt% of the binder resin, 0.1 wt% to 20 wt% of the polymerizable compound, and the remaining amount of the solvent with respect to the total amount of the curable composition can do.

The curable composition comprises malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; Or it may further include a combination thereof.

Another embodiment provides a resin film prepared using the curable composition.

Another embodiment provides a display device including the resin film.

The display device may further include a color filter and a liquid crystal layer, the color filter may be located on one side of the liquid crystal layer, and the resin film may be located on the other side of the liquid crystal layer.

The specific details of other aspects of the invention are included in the detailed description below.

In the curable composition according to an embodiment, by mixing and using a polymerizable compound having a specific structure in a specific weight ratio, it is possible to minimize the curing shrinkage during the thermal process while maintaining the luminance equal to or higher than that of the prior art, so that the cured layer of the thermosetting composition (Resin film) It is possible to solve the problem of interfacial loss or cracks during lamination.

1 is a schematic diagram illustrating a display device (LCD) to which a resin film manufactured using a curable composition according to an embodiment is applied.

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

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, , "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, and "heteroarylene group" means a C3 to C20 hetero It means an arylene group, and "alkoxyylene group" means a C1 to C20 alkoxyylene group.

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

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom among N, O, S and P is included in the formula.

In addition, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" is "acrylic acid" and "methacrylic acid" “It means that both are possible.

Unless otherwise specified herein, "combination" means mixing or copolymerization.

As used herein, the cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 5-1 to 5-11 are included in the backbone of the resin.

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

In addition, unless otherwise specified in the present specification, "*" means a moiety connected to the same or different atoms or chemical formulas.

The curable composition according to an embodiment includes (A) quantum dots; (B) binder resin; (C) a polymerizable compound comprising a first polymerizable compound and a second polymerizable compound; and (D) a solvent, wherein the first polymerizable compound is represented by the following Chemical Formula 1-2, the second polymerizable compound is represented by the following Chemical Formula 2, and the first polymerizable compound and the second polymerizable compound The compound is included in a weight ratio of 5:1 to 1:1.

[Formula 1-2]

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delete

[Formula 2]

In Formula 1-2 and Formula 2,

R ¹ is represented by the following formula (3),

R ² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ to L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[Formula 3]

In Formula 3,

R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the first polymerizable compound and the second polymerizable compound may be included in a weight ratio of 3:1 to 1:1, for example, 3:1 to 2:1 by weight.

One embodiment relates to a curable composition including quantum dots, such as a thermosetting composition, which has recently been established as a new technological trend in the display field. The quantum dot-containing curable composition applied to the display consists of a binder resin, a colorant, a solvent, an additive, etc. like the existing curable composition, and uses quantum dots instead of colorants such as pigments/dyes as a material to produce color characteristics, and additionally light diffusion It may further include an agent and the like.

Quantum dots represented by CdSe, InP, etc. have rapidly developed in terms of luminous efficiency (Quantum Yield), and synthetic methods with luminous efficiency close to 100% have been introduced. An example is the commercialization of QD SUHDTV to which quantum dot sheets are applied. As the next version, QD TV is being developed as a self-emitting version rather than a filling method in the color resist layer by including quantum dots in the color resist layer of the existing LED TV (pigments and dyes are excluded). The core of TV development to which this quantum dot-containing resin composition is applied is maintaining the patterning properties of the composition and the light efficiency of quantum dots in processes such as thermal processing (pre-baking)-exposure-development-washing-deposition and thermal processing (post-baking). The key to product development is whether to do it or not to implement the pattern well.

However, the method of including quantum dots in the color resist layer of the existing LED TV so that the color resist layer emits light is disadvantageous in terms of cost and there is a limit to minimizing the shrinkage rate in the thermal process. After inserting a quantum dot sheet as a separate layer without being included in the resist layer, a blue light (light source) is incident on the quantum dot sheet, and research is being conducted on a method of converting it into white light. At this time, since blue light should be converted into white light, the quantum dot sheet should include both green quantum dots and red quantum dots.

The quantum dots, which play a key function in converting blue light, are surrounded by a hydrophobic ligand, and when the quantum dots having such hydrophobic properties are added to a composition having hydrophilicity (eg, a curable composition containing an epoxy-based binder resin, etc.), dispersibility This falling problem is occurring, and in order to solve this dispersibility problem, a lot of research on ligand substitution and passivation on the surface of quantum dots is being conducted. However, the patterning process using the quantum dot-containing curable composition causes a significant decrease in sensitivity, and there is a problem in that it is difficult to ensure patternability.

In addition, in the case of the quantum dot-containing curable composition, the content of inorganic particles is large, and since the content of organic matter is relatively low, fairness is deteriorated. Due to this, it is very difficult to form a pattern shape in the forward direction, not only due to deterioration of developability, but also due to deterioration of the melting characteristic of the pattern during the post-baking process.

The conventionally known undercut improvement of photoresist is improved by applying a binder resin with a low melting point such as cardo-based resin to the composition to post-baking the undercut after development, or by introducing an epoxy group into the binder resin to enhance adhesion in the pre-baking process. However, the curable composition containing quantum dots has a high mineral content as described above, so melting properties do not appear only by application of cardo-based resin, so there is a limitation in improving undercut (curable compositions containing quantum dots have a high mineral content, so they do not melt even after post-baking. ), the binder resin into which the epoxy group is introduced has a problem in that the residue properties are greatly reduced. In addition, since the acrylic resin is one cause of lowering the efficiency of the quantum dots in the composition, it is difficult to use the conventionally known acrylic resin as it is.

Furthermore, the acrylic resin or epoxy-based binder resin, which is a binder resin used in the conventional quantum dot-containing curable composition, shows a cure shrinkage of about 15% to 20% in the post-baking step during the thermal curing process, and in an additional thermal process step after post-baking It shows a cure shrinkage of about 5%, so there is a problem in that the interface peeling off of the resin film occurs, and there is a problem in that cracks in the resin film occur even if the interface peeling off does not occur. In the case of an epoxy-based binder resin, quantum efficiency or dispersibility of quantum dots is lowered by an epoxy curing mechanism and an epoxy structure (as described above, the quantum dot surface is hydrophobic, whereas the network formed by the epoxy structure has hydrophilicity) In the case of acrylic resins, there is no problem of lowering quantum efficiency of quantum dots because of compatibility with quantum dots.

However, according to one embodiment, as a polymerizable compound in the quantum dot-containing curable composition, the first polymerizable compound represented by Formula 1-2 and the second polymerizable compound represented by Formula 2 are mixed in a ratio of 5:1 to 1:1. By using a mixture in a weight ratio, for example, 3:1 to 1:1, for example, 3:1 to 2:1, it does not negatively affect quantum efficiency or dispersion of quantum dots, thereby preventing luminance degradation and at the same time thermal process By minimizing the curing shrinkage during curing, it is possible to maintain excellent film quality of the resin film (cured film) (that is, problems such as interfacial separation of the resin film and cracks can be solved).

Hereinafter, each component will be described in detail.

(A) Quantum dots

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

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

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

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

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

In one embodiment, since interest in the environment has recently increased significantly around the world and regulations on toxic substances are being strengthened, instead of a light emitting material having a cadmium-based core, quantum yield is somewhat low, but eco-friendly Although a non-cadmium-based light emitting material (InP/ZnS) was used, it is not necessarily limited thereto.

The structure of the quantum dot is not particularly limited, but in the case of the quantum dot having the core/shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example 5 nm to 15 nm.

For example, the quantum dots may include red quantum dots, green quantum dots, or a combination thereof. For example, the quantum dots may include both green quantum dots and red quantum dots. In this case, the green quantum dot may be included in an amount greater than that of the red quantum dot. The red quantum dots may have an average particle diameter of 10 nm to 15 nm. The green quantum dots may have an average particle diameter of 5 nm to 8 nm.

On the other hand, for the dispersion stability of the quantum dots, the photosensitive resin composition according to an embodiment may further include a dispersing agent. The dispersing agent helps to uniformly disperse a light conversion material such as quantum dots in the curable composition, and any nonionic, anionic or cationic dispersant may be used. Specifically, polyalkylene glycol or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide Adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1 wt% to 100 wt%, such as 10 wt% to 20 wt%, based on the solid content of the light conversion material such as quantum dots.

For example, the quantum dots may be included in an amount of 1 wt% to 40 wt%, such as 1 wt% to 20 wt%, based on the total amount of the curable composition according to an embodiment. When the quantum dots are included within the above range, the light conversion rate is excellent, the pattern characteristics and the development characteristics are not impaired, and excellent processability may be obtained.

(B) binder resin

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

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof 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 wt% to 50 wt%, for example 10 wt% to 40 wt%, based on the total amount of the acrylic resin.

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

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

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

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

The cardo-based resin may include a repeating unit represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁷ R ¹⁸ , SiR ¹⁹ R ²⁰ (wherein R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or Any one of the linking groups represented by Formulas 5-1 to 5-11,

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

(In Formula 5-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.)

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

Z ² is an acid anhydride residue,

t1 and t2 are each independently an integer of 0 to 4.

The weight average molecular weight of the cardo-based resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the cardo-based resin is within the above range, a pattern can be formed without a residue when the photosensitive organic film is manufactured, there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based resin may include a functional group represented by the following Chemical Formula 6 at at least one of both terminals.

[Formula 6]

In Formula 6,

Z ³ may be represented by the following Chemical Formulas 6-1 to 6-7.

[Formula 6-1]

(In Formula 6-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

(In Formula 6-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group, or C2 to C20 alkenylamine group.)

[Formula 6-6]

[Formula 6-7]

The cardo-based resin may include, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, phenol anhydride compounds such as rylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid 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 compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the binder resin includes a cardo-based resin, the developability of the photosensitive resin composition including the binder resin is excellent, and the sensitivity during photocuring is good, so that it is excellent in fine pattern formation.

The binder resin may include a thiol group.

The binder resin may be included in an amount of 1 wt% to 40 wt%, for example 3 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(C) polymerizable compound

The curable composition according to an embodiment includes a polymerizable compound, the polymerizable compound includes a first polymerizable compound and a second polymerizable compound having different structures, and the first polymerizable compound is in Formula 1 -2, the second polymerizable compound may be represented by Formula 2, and the first polymerizable compound and the second polymerizable compound may be included in a weight ratio of 5:1 to 1:1.

For example, the first polymerizable compound and the second polymerizable compound may be included in a weight ratio of 3:1 to 1:1, such as 3:1 to 2:1.

Meanwhile, the curable composition according to the exemplary embodiment may further include a monomer or oligomer generally used in a conventional curable composition.

The polymerizable compound may be used after treatment with an acid anhydride in order to provide better developability.

The polymerizable compound may be included in an amount of 0.1 wt% to 20 wt%, such as 1 wt% to 10 wt%, based on the total amount of the curable composition. When the polymerizable compound is included within the above range, curing occurs sufficiently in the pattern forming process, and reliability is excellent, and heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern are also excellent.

(D) solvent

The curable composition according to an embodiment may include, as a solvent, alcohols such as methanol and ethanol; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, -n-butyl acetate, and isobutyl acetate; lactic acid alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; or ketonic acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, cyclohexyl acetate, etc. may be used, but are not limited thereto.

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

For example, the solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, 2-part The polar solvent may include oxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The solvent may be included in a balance based on the total amount of the photosensitive resin composition, for example, 20 wt% to 80 wt%, for example 35 wt% to 80 wt%. When the solvent is included within the above range, since the curable composition has an appropriate viscosity, it may have excellent coatability during spin coating and large-area coating using a slit.

Diffuser (or Diffuser Dispersion)

The curable composition according to an embodiment may further include a diffusing agent.

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

The diffusing agent reflects light not absorbed by the quantum dots, and enables the quantum dots to absorb the reflected light again. That is, the diffusing agent may increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

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

The dispersing agent may be included in an amount of 0.1 wt% to 20 wt%, for example, 0.1 wt% to 5 wt%, based on the solid content, based on the total amount of the curable composition. When the diffusing agent is included in an amount of less than 0.1% by weight based on the total amount of the curable composition, it is difficult to expect an effect of improving the light conversion efficiency by using the diffusing agent, and when it is included in an amount exceeding 20% by weight, the pattern characteristics may be deteriorated there is

other additives

In order to improve the stability and dispersibility of the quantum dots, the curable composition according to an embodiment may further include a thiol-based additive.

The thiol-based additive may be substituted on the shell surface of the quantum dots to improve the dispersion stability of the quantum dots to a solvent, thereby stabilizing the quantum dots.

The thiol-based additive may have 2 to 10, for example, 2 to 4 thiol groups (-SH) at the terminal depending on the structure thereof.

For example, the thiol-based additive may include at least two or more functional groups represented by the following Chemical Formula 4 at the terminal thereof.

[Formula 4]

In Formula 4,

L ¹³ and L ¹⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted It is a C2 to C20 heteroarylene group.

For example, specific examples of the thiol-based additive include pentaerythritol tetrakis (3-mercaptopropionate) represented by the following Chemical Formula 4a, and trimethylolpropane tris represented by the following Chemical Formula 4b. (3-mercaptopropionate) (trimethylolpropane tris (3-mercaptopropionate)), pentaerythritol tetrakis (mercapto acetate) represented by the following formula 4c Pentaerythritol tetrakis (mercaptoacetate), trimethylolpropane represented by the following formula 4d From the group consisting of tris (2-mercaptoacetate) (trimethylolpropane tris (2-mercaptoacetate)), glycol di-3-mercaptopropionate (Glycol di-3-mercaptopropionate) represented by the following formula 4e, and combinations thereof Any one selected can be mentioned.

[Formula 4a]

[Formula 4b]

[Formula 4c]

[Formula 4d]

[Formula 4e]

The thiol-based additive may be included in an amount of 0.1 wt% to 10 wt%, such as 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. For example, the thiol-based additive may be included in an amount of 0.1 wt% to 10 wt%, for example 0.5 wt% to 8 wt%, based on the total amount of solids constituting the photosensitive resin composition. When the thiol-based additive is included within the above range, the stability of the light conversion material such as quantum dots can be improved, and the thiol group in the component reacts with the acrylic group of the resin or monomer to form a covalent bond, thereby improving the heat resistance of the light conversion material such as quantum dots may have an effect.

The curable composition according to an embodiment may further include a polymerization inhibitor including a hydroquinone-based compound, a catechol-based compound, or a combination thereof. As the curable composition according to an embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, it is possible to prevent crosslinking at room temperature during exposure after printing (coating) the curable composition.

For example, the hydroquinone-based compound, catechol-based compound, or a combination thereof is hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyroga Rol, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum (Tris(N-hydroxy-N) -nitrosophenylaminato-O,O')aluminium) 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, and the polymerization inhibitor in the dispersion form is 0.001 wt% to 1 wt%, such as 0.01 wt% to 0.1 wt%, based on the total amount of the curable composition can be included as When the stabilizer is included within the above range, it is possible to solve the problem of aging at room temperature and, at the same time, to prevent a decrease in sensitivity and a surface peeling phenomenon.

The curable composition according to an embodiment may include malonic acid in addition to the thiol-based additive and polymerization inhibitor; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; Or it may further include a combination thereof.

For example, the curable composition 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, and an epoxy group in order to improve adhesion to the substrate.

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

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

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

As the fluorine-based surfactant, BM-1000 ^® of BM Chemie, BM-1100 ^® , etc.; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® and the like of Dai Nippon Inky Chemical High School Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , copper FC-170C ^® , copper FC-430 ^® , copper FC-431 ^® , etc.; Saffron S-112 ^® , Copper S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® from Asahi Grass Co., Ltd., etc.; SH-28PA ^® , Copper-190 ^® , Copper-193 ^® , SZ-6032 ^® , SF-8428 ^® , etc. of Toray Silicone Co., Ltd.; F-482, F-484, F-478, F-554 commercially available fluorine-based surfactants of DIC Co., Ltd. may be used.

The fluorine-based surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the curable composition. When the fluorine-based surfactant is included within the above range, coating uniformity is secured, stains do not occur, and wettability to a glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be further added to the curable composition within a range that does not impair physical properties.

Another embodiment provides a resin film prepared using the above-described curable composition.

The manufacturing method of the resin film includes the steps of forming a pattern by applying the above-described curable composition to a substrate by an inkjet spraying method (S1); and curing the pattern (S2).

(S1) forming a pattern

The curable composition is preferably applied on the substrate in a thickness of 0.5 to 10 μm by an inkjet dispersion method. In the inkjet jetting, a pattern may be formed by jetting only a single color and repeatedly jetting according to the required number of colors, or a pattern may be formed by simultaneously jetting the required number of colors in order to reduce the process.

(S2) curing step

A cured resin film can be obtained by curing the obtained pattern. At this time, as a method of hardening, a thermosetting process is preferable. The thermosetting process may be a process of heating at a temperature of about 100° C. or higher for about 3 minutes to first remove the solvent in the curable composition, and then curing it by heating at a temperature of 160° C. to 300° C., more preferably 180 It may be a process of curing by heating at a temperature of ℃ to 250 ℃ for about 30 minutes.

Another embodiment provides a display device including the resin film.

The display device may further include a color filter and a liquid crystal layer, the color filter may be positioned on one side of the liquid crystal layer, and the resin film may be positioned on the other side of the liquid crystal layer.

Referring to FIG. 1 , the display device is manufactured using color resist layers 6 , 7 , 8 , in which a color filter is present by a column spacer based on a liquid crystal layer 3 , and a curable composition according to an embodiment. The resin films 2 are positioned to face each other. An overcoat layer 4 may further exist between the color resist layers 6 , 7 , 8 and the liquid crystal layer 3 , and a glass 5 on one surface of the color resist layers 6 , 7 , 8 and the overcoat layer 4 . ) may exist. The glass 5 may be positioned in a direction opposite to the liquid crystal layer 3 . In addition, a silica deposition layer (not shown) may be present on one surface of the resin film, and the silica deposition layer absorbs blue light from a light source (Blue LED) through the light guide plate 1 . In the display device according to FIG. 1, since the layer (resin film) 2 containing the quantum dots 9 and 10 is configured as a separate layer from the color resist layers 6, 7, 8, the quantum efficiency of the quantum dots is reduced. can be prevented Also, the light guide plate 1 may be a glass light guide plate, not a PMMA light guide plate. By using the glass light guide plate 1 instead of the PMMA light guide plate, the thickness of the panel can be reduced, so that the luminance improvement effect can be expected.

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

(Preparation of curable composition)

Examples 1 to 5 and Comparative Examples 1 to 5

Curable compositions according to Examples 1 to 5 and Comparative Examples 1 to 5 were prepared with the compositions shown in Table 1 by using the components mentioned below.

(A) Quantum dots

(A-1) InP/ZnS quantum dots (fluorescence λ _em =635nm, FWHM=40nm, Red QD, Hansol Chemical)

(A-2) InP/ZnS quantum dots (fluorescence λ _em =538nm, FWHM=40nm, Green QD, Hansol Chemical)

(B) binder resin

Cardo-based resin (TB04, Tacoma)

(C) polymerizable compound

(C-1) V1000 (Osaka Organic Chemical Industry Ltd.)

(C-2) DPCA-120 (NIKKA FINE TECHNO. CO., LTD.)

(C-3) M240 (Miwon Specialty Chemical Co., Ltd.)

(C-4) M360 (Miwon Specialty Chemical Co., Ltd.)

(C-5) dipentaerythritol hexamethacrylate (DPHA, NIKKA FINE TECHNO. CO., LTD.)

(D) solvent

Propylene glycol monomethyl ether acetate (PGMEA, Daicel Chemical)

(E) diffusion agent

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

(F) other additives

Fluorine surfactant (F-554, DIC)

(Unit: % by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A) Quantum dots (A-1) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (A-2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (B) binder resin 15 15 15 15 15 15 15 15 15 15 (C) polymerizable compound (C-1) 5 - - - 4 - - - - - (C-2) - 5 4 3 - - - - 5.2 2.5 (C-3) - - - - - - 5 - - - (C-4) - - - - - - - 5 - - (C-5) One One 2 3 2 6 One One 0.8 3.5 (D) solvent 75.5 75.5 75.5 75.5 75.5 75.5 75.5 75.5 75.5 75.5 (E) diffusion agent 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (F) other additives 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Evaluation: Evaluation of curing shrinkage and luminance of the composition

15 ml of each of the curable compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were taken and coated on a glass substrate to a thickness of about 10 μm using a spin coater (Mikasa, Opticoat MS-A150). Afterwards, pre-baking (PRB) was performed at 100° C. for 3 minutes using a hot-plate, followed by post-baking divided into two steps (POB I, POB II) (180° C., N ₂ , 30 minutes) ), the thickness of each step was measured with a thickness measuring instrument (Tencor) to calculate the shrinkage rate. In addition, the luminance was measured using a CAS spectrometer on a 447 nm BLU after POB I. Specifically, the shrinkage ratio is a value confirming the shrinkage ratio by measuring the thickness of each single film after PRB and after POB-I. The measurement results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Shrinkage (%) 5.3 5.1 4.8 4.9 5.2 13.4 6.3 6.5 5.7 5.9 Luminance (%) 97 98 98 98 98 97 98 98 97 97

As shown in Table 2, in the case of Examples 1 to 5, it can be confirmed that compared to Comparative Examples 1 to 5, while having a luminance equal to or higher than that of Comparative Examples 5, the cure shrinkage rate is low. In particular, in the case of Examples 3 and 4, it can be seen that the luminance is excellent and the cure shrinkage rate is also the lowest.

The present invention is not limited to the above embodiments, but can be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains can take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented as Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

1 light guide plate
Resin film according to the second embodiment
3 liquid crystal layer
4 overcoat layer
5 glass
6 blue color resist
7 green color resist
8 red color resist
9 green quantum dots
10 red quantum dots

Claims (15)

(A) quantum dots;
(B) a binder resin comprising a cardo-based resin;
(C) a polymerizable compound comprising a first polymerizable compound and a second polymerizable compound; and
(D) solvent
including,
The first polymerizable compound is represented by the following formula 1-2,
The second polymerizable compound is represented by the following formula (2),
A curable composition comprising the first polymerizable compound and the second polymerizable compound in a weight ratio of 3:1 to 1:1:
[Formula 1-2]

[Formula 2]

In Formula 1-2 and Formula 2,
R ¹ is represented by the following formula (3),
R ² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ to L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
[Formula 3]

In Formula 3,
R ³ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
delete delete According to claim 1,
The binder resin is a curable composition having a weight average molecular weight of 500 g / mol to 50,000 g / mol.
According to claim 1,
The quantum dot absorbs light of 360 nm to 780 nm, and the curable composition is a quantum dot that emits fluorescence at 500 nm to 700 nm.
According to claim 1,
The quantum dot is a curable composition comprising a green quantum dot and a red quantum dot.
According to claim 1,
The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide, 2-butoxyethanol , N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.
According to claim 1,
The curable composition further comprises a diffusing agent.
9. The method of claim 8,
The curable composition comprising the dispersing agent in an amount of 0.1 wt% to 20 wt% based on the total amount of the curable composition.
9. The method of claim 8,
The dispersing agent is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
According to claim 1,
The curable composition further comprises a thiol-based additive.
According to claim 1,
The curable composition includes 1 wt% to 40 wt% of the quantum dots, 1 wt% to 40 wt% of the binder resin, 0.1 wt% to 20 wt% of the polymerizable compound, and the remaining amount of the solvent with respect to the total amount of the curable composition A curable composition.
According to claim 1,
The curable composition comprises malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; Or a curable composition further comprising a combination thereof.
A resin film prepared by using the curable composition of any one of claims 1 and 4 to 13.
A display device comprising the resin film of claim 14 .

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