WO2020189851A1 - Curable composition containing quantum dot and resin film and display device each using same - Google Patents

Abstract

Provided are; a curable composition comprising (A) a quantum dot, (B-1) an acrylic binder resin, (B-2) a cardo-based binder resin, and (C) a solvent; a resin film manufactured using the curable composition; and a display device comprising the resin film.

Description

Curable composition containing quantum dots, resin film and display device using the same

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

Color filters are used in liquid crystal displays, optical filters of cameras, and the like, and are manufactured by coating fine areas colored in three or more colors on a solid-state imaging device or a transparent substrate. Such a colored thin film may be formed by a conventional dyeing method, a printing method, a pigment dispersion method, an inkjet method, or the like.

In the dyeing method, an image with a dyeing base such as a natural photosensitive resin such as gelatin, an amine-modified polyvinyl alcohol, or an amine-modified acrylic resin is formed on a substrate in advance, and then dyed with a dye such as 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 are good, but there are disadvantages in that light resistance, moisture resistance and heat resistance are poor.

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

The pigment dispersion method is a method of forming a colored thin film by repeating a series of processes of coating, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method has the advantage of improving heat resistance and durability and maintaining a uniform thickness of the film. In addition, the implementation of the fine pattern is excellent and the manufacturing method is relatively easy, so it is widely adopted. For example, in Korean Patent Publication No. 1992-7002502, Korean Patent Publication No. 1994-0005617, Korean Patent Publication No. 1995-0011163, and Korean Patent Publication No. 1995-7000359, the preparation of a colored photosensitive resin composition using a pigment dispersion method. A method is being proposed.

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

In order to overcome this problem, in recent years, 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 a color filter, materials required for the process can be reduced and the process can be simplified.

In the case of manufacturing a color filter using the above inkjet ink, it is common to mix and use two or more types of pigments in order to secure required color characteristics. In particular, in a red filter, a dichitopyrrolopyrrole-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 is added, or isoindolinone-based yellow pigments, for example C.I. It is common to add Pigment Yellow 139. In some cases, other yellow and orange pigments, for example C.I. Pigment Yellow 138, C.I Pigment Yellow 150, C.I. Pigment Orange 38 or the like may be added. The pigments have excellent color characteristics, light resistance, and heat resistance, and have been commonly used as materials for color filters. However, as the use of LCD color filters is expanded in recent years, the required level of physical properties is increasing day by day. Therefore, in order to increase color characteristics such as improved brightness and color purity when transmitted, studies to atomize and finely disperse the pigments are being conducted, but in fact, there is a limit to the expression of color characteristics of a color filter only with a combination of these pigments.

One embodiment is to provide a curable composition containing quantum dots that minimizes curing shrinkage during a thermal process and improves reliability (prevents luminance decrease) by preventing a decrease in quantum dot efficiency.

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

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

One embodiment is (A) quantum dots; (B-1) acrylic binder resin; (B-2) a structural unit represented by the following Formula 1-1, a structural unit represented by the following Formula 1-2, and a structural unit represented by the following Formula 1-3, and at both ends, represented by the following Formula 2 Cardo-based binder resin containing a structural unit; And (C) provides a curable composition containing a solvent.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2]

In Formula 1-1, Formula 1-2, Formula 1-3, and Formula 2,

R ¹ is a substituted or unsubstituted acrylate group,

R ² is a substituted or unsubstituted C6 to C20 thioaryl group,

R ³ and R ⁴ are each independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,

X ¹ is a substituted or unsubstituted tetravalent organic group,

X ² is a substituted or unsubstituted divalent organic group.

The acrylate group may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ⁵ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The cardo-based binder resin may satisfy Equation 1 below.

[Equation 1]

0.1 ≤ a / a+b ≤ 0.5

In Equation 1,

a means the number of acrylate groups in the cardo-based binder resin,

b means the number of thioaryl groups in the cardo-based binder resin.

The curable composition may further include a cardo-based binder resin (B-3) comprising a structural unit represented by Formula 1-3 below and a structural unit represented by Formula 2 below at both ends.

[Formula 1-3]

[Formula 2]

In Chemical Formulas 1-3 and 2,

R ² to R ⁴ are each independently a substituted or unsubstituted C6 to C20 thioaryl group,

X ¹ is a substituted or unsubstituted tetravalent organic group,

X ² is a substituted or unsubstituted divalent organic group.

X ¹ may be represented by any one selected from the group consisting of the following Chemical Formulas X-1 to X-3.

[Formula X-1]

[Formula X-2]

[Formula X-3]

In Formula X-1,

L ¹ is a single bond, an oxygen atom, a sulfur atom, *-C(=O)-* or *-CR ^a1 R ^a2 -* (wherein R ^a1 and R ^a2 are each independently a halogen atom substituted or unsubstituted C1 to C10 alkyl group).

The X ² may be represented by any one selected from the group consisting of the following Formula X-4 to Formula X-10.

[Formula X-4]

(In Formula X-4, 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 X-5]

[Formula X-6]

[Formula X-7]

[Formula X-8]

(In Formula X-8, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group)

[Formula X-9]

[Formula X-10]

The cardo-based binder resin and the acrylic binder resin may be included in a weight ratio of 8:2 to 4:6.

The cardo-based binder resin may have a weight average molecular weight of 5,000 g/mol to 12,000 g/mol.

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

The curable composition may further include a reactive unsaturated compound.

The curable composition may further include a diffusion agent.

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

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

The curable composition may further include a sulfur-containing compound.

The sulfur-containing compound may include at least two or more functional groups represented by the following formula (4) at the terminal.

[Formula 4]

In Chemical Formula 4,

L ⁷ and L ⁸ 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 comprises 1% to 30% by weight of the quantum dots, 1% to 30% by weight of the acrylic binder resin, 1% to 30% by weight of the cardo binder resin, and the balance of the solvent based on the total amount of the curable composition. Can include.

The curable composition is malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; 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.

Other specifics of aspects of the present invention are included in the detailed description below.

Epoxy-based binder resin, which is a thermosetting binder resin mainly used in conventional quantum dot-containing compositions, has a high curing shrinkage rate of the resin during thermal processing, and interfacial dropping or cracking occurs when the cured layer (resin film) of the thermosetting composition containing the same is laminated. However, in the curable composition according to an embodiment, by mixing a cardo-based binder resin having a specific structure with an acrylic-based binder resin, it is possible to minimize the curing shrinkage during the thermal process and prevent the occurrence of interfacial dropping or cracking. In addition, by improving the quantum efficiency and dispersibility of the quantum dot, it is possible to prevent a decrease in luminance.

1 is a schematic diagram showing 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 presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified in the specification, "alkyl group" refers to a C1 to C20 alkyl group, "alkenyl group" refers to a C2 to C20 alkenyl group, and "cycloalkenyl group" refers to a C3 to C20 cycloalkenyl group, , "Heterocycloalkenyl group" refers to a C3 to C20 heterocycloalkenyl group, "aryl group" refers to a C6 to C20 aryl group, and "arylalkyl group" refers to a C6 to C20 arylalkyl group, and "alkylene group" Refers to a C1 to C20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, and "heteroarylene group" refers to a C3 to C20 hetero It means an arylene group, and the "alkoxyl group" means a C1-C20 alkoxyl group.

Unless otherwise specified in the specification, "substituted" 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 salt thereof, sulfonic acid group or salt thereof, phosphoric acid or 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.

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

In addition, unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid. "It means both are possible.

Unless otherwise specified in the specification, "combination" means mixing or copolymerization.

Unless otherwise defined in the chemical formula 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 at the position.

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

The curable composition according to one embodiment includes (A) quantum dots; (B-1) acrylic binder resin; (B-2) a structural unit represented by the following Formula 1-1, a structural unit represented by the following Formula 1-2, and a structural unit represented by the following Formula 1-3, and at both ends, represented by the following Formula 2 Cardo-based binder resin containing a structural unit; And (C) a solvent.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2]

In Formula 1-1, Formula 1-2, Formula 1-3, and Formula 2,

R ¹ is a substituted or unsubstituted acrylate group,

R ² is a substituted or unsubstituted C6 to C20 thioaryl group,

R ³ and R ⁴ are each independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,

X ¹ is a substituted or unsubstituted tetravalent organic group,

X ² is a substituted or unsubstituted divalent organic group.

As a concept of applying quantum dots to existing LCD-based TVs, various types of panels are being developed. Recently, development of quantum dot-glass (QD-galss) that cures after coating a resin composition containing quantum dots on a glass light guide plate in place of the existing PMMA light guide plate to improve luminance, etc. is in progress. The demand for panels that can be expected to reduce the thickness of the panel and to improve luminance at the same time while retaining the basic panel operating mechanism and optical characteristics of QLED TVs with quantum dot sheets has increased significantly.

One embodiment is a curable composition applicable to a quantum dot glass (QD-glass), and representative properties required for a curable composition applied to a quantum dot glass (QD-glass) are as follows.

1. Low shrinkage: After coating and heat curing on a large-area glass light guide plate, the shrinkage rate and modulus by the inorganic material deposition process should be extremely low (for example, less than 10%), but the interface of each layer is dropped or cracked. Can be prevented.

2. Luminance: Since it is a light-emitting curable resin composition containing quantum dots, it is possible to prevent a decrease in luminance by preventing a decrease in the quantum efficiency of the quantum dots, such as not reducing the dispersion degree of the quantum dots.

3. High light intensity reliability: Put the prepared specimen on the light source (BLU) by “coating the curable composition containing quantum dots and then heat curing → SiOx deposition → overcoating”, and irradiate the amount of light more than 10 times the normal amount of light of the light source (BLU). While checking whether or not the luminance decreases over time, the luminance decrease should not occur.

One embodiment relates to a curable composition, such as a thermosetting composition, including quantum dots, which has become a new technology trend in the recent display field. The curable composition containing quantum dots applied to the display is composed of a binder resin, colorant, solvent, and additives, like the existing curable composition, and uses quantum dots instead of colorants such as pigments/dyes as a material for color characteristics, and additionally diffuses light. And/or a sulfur-containing compound, etc. may be further included.

Quantum dots represented by CdSe and InP have rapidly developed in terms of luminous efficiency, and synthetic methods with luminous efficiency close to 100% are being introduced. An example is that QD SUHDTV with quantum dot sheet is now commercialized. As the next version, QD TVs are being developed as a self-luminous version instead of a filler method in the color resist layer by including quantum dots in the color resist layer of existing LED TVs (excluding pigments and dyes). The key to the development of a TV using this quantum dot-containing resin composition is to maintain the optical efficiency of quantum dots well in the process of patterning and thermal process (prebaking)-exposure-development-water washing-deposition and thermal process (post-baking) of the composition composition. Whether or not to implement the pattern well is the key to product development.

However, the method of including quantum dots in the color resist layer of an existing LED TV so that the color resist layer emits light is very 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, research on a method of injecting blue light (a light source) onto the quantum dot sheet and converting it into white light is being conducted. In this case, the blue light must be converted into white light, and the quantum dot sheet must include both green quantum dots and red quantum dots.

The quantum dots, which play a key function in the blue light conversion, are surrounded by a hydrophobic ligand, and when these hydrophobic quantum dots are added to a composition having hydrophilicity (eg, a curable composition containing an epoxy-based binder resin, etc.), dispersibility Since this falling problem occurs, a lot of studies on ligand substitution and passivation on the surface of quantum dots have been conducted in order to solve the dispersibility problem. However, the patterning process using the curable composition containing quantum dots causes a significant decrease in sensitivity, and thus it is difficult to secure patternability.

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

The conventionally known undercut of a photoresist is improved by applying a binder resin having a low melting point like a cardo-based binder 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 prebaking process.

However, as described above, the curable composition containing quantum dots has a high content of inorganic substances, so the melting property does not appear only by the application of the cardo-based binder resin, so there is a limit to improving the undercut (the curable composition containing quantum dots has a high inorganic content and does not melt even after post-baking. There is a problem), the binder resin into which the epoxy group is introduced has a problem that the residue characteristics are greatly deteriorated.

Furthermore, the conventional epoxy-based binder resin, which is a thermosetting binder resin mainly used in curable compositions, exhibits a curing shrinkage of about 15% to 20% in the post-baking step during the thermosetting process of the quantum dot-containing composition, and additional heat after post-baking. In the process step, curing shrinkage of about 5% is shown, and there is a problem in that the interfacial dropping of the resin film occurs, and there is a problem that a crack in the resin film occurs even if the interface does not fall off. This problem is due to the decrease in the quantum efficiency or dispersibility of the quantum dot by the epoxy curing mechanism and the epoxy structure (as described above, the surface of the quantum dot is hydrophobic, whereas the network formed by the epoxy structure has hydrophilicity). That is, the epoxy-based binder resin causes a decrease in dispersibility of quantum dots and a decrease in quantum efficiency due to this, and furthermore, yellowing or the like occurs during high light intensity evaluation, leading to a decrease in luminance.

In addition, most of the acrylic-based binder resins are one cause of lowering the efficiency of quantum dots in the composition, and it is difficult to use conventionally known acrylic-based binder resins as they are.

On the other hand, even if it is an acrylic binder resin, some are compatible with quantum dots. Accordingly, in the case of some acrylic binder resins that are compatible with quantum dots, there is no problem in quantum efficiency, but there is also a problem in that the shrinkage rate is high during curing, so that the same problem as the above-described epoxy-based binder resin is encountered.

Recently, in order to improve the shrinkage rate, attempts have been made to minimize the shrinkage rate due to hardening by minimizing the intermolecular free volume by ππstacking between the fluorene cores constituting the backbone of the cardo-based binder resin. It was confirmed that there is a problem of decomposition due to being vulnerable to the amount of light, and this decreases the stability of the quantum dot, so that the luminance decrease occurs when evaluating the reliability of the high light intensity.

However, according to one embodiment, by using the acrylic binder resin together with the cardo-based binder resin having a specific structure, it is possible to simultaneously solve the conventional problems of the shrinkage rate and high light intensity reliability. The problem of shrinkage due to curing can be solved by minimizing the intermolecular free volume by ππstacking between fluorene cores in the cardo-based binder resin structure having a specific structure, and reducing the efficiency of quantum dots by applying an acrylic binder binder when irradiated with high light intensity. By preventing the high light intensity improvement can be achieved.

Hereinafter, each component will be described in detail.

(A) quantum dots

The quantum dot absorbs light in a wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emits fluorescence in a wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm, or may emit fluorescence from 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.

Each of the quantum dots may 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 dots have a half-width in the above range, as the color purity is high, there is an effect of increasing the color reproduction rate when used as a color material in a color filter.

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

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

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. , 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 limited thereto.

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

The structure of the quantum dot is not particularly limited, but in the case of the quantum dot of the core/shell structure, the size (average particle diameter) of each of the entire quantum dots 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 and red quantum dots. In this case, the green quantum dots may be included in an amount higher than that of the red quantum dots. 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 the embodiment may further include a dispersant. The dispersant helps to uniformly disperse a photo-conversion material such as quantum dots in the curable composition, and nonionic, anionic or cationic dispersants 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, and the like 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% to 100% by weight, such as 10% to 20% by weight, based on the solid content of a photo-conversion material such as quantum dots.

The quantum dots may be included in an amount of 1% to 40% by weight, such as 1% to 30% by weight, 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 and the pattern characteristics and development characteristics are not impaired, so that excellent fairness may be obtained.

(B-1) Acrylic binder resin

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy 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% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (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 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 binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl meth Acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

When the acrylic-based binder resin is mixed with a cardo-based binder resin, which will be described later, it has a very great effect in preventing a decrease in luminance.

The weight average molecular weight of the acrylic binder resin may be 3,000 g/mol to 150,000 g/mol, such as 5,000 g/mol to 50,000 g/mol, such as 20,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the curable composition according to an embodiment are excellent, the viscosity is appropriate, and adhesion to the substrate is excellent.

The acid value of the acrylic binder resin may be 15 mgKOH/g to 60 mgKOH/g, such as 20 mgKOH/g to 50 mgKOH/g　. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The acrylic binder resin may be included in an amount of 1% to 30% by weight, for example, 1% to 20% by weight, based on the total amount of the curable composition according to an embodiment. When the acrylic binder resin is included within the above range, developability is excellent and crosslinking property is improved, so that excellent surface smoothness can be obtained.

(B-2) Cardo binder resin

The curable composition according to an embodiment includes a structural unit represented by Formula 1-1, a structural unit represented by Formula 1-2, and a structural unit represented by Formula 1-3, and at both ends, Formula 2 It includes a cardo-based binder resin containing a structural unit represented by.

The cardo-based binder resin includes both a vinyl group and a thioaryl group in an acrylate group capable of curing in the structure, thereby solving the aforementioned undercut problem and improving development margin.

When there is no thioaryl group in the cardo-based binder resin structure, optical properties, that is, the light retention rate, are greatly reduced, and when an acrylate group is not present in the binder resin, the pattern property is greatly reduced due to undercut.

For example, the acrylate group may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ⁵ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the vinyl group in the acrylate group is a curing site, and the acrylate group is 10% to 50%, such as 20% to 30% based on the total content (100%) of acrylate groups and thioaryl groups present in the cardo-based binder resin. It may be present in an amount of %. When the content of the acrylate group is within the above range, it is possible to solve the undercut problem by helping the undercut during UV curing, and is advantageous in terms of pattern formation.

For example, the cardo-based binder resin may satisfy Equation 1 below.

[Equation 1]

0.1 ≤ a / a+b ≤ 0.5

In Equation 1,

a means the number of acrylate groups in the cardo-based binder resin,

b means the number of thioaryl groups in the cardo-based binder resin.

In Formulas 1-1 to 1-3, X ¹ may be represented by any one selected from the group consisting of the following Formulas X-1 to X-3.

[Formula X-1]

[Formula X-2]

[Formula X-3]

In Formula X-1,

L ¹ is a single bond, an oxygen atom, a sulfur atom, *-C(=O)-* or *-CR ^a1 R ^a2 -* (wherein R ^a1 and R ^a2 are each independently a halogen atom substituted or unsubstituted C1 to C10 alkyl group).

For example, in Formula X-1, L ¹ may be a sulfur atom.

In Formula 2, X ² may be represented by any one selected from the group consisting of the following Formulas X-4 to X-10.

[Formula X-4]

(In Formula X-4, 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 X-5]

[Formula X-6]

[Formula X-7]

[Formula X-8]

(In Formula X-8, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group)

[Formula X-9]

[Formula X-10]

The cardo-based binder resin (B-2) and the acrylic binder resin may be preferably included in a weight ratio of 8:2 to 4:6, such as 7:3 to 5:5. When the cardo-based binder resin (B-2) is included in an excessive amount compared to the acrylic-based binder resin, a problem may occur in the long-term reliability (lower brightness) of the film, and the cardo-based binder resin (B-2) is the acrylic binder resin If it is included in an excessively small amount, a problem may occur in the roughness of the film surface.

The cardo-based binder resin (B-2) may have a weight average molecular weight of 5,000 g/mol to 12,000 g/mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, pattern formation is well performed without residues, there is no loss of film thickness during development, and a good pattern can be obtained. In particular, when considering the structure of the cardo-based binder resin (B-2), it is very difficult to form a polymer when the weight average molecular weight of the cardo-based binder resin (B-2) is less than 5,000 g/mol, and the binder resin When the weight average molecular weight of is more than 12,000 g/mol, there is a problem that it dissolves as a peeling type during KOH development, resulting in foreign matters.

The cardo-based binder resin (B-2) may be included in an amount of 1% to 30% by weight, for example, 1% to 20% by weight based on the total amount of the curable composition. When the cardo-based binder resin (B-2) is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(B-3) Cardo-based binder resin

In addition to the aforementioned cardo-based binder resin, the curable composition according to an embodiment is a cardo-based binder resin, for example, a cardo-based resin composed of a structural unit represented by the following formula 1-3 and a structural unit represented by the following formula 2 at both ends. It may further include a binder resin.

[Formula 1-3]

[Formula 2]

In Chemical Formulas 1-3 and 2,

R ² to R ⁴ are each independently a substituted or unsubstituted C6 to C20 thioaryl group,

X ¹ is a substituted or unsubstituted tetravalent organic group,

X ² is a substituted or unsubstituted divalent organic group.

The definitions for X ¹ and X ² are as described above.

The cardo-based binder resin (B-3) may have a weight average molecular weight of 2,000 g/mol to 5,000 g/mol, for example, 2,000 g/mol to 4,800 g/mol. When the cardo-based binder resin (B-3) having a weight average molecular weight in the above range is mixed with the aforementioned cardo-based binder resin (B-2) having a different weight average molecular weight, the shrinkage can be greatly reduced, and the brightness is lowered. It is also effective in preventing.

The cardo-based binder resin (B-3) may be included in an amount of 1% to 30% by weight, for example, 1% to 20% by weight based on the total amount of the curable composition. When the cardo-based binder resin (B-3) is included within the above range, the curing shrinkage rate can be greatly reduced.

(C) solvent

The curable composition according to an embodiment includes alcohols such as methanol and ethanol as a solvent; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; Acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic 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, and the like may be used, but are not limited thereto.

For example, the solvent may include glycol ethers such as ethylene glycol monoethyl ether and ethylene diglycol methyl ethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; It is preferable to use alcohols such as ethanol, 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 It may be a polar solvent including oxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ butyrolactone, or a combination thereof.

The solvent may be included in the balance with respect to the total amount of the photosensitive resin composition, for example 30% to 80% by weight, such as 40% to 80% by weight. When the solvent is included within the above range, since the curable composition has an appropriate viscosity, excellent coating properties may be obtained during spin coating and large area coating using a slit.

Reactive unsaturated compounds

The curable composition according to an embodiment may further include a reactive unsaturated compound. The reactive unsaturated compound may be used by mixing monomers or oligomers generally used in conventional curable compositions.

The reactive unsaturated compound may be an acrylate compound. For example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate , Novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6 -Hexanediol dimethacrylate, Japanese Chemical Company KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 can be used by selecting or mixing one or more.

For example, the reactive unsaturated compound is ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol di Acrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane Triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate and Any one compound selected from the group consisting of 1,6-hexanedioldimethacrylate (the first reactive unsaturated compound) and KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 and It may be a mixture of any one compound (second reactive unsaturated compound) selected from the group consisting of KAYARAD DPEA-12. In this case, the content of the first reactive unsaturated compound may be less than or equal to the content of the second reactive unsaturated compound.

The reactive unsaturated compound may be used after treatment with an acid anhydride in order to impart better developability.

The reactive unsaturated compound may be included in an amount of 1% to 10% by weight, such as 2% to 8% by weight, based on the total amount of the curable composition. When the reactive unsaturated compound is included within the above range, curing occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, and excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern.

Diffuser

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

For example, the diffusion 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 above-described quantum dots, and allows the reflected light to be absorbed again. That is, the diffusion agent may increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

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

The diffusion agent may be used in the form of a dispersion solution dispersed in a solvent for stability of dispersion in the curable composition.

The diffusion agent may be included in an amount of 0.1% to 20% by weight, such as 0.1% to 5% by weight, based on the total amount of the curable composition. When the diffusion 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 the effect of improving the light conversion efficiency by using the diffusion agent, and when it is included in an amount exceeding 20% by weight, 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 sulfur-containing compound, thereby significantly reducing the curing shrinkage rate and at the same time preventing a decrease in brightness.

The sulfur-containing compound may be substituted on the shell surface of the quantum dot to improve the dispersion stability of the quantum dot in a solvent, thereby stabilizing the quantum dot.

The sulfur-containing compound may have 2 to 10, for example, 2 to 4 thiol groups (-SH) at the ends according to its structure.

For example, the sulfur-containing compound may include at least two or more functional groups represented by the following formula (4) at the terminal.

[Formula 4]

In Chemical Formula 4,

L ⁷ and L ⁸ 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, the sulfur-containing compound may be represented by the following formula (5).

[Formula 5]

In Chemical Formula 5,

L ⁷ and L ⁸ 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 Is a C2 to C20 heteroarylene group,

u1 and u2 are each independently an integer of 0 or 1.

For example, in Formulas 4 and 5, L ⁷ and L ⁸ may each independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

Specific examples of the sulfur-containing compound include pentaerythritol tetrakis (3-mercaptopropionate) represented by the following formula 4a, trimethylolpropane tris (3) represented by the following formula 4b. -Mercaptopropionate) (trimethylolpropane tris (3-mercaptopropionate)), pentaerythritol tetrakis (mercaptoacetate) represented by the following formula 4c, Pentaerythritol tetrakis (mercaptoacetate), trimethylolpropane tris represented by the following formula 4d ( 2-mercaptoacetate) (trimethylolpropane tris (2-mercaptoacetate)), glycol di-3-mercaptopropionate represented by the following formula 4e (Glycol di-3-mercaptopropionate) and any selected from the group consisting of a combination thereof There is one.

[Formula 4a]

[Formula 4b]

[Formula 4c]

[Formula 4d]

[Formula 4e]

The sulfur-containing compound may be included in an amount of 0.1% to 15% by weight, such as 0.1% to 5% by weight, based on the total amount of the curable composition. When the sulfur-containing compound is included within the above range, stability of a photo-conversion material such as quantum dots may be improved. For example, when the sulfur-containing compound contains a thiol group, the thiol group is the acrylic group of the above-described binder resin or reactive unsaturated compound. By reacting to form a covalent bond, it may also have an effect of improving the heat resistance of a photoconversion material such as a quantum dot.

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

For example, the hydroquinone-based compound, the 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 Roll, 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 limited thereto.

The hydroquinone compound, the catechol 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% to 1% by weight, such as 0.01% to 0.1% by weight, based on the total amount of the curable composition. Can be included as When the stabilizer is included in the above range, it is possible to solve the problem with aging at room temperature and to prevent sensitivity reduction and surface peeling.

The curable composition according to an embodiment includes malonic acid in addition to the thiol-based additive and polymerization inhibitor; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; 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, or an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, γ glycidoxy propyl Trimethoxysilane, βepoxycyclohexyl)ethyltrimethoxysilane, and the like, 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, the curable composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defects from being generated, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Dainippon ingki Kagaku Kogyo (state) of the mechanical社pack F 142D ^®, Mecca pack ^® F 172, F 173 Mecca pack ^®, Mecca pack ^® F 183, and the like; Sumitomo M. (Note)社pro rod FC-135 ^®, Pro Rad FC-170C ^®, Pro rod FC-430 ^®, Pro rod FC-431 ^®, and the like; Asahi Grass (Note)社of Saffron S-112 ^®, Saffron S-113 ^®, Saffron S-131 ^®, Saffron S-141 ^®, Saffron S-145 ^®, and the like; Toray silicone ^{(Note)社SH-28PA ®, SH} -190 ®, SH-193 ®, SZ-6032 ®, SF-8428 ® , and the like; A fluorine-based surfactant marketed under the names of DIC Corporation's F-482, F-484, F-478, F-554, etc. can be used.

The fluorine-based surfactant may be used in an amount of 0.001 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 ensured, 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 by using the above-described curable composition.

The method of manufacturing the resin film includes the steps of forming a pattern by applying the above-described curable composition on a substrate by an ink jet spray method (S1); And curing the pattern (S2).

(S1) forming a pattern

It is preferable that the curable composition is applied on a substrate in a thickness of 0.5 to 10 µm in an ink jet dispersion method. The inkjet spraying can form a pattern by spraying only a single color and spraying repeatedly according to the number of required colors, and the pattern can be formed by simultaneously spraying the required number of colors to reduce the process.

(S2) curing step

A cured resin film can be obtained by curing the obtained pattern. At this time, a thermal curing process is preferable as a method of curing. The thermal curing process may be a process of first removing the solvent in the curable composition by heating at a temperature of about 100° C. or higher for about 3 minutes, and then curing by heating at a temperature of 160° C. to 300° C., and 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, and the color filter may be disposed on one side of the liquid crystal layer, and the resin film may be disposed on the other side of the liquid crystal layer.

Referring to FIG. 1, the display device includes a color resist layer having color filters 6, 7, 8 and a curable composition according to an embodiment by a column spacer (not shown) based on the liquid crystal layer 3 The resin film 2 manufactured by using is positioned opposite. The color resist layer may be surrounded by an overcoat layer 4, and a glass 5 is positioned on the color resist layer. 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 formed of a layer separate from the color resist layer, the quantum efficiency of the quantum dots can be prevented from deteriorating. In addition, the light guide plate may be a glass light guide plate, not a PMMA light guide plate. By using a glass light guide plate instead of the PMMA light guide plate, the thickness of the panel can be made thin, and an effect of improving luminance 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 7, Comparative Example 1 and Comparative Example 2

Using the components mentioned below, curable compositions according to Examples 1 to 7, Comparative Examples 1 and 2 were prepared with the compositions shown in Table 1 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

(B-1) Acrylic binder resin (SHOWA DENKO, SP-RY67-1)

(B-2) Cardo binder resin

Binder resin (TAKOMA, TSR-TA01-2) comprising the structural units represented by the following Formulas E-1, E-3, and E-4, and including the structural units represented by Formula E-5 at both ends (TAKOMA, TSR-TA01-2 ) (Weight average molecular weight: 8,000 g/mol)

[Formula E-1]

[Formula E-3]

[Formula E-4]

[Formula E-5]

(In Formula E-5,

R ^x and R ^y are each independently *-O(C=O)CHCH ₂ or an unsubstituted thiophenyl group.)

(B-3) Cardo-based binder resin

Binder resin (TAKOMA, TSR-TB04) containing the structural unit represented by Formula E-1 and including the structural unit represented by the following Formula E-2 at both ends (weight average molecular weight: 4,500 g/mol)

[Formula E-2]

(C) solvent

(C-1) Propylene glycol monomethyl ether acetate (PGMEA) (Sigma-Aldrich)

(C-2) Cyclohexyl acetate (Sigma-Aldrich)

(D) reactive unsaturated compound

(D-1) acrylate monomer (DPHA, Nippon kayaku)

(D-2) Acrylate-based monomer (DPCA-120, Nippon kayaku)

(E) diffusion agent

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

(F) sulfur-containing compound

Pentaerythritol tetrakis (3-mercaptopropionate) (BRUNO BOCK)

(G) other additives

(G-1) Fluorine surfactant (F-554, DIC)

(G-2) Silane coupling agent (KBM803, Shinetsu)

(Unit: wt%)

		Example							Comparative example
		One	2	3	4	5	6	7	One	2
(A) quantum dots	(A-1)	1.1	1.1	1.1	1.1	1.1	1.1	1.1	1.1	1.1
	(A-2)	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
(B) binder resin	(B-1)	6.5	6.5	3.9	2.6	7.8	1.3	9.1	-	13
	(B-2)	6.5	6.5	9.1	10.4	5.2	11.7	3.9	13	-
	(B-3)	4.5	4.5	4.5	4.5	4.5	4.5	4.5	4.5	4.5
(C) solvent	(C-1)	5.3	5.3	5.3	5.3	5.3	5.3	5.3	5.3	5.3
	(C-2)	70	70.3	70	70	70	70	70	70	70
(D) reactive unsaturated compound	(D-1)	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.2
	(D-2)	3.3	2.2	3.3	3.3	3.3	3.3	3.3	3.3	3.3
(E) diffusion agent		0.18	0.18	0.18	0.18	0.18	0.18	0.18	0.18	0.18
(F) sulfur-containing compound		-	0.8	-	-	-	-	-	-	-
(G) other additives	(G-1)	0.02	0.02	0.02	0.02	0.02	0.02	0.02	0.02	0.02
	(G-2)	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1

Evaluation: Evaluation of curing shrinkage rate and high light intensity reliability (luminance retention rate) of the composition

Each 15 ml of the curable composition prepared in Examples 1 to 7, Comparative Example 1 and Comparative Example 2 was taken, and coated on a glass substrate to a thickness of about 10 μm using a spin coater (Mikasa, Opticoat MS-A150). After, pre-baking at 100° C. for 3 minutes using a hot-plate, followed by dividing post-baking into two steps (POB I, POB II) (180° C. ₂ , 30 minutes), and then The shrinkage rate was calculated by measuring the thickness at each step. In addition, after POB I, the prepared specimen was placed on the 450nm BLU, irradiated for 168 hours at a light intensity of 80mW/cm ^2, and then the luminance change was measured using a CAS spectrometer on the 447nm BLU, and the luminance retention rate after 168 hours compared to the initial measured value was calculated. The measurement results are shown in Table 2 below.

	Example							Comparative example
	One	2	3	4	5	6	7	One	2
Shrinkage after POB I stage (%)	4.9	4.7	4.6	5.8	5.9	6.8	7.0	4.9	8.9
Luminance retention rate (%)	95	100	98	95	94	92	95	78	94

As shown in Table 2, in the case of Examples 1 to 7, it can be seen that the curing shrinkage is low and the luminance retention is high as compared to Comparative Examples 1 and 2. In particular, when the cardo-based binder resin and the acrylic-based binder resin having a specific structure are included in a weight ratio of 8:2 to 4:6, more specifically 7:3 to 5:5, the curing shrinkage is lower and the luminance retention is higher. You can also check.

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

Claims (21)

1. (A) quantum dots;

   (B-1) acrylic binder resin;

   (B-2) a structural unit represented by the following Formula 1-1, a structural unit represented by the following Formula 1-2, and a structural unit represented by the following Formula 1-3, and at both ends, represented by the following Formula 2 Cardo-based binder resin containing a structural unit; And

   (C) solvent

   Curable composition comprising:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   [Formula 2]

   

   In Formula 1-1, Formula 1-2, Formula 1-3, and Formula 2,

   R ¹ is a substituted or unsubstituted acrylate group,

   R ² is a substituted or unsubstituted C6 to C20 thioaryl group,

   R ³ and R ⁴ are each independently a substituted or unsubstituted acrylate group or a substituted or unsubstituted C6 to C20 thioaryl group,

   X ¹ is a substituted or unsubstituted tetravalent organic group,

   X ² is a substituted or unsubstituted divalent organic group.
2. The method of claim 1,

   The acrylate group is a curable composition represented by Formula 3:

   [Formula 3]

   

   In Chemical Formula 3,

   R ⁵ to R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
3. The method of claim 1,

   The cardo-based binder resin is a curable composition satisfying the following Equation 1:

   [Equation 1]

   0.1 ≤ a / a+b ≤ 0.5

   In Equation 1,

   a means the number of acrylate groups in the cardo-based binder resin,

   b means the number of thioaryl groups in the cardo-based binder resin.
4. The method of claim 1,

   The curable composition further comprises a cardo-based binder resin (B-3) consisting of a structural unit represented by the following Formula 1-3 and a structural unit represented by the following Formula 2 at both ends:

   [Formula 1-3]

   

   [Formula 2]

   

   In Chemical Formulas 1-3 and 2,

   R ² to R ⁴ are each independently a substituted or unsubstituted C6 to C20 thioaryl group,

   X ¹ is a substituted or unsubstituted tetravalent organic group,

   X ² is a substituted or unsubstituted divalent organic group.
5. The method of claim 1,

   The X ¹ is a curable composition represented by any one selected from the group consisting of the following formulas X-1 to X-3:

   [Formula X-1]

   

   [Formula X-2]

   

   [Formula X-3]

   

   In Formula X-1,

   L ¹ is a single bond, an oxygen atom, a sulfur atom, *-C(=O)-* or *-CR ^a1 R ^a2 -* (wherein R ^a1 and R ^a2 are each independently a halogen atom substituted or unsubstituted C1 to C10 alkyl group).
6. The method of claim 1,

   The X ² is a curable composition represented by any one selected from the group consisting of the following formulas X-4 to X-10.

   [Formula X-4]

   

   (In Formula X-4, 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 X-5]

   

   [Formula X-6]

   

   [Formula X-7]

   

   [Formula X-8]

   

   (In Formula X-8, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group)

   [Formula X-9]

   

   [Formula X-10]

   
7. The method of claim 1,

   The cardo-based binder resin and the acrylic-based binder resin are curable composition contained in a weight ratio of 8:2 to 4:6.
8. The method of claim 1,

   The cardo-based binder resin is a curable composition having a weight average molecular weight of 5,000 g/mol to 12,000 g/mol.
9. The method of claim 1,

   The quantum dots are quantum dots that absorb light of 360 nm to 780 nm and emit fluorescence at 500 nm to 700 nm.
10. The method of claim 1,

    The quantum dot is a curable composition comprising a green quantum dot and a red quantum dot.
11. The method of claim 1,

    The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylenediglycol methylethyl ether, diethylene glycol dimethyl ether, dimethylacetamide, 2-butoxyethanol , N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ butyrolactone or a curable composition comprising a combination thereof.
12. The method of claim 1,

    The curable composition further comprises a reactive unsaturated compound.
13. The method of claim 1,

    The curable composition further comprises a diffusing agent.
14. The method of claim 13,

    The curable composition containing the diffusion agent in an amount of 0.1% to 20% by weight based on the total amount of the curable composition.
15. The method of claim 13,

    The diffusing agent is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
16. The method of claim 1,

    The curable composition further comprises a sulfur-containing compound.
17. The method of claim 16,

    The sulfur-containing compound is a curable composition comprising at least two or more functional groups represented by the following formula (4) at the terminal:

    [Formula 4]

    

    In Chemical Formula 4,

    L ⁷ and L ⁸ 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.
18. The method of claim 1,

    The curable composition comprises 1% to 30% by weight of the quantum dots, 1% to 30% by weight of the acrylic binder resin, 1% to 30% by weight of the cardo binder resin, and the balance of the solvent based on the total amount of the curable composition. Curable composition comprising.
19. The method of claim 1,

    The curable composition is malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; Or a curable composition further comprising a combination thereof.
20. A resin film prepared by using the curable composition of any one of claims 1 to 19.
21. A display device comprising the resin film of claim 20.

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