KR20210133045A - Curable composition including quantum dot, resin layer using the same and display device - Google Patents

Abstract

The present invention stably passivates quantum dots through a specific surface modification material to significantly improve the dispersibility of quantum dots with respect to all of a polymerizable compound, a hydrophilic solvent, and a hydrophobic solvent, thereby improving the reliability of a display device through prevention of quantum efficiency degradation of quantum dots. Provided is a curable composition comprising quantum dots surface-modified with a compound represented by chemical formula (1), a resin film prepared using the curable composition, and a display device comprising the resin film. In chemical formula 1, each substituent is the same 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.

A color filter is used for a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine area colored in 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 a 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 is a disadvantage 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. 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. Since the inkjet printing method does not require a separate process such as coating, exposure, and development 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 is 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 or the like may be added. The above pigments have excellent color characteristics, light resistance and heat resistance, and have been frequently used as a material for color filters. Therefore, in order to increase color characteristics such as improvement of brightness and color purity when transmitted, research is being conducted to atomize and finely disperse the pigments, but in fact, there is a limit to the expression of color characteristics of a color filter only by a combination of these pigments.

Accordingly, attempts have been made to replace the pigments with quantum dots, and as a result, quantum dots have been established as a new technological trend in the display field, and the quantum dots are currently applicable to various display devices, electronic devices, etc. in addition to TVs and LEDs. . Quantum dots, represented by CdSe and InP, have been actively studied in terms of luminous efficiency (Quantum Yield), and synthetic methods with luminous efficiency close to 100% are being introduced. has been commercialized. However, the QD SUHDTV has limitations as a filtering type product in which light is filtered in the color filter layer. Research to develop a self-emission type quantum dot TV in the filter layer, not the filtering type, is currently ongoing.

In addition, various types of display devices to which quantum dots are applied have been studied, but in order to achieve fairness and performance in all cases, it is necessary to adjust the formulation with the organic material composition. However, an organic composition capable of sufficiently stabilizing the quantum dots (passivation) while the quantum dots are mixed with the organic composition (monomer, binder resin, initiator, other additives, etc.) and undergo a curing step (thermal curing or photocuring) has not yet been developed. , the quenching of quantum dots is inevitably occurring in the process. Therefore, the development of an organic material composition capable of preventing quenching by sufficiently stabilizing the quantum dot is emerging as an important issue in the development of a quantum dot-applied display device.

On the other hand, recently, the need for a solvent-free curable composition that is easier to apply to an actual process than a solvent-type curable composition is increasing.

One embodiment is to provide a surface-modified quantum dot-containing curable composition that sufficiently stabilizes quantum dots through quantum dot surface modification, and has greatly improved dispersibility for both a polymerizable compound and a solvent.

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 provides a curable composition comprising quantum dots surface-modified with a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,

L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *-C(=O)O-*, or represented by the following formula L-1,

[Formula L-1]

In the formula L-1,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

X is an oxygen atom or a sulfur atom,

n is an integer from 1 to 20;

In Formula 1, L ¹ is represented by Formula L-1, and L ² to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-C(=O)O-* can be

In Formula 1, L ¹ may be represented by Formula L-1-1, Formula L-1-2, or a combination thereof.

[Formula L-1-1]

[Formula L-1-2]

In the above formulas L-1-1 and L-1-2,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently an integer from 1 to 10.

The compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,

L ² , L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently an integer from 1 to 10.

The compound represented by Formula 1 may be represented by any one of Formulas 2 to 6 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

The curable composition may further include a polymerizable compound having a carbon-carbon double bond at the terminal thereof.

The polymerizable compound may be a polymerizable monomer having at least one functional group represented by the following Chemical Formula 7-1 or a functional group represented by the following Chemical Formula 7-2 at the terminal thereof.

[Formula 7-1]

[Formula 7-2]

In Formulas 7-1 and 7-2,

L ⁶ is a substituted or unsubstituted C1 to C20 alkylene group,

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

The quantum dots may have a core-shell structure, and the shell may include Zn.

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, red quantum dots, or a combination thereof.

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

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

The curable composition may further include at least one selected from the group consisting of a binder resin and a solvent.

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

The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide , dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γbutyrolactone, acetone or a combination thereof may include

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

By stably passivating the quantum dots through a specific surface modification material, the dispersibility of the quantum dots in all polymerizable compounds, hydrophilic solvents, and hydrophobic solvents is greatly improved, and the reliability of the display device can be improved by preventing the decrease in quantum efficiency of quantum dots. have.

1 is a diagram illustrating a surface-modified quantum dot constituting a curable composition according to an embodiment.
2 is a diagram illustrating a process in which the surface-modified quantum dots are dispersed in a PGMEA (propylene glycol monomethyl ether acetate) solvent after the curable composition according to an embodiment surface-modifies the quantum dots.
3 is a photograph of a PGMEA dispersion in which the surface-modified quantum dots are well dispersed.
4 is a reaction scheme schematically illustrating a synthesis method of each of the compounds represented by Chemical Formulas 2 to 6.

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 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, and "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 refers to an arylene group, and "alkoxyylene group" refers to 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.

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.

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 8-1 to 8-11 are included in the backbone of the resin.

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 dot surface-modified with a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,

L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *-C(=O)O-*, or represented by the following formula L-1,

[Formula L-1]

In the formula L-1,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

X is an oxygen atom or a sulfur atom,

n is an integer from 1 to 20;

Various types of panels are being developed with the concept of applying quantum dots to existing LCD-based TVs (filtering type). Recently, instead of the existing PMMA light guide plate to improve luminance, the development of quantum dot-glass (QD-galss) that cures after coating a resin composition containing quantum dots on a glass light guide plate is in progress. The demand for a panel that can reduce the thickness of the panel while retaining the advantages of the basic panel operation mechanism and optical characteristics of QLED TV to which the quantum dot sheet is applied, and further improving the luminance, has greatly increased.

In general, in order to provide a composition that meets the above requirements, it is important that the quantum dots in the composition stably exist regardless of any process. That is, stabilization of quantum dots is an important factor in providing a display device having excellent reliability. That is, the core of TV development to which the quantum dot-containing curable composition is applied depends on how well the quantum dots are stabilized in the process such as the patterning properties of the composition composition and the thermal process, how well the light efficiency of the quantum dots is maintained and the patternability is well implemented. .

Usually, for the purpose of stabilizing the quantum dot, a material capable of serving as a ligand of the quantum dot, for example, a monomolecular compound such as carboxylic acid, thiol, or amine, an oligomer thereof, or a polymer material including the same is added. These ligand materials coordinate to the quantum dot in the cured composition (ligand stabilizes the dangling bond on the surface of the quantum dot), thereby stabilizing the outermost atoms of the quantum dot, suppressing the quenching of the quantum dot (improving the stability of the quantum dot itself), and at the same time The dispersibility of quantum dots in a hydrophobic solvent is improved.

However, when considering the conditions of quantum dot synthesis, in most cases, the above-described ligand system cannot be changed as desired, and thus quantum dots are dispersed only in a very limited hydrophobic solvent, which is a significant limitation to the application of quantum dots (QD application). Currently, InP-based quantum dot liagnd is mostly composed of oleic acid, trioctylamine, trioctylphosphine (-oxide), etc. Dispersible solvents include hexane, cyclohexane, chloroform, and toluene. It is not a substance, and the physical properties required for the process (melting point, boiling point, vapor pressure, compatibility with other solvents, etc.) are also not suitable. Due to the hydrophobic properties of the surface of the quantum dot, compatibility and dispersion are not possible with respect to not only the solvent but also the curable polymerizable compound or binder resin, thereby limiting the application of quantum dots.

In order to solve the above problems, a solvent capable of dispersing QD-oleate (quantum dots having oleic acid on the outermost surface), which is mainly used, was screened. A long alkyl ester-based solvent has been found, and it is currently being used as a quantum dot dispersion solvent in the electronic material process. However, due to the unique smell of CHA, there are not many difficulties for workers in the process, and when quantum dots are dispersed in CHA and stored for a long time, dispersibility and quantum efficiency (QY) are significantly lowered.

There was also an attempt to change the electronic material process to an inkjet process instead of a traditional photoresist process. Existing quantum dot dispersion solvents (chloroform, toluene, cyclohexyl acetate) have characteristics such as low boiling point, low vapor pressure (room temperature), and low surface energy. In this case, it was only confirmed that the inkjet process application itself was impossible. From this point of view, quantum dots are well dispersed in inkjet processable solvents and a quantum dot dispersion technology that can maintain long-term dispersibility and quantum efficiency is needed, and the inventors have gone through so much trial and error, ) led to the development of a ligand with good surface affinity (affinity), and by using this to surface-modify the ligand of QD-oleate, the surface-modified quantum dots in a solvent and polymerizable compound advantageous for display processes, especially inkjet processes (consisting of core-shell-ligand; see FIG. 1) could be easily dispersed.

On the other hand, the quantum dots constituting the curable composition according to the embodiment are well dispersed in solvents or polymerizable compounds that can be used in the inkjet process, and the curable composition according to the embodiment may be a solvent-type curable composition or a solvent-free curable composition. have.

For example, the curable composition may further include a polymerizable compound, a photoinitiator, a solvent, a binder resin, or a combination thereof, in addition to the quantum dots, and may further include a light diffusing agent and other additives to be described later. .

Hereinafter, each component will be described in detail.

quantum dots

The quantum dots included in the curable composition according to an embodiment are surface-modified with the compound represented by Formula 1 above.

Since the compound represented by Formula 1 has excellent affinity with the quantum dot surface, it is advantageous for a display process, particularly an inkjet (INKJET) process, by substituting a ligand for QD-oleate. The dispersion stability can be greatly improved. Since the *-C (= O) NHOH functional group at the end of the compound represented by Formula 1 can be easily synthesized in one step from carboxylic acid, acid chloride, methyl ester, etc., it is a compound represented by Formula 1 containing the functional group. The surface-modified quantum dots are hydrophilic solvents such as PGMEA (Ethanol, ethylene glycol, ethyl acetate, acetone, γ-butyrolactone (GBL), Di(propylene glycol) methyl ether acetate (DPMA), dimethyl adipate (DMA), as well as hydrophobic solvents. Since it is possible to disperse the quantum dots, it is possible to greatly expand the field of application of quantum dots (that is, the quantum dots used in the curable composition according to one embodiment can be an important tool for future applications of quantum dots). The quantum dots surface-modified with the compound represented by can be directly dispersed not only in the solvent but also in a number of polymerizable compounds (acryl monomer, 2-hydroxyethylacrylate (HEA), HDDA, etc.). When the compound represented by the formula (1) is dispersed in the above, the quantum efficiency decrease is prevented, unlike in the prior art, and the dispersion stability is also excellent.

In Formula 1, L ¹ is represented by Formula L-1, and L ² to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-C(=O)O— * can be

For example, L ¹ may be represented by Formula L-1-1, Formula L-1-2, or a combination thereof.

[Formula L-1-1]

[Formula L-1-2]

In the above formulas L-1-1 and L-1-2,

L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently an integer from 1 to 10.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,

L ² , L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n1 and n2 are each independently an integer of 1 to 10.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 2 to 6, but is not necessarily limited thereto.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

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 half width in the above range, as the color purity is high, color gamut is increased when used as a color material in a color filter.

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. For example, the shell may include Zn.

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 of the core/shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example 5 nm to 15 nm.

For example, the quantum dots may 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 curable 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%, for example 10 wt% to 20 wt%, based on the solid content of the light conversion material such as quantum dots.

The quantum dots may be included in an amount of 5 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the solvent-type curable composition when the curable composition according to an embodiment is a solvent-type curable composition, and in one embodiment When the curable composition according to the above is a solvent-free curable composition, it may be included in an amount of 20 wt% to 95 wt%, such as 20 wt% to 93 wt%, based on the total amount of the solvent-free curable composition. When the quantum dots are included within the above range, the light conversion rate is excellent and the pattern characteristics and the developing characteristics are not impaired, and thus excellent processability may be obtained.

polymeric compound

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

For example, the polymerizable compound may be a polymerizable monomer having a carbon-carbon double bond at the terminal.

For example, the polymerizable compound may be a polymerizable monomer having at least one functional group represented by the following Chemical Formula 7-1 or a functional group represented by the following Chemical Formula 7-2 at the terminal thereof.

[Formula 7-1]

[Formula 7-2]

In Formulas 7-1 and 7-2,

L ⁶ is a substituted or unsubstituted C1 to C20 alkylene group,

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

When the polymerizable compound includes at least one carbon-carbon double bond at the terminal, specifically, at least one functional group represented by Formula 7-1 or a functional group represented by Formula 7-2, the compound represented by Formula 1 - A crosslinked structure may be formed with a C(=O)NH—OH functional group, and one crosslinked product thus formed may serve to stabilize the quantum dots.

For example, examples of the polymerizable compound including at least one functional group represented by Formula 7-1 at the terminal include divinyl benzene, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl triazine, diallyl phthalate, or a combination thereof, but is not necessarily limited thereto.

For example, examples of the polymerizable compound including at least one functional group represented by Chemical Formula 7-2 at the terminal include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexane. diol 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, polyfunctional epoxy (meth) acrylate, polyfunctional urethane (meth) acrylate, KAYARAD from Nippon Chemical DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 or a combination thereof may be mentioned, but is not necessarily limited thereto.

The polymerizable compound may be used by treating it with an acid anhydride in order to provide more excellent developability.

When the curable composition according to an embodiment is a solvent-type curable composition including a solvent, the polymerizable compound is 0% to 30% by weight, such as 1% to 30% by weight, such as based on the total amount of the solvent-type curable composition. It may be included in 3 wt% to 30 wt%. In addition, when the curable composition according to an embodiment is a solvent-free curable composition that does not include a solvent, the polymerizable compound is present in an amount of 2 wt% to 80 wt%, such as 20 wt% to 80 wt%, based on the total amount of the solvent-free curable composition. %, such as 30% to 80% by weight. When the polymerizable compound is included within the above range, curing occurs sufficiently upon exposure in the pattern forming process, and reliability is excellent, and the heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern are also excellent.

polymerization initiator

The curable composition according to the exemplary embodiment may further include a polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

The photopolymerization initiator is an initiator generally used in the curable resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, an aminoketone-based compound and the like may be used, but is not necessarily limited thereto.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4 -bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc. are mentioned. .

Examples of the oxime-based compound include an O-acyloxime-based compound, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, and 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used Specific examples of the O-acyloxime compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate etc. are mentioned.

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

As the photopolymerization initiator, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, or a biimidazole-based compound may be used in addition to the above compound.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light to enter an excited state and then transferring the energy.

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

Examples of the thermal polymerization initiator include peroxide, specifically benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide Oxide, hydroperoxide (eg tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, 2,2-azo-bis(isobutyronitrile), t-butyl perbenzo ate, and the like, and 2,2'-azobis-2-methylpropionitrile, but is not necessarily limited thereto, and any one widely known in the art may be used.

The polymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, such as 0.5 wt% to 5 wt%, based on the total amount of the curable composition. When the polymerization initiator is included within the above range, curing occurs sufficiently during exposure or thermal curing to obtain excellent reliability, and by preventing a decrease in transmittance due to an unreacted initiator, deterioration of optical properties of quantum dots can be prevented.

light diffuser

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

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

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

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

The light diffusing agent may be in the form of a dispersion dispersed in a solvent for dispersion stability on the curable composition.

The light diffusing agent 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 light diffusing agent is included in the above content range, an effect of improving light conversion efficiency by using the diffusing agent can be expected, and pattern characteristics can also be improved.

binder resin

The curable composition may further include a binder resin.

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

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 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%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene 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 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.

The cardo-based binder resin may include a repeating unit represented by the following Chemical Formula 8.

[Formula 8]

In the formula (8),

R ³¹ and R ³² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ³³ and R ³⁴ 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 ³⁵ R ³⁶ , SiR ³⁷ R ³⁸ (wherein R ³⁵ to R ³⁸ 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 8-1 to 8-11,

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

[Formula 8-4]

[Formula 8-5]

(In Formula 8-5,

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 8-6]

[Formula 8-7]

[Formula 8-8]

[Formula 8-9]

[Formula 8-10]

[Formula 8-11]

Z ² is an acid anhydride residue,

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

The cardo-based resin may include a functional group represented by the following Chemical Formula 9 at at least one of both terminals.

[Formula 9]

In Formula 9,

Z ³ may be represented by the following Chemical Formulas 9-1 to 9-7.

[Formula 9-1]

(In Formula 9-1, 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 9-2]

[Formula 9-3]

[Formula 9-4]

[Formula 9-5]

(In Formula 9-5, 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 9-6]

[Formula 9-7]

The cardo-based binder 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 acid anhydride; glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methyl pyrrolidone; 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 an acrylic binder resin, a cardo-based binder resin, or a combination thereof, the developability of the curable composition is excellent, the sensitivity during photocuring is good, so the fine pattern formation is excellent, and it is very effective in preventing the decrease in luminance. It may work.

The weight average molecular weight of the binder resin may be 1,000 g/mol to 150,000 g/mol, for example, 2,000 g/mol to 50,000 g/mol. When the weight average molecular weight of the binder resin is within the above range, the physical and chemical properties of the curable composition according to the embodiment are excellent, the viscosity is appropriate, and the adhesion to the substrate is excellent.

The binder resin may be included in an amount of 1 wt% to 30 wt%, for example, 1 wt% to 20 wt%, based on the total amount of the curable composition. When the binder resin is included within the above range, it is possible to significantly lower the cure shrinkage.

menstruum

When the curable composition according to an embodiment is a solvent-type curable composition, it may further include a solvent.

Examples of the solvent include 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, and the like may be used, but are not limited thereto.

For example, the solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl Acetamide, dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone or these It may be desirable to use a combination.

For example, the solvent may be 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, dimethyl adipate. , 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The solvent may be included as a balance based on the total amount of the solvent-type curable resin composition, for example, 20 wt% to 70 wt%, for example 30 wt% to 60 wt%. When the solvent is included within the above range, since the solvent-type curable composition has an appropriate viscosity, it may have excellent coatability during spin coating and large-area coating using a slit.

other additives

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, 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 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 form of the dispersion 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 may be included as When the stabilizer is included within the above range, it is possible to solve the problem over time 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 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-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycan Cydoxy propyl trimethoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

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 ^® and the like; ^{Mecha Pack F 142D ®} , Mecha Pack F 172 ^® , Mecha Pack F 173 ^® , Mecha Pack F 183 ^® and the like of Dai Nippon Inki Chemical High School Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , Prorad FC-170C ^® , Prorad FC-430 ^® , Prorad FC-431 ^® and the like; Asahi Grass Co., Ltd. Saffron S-112 ^® , Saffron S-113 ^® , Saffron S-131 ^® , Saffron S-141 ^® , Saffron S-145 ^® and the like; ^{SH-28PA ®} , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , SF-8428 ^{® 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, other additives such as antioxidants and stabilizers may be further added to the curable composition in a certain amount within a range that does not impair physical properties.

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

One of the methods of manufacturing the resin film includes the steps of forming a pattern by applying the above-described curable composition on 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 20 μm by an inkjet dispersion method. In the inkjet spraying, a pattern can be formed by spraying only a single color for each nozzle and repeatedly spraying according to the required number of colors. can also be formed.

(S2) curing step

A pixel can be obtained by curing the obtained pattern. In this case, as a curing method, both a thermosetting process and a photocuring process may be applied. The thermosetting process is preferably cured by heating at a temperature of 100 ° C. or higher, more preferably by heating at 100 ° C. to 300 ° C. to cure, and more preferably by heating at 160 ° C. to 250 ° C. can In the photocuring process, actinic rays such as UV rays of 190 nm to 450 nm, for example 200 nm to 500 nm, are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used.

Another one of the methods for manufacturing the resin film is to prepare a cured film using a lithography method using the above-described curable composition, and the manufacturing method is as follows.

(1) Application and coating film formation step

The above-mentioned curable composition is applied to a desired thickness, for example, 2 µm to 10 µm, using a method such as spin or slit coat method, roll coat method, screen printing method, and applicator method on a substrate subjected to a predetermined pretreatment. After that, the coating film is formed by heating at a temperature of 70° C. to 90° C. for 1 minute to 10 minutes to remove the solvent.

(2) exposure step

After interposing a mask of a predetermined shape to form a pattern required for the obtained coating film, actinic rays such as UV rays of 190 nm to 450 nm, for example 200 nm to 500 nm, are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used.

The exposure amount varies depending on the type, compounding amount, and dry film thickness of each component of the curable composition, but is, for example, 500 mJ/cm ² or less (by a 365 nm sensor) when a high-pressure mercury lamp is used.

(3) development step

Following the exposure step, an image pattern is formed by dissolving and removing unnecessary portions using an alkaline aqueous solution as a developer so that only the exposed portions remain. That is, when developing with an alkali developer, the unexposed portion is dissolved and an image color filter pattern is formed.

(4) post-processing step

In order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, and the like, the image pattern obtained by the above development can be cured by heating again or by irradiation with actinic rays or the like.

Another embodiment provides a display device including the resin film.

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.

(Synthesis of surface modification material)

Each of the compounds represented by Chemical Formulas 2 to 6 is synthesized as shown in FIG. 4 .

(Preparation of surface-modified quantum dot dispersion solution)

Preparation 1-1

To 10 g of InP/ZeSe/ZnS-oleate ligand QD (quantum dots; solid content 20%) solution dispersed in cyclohexane, 2 g of the compound represented by the following formula 2 and _{10 mg of ZnCl 2} were added, stirred at room temperature for 1 hour, and the temperature was raised to 70°C. After stirring for 3 hours, the reaction mass was lowered to room temperature. After stirring at room temperature for 1 hour, use a centrifuge (7000 rpm, 10 min) to capture the precipitate, and then remove the solution. After separating the surface-modified quantum dot powder by drying it at room temperature for 3 hours using a vacuum oven (2g), it is dispersed in 6g of PGMEA to make a quantum dot dispersion solution with a solid content of 25%.

[Formula 2]

Preparation 1-2

Except for using acetone instead of PGMEA, it was carried out in the same manner as in Preparation Example 1-1.

Preparation 1-3

Except for using DPMA (Di(propylene glycol) methyl ether acetate) instead of PGMEA, it was the same as in Preparation Example 1-1.

Preparation Example 1-4

2 g of the surface-modified quantum dot powder was dispersed in 2 g of Triallyl cyanurate (TCI), a polymerizable compound instead of PGMEA, to prepare a quantum dot dispersion solution, and the same as in Preparation Example 1-1.

Preparation 1-5

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound DPHA (Nippon Kayaku) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 1-1.

Preparation 2-1

Except for using the compound represented by the following formula (3) instead of the compound represented by the formula (2), it was carried out in the same manner as in Preparation Example 1-1.

[Formula 3]

Preparation Example 2-2

Except for using acetone instead of PGMEA, it was carried out in the same manner as in Preparation Example 2-1.

Preparation 2-3

Except for using DPMA (Di(propylene glycol) methyl ether acetate) instead of PGMEA, it was the same as in Preparation Example 2-1.

Preparation 2-4

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound Triallyl cyanurate (TCI) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 2-1.

Preparation Example 2-5

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound DPHA (Nippon Kayaku Co.) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 2-1.

Production Example 3-1

Except for using the compound represented by the following formula (4) instead of the compound represented by the formula (2), it was carried out in the same manner as in Preparation Example 1-1.

[Formula 4]

Preparation 3-2

Except that acetone was used instead of PGMEA, it was carried out in the same manner as in Preparation Example 3-1.

Production Example 3-3

Except for using DPMA (Di(propylene glycol) methyl ether acetate) instead of PGMEA, the same procedure as in Preparation Example 3-1 was used.

Preparation 3-4

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound Triallyl cyanurate (TCI) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 3-1.

Preparation 3-5

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound DPHA (Nippon Kayaku Co.) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 3-1.

Preparation 4-1

Except for using the compound represented by the following formula (5) instead of the compound represented by the formula (2), it was carried out in the same manner as in Preparation Example 1-1.

[Formula 5]

Preparation 4-2

Except for using acetone instead of PGMEA, it was carried out in the same manner as in Preparation Example 4-1.

Preparation 4-3

Except for using DPMA (Di(propylene glycol) methyl ether acetate) instead of PGMEA, it was the same as in Preparation Example 4-1.

Preparation 4-4

2 g of the surface-modified quantum dot powder was dispersed in 2 g of Triallyl cyanurate (TCI), a polymerizable compound instead of PGMEA, to prepare a quantum dot dispersion solution, and the same as in Preparation Example 4-1.

Preparation 4-5

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound DPHA (Nippon Kayaku) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 4-1.

Preparation 5-1

Except for using the compound represented by the following formula (6) instead of the compound represented by the formula (2), it was carried out in the same manner as in Preparation Example 1-1.

[Formula 6]

Preparation 5-2

Except for using acetone instead of PGMEA, it was carried out in the same manner as in Preparation Example 5-1.

Preparation 5-3

Except for using DPMA (Di(propylene glycol) methyl ether acetate) instead of PGMEA, it was the same as in Preparation Example 5-1.

Preparation 5-4

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound Triallyl cyanurate (TCI) instead of PGMEA to prepare a quantum dot dispersion solution, but the same as in Preparation Example 5-1.

Preparation 5-5

2 g of the surface-modified quantum dot powder was dispersed in 2 g of a polymerizable compound DPHA (Nippon Kayaku Co.) instead of PGMEA to prepare a quantum dot dispersion solution, and the same as in Preparation Example 5-1.

(Preparation of curable composition)

Examples 1 to 25 and Comparative Examples 1 to 4

Curable compositions according to Examples 1 to 25 and Comparative Examples 1 to 4 were prepared with the compositions shown in Tables 1 to 3 by using the components mentioned below.

(A) Quantum dot dispersion solution

(A-1) Quantum dot dispersion solution according to Preparation Example 1-1

(A-2) Quantum dot dispersion solution according to Preparation Example 1-2

(A-3) Quantum dot dispersion solution according to Preparation Example 1-3

(A-4) Quantum dot dispersion solution according to Preparation Example 1-4

(A-5) Quantum dot dispersion solution according to Preparation Example 1-5

(A-6) Quantum dot dispersion solution according to Preparation Example 2-1

(A-7) Quantum dot dispersion solution according to Preparation Example 2-2

(A-8) Quantum dot dispersion solution according to Preparation Example 2-3

(A-9) Quantum dot dispersion solution according to Preparation Example 2-4

(A-10) Quantum dot dispersion solution according to Preparation Example 2-5

(A-11) Quantum dot dispersion solution according to Preparation Example 3-1

(A-12) Quantum dot dispersion solution according to Preparation Example 3-2

(A-13) Quantum dot dispersion solution according to Preparation 3-3

(A-14) Quantum dot dispersion solution according to Preparation 3-4

(A-15) Quantum dot dispersion solution according to Preparation Example 3-5

(A-16) Quantum dot dispersion solution according to Preparation Example 4-1

(A-17) Quantum dot dispersion solution according to Preparation Example 4-2

(A-18) Quantum dot dispersion solution according to Preparation Example 4-3

(A-19) Quantum dot dispersion solution according to Preparation Example 4-4

(A-20) Quantum dot dispersion solution according to Preparation Example 4-5

(A-21) Quantum dot dispersion solution according to Preparation Example 5-1

(A-22) Quantum dot dispersion solution according to Preparation Example 5-2

(A-23) Quantum dot dispersion solution according to Preparation Example 5-3

(A-24) Quantum dot dispersion solution according to Preparation Example 5-4

(A-25) Quantum dot dispersion solution according to Preparation Example 5-5

(A-26) InP/ZeSe/ZnS-oleate ligand QD dispersion (quantum dots; solid content 20% in cyclohexane)

(B) polymerizable compound

(B-1) Triallyl cyanurate (TCI)

(B-2) Dipentaerythritol hexamethacrylate (DPHA, Nippon Kayaku)

(C) polymerization initiator

Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO, Sigma-Aldrich)

(D) binder resin

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

(E) solvent

(E-1) PGMEA (Sigma-Aldrich)

(E-2) Acetone (Sigma-Aldrich)

(E-3) DPMA (Di(propylene glycol) methyl ether acetate; Sigma-Aldrich)

(E-4) CHA (cyclohexyl acetate; Sigma-Aldrich)

(F) diffusion agent

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

(G) other additives

Fluorine surfactant (F-554, DIC Corporation)

(Unit: % by weight) Example One 2 3 4 5 6 7 8 9 10 (A) Quantum dots (A-1) 40 - - - - - - - - - (A-2) - 40 - - - - - - - - (A-3) - - 40 - - - - - - - (A-4) - - - 91.5 - - - - - - (A-5) - - - - 91.5 - - - - - (A-6) - - - - - 40 - - - - (A-7) - - - - - - 40 - - - (A-8) - - - - - - - 40 - - (A-9) - - - - - - - - 91.5 - (A-10) - - - - - - - - - 91.5 (B) polymerizable compound (B-1) - - - 2 - - - - 2 - (B-2) - - - - 2 - - - - 2 (C) polymerization initiator 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (D) binder resin 15 15 15 - - 15 15 15 - - (E) solvent (E-1) 38.5 - - - - 38.5 - - - - (E-2) - 38.5 - - - - 38.5 - - - (E-3) - - 38.5 - - - - 38.5 - - (F) diffusion agent 4 4 4 4 4 4 4 4 4 4 (G) other additives One One One One One One One One One One

(Unit: % by weight) Example 11 12 13 14 15 16 17 18 19 20 (A) Quantum dots (A-11) 40 - - - - - - - - - (A-12) - 40 - - - - - - - - (A-13) - - 40 - - - - - - - (A-14) - - - 91.5 - - - - - - (A-15) - - - - 91.5 - - - - - (A-16) - - - - - 40 - - - - (A-17) - - - - - - 40 - - - (A-18) - - - - - - - 40 - - (A-19) - - - - - - - - 91.5 - (A-20) - - - - - - - - - 91.5 (B) polymerizable compound (B-1) - - - 2 - - - - 2 - (B-2) - - - - 2 - - - - 2 (C) polymerization initiator 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (D) binder resin 15 15 15 - - 15 15 15 - - (E) solvent (E-1) 38.5 - - - - 38.5 - - - - (E-2) - 38.5 - - - - 38.5 - - - (E-3) - - 38.5 - - - - 38.5 - - (F) diffusion agent 4 4 4 4 4 4 4 4 4 4 (G) other additives One One One One One One One One One One

(Unit: % by weight) Example comparative example 21 22 23 24 25 One 2 3 4 (A) Quantum dots (A-21) 40 - - - - - - - - (A-22) - 40 - - - - - - - (A-23) - - 40 - - - - - - (A-24) - - - 91.5 - - - - - (A-25) - - - - 91.5 - - - - (A-26) - - - - - 40 40 40 40 (B) polymerizable compound (B-1) - - - 2 - - - - - (B-2) - - - - 2 - - - - (C) polymerization initiator 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (D) binder resin 15 15 15 - - 15 15 15 15 (E) solvent (E-1) 38.5 - - - - 38.5 - - - (E-2) - 38.5 - - - - 38.5 - - (E-3) - - 38.5 - - - - 38.5 - (E-4) - - - - - - - - 38.5 (F) diffusion agent 4 4 4 4 4 4 4 4 4 (G) other additives One One One One One One One One One

Evaluation 1: Evaluation of dispersibility of quantum dot dispersion solution

Using a particle size analyzer to measure the particle size of each quantum dot dispersion solution (A-1 to A-26) used in the curable compositions according to Examples 1 to 25 and Comparative Examples 1 to 4 three times, respectively, The average was obtained, and the results are shown in Table 4 below.

Quantum dot dispersion solution A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 particle size (nm) 14.5 14.6 14.6 15.4 15.5 14.7 14.7 14.8 15.5 15.4 Quantum dot dispersion solution A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 particle size (nm) 14.8 14.6 14.6 15.3 15.5 14.7 14.7 14.9 15.3 15.5 Quantum dot dispersion solution A-21 A-22 A-23 A-24 A-25 A-26 particle size (nm) 14.7 14.7 14.9 15.3 15.5 16.2

From Table 4, the quantum dot dispersion solutions (A-1 to A-25) used in Examples 1 to 25 are compared with the quantum dot dispersion solutions (A-26) used in Comparative Examples 1 to 4, Since there is little difference in particle size, it can be confirmed that dispersion stability in a solvent and a polymerizable compound is excellent.

Evaluation 2: Evaluation of light conversion rate after inkjet process

15 ml of each of the curable compositions according to Examples 1 to 25 and Comparative Examples 1 to 4 were taken, ink-jetted on a glass substrate, and then heated at 200° C. for 1 minute using a hot-plate. After curing to form a coating film, the light conversion rate for each coating film was measured with a CAS 140 CT spectrometer, and the results are shown in Table 5 below.

Example One 2 3 4 5 6 7 8 9 10 Photoconversion rate (%) 77 76 73 74 80 76 76 75 75 78 Example 11 12 13 14 15 16 17 18 19 20 Photoconversion rate (%) 77 76 72 73 77 74 75 74 74 76 Example comparative example 21 22 23 24 25 One 2 3 4 Photoconversion rate (%) 76 76 73 75 79 NG
(non-dispersion) NG
(non-dispersion) NG
(non-dispersion) 70

As shown in Table 5, in the case of Examples 1 to 25, compared with Comparative Examples 1 to 4, it can be confirmed that the decrease in the light conversion rate after thermal curing is not large.

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.

Claims (18)

A curable composition comprising quantum dots surface-modified with a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, *-C(=O)O-*, or represented by the following formula L-1,
[Formula L-1]

In the formula L-1,
L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,
X is an oxygen atom or a sulfur atom,
n is an integer from 1 to 20;
According to claim 1,
Wherein L ¹ is represented by the general formula L-1,
The L ^{2 To} L ⁴ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or *-C (=O) O-* The curable composition.
According to claim 1,
Wherein L ¹ is a curable composition represented by the following Chemical Formula L-1-1, Chemical Formula L-1-2, or a combination thereof:
[Formula L-1-1]

[Formula L-1-2]

In the above formulas L-1-1 and L-1-2,
L ⁵ is a substituted or unsubstituted C1 to C20 alkylene group,
n1 and n2 are each independently an integer from 1 to 10.
4. The method of claim 3,
The compound represented by Formula 1 is a curable composition represented by any one of Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
R ¹ is a hydrogen atom, a hydroxy group, a carboxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 an aryl group,
L ² , L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
n1 and n2 are each independently an integer from 1 to 10.
According to claim 1,
The compound represented by Formula 1 is a curable composition represented by any one of Formulas 2 to 6 below.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

According to claim 1,
The curable composition further comprises a polymerizable compound having a carbon-carbon double bond at the terminal.
7. The method of claim 6,
A curable composition wherein the polymerizable compound is a polymerizable monomer having at least one functional group represented by the following Chemical Formula 7-1 or a functional group represented by the following Chemical Formula 7-2 at the terminal thereof:
[Formula 7-1]

[Formula 7-2]

In Formulas 7-1 and 7-2,
L ⁶ is a substituted or unsubstituted C1 to C20 alkylene group,
R ² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
According to claim 1,
The quantum dots have a core-shell structure,
The shell is a curable composition comprising Zn.
According to claim 1,
The quantum dot is a curable composition that absorbs light of 360 nm to 780 nm, and emits fluorescence at 500 nm to 700 nm.
10. The method of claim 9,
The quantum dot is a curable composition comprising a green quantum dot and a red quantum dot.
According to claim 1,
The curable composition further comprises a polymerization initiator, a light diffusing agent, or a combination thereof.
12. The method of claim 11,
The light diffusing 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 at least one selected from the group consisting of a binder resin and a solvent.
14. The method of claim 13,
The binder resin is a curable composition comprising an acrylic binder resin, a cardo-based binder resin, or a combination thereof.
14. The method of claim 13,
The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, cyclohexyl acetate, ethanol, ethylene glycol dimethyl ether, ethylene glycol butyl ether acetate, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, dimethyl acetamide , dimethyl adipate, cyclohexyl acrylate, hydroxyethyl acrylate, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, acetone or a combination thereof A curable composition comprising.
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 to 16.
A display device comprising the resin film of claim 17 .

Images