KR20240004020A - Curable composition, cured layer using the composition, color filter including the cured layer and display device including the color filter - Google Patents

Abstract

(A) Quantum dots passivated with indium oxide; and (B) a curable composition containing a polymerizable compound, a cured film manufactured using the curable composition, a color filter containing the cured film, and a display device containing the color filter.

Description

A curable composition, a cured film manufactured using the composition, a color filter comprising the cured film, and a display device comprising the color filter {CURABLE COMPOSITION, CURED LAYER USING THE COMPOSITION, COLOR FILTER INCLUDING THE CURED LAYER AND DISPLAY DEVICE INCLUDING THE COLOR FILTER}

This description relates to a curable composition, a cured film manufactured using the composition, a color filter comprising the cured film, and a display device comprising the color filter.

In the case of general quantum dots, the solvent in which they are dispersed is limited due to their hydrophobic surface characteristics, and as a result, it is true that they face many difficulties in introducing them into polar systems such as binders or curable monomers.

For example, even in the case of quantum dot ink compositions that are being actively studied, at the initial stage, they were dispersed in solvents used in curable compositions with relatively low polarity and high hydrophobicity. For this reason, it was difficult to include more than 20% by weight of quantum dots relative to the total amount of the composition, making it impossible to increase the luminous efficiency of the ink beyond a certain level, and even if additional quantum dots were added and dispersed to increase luminous efficiency, ink-jetting was not possible. This possible point also exceeded the range, so fairness could not be satisfied.

In addition, in order to achieve a viscosity range that allows ink-jetting, a method of lowering the ink solid content by including more than 50% by weight of solvent relative to the total amount of the composition has been used, and this method also has somewhat satisfactory results in terms of viscosity. However, during ink-jetting, there are problems such as nozzle drying due to solvent volatilization, nozzle clogging, and single film thickness decrease over time after ink-jetting, and the thickness deviation after curing is severe. It has the disadvantage of being difficult to apply to actual processes.

Therefore, the solvent-free type of quantum dot ink that does not contain a solvent is the most desirable form to apply in actual processes, and the current technology for applying quantum dots themselves to solvent-type compositions is evaluated to have reached a certain limit.

In the case of solvent-free curable compositions (quantum dot ink compositions), due to the nature of containing an excessive amount of polymerizable compounds, clogging and discharge defects due to nozzle drying due to volatility, and single film thickness reduction due to volatilization of the ink composition jetted within the pattern partition pixels etc. becomes a problem. Therefore, it is best to lower the viscosity of the solvent-free curable composition as much as possible. Accordingly, efforts have been made to lower the viscosity of the solvent-free curable composition by modifying the structure of the polymerizable compound, such as increasing the molecular weight of the polymerizable monomer or introducing a chemical structure containing a hydroxy group.

However, in addition to the viscosity of solvent-free curable compositions, the high durability of quantum dots has also recently become an important issue. Unlike in the past, as the amount of light from the light source being used is increasing, it has been revealed through several recent studies that the development of quantum dots that are not vulnerable to such high amounts of light, that is, have excellent durability, and the viscosity of the curable composition are equally important.

However, in addition to the viscosity of the curable composition, efforts to improve the durability of quantum dots included in the curable composition have been very insufficient, and research on this has recently begun.

One embodiment is to provide a curable composition containing quantum dots with excellent durability.

Another embodiment is to provide a cured film manufactured using the curable composition and having excellent long-term reliability.

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

Another embodiment is to provide a display device including the color filter.

One embodiment includes (A) quantum dots passivated with indium oxide; and (B) a polymerizable compound.

The quantum dot includes an indium oxide passivation layer, and the passivation layer may have a thickness of 0.1 nm to 1 nm.

The quantum dot may be a quantum dot whose surface has been surface modified with a surface modification material.

The surface modification material may be represented by Formula 1 and/or Formula 2 below.

[Formula 1]

In Formula 1,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ² is represented by the following formula R-1,

[Formula R-1]

In the above formula R-1,

X is CR (R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or N,

L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

n1 is an integer from 0 to 20.

[Formula 2]

In Formula 2,

L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ³ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n2 is an integer from 0 to 20.

The surface modification material includes compounds represented by Formula 1 and Formula 2, and the compound represented by Formula 1 may be included in an amount equal to or less than the compound represented by Formula 2 relative to the total amount of the surface modification material. there is.

The compound represented by Formula 1 and the compound represented by Formula 2 may be included in a weight ratio of 1:9 to 5:5 relative to the total amount of the surface modification material.

The compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

L ¹ , L ² , L ⁵ and L ⁶ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 and n2 are each independently integers from 0 to 20.

The compound represented by Formula 1 may be represented by Formula 1A or Formula 1B below.

[Formula 1A]

[Formula 1B]

The compound represented by Formula 2 may be represented by Formula 2A or Formula 2B below.

[Formula 2A]

[Formula 2B]

The curable composition may be a solvent-free curable composition.

The solvent-free curable composition includes 5 to 60 wt% of the quantum dots, based on the total amount of the solvent-free curable composition; And it may include 40% by weight to 95% by weight of the polymerizable compound.

The curable composition may further include a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.

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

The curable composition may further include a solvent.

The curable composition includes 1% to 40% by weight of the quantum dots, based on the total weight of the curable composition; 1% to 20% by weight of the polymerizable compound; And it may include 40% by weight to 80% by weight of the solvent.

The curable composition includes malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or, it may further include a combination thereof.

Another embodiment provides a cured film manufactured using the curable composition.

Another embodiment provides a color filter including the cured film.

Another embodiment provides a display device including the color filter.

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

By coating (or passivating) the surface of the quantum dots with indium oxide and then using it in a curable composition, the cured single film of the curable composition containing the quantum dots can maintain luminous efficiency at a high level even after going through several curing processes.

Figure 1 is a diagram showing quantum dots coated (or passivated) with indium oxide and simultaneously surface modified with a surface modification material.

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 herein, “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, “arylalkyl group” refers to a C6 to C20 arylalkyl group, and “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 heteroarylene group. It means an arylene group, and “alkoxylene group” means a C1 to C20 alkoxylene group.

Unless otherwise specified herein, “substitution” means that at least one hydrogen atom is replaced by 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 its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl 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.

Also, unless otherwise specified herein, “hetero” means that at least one hetero atom of N, O, S, and P is included in the chemical formula.

Also, unless otherwise specified in the specification, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acrylic acid” means “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 this specification, if a chemical bond is not drawn at a position where a chemical bond should be drawn, it means that a hydrogen atom is bonded at that position.

Additionally, unless otherwise specified in the specification, “*” refers to a portion connected to the same or different atom or chemical formula.

The quantum dot-containing curable composition according to the present invention includes quantum dots passivated with indium oxide, so that the durability of the quantum dots is excellent, and a cured single film made from the curable composition can maintain high luminous efficiency for a long time.

In quantum dot applications, the most important factor for commercialization is stabilizing the durability and reliability of quantum dot particles in quantum dot displays. In particular, OLED, which is currently used as a blue backlight unit, is gradually being replaced by NED or μLED, and the light amount of the NED or μLED blue backlight (blue BLU) is about 10 to 100 times greater than that of the OLED. high.

However, looking at most quantum dot displays currently on the market, the long-term reliability of the solid quantum dot film single layer appears to be very weak, so in case the light source is replaced by a blue backlight with a higher light quantity, high durability is required. The need for quantum dots is increasingly being emphasized.

When quantum dot particles absorb blue light, most of it is converted into luminous light and gives off energy, but some of it is dissipated as heat due to minute lattice vibrations. However, as blue light energy increases, more heat is dissipated due to increased heat generation on the surface of the quantum dot, which is a major cause of deterioration in the performance of the quantum dot. In addition, even if quantum dots are surface modified with a conventional surface modification material, when a blue backlight with a high amount of light is used, there is a limitation in that the meaning of quantum dot surface modification to improve the light resistance of quantum dots may be greatly faded.

Accordingly, the present inventors accurately recognized the above problem, and in order to ensure that the quantum dots maintain their durability even when using a blue backlight with a high amount of light, after conducting numerous researches and experiencing a lot of trial and error, they finally achieved the surface of the quantum dots. It was confirmed that the above problem could be solved by coating with indium oxide, and the present invention was completed.

Hereinafter, each component constituting the curable composition according to one embodiment will be described in detail.

quantum dot

The surface of the quantum dots in the curable composition according to one embodiment is coated or passivated with indium oxide (In ₂ O ₃ ). Through this, the durability of quantum dots, specifically heat stability, can be greatly improved. The oxide must be indium oxide, and when metal oxides other than indium, such as manganese, iron, and zinc, are used, a double peak is generated and the problem of color purity deterioration inevitably occurs. The quantum dot surface must be coated or passivated with indium oxide.

One embodiment may provide a curable composition, specifically a solvent-free curable composition, including quantum dots whose surface is coated or passivated with indium oxide (In ₂ O ₃ ), and such a curable composition has never been attempted yet in this technical field. It must be a curable composition with a new type of composition that has never been used before.

For example, the quantum dot includes an indium oxide passivation layer (or coating layer), and the passivation layer (or coating layer) may have a thickness of 1 nm or less, for example, 0.1 nm to 1 nm. When quantum dots as a component used in a curable composition have a passivation layer, the thickness of the passivation layer corresponds to a configuration that directly affects the durability of the quantum dots and the luminous efficiency maintenance rate of the cured single film manufactured by the curable composition. , can be very important. For example, if the thickness of the passivation layer is less than 0.1 nm, it may be difficult to expect a passivation effect because the thickness is too thin (in addition, manufacturing the passivation layer itself with a thickness of less than 0.1 nm is not easy in terms of the process). If the thickness of the passivation layer is more than 1 nm, the thickness may be too thick and the effect of quantum dot surface modification by the surface modification material described later may be halved.

Meanwhile, as is well known, the most efficient existing ligand structure that can passivate the surface of quantum dots with organic ligands is a ligand containing a thiol group, and carboxylic acid-type ligands are used to passivate the surface of quantum dots with organic ligands. The interaction with the surface is relatively weak, and the phosphoric acid-type ligand has good dispersibility of quantum dots, but has a weakness that reduces efficiency (causing color change).

Current display technologies have been developed, starting with LCD in the past, OLED, NED, and recently micro LED. As mentioned above, the intensity of blue light is increasing, and the durability of quantum dots is expected to be significantly improved compared to the current level. There is a need.

Accordingly, in order to maximize the improvement of the durability of the quantum dots, the surface of the quantum dots passivated with the indium oxide can be further surface modified with a thiol group-containing ligand (surface modification material).

For example, the thiol group-containing surface modification material may be a bidentate thiol ligand, specifically a surface modification material represented by the following formula (1), or a surface modification material represented by the following formula (2), and these may be applied simultaneously. When the quantum dot surface is further surface modified with the surface modification material in addition to the indium oxide coating layer, the initial luminous efficiency is maintained even when exposed to strong blue light for a long time when the final quantum dot-containing curable composition is mounted on a display panel in the form of a single film. It is possible to provide quantum dots with good light resistance properties that maintain and a curable composition containing quantum dots containing the same.

[Formula 1]

In Formula 1,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ² is represented by the following formula R-1,

[Formula R-1]

In the above formula R-1,

X is CR (R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or N,

L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

n1 is an integer from 0 to 20.

[Formula 2]

In Formula 2,

L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ³ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n2 is an integer from 0 to 20.

In the case of quantum dots that are simultaneously surface-modified with the surface modification materials represented by Formula 1 and Formula 2, it is very easy to prepare a high-concentration or highly concentrated quantum dot dispersion (improved dispersibility of quantum dots with respect to polymerizable monomers, which will be described later), resulting in low viscosity and light resistance. It can have a significant impact on improving properties, and can be particularly advantageous in implementing solvent-free curable compositions. Furthermore, light resistance properties can be further improved by controlling the mixing weight ratio of the surface modification materials represented by Formula 1 and Formula 2.

For example, the surface modification material represented by Formula 1 may be included in an amount equal to or smaller than the surface modification material represented by Formula 2 relative to the total amount of the quantum dot surface modification material.

For example, with respect to the total amount of the quantum dot surface modification material, the surface modification material represented by Formula 1 and the surface modification material represented by Formula 2 have a weight ratio of 1:9 to 5:5, for example, 1:9 to 3:7. , for example, may be included in a weight ratio of 1:9 to 2:8. When the surface modification material represented by Formula 1 and the surface modification material represented by Formula 2 have the above weight ratio, the curable composition according to one embodiment has a low viscosity, for example, 30 cPs, for example, 29 cPs or less. It can maintain high light resistance properties while maintaining high light resistance.

For example, the surface modification material represented by Formula 1 may be represented by the following Formula 1-1 or Formula 1-2, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

L ¹ , L ² , L ⁵ and L ⁶ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 and n2 are each independently integers from 0 to 20.

For example, the surface modification material represented by Formula 1 may be represented by Formula 1A or Formula 1B below, but is not necessarily limited thereto.

[Formula 1A]

[Formula 1B]

For example, the surface modification material represented by Formula 2 may be represented by Formula 2A or Formula 2B below, but is not necessarily limited thereto.

[Formula 2A]

[Formula 2B]

When quantum dots surface-modified with the surface modification material represented by Formula 1 and the surface modification material represented by Formula 2 are added to a polymerizable compound described later and stirred, a very transparent dispersion can be obtained, which is achieved by surface modification of quantum dots. It serves as a measure to confirm that something was done very well.

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

For example, when the curable composition according to one embodiment is a solvent-free curable composition, the quantum dots are present in an amount of 5% by weight to 60% by weight, such as 10% by weight to 60% by weight, such as 20% by weight to 60% by weight, such as 30% by weight. It may be included in 50% by weight. When the quantum dots are included within the above range, high light retention rate and light efficiency can be achieved even after curing.

For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the quantum dots may be included in an amount of 1% to 40% by weight, for example, 3% to 30% by weight, based on the total amount of the curable composition. When the quantum dots are included within the above range, optical conversion rate and pattern characteristics may be excellent.

To date, curable compositions (inks) containing quantum dots have been developed to specialize in thiol-based binders or monomers with good compatibility with quantum dots, and are even being commercialized.

For example, the quantum dots absorb light in a wavelength range of 360 nm to 780 nm, for example, 400 nm to 780 nm, and emit fluorescence in a wavelength range of 500 nm to 700 nm, for example, 500 nm to 580 nm, or emit fluorescence in a wavelength range of 600 nm to 680 nm. You can. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ _em ) of 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, color purity is high, which has the effect of increasing 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 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 each independently consist of a core made of group II-IV, group III-V, etc., core/shell, core/first shell/ It may have a structure such as a second shell, an alloy, or 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. , but is not necessarily limited to this. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

In one embodiment, as interest in the environment has recently greatly increased worldwide and regulations on toxic substances have been strengthened, a light-emitting material with a cadmium-based core may be used instead of a light-emitting material, which has a somewhat low quantum yield but is environmentally friendly. Non-cadmium-based light emitting materials (InP/ZnS, InP/ZeSe/ZnS, etc.) were used, but are not necessarily limited thereto.

In the case of the quantum dots 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 each independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may each independently have an average particle diameter of 10 nm to 15 nm. The green quantum dots may each independently have an average particle diameter of 5 nm to 8 nm.

Meanwhile, for the dispersion stability of the quantum dots, the curable composition according to one embodiment may further include a dispersant. The dispersant helps the light conversion material such as quantum dots to be uniformly dispersed within the curable composition, and nonionic, anionic, or cationic dispersants can all be used. Specifically, polyalkylene glycol or its esters, polyoxy alkylene, 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. can be used, and these can be used alone or in a mixture of two or more types. The dispersant may be used in an amount of 0.1% to 100% by weight, for example, 10% to 20% by weight, based on the solid content of the light conversion material such as quantum dots.

polymerizable compound

The curable composition according to one embodiment includes a polymerizable compound, and the polymerizable compound may have a carbon-carbon double bond at the terminal.

The polymerizable compound having a carbon-carbon double bond at the terminal may be included in an amount of 40% by weight to 95% by weight, for example, 50% by weight to 90% by weight, based on the total amount of the solvent-free curable composition. When the content of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, it is possible to manufacture a solvent-free curable composition having a viscosity capable of ink jetting. In addition, the quantum dots in the prepared solvent-free curable composition have excellent dispersibility. , optical characteristics can also be improved.

For example, the polymerizable compound having a carbon-carbon double bond at the terminal may have a molecular weight of 170 g/mol to 1,000 g/mol. When the molecular weight of the polymerizable compound having a carbon-carbon double bond at the terminal is within the above range, it can be advantageous for ink-jetting because it does not impair the optical properties of the quantum dots and does not increase the viscosity of the composition.

For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following formula (6), but is not necessarily limited thereto.

[Formula 6]

In Formula 6 above,

R ⁶ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ⁷ and L ⁹ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

L ⁸ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or an ether group (*-O-*).

For example, the polymerizable compound having a carbon-carbon double bond at the terminal may be represented by the following formula 6-1 or 6-2, but is not necessarily limited thereto.

[Formula 6-1]

[Formula 6-2]

For example, polymerizable compounds having a carbon-carbon double bond at the terminal include, in addition to the compounds represented by Formula 6-1 or Formula 6-2, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, It may further include triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

In addition, in addition to the polymerizable compound having a carbon-carbon double bond at the terminal, it may further include a monomer commonly used in conventional thermosetting or photocuring compositions. For example, the monomer may be bis[1-ethyl(3-ox). [cetanyl)] It may further include oxetane-based compounds such as methyl ether.

In addition, when the curable composition includes a solvent, the polymerizable compound may be included in an amount of 1% to 20% by weight, 1% to 15% by weight, such as 5% to 15% by weight, based on the total amount of the curable composition. there is. When the polymerizable compound is included within the above range, the optical properties of the quantum dots can be improved.

light diffuser

The curable composition according to one embodiment may further include a light diffuser.

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

The light diffuser reflects light that is not absorbed by the quantum dots and allows the quantum dots to reabsorb the reflected light. That is, the light diffuser can increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion efficiency of the curable composition.

The light diffuser 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 diffuser is within the above range, a better light diffusion effect can be achieved and light conversion efficiency can be increased.

The light diffuser may be included in an amount of 1% to 20% by weight, such as 2% to 15% by weight, such as 3% to 10% by weight, based on the total amount of the curable composition. If the light diffuser is included in less than 1% by weight based on the total amount of the curable composition, it is difficult to expect an effect of improving light conversion efficiency due to the use of the light diffuser, and if it is included in more than 20% by weight, there is a problem of quantum dot precipitation. There is a risk that this may occur.

polymerization initiator

The curable composition according to one 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 commonly used in photosensitive resin compositions, for example, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and aminoketone-based compounds. etc. may be used, but are not necessarily limited thereto.

Examples of the acetophenone-based compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t-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.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 Examples include '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone, etc. can be 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 compounds 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. .

Examples of the oxime-based compounds include O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used. Specific examples of the O-acyloxime compounds 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)-butane-1-oneoxime- O-acetate, etc. can be mentioned.

Examples of the aminoketone-based compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1), etc.

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

The photopolymerization initiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transmits the energy to cause a chemical reaction.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. can be mentioned.

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

The polymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 1% to 4% by weight, 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 heat curing to obtain excellent reliability, and a decrease in transmittance due to unreacted initiator can be prevented, thereby preventing a decrease in the optical properties of the quantum dots.

binder resin

The curable composition according to one embodiment may further include a binder resin.

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

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

Specific examples of the acrylic binder resin include polybenzyl methacrylate, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/ Examples include, but are not limited to, 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and these can be used alone or in combination of two types. The above can also be used in combination.

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

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

The cardo-based resin can be used in a typical curable resin (or photosensitive resin) composition, for example, the one shown in Korean Patent Publication No. 10-2018-0067243 can be used, but is not limited thereto.

The cardo-based resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic acid dianhydride, Anhydride compounds such as rylene tetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic 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-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

The weight average molecular weight of the cardo-based resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. If the weight average molecular weight of the cardo-based resin is within the above range, a pattern can be easily formed without residue when producing a cured film, there is no loss of film thickness when developing the curable composition, and a good pattern can be obtained.

When the binder resin is a cardo-based resin, the curable composition containing it, especially the photosensitive resin composition, has excellent developability, has good sensitivity during photocuring, and has excellent fine pattern formation.

The epoxy resin is a monomer or oligomer that can be polymerized by heat, and may include compounds having a carbon-carbon unsaturated bond and a carbon-carbon cyclic bond.

The epoxy resin may include, but is not limited to, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.

As commercial products of these compounds, bisphenyl epoxy resins include YX4000, YX4000H, YL6121H, YL6640, and YL6677 from Yukashell Epoxy Co., Ltd.; Cresol novolak-type epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Yukashell Epoxy Co., Ltd. )'s Epicoat 180S75; Bisphenol A type epoxy resins include Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 from Yukashell Epoxy Co., Ltd.; Bisphenol F-type epoxy resins include Epicoat 807 and 834 from Yukashell Epoxy Co., Ltd.; Phenolic noblock-type epoxy resins include Epicoat 152, 154, and 157H65 from Yukashell Epoxy Co., Ltd. and EPPN 201 and 202 from Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CY175, CY177 and CY179 from CIBA-GEIGY A.G., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 from U.C.C., and Shodine 509 from Showa Denko Co., Ltd. , Araldite CY-182, CY-192 and CY-184 from CIBA-GEIGY A.G., Epicron 200 and 400 from Dainipbon Ink Kogyo Co., Ltd., and Epicot 871 and 872 from Yukashell Epoxy Co., Ltd. and EP1032H60, ED-5661 and ED-5662 from Celanese Coatings Co., Ltd.; Aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yukashell Epoxy Co., Ltd., Eporite 100MF from Kyoesha Yushi Chemical Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd. You can.

For example, when the curable composition according to one embodiment is a solvent-free curable composition, the binder resin may be included in an amount of 0.5% by weight to 10% by weight, for example, 1% by weight to 5% by weight, based on the total amount of the curable composition. In this case, the heat resistance and chemical resistance of the solvent-free curable composition can be improved, and the storage stability of the composition can also be improved.

For example, when the curable composition according to one embodiment is a curable composition containing a solvent, the binder resin may be included in an amount of 1% to 30% by weight, for example, 3% to 20% by weight, based on the total amount of the curable composition. In this case, it is excellent and can improve pattern characteristics, heat resistance, and chemical resistance.

Other additives

To improve the stability and dispersibility of the quantum dots, the curable composition according to one embodiment may further include a polymerization inhibitor.

The polymerization inhibitor may include a hydroquinone-based compound, a catechol-based compound, or a combination thereof, but is not necessarily limited thereto. As the curable composition according to one embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, room temperature crosslinking can be prevented during exposure to light after printing (coating) the curable composition.

For example, the hydroquinone-based compound, catechol-based compound, or combinations thereof include 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 -nitrosophenylamineto-O,O')aluminium) or a combination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, 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% by weight to 3% by weight, for example, 0.01% by weight to 2% by weight, based on the total amount of the curable composition. It can be included as a percentage. When the polymerization inhibitor is included within the above range, it is possible to solve the problem of aging at room temperature and prevent deterioration of sensitivity and surface peeling.

In addition, the curable composition according to one embodiment includes malonic acid to improve heat resistance and reliability; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or it may further include a combination thereof.

For example, the curable composition according to one embodiment may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, carboxyl group, methacryloxy group, isocyanate group, or epoxy group 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, and γ glycidoxy propyl. Trimethoxysilane, β-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be used, and these can be used alone or in combination of two or more.

The silane-based coupling agent may be included in an amount of 0.01 parts by weight 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, if necessary, to improve coating properties and prevent defects, that is, to improve leveling performance.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g/mol to 10,000 g/mol, and specifically, may have a weight average molecular weight of 6,000 g/mol to 10,000 g/mol. Additionally, the fluorine-based surfactant may have a surface tension of 18 mN/m to 23 mN/m (measured in 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). If the weight average molecular weight and surface tension of the fluorine-based surfactant are within the above range, leveling performance can be further improved, stains can be prevented during high speed coating, and there are fewer film defects due to less bubble generation. , gives excellent properties to slit coating, a high-speed coating method.

Examples of the fluorine-based surfactants include BM-1000 ^® and BM-1100 ^® from BM Chemie; Mecha pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , etc. from Dai Nippon Inki Chemicals Co., Ltd.; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® , etc. from Sumitomo 3M Co., Ltd.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® , etc.; Toray Silicone Co., Ltd.'s SH-28PA ^® , Dong-190 ^® , Dong-193 ^® , SZ-6032 ^® , SF-8428 ^® , etc.; Fluorine-based surfactants commercially available under names such as F-482, F-484, F-478, and F-554 from DIC Co., Ltd. can be used.

Additionally, the curable composition according to one embodiment may use a silicone-based surfactant along with the fluorine-based surfactant described above. Specific examples of the silicone-based surfactant include TSF400, TSF401, TSF410, and TSF4440 manufactured by Toshiba Silicone, but are not limited thereto.

Surfactants including the fluorine-based surfactant may be included in an amount of 0.01 parts by weight to 5 parts by weight, for example, 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the curable composition. When the surfactant is contained within the above range, the occurrence of foreign substances in the sprayed composition is reduced.

Additionally, a certain amount of other additives such as antioxidants may be added to the curable composition according to one embodiment within a range that does not impair the physical properties.

menstruum

Meanwhile, the curable composition according to one embodiment may further include a solvent.

The solvent includes, for example, 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 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; Alternatively, there are compounds of keto 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. Examples include ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., 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 or a combination thereof.

For example, the solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrroli It may be a polar solvent including dine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The solvent may be included in an amount of 40% to 80% by weight, for example, 45% to 80% by weight, based on the total amount of the curable composition. When the solvent is included within the above range, the solvent-type curable composition has an appropriate viscosity and can have excellent coating properties during large-area coating using spin coating and slit.

Another embodiment provides the curable composition, for example, a cured film manufactured using the curable composition, a color filter including the cured film, and a display device including the color filter.

One of the methods for producing the cured film includes forming a pattern by applying the curable composition on a substrate using an inkjet spraying method (S1); and curing the pattern (S2).

(S1) Step of forming a pattern

The curable composition is preferably applied to the substrate at a thickness of 0.5 to 20 ㎛ by inkjet dispersion. The inkjet spraying can form a pattern by spraying only a single color per nozzle and spraying repeatedly according to the number of colors required. To reduce the process, the pattern can be formed by spraying the required number of colors simultaneously through each inkjet nozzle. It can also be formed.

(S2) Curing step

Pixels can be obtained by curing the obtained pattern. At this time, as a curing method, either a thermal curing process or a photo curing process can be applied. The thermal curing process is preferably performed by heating to a temperature of 100°C or higher, more preferably by heating to 100°C to 300°C, and more preferably by heating to 160°C to 250°C. You can. The photocuring process irradiates active rays such as UV light of 190 nm to 450 nm, for example, 200 nm to 500 nm. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

Another method of manufacturing the cured film is to manufacture the cured film using the lithography method using the curable composition, and the manufacturing method is as follows.

(1) Application and film formation stage

The curable composition is applied to a desired thickness, for example, 2㎛ to 10㎛, using a method such as spin or slit coating, roll coating, screen printing, or applicator method on a substrate that has undergone a predetermined pretreatment. Afterwards, the solvent is removed by heating at a temperature of 70°C to 90°C for 1 to 10 minutes to form a coating film.

(2) exposure step

In order to form the necessary pattern on the obtained coating film, a mask of a predetermined shape is interposed, and then actinic rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm, are irradiated. Light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

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

(3) Development stage

Following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed parts remaining to form an image pattern. That is, when developing with an alkaline developer, the unexposed portion is dissolved and an image color filter pattern is formed.

(4) Post-processing step

The image pattern obtained by the above phenomenon can be cured by heating again or irradiating with actinic rays, etc., in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc.

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

(Preparation of curable composition)

Example 1

In general, in core-shell quantum dots, the thicker the shell, the better the stability. Therefore, instead of the red quantum dots with a thick shell, green quantum dots with a thinner shell were used to surface modify the quantum dots. Specifically, 13.13 g of indium acetate (III) and 10 mL of oleylamine were added to 30 g of a CHA (cyclohexyl acetate) solution containing quantum dots and stirred at 170°C for 1 hour. After preparing 600g of ethanol in a 1L capacity nalgene bottle, the quantum dot reaction solution was added and precipitated. It was centrifuged at 6000 rpm for 5 minutes, the clear filtrate was poured out, and the wet quantum dot particles were vacuum dried for 24 hours. The obtained quantum dot powder was redispersed in CHA at a concentration of 25%. 2.2 g of the compound represented by the following formula 2A was added to 26.66 g of quantum dot redispersion and stirred at 100°C for 24 hours. Prepare 400g of cyclohexane in a Nalgene bottle, add quantum dot reaction solution to it, and precipitate it. After centrifugation, the filtrate was removed and vacuum dried for 24 hours to obtain quantum dot powder (thickness of indium oxide coating layer; 1 nm).

Quantum dot powder was dispersed at a concentration of 50% in a polymerizable compound (M200, Miwon Chemical Co., Ltd.) represented by the following formula 6-2 and stirred for 12 hours to make a dispersion solution, and then a polymerization inhibitor (methylhydroquinone; TOKYO) was added. Add CHEMICAL Co., Ltd. and stir for 5 minutes. Next, after adding the photopolymerization initiator (TPO-L; Polynetron Co., Ltd.), a light diffuser (titanium dioxide dispersion; rutile type TiO ₂ ; D50 (180nm); solid content 50% by weight; Iridos Co., Ltd.) was added to increase curability. A composition was prepared.

(For example, in the case of Example 1, 41 g of the surface-modified green quantum dots and 41 g of a polymerizable compound represented by the following formula 6-2 were mixed and stirred to prepare a green quantum dot dispersion, and then the formula 6- 10 g of another curable monomer represented by number 2 and 1 g of a polymerization inhibitor were added and stirred for 5 minutes, and then 3 g of a photopolymerization initiator and 4 g of a light diffuser were added and stirred to prepare a curable composition (ink).)

[Formula 2A]

[Formula 6-2]

(Synthesis of the compound (second surface modification material) represented by Formula 2A:

Put 100g of PH-4 (Han Nong Chemical) into a two-neck round bottom flask and sufficiently dissolve in 300mL of tetrahydrofuran (THF). Add 15.4 g of NaOH and 100 mL of water at 0°C and dissolve sufficiently until a clear solution is formed. A solution of 73 g of para-toluene sulfonic chloride dissolved in 100 mL of THF is slowly injected at 0°C. Injection was carried out for 1 hour, and then stirred at room temperature for 12 hours. After completion of the reaction, an excess amount of methylene chloride is added and stirred, then a saturated NaHCO ₃ solution is added and extraction, titration, and moisture removal are performed. After removing the solvent, dry in a vacuum oven for 24 hours. 50 g of the obtained dried material was placed in a two-necked round bottom flask and thoroughly stirred in 300 mL of ethanol. Afterwards, add 27g of Thiourea, disperse, and reflux at 80°C for 12 hours. Afterwards, an aqueous solution of 4.4 g of NaOH dissolved in 20 mL of water was injected and stirred for an additional 5 hours. An excess amount of methylene chloride was added. After stirring, an aqueous hydrochloric acid solution was added and extraction, titration, moisture removal, and solvent removal were sequentially performed. By drying in a vacuum oven for 24 hours, a compound represented by the following formula 2A is obtained.)

Example 2

It was the same as Example 1, except that instead of 2.2g of the compound represented by Formula 2A, 1.98g of the compound represented by Formula 2A and 0.22g of the compound represented by Formula 1A below were used.

[Formula 1A]

(Synthesis of the compound (first surface modification material) represented by Formula 1A:

Add 10g of triethylene glycol monomethyl ether (TCI) and 11g of allyl bromide (TCI) to a flask and dissolve in 100mL of dimethylformamide (DMF). After cooling the flask, add 3g of 60% NaH portion-wise and stir for 10 hours. Add 50mL water here, complete the reaction, and then transfer to the separation funnel. Add 300mL of ethyl acetate, add 50mL of saturated sodium bicarbonate solution, and repeat extraction three times. Separate the organic layer, add MgSO- ₄ to it, and stir for 1 hour. After filtering, it is concentrated and further dried in a drying oven for 24 hours. Put 8g of the obtained intermediate back into the flask and dissolve in 100mL of methylene chloride. Add 10 g of m-CPBA (sigma Aldrich) and stir at 50°C for 10 hours. After removing the solvent, redisperse in 100 mL of water, add a drop of sulfuric acid, and stir at 60°C for 6 hours. The mixture separated from moisture using a suction filter is column purified (ethanol 3% methylene chloride mixed solvent). The solvent is removed and TEGME-diol is obtained. This obtained product was redispersed in THF/DIW (5/5) solvent, and 2.2 equivalents of NaOH was added to the dispersion solution under an ice bath and stirred for 10 minutes. Add 2.2 equivalents of p-toluenesulfonic chloride (Samchun Chemical) (30% THF) solution drop-wise and stir at room temperature (23°C) for 12 hours. Dissolve in 300mL of methylene chloride, add diluted hydrochloric acid solution, extract and neutralize three times. After removing moisture and solvent, vacuum dry for 24 hours. Put the obtained product in a flask, dissolve it in 300 mL of acetone, add 2.2 equivalents of potassium thioacetate (TCI), and stir at 60°C for 12 hours. Add 300 mL of methylene chloride and 200 mL of water, extract 3 times, remove moisture and solvent, and vacuum dry for 24 hours. Dissolve the obtained product in 300 mL of ethanol, add 2.5 equivalents of hydrochloric acid, and stir at 100°C for 12 hours. Excess methlylene chloride and water are added, extracted 5 times, neutralized, solvent removed, and vacuum dried for 24 hours to obtain a compound represented by the following formula 1A.)

Example 3

It was the same as Example 1, except that the thickness of the indium oxide coating layer was controlled to 0.5 nm.

Example 4

It was the same as Example 1, except that the thickness of the indium oxide coating layer was controlled to 1.5 nm.

Comparative Example 1

It was the same as Example 1, except that indium oxide was not coated.

Comparative Example 2

It was the same as Example 1, except that zinc oxide was coated instead of indium oxide.

Comparative Example 3

It was the same as Example 1, except that manganese oxide was coated instead of indium oxide.

Evaluation: Evaluation of the light resistance properties of the curable composition

The light resistance properties were evaluated for each of the curable compositions according to Examples 1 to 4 and Comparative Examples 1 to 3, and the results are shown in Table 1 below.

(Evaluation of light resistance characteristics)

2 mL of the curable composition prepared above was spin-coated on a glass substrate at 1,500 rpm, and then exposed to 5 J for 9 seconds in a nitrogen UV exposure machine (395 nm). The QD film (9 ㎛) formed was measured using a light efficiency meter (QE-2100, The initial blue light conversion rate was measured using Otsuka Co., Ltd.).

Afterwards, the substrate on which the QD film was formed was baked (POB; post baking) on a hot plate at 180°C in a nitrogen atmosphere for 30 minutes and 1 hour, and then cooled at room temperature (23°C) for 3 hours. At this time, the baking was performed three times, and the blue light conversion rate was measured with a light efficiency meter at each end of baking, and then the thermal process maintenance rate (%) was calculated using the following calculation formula.

Thermal process maintenance rate (%) = [light conversion rate (after baking)/initial light conversion rate] * 100

(unit: %) Thermal process maintenance rate after one POB Thermal process maintenance rate after 2 POB Thermal process maintenance rate after 3 POB Example 1 100 98.6 98.5 Example 2 100 99.1 99.0 Example 3 100 98.5 98.4 Example 4 100 98.5 98.0 Comparative Example 1 100 98.4 97.1 Comparative Example 2 100 98.3 96.5 Comparative Example 3 100 98.4 96.5

From Table 1, compared to the curable compositions according to Examples 1 to 4, the curable compositions according to Examples 1 to 3 have excellent light resistance as the decrease in thermal process maintenance rate is minimized as the number of POB increases. You can check it.

The present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art may recognize other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

1 quantum dot
2 Passivation layer
3 Surface modification materials

Claims (19)

(A) Quantum dots passivated with indium oxide; and
(B) Polymerizable compounds
A curable composition comprising a.
According to paragraph 1,
The quantum dot includes an indium oxide passivation layer,
The passivation layer is a curable composition having a thickness of 0.1 nm to 1 nm.
According to paragraph 1,
A curable composition wherein the quantum dots are quantum dots whose surface has been surface modified with a surface modification material.
According to paragraph 3,
The surface modification material is a curable composition represented by the following Chemical Formula 1 and/or Chemical Formula 2.
[Formula 1]

(In Formula 1 above,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R ² is represented by the following formula R-1,
[Formula R-1]

In the above formula R-1,
X is CR (R is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) or N,
L ⁵ and L ⁶ are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,
n1 is an integer from 0 to 20)
[Formula 2]

(In Formula 2 above,
L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ³ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
n2 is an integer from 0 to 20)
According to paragraph 4,
The surface modification material includes compounds represented by Formula 1 and Formula 2,
A curable composition in which the compound represented by Formula 1 is included in an amount equal to or less than that of the compound represented by Formula 2 relative to the total amount of the surface modification material.
According to clause 5,
A curable composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are included in a weight ratio of 1:9 to 5:5 relative to the total amount of the surface modification material.
According to paragraph 4,
The compound represented by Formula 1 is a curable composition represented by the following Formula 1-1 or Formula 1-2:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,
L ¹ , L ² , L ⁵ and L ⁶ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
n1 and n2 are each independently integers from 0 to 20.
In clause 7,
The compound represented by Formula 1 is a curable composition represented by Formula 1A or Formula 1B below.
[Formula 1A]

[Formula 1B]

According to paragraph 4,
The compound represented by Formula 2 is a curable composition represented by Formula 2A or Formula 2B below.
[Formula 2A]

[Formula 2B]

According to paragraph 1,
The curable composition is a solvent-free curable composition.
According to clause 10,
The solvent-free curable composition is, relative to the total amount of the solvent-free curable composition,
5% to 60% by weight of the quantum dots; and
40% to 95% by weight of the polymerizable compound
A solvent-free curable composition comprising a.
According to paragraph 1,
The curable composition further includes a polymerization initiator, a light diffuser, a polymerization inhibitor, or a combination thereof.
According to clause 12,
The light diffuser is a curable composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
According to paragraph 1,
The curable composition further includes a solvent.
According to clause 14,
The curable composition includes 1% to 40% by weight of the quantum dots, based on the total weight of the curable composition; 1% to 20% by weight of the polymerizable compound; And a curable composition comprising 40% by weight to 80% by weight of the solvent.
According to paragraph 1,
The curable composition includes malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agent; leveling agent; Fluorine-based surfactant; Or a curable composition further comprising a combination thereof.
A cured film manufactured using the curable composition according to any one of claims 1 to 16.
A color filter comprising the cured film of claim 17.
A display device comprising the color filter of claim 18.