KR20240108206A - Light-emitting down conversion organic nano-dot, composition for color conversion film comprising thereof, and conversion film, display device and light emitting diode device prepared therefrom - Google Patents

Abstract

Long-wavelength switching luminescent organic nanoparticles containing first and second organic phosphors, wherein the first organic phosphor has a molar extinction coefficient (ε) of 10,000 L/mol·cm or more at a wavelength of 450 nm, Long-wavelength conversion luminescent organic nanoparticles in which the emission spectrum of the first organic phosphor overlaps the absorption spectrum of the second organic phosphor, a composition for a color conversion film containing the same, a color conversion film manufactured therefrom, and a display device and a light emitting diode device is provided.

Description

Long-wavelength conversion light-emitting organic nanoparticles, compositions for color conversion films containing the same, color conversion films manufactured therefrom, display devices, and light-emitting diode devices {LIGHT-EMITTING DOWN CONVERSION ORGANIC NANO-DOT, COMPOSITION FOR COLOR CONVERSION FILM COMPRISING THEREOF, AND CONVERSION FILM, DISPLAY DEVICE AND LIGHT EMITTING DIODE DEVICE PREPARED THEREFROM}

The present invention relates to long-wavelength conversion (DC) light-emitting organic nanoparticles, a composition for a color conversion film containing the same, and a color conversion film, display device, and light-emitting diode device manufactured therefrom.

To create white light using a light emitting diode as a light source, a method is mainly used to use a blue light emitting diode as a light source and convert the light source from the blue light emitting diode into white light using a color conversion film made of phosphors, organic dyes, quantum dots, etc. do. At this time, the material of the color conversion film must have a wide full width at half maximum (FWHM) to have a high color rendering index and must have good heat resistance to withstand the heat of the light emitting diode. In comparison, the material of the color conversion film used in the display must have good color purity, unlike light emitting diodes for light sources, so mainly fluorescence, phosphorescence, and quantum dots that exhibit light emission characteristics with a small half width are used.

The method of using blue LED and yellow phosphor, which is most widely used in light emitting diodes, has the disadvantage of having a high correlated color temperature because the color rendering index is low and the yellow phosphor emits little red light. When organic dyes are used in the color conversion layer, they have the property of agglomerating when emitting light, causing a extinction phenomenon and low photochemical stability.

Quantum dots (QDs) using inorganic materials have the advantage of good photoluminescence quantum yield (PLQY), fast reaction time, and high reliability, but they are very vulnerable to moisture and have poor heat resistance of less than 100 °C, so they do not emit light. It is difficult to use as a color conversion film for diodes and has the disadvantage of using heavy metals such as cadmium, arsenic, and lead. Specifically, heavy metals such as lead, cadmium, mercury, chromium, and arsenic have a high ability to accumulate in the body, and are emerging as a major public health problem. Heavy metals absorbed into the body accumulate in the hair and tissues of each organ of the body through the blood, and the residence time of heavy metals in the body is relatively short in blood or urine, but in the case of hair, they last for a relatively long time. In general, the accumulation of heavy metals in the body occurs through a chain of food chains, and shows bioaccumulation characteristics in which the concentration in the body becomes higher in predators compared to prey. In particular, cadmium, which is used as a fluorescent substance, can cause serious damage to the stomach, lungs, and bones.

In order to apply organic materials or organic nanoparticles to display devices, etc., they cannot be used alone and must be manufactured and used in the form of a film. Films manufactured using organic materials directly have lower light stability than films manufactured using organic nanoparticles. In order to manufacture organic nanoparticles into a film, it is necessary to satisfy the following conditions: maintain the properties of the organic nanoparticles, have good dispersibility in the resin, do not deteriorate in properties even when exposed to incident light for a long time, and have excellent room temperature stability. .

Registered Patent No. 10-2081481 Public Patent No. 10-2020-0105407

One of the many purposes of the present invention is to provide long-wavelength conversion organic nanoparticles obtained from a light-emitting organic material that has excellent color conversion efficiency and thermal stability and does not use heavy metals, a composition for a color conversion film containing the same, and a color conversion film prepared therefrom. It provides films, display devices, and light emitting diode devices.

One aspect of the present invention is a long-wavelength switching luminescent organic nanoparticle comprising a first and a second organic phosphor, wherein the first organic phosphor has a molar extinction coefficient (ε) of 10,000L at a wavelength of 450 nm. /mol·cm or more, and the emission spectrum of the first organic phosphor overlaps the absorption spectrum of the second organic phosphor.

In one embodiment, the Förster radius between the first and second organic phosphors ( ; R _O ) may be 7.0 nm or less.

In one embodiment, the weight ratio of the first and second organic phosphors may be 5.0:5.0 to 9.5:0.5.

In one embodiment, the long-wavelength switching light-emitting organic nanoparticles may have an average particle diameter of 100 to 170 nm and a standard deviation of the particle diameter of 500 nm or less.

In one embodiment, the long-wavelength switching light-emitting organic nanoparticle may have a core-shell structure in which the first and second organic phosphors are surrounded by a surfactant.

In one embodiment, the surfactant may be one or more selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants.

In one embodiment, the PLQY of the first organic phosphor may be 50%.

In one embodiment, the first organic phosphor is one of the following compounds: BB-1 to BB-11, BD-1 to BD-9, BM-1 to BM-12, BPer-1 to BPer-20, and BPyr-1. It may be one or more types selected from the group consisting of BPyr-11.

In one embodiment, the second organic phosphor may be a delayed fluorescence material.

In one embodiment, the delayed fluorescent material may be a compound represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

L is any one selected from the group consisting of an aryl group, an arylene group, and a carbon-nitrogen single bond,

When L is an aryl group, A is a cyano group substituted by 1 or 2 of the aryl group, D is a substituent of 4 or 5 substituted by the aryl group, and each of the substituents is independently a nitrogen substituted with a hydrocarbon group having 1 to 10 carbon atoms. It is a heteroaryl group containing an atom,

When L is an arylene group, A is a substituted or unsubstituted triazine group, and D is a substituted or unsubstituted heteroaryl group, which contains a nitrogen atom bonded to the arylene group. It contains a non-conjugated pentagonal or hexagonal ring, and is a multi-fused ring fused to the conjugated or non-conjugated pentagonal or hexagonal ring, with 1 to 9 rings within the multi-fused ring. Contains a nitrogen atom or one Group 16 element,

When L is a carbon-nitrogen single bond, D is a fused ring of 10 to 40 carbon atoms, and is a conjugated or non-conjugated pentagon containing the nitrogen atom of L or Contains a hexagonal ring, and includes a substituted or unsubstituted aryl group forming a conjugated ring with the conjugated or unconjugated pentagonal or hexagonal ring, and the conjugated or unconjugated pentagonal or hexagonal ring is substituted or unsubstituted. It is a ring that does not contain or contains a Group 16 element in the ring, contains 1 or 2 nitrogen atoms in the ring, and A is a heterocycle having 15 to 40 carbon atoms, containing the carbon atom bonded to L. A pentagon containing an aryl group, containing a ring structure containing a boron atom and an oxygen atom in the ring, forming a fused ring with the aryl group containing the carbon atom, or containing two nitrogen atoms conjugated. or a hexagonal ring structure.)

In one embodiment, the compound represented by Formula 1 may be one or more selected from the group consisting of compounds T-1 to T-32 below.

In one embodiment, the second organic phosphor may be a boron compound represented by Formula 2 below.

[Formula 2]

(In Formula 2 above,

R ₁ to R ₅ are each independently hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted At least one member selected from the group consisting of a substituted or unsubstituted heterocycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group; ,

X ₁ to X ₄ are each independently hydrogen, or combine with each other to form a ring.)

In one embodiment, the boron compound represented by Formula 2 may be one or more selected from the group consisting of compounds D-1 to D-30 below.

In one embodiment, the second organic phosphor may be a boron compound represented by Formula 3 below.

[Formula 3]

(In Formula 3 above,

C ₁ to C ₃ each have a 5-membered or 6-membered ring structure

R ₁₁ and R ₁₂ may each independently be substituted with 1, 2, or 3, and the substituents include hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amidino, and hydrazino groups. , hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted thioether group, substituted or unsubstituted Cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted heterocycloalkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or It corresponds to any one selected from the group consisting of an unsubstituted heteroaryl group and a substituted or unsubstituted heteroaryloxy group, or two or more substituents combine with each other to form a ring,

R ₁₃ is hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted Or an unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted thioether group, a substituted or unsubstituted heterocycloalkyl group, Any selected from the group consisting of a substituted or unsubstituted heterocycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group. Corresponds to one,

Y ₁ and Y ₂ are each independently a fluorine group or an alkoxy group.)

In one embodiment, the boron compound represented by Formula 3 may be one or more selected from the group consisting of compounds B-1 to B-51 below.

Another aspect of the present invention provides a composition for a color conversion film, comprising the long-wavelength conversion luminescent organic nanoparticles and a water-soluble polymer resin.

In one embodiment, the composition for the color conversion film may include 1 to 20 parts by weight of the long-wavelength conversion luminescent organic nanoparticles based on 100 parts by weight of the water-soluble polymer resin.

Another aspect of the present invention provides a color conversion film manufactured using the composition for the color conversion film.

Another aspect of the present invention provides a display device or light emitting diode device including the color conversion film.

According to the present invention, using these long-wavelength switching luminescent organic nanoparticles, a film with excellent photochemical stability, high color conversion efficiency, high heat resistance, good film hardness characteristics, high uniformity, and long-term performance is produced. A color conversion film can be provided. In particular, the color conversion film of the present invention uses long-wavelength switching light-emitting organic nanoparticles that do not use quantum dots, so environmental pollution problems can be prevented.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration described in the description or claims of the invention in this specification.

Figure 1a is a graph showing the room temperature photoluminescence spectra for the 4tBuMB solution, the 4tBuMB ROND solution, and the Per-4tBuMB DC-ROND solution, and Figure 1b is a graph showing the room temperature photoluminescence spectra for the tPhBODIPY solution, the tPhBODIPY GOND solution, and the Per-tPhBODIPY DC-GOND solution. This is a graph showing the photoluminescence spectrum.
Figure 2a is a graph showing the room temperature photoluminescence spectrum of the color conversion film according to Preparation Example 2-1 and Preparation Example 2-2, and Figure 2b is a graph showing the room temperature photoluminescence spectrum of the color conversion film according to Preparation Example 2-3 and Preparation Example 2-4. This is a graph showing the photoluminescence spectrum.
Figure 3a is a graph showing the absorption spectrum of the color conversion film according to Preparation Example 2-2, and Figure 3b is a graph showing the photoluminescence spectrum of the color conversion film according to Preparation Example 2-2.
Figure 4a is a graph showing the absorption spectrum of the color conversion film according to Preparation Example 2-4, and Figure 3b is a graph showing the photoluminescence spectrum of the color conversion film according to Preparation Example 2-4.
Figure 5a is a graph showing the light intensity (Radiant Power) of the color conversion film according to Preparation Example 3-1 and Preparation Example 3-2, and Figure 5b is a graph showing the color conversion film according to Preparation Example 3-3 and Preparation Example 3-4. This is a graph showing the light intensity (Radiant Power).
Figure 6a is a graph showing the light intensity (radiant power) of the color conversion film according to Preparation Example 6-1 and Preparation Example 6-2.
Figure 6b is a photograph observing the photoluminescence and DC-GROND color conversion film of the DC-GROND solution of Preparation Example 6-1 in a UV lamp.

Prior to the detailed description of the present invention, the terms and words used in the specification and claims described below should not be construed as limited to their ordinary or dictionary meanings, and the inventor should use his/her invention in the best possible manner. For explanation purposes, it is stated that the term should be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that the concept of the term can be appropriately defined. Accordingly, the embodiments described in this specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and do not represent the entire technical idea of the present invention, and therefore, at the time of filing the present application, there are various options that can replace them. It should be understood that there are equivalents and variations.

Throughout this specification, when a part 'includes' a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary. Additionally, throughout this specification, the singular form also includes the plural form unless otherwise specified.

When a range of numerical values is described herein, unless the specific range is stated otherwise, the value has the precision of significant figures given in accordance with the standard rules in chemistry for significant figures. For example, the number 10 includes the range 5.0 to 14.9, and the number 10.0 includes the range 9.50 to 10.49.

Long-wavelength switching luminescent organic nanoparticles

One aspect of the present invention provides long-wavelength switching luminescent organic nanoparticles containing first and second organic phosphors. Here, the first organic phosphor may be a blue or blue-green phosphor, and the second organic phosphor may be a green or red phosphor.

As an organic phosphor, when green or red phosphor is used alone, PLQY may decrease due to a certain level of self-quenching behavior, and CCE may decrease due to low light absorption in the blue region. In the present invention, excellent PLQY and CCE can be secured simultaneously by using a combination of blue or blue-green phosphor and green or red phosphor.

The ratio (weight ratio) of the first and second organic phosphors may be 5.0:5.0 to 9.5:0.5. If the ratio is less than 5:5, it may be difficult to secure the desired level of PLQY and CCE, and excessive absorption of ambient light may occur, reducing the contrast ratio (CR). Conversely, if the ratio exceeds 9.5:0.5, the blue light reduction rate and color conversion rate to green or red may be too low.

The average particle diameter of the long-wavelength-converted luminescent organic nanoparticles may be 100 to 170 nm, preferably 110 to 160 nm, and more preferably 120 to 150 nm.

The standard deviation of the particle size of the long-wavelength conversion luminescent organic nanoparticles may be 500 nm or less, preferably 450 nm or less, more preferably 400 nm or less, even more preferably 350 nm or less, and even more preferably 300 nm. It may be less than or equal to 280 nm, most preferably less than 280 nm.

A color conversion film using long-wavelength switching light-emitting organic nanoparticles having an average particle size and standard deviation of particle size in the above range has the advantages of excellent color conversion efficiency, UV stability, and room temperature stability.

first organic phosphor

The first organic phosphor may be a blue or blue-green phosphor, and if the molar extinction coefficient (ε) at a wavelength of 450 nm is 10,000 L/mol·cm or more, various phosphors already known in the technical field to which the present invention pertains can be used. Available.

The photoluminescence quantum yield (PLQY) of the first organic phosphor may be 50% or more, preferably 60% or more, and more preferably 70% or more. If the PLQY is less than 50%, it may be difficult to secure the color conversion rate to the long wavelength at the desired level. Here, the photoluminescence quantum efficiency of the first organic phosphor is the value measured using the integrating sphere built into the JASCO-FP 8500 equipment for a solution in which the first organic phosphor was dissolved in a minimum amount of THF and then dispersed in deionized water. indicates.

The first organic phosphor is, for example, the following compounds BB-1 to BB-11, BD-1 to BD-9, BM-1 to BM-12, BPer-1 to BPer-20 and BPyr-1 to BPyr-11. It may be one or more types selected from the group consisting of, but is not limited thereto.

second organic phosphor

The second organic phosphor may be a green or red phosphor, and if the emission spectrum of the first organic phosphor overlaps with the absorption spectrum of the second organic phosphor, various phosphors already known in the art to which the present invention pertains can be used.

Foerster radius between the first and second organic phosphors ( ; R _O ) may be 7.0 nm or less, preferably 6.0 nm or less, more preferably 5.0 nm or less, and even more preferably 4.5 nm or less. If the Förster radius is too large, energy transfer between the first and second organic phosphors may be significantly reduced.

The Förster radius refers to the maximum distance at which energy transfer can occur between the first and second organic phosphors, and is defined by Equation 1 below.

[Equation 1]

(In Equation 1, N _A is Avogadro's constant, κ ² is the dipole orientation factor, Q _D is the photoluminescence quantum efficiency of the first organic phosphor, n is the refractive index of the medium, and J is the spectral overlap defined by Equation 2 below It is a spectral overlap integral, and the difference between κ ² and n values depending on organic substances is small and can be ignored.)

[Equation 2]

(In Equation 2 above, λ is the wavelength, f _D (λ) is the normalized emission intensity of the emission spectrum of the first organic phosphor, and ε _A is the molar extinction coefficient of the second organic phosphor. )

Meanwhile, the Förster radius can also be obtained by the FRET efficiency (E) defined by Equation 3 below.

[Equation 3]

(In Equation 3 above, r means the distance between the first and second organic phosphors.)

When long-wavelength switching light-emitting organic nanoparticles are used as light-emitting diodes, they must have a wide half width, so it is desirable to use a delayed fluorescence material as the second organic phosphor.

Delayed fluorescent material is a material that can increase internal quantum efficiency. Heat-activated delayed fluorescence is a material that emits fluorescence by moving three triplet exciton particles, which are particles annihilated by heat or vibration, to the level of singlet exciton using heat. It is preferable that the material is Thermally Activated Delayed Fluorescence (TADF).

There is no particular limitation on the delayed fluorescent material having these characteristics, but examples include compounds represented by the following formula (1).

[Formula 1]

(In Formula 1, L is any one selected from the group consisting of an aryl group, an arylene group, and a carbon-nitrogen single bond, and when L is an aryl group, A is a cyano group substituted by 1 or 2 of the aryl group, and D is The aryl group is 4 or 5 substituted, and each substituent is independently a heteroaryl group containing a nitrogen atom substituted with a hydrocarbon group having 1 to 10 carbon atoms, and when L is an arylene group, A is substituted or unsubstituted. is a triazine group, and D is a substituted or unsubstituted heteroaryl group, a conjugated or non-conjugated pentagonal or hexagonal ring containing a nitrogen atom bonded to the arylene group. It is a multi-fused ring fused to the conjugated or unconjugated pentagonal or hexagonal ring, and contains 1 to 9 nitrogen atoms or one group 16 element in the multi-fused ring, L When this carbon-nitrogen single bond, D is a fused ring of 10 to 40 carbon atoms, and is a conjugated or non-conjugated pentagon or hexagon containing the nitrogen atom of L. Contains a ring, and includes a substituted or unsubstituted aryl group forming a conjugated ring with the conjugated or unconjugated pentagonal or hexagonal ring, and the conjugated or unconjugated pentagonal or hexagonal ring is substituted or unsubstituted. A ring that does not contain or includes a Group 16 element in the ring, contains 1 or 2 nitrogen atoms in the ring, and A is a heterocycle having 15 to 40 carbon atoms, and is an aryl ring containing a carbon atom bonded to L. A pentagonal group containing a ring structure containing a boron atom and an oxygen atom in the ring, forming a fused ring with an aryl group containing the carbon atom, or containing two nitrogen atoms conjugated; or (Contains a hexagonal ring structure.)

The compound represented by Formula 1 may be, for example, one or more selected from the group consisting of the following compounds T-1 to T-32, but is not limited thereto.

When applying long-wavelength switching luminescent organic nanoparticles for display purposes, they must have high color purity, so it is preferable to use a boron compound with a narrow half width as the second organic phosphor.

There is no particular limitation on the boron compound suitable for use in displays, but for example, it may be a boron compound represented by the following formula (2).

[Formula 2]

(In Formula 2, R ₁ to R ₅ are each independently hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted hetero A group consisting of a cycloalkyl group, a substituted or unsubstituted heterocycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group. corresponds to any one selected from, and X ₁ to X ₄ are each independently hydrogen, or combine with each other to form a ring)

The boron compound represented by Formula 2 may be, for example, one or more selected from the group consisting of the following compounds D-1 to D-30, but is not limited thereto.

Additionally, a boron compound suitable for use in displays may be, for example, a boron compound represented by the following formula (3).

[Formula 3]

(In Formula 3, C ₁ to C ₃ each have a 5-membered or 6-membered ring structure, and R ₁₁ and R ₁₂ may each be independently substituted by 1, 2, or 3, and the substituents are hydrogen, deuterium, , halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group. , substituted or unsubstituted alkoxy group, substituted or unsubstituted thioether group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted hetero Corresponds to any one selected from the group consisting of a cycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group, or two The above substituents combine with each other to form a ring, and R ₁₃ is hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted thioether group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group , substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted heterocycloalkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group and substituted or unsubstituted corresponds to any one selected from the group consisting of heteroaryloxy groups, and Y ₁ and Y ₂ are each independently a fluorine group or an alkoxy group)

The boron compound represented by Formula 3 may be, for example, one or more selected from the group consisting of the following compounds B-1 to B-51, but is not limited thereto.

Long-wavelength switching luminescent organic nanoparticles may have a core-shell structure in which the first and second organic phosphors are surrounded by a surfactant. In this case, the shape and size of the organic nanoparticles are uniform, increasing the yield of the organic nanoparticles. This has the advantage of improving the characteristics of the color conversion film by making it easier to control the size of the long-wavelength conversion luminescent organic nanoparticles by controlling the concentration of the surfactant, but it is not limited to this.

The surfactant may be one or more selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants, but is not limited thereto.

Anionic surfactant refers to a surfactant whose hydrophilic group is an anion when dissolved in water. The hydrophilic group of an anionic surfactant may be one or more selected from the group consisting of carboxylate, sulfate, sulfonate, and phosphate, but is limited thereto. It doesn't work.

Cationic surfactant refers to a surfactant whose hydrophilic group is cationic when dissolved in water, and may contain a nitrogen atom with a positive charge. Specifically, it may be TBAOleate (Tetrabutylammonium oleate), but is limited thereto. That is not the case.

A zwitterionic surfactant refers to a surfactant that, when dissolved in water, has the properties of an anionic surfactant in an alkaline region and a cationic surfactant in an acidic region.

A nonionic surfactant is a surfactant with a hydrophilic group that does not ionize when dissolved in water. It refers to a surfactant that has no charge even when dissolved in water. For example, a hydrophilic polyethylene oxide chain and a lipophilic to hydrophobic group. It may be Triton X100 having an aromatic hydrocarbon group, but is not limited thereto.

In the present invention, there is no particular limitation on the method for producing long-wavelength switching luminescent organic nanoparticles, but for example, (S1) mixing first and second organic phosphors and a surfactant to prepare a first mixture; (S2) preparing a dispersion by adding an anti-solvent for the first and second organic phosphors to the first mixture; and (S3) dialyzing the dispersion and drying the dialyzed dispersion to produce long-wavelength switching luminescent organic nanoparticles.

(S1) step

The descriptions of the first and second organic phosphors and surfactants constituting the first mixture in step (S1) are as described above.

In step (S1), the mixing ratio (weight ratio) of the first and second organic phosphors and the surfactant may be 1:20 to 1:1,000, preferably 1:200 to 1:800, and more preferably It may be 1:400 to 1:600, but is not limited thereto. When the mixing ratio (weight ratio) of the first and second organic phosphors and the surfactant satisfies the above range, long-wavelength switching luminescent organic nanoparticles with small and uniform particle size can be obtained.

When the concentration of the surfactant exceeds the critical micelle concentration, the hydrophobic portion of the surfactant surrounds the first and second organic phosphors to form micelles, and these micelles are dispersed in the solvent. This makes the shape and size of the long-wavelength-switched light-emitting organic nanoparticles uniform, thereby improving the yield of the long-wavelength-switched light-emitting organic nanoparticles. Meanwhile, the particle size of long-wavelength conversion luminescent organic nanoparticles can be controlled by controlling the concentration of the surfactant, so the characteristics of the color conversion film can be further improved.

(S2) step

The anti-solvent added in step (S2) may be one or more selected from the group consisting of aqueous solvents, alcohol-based solvents, ketone-based solvents, ether-based solvents, sulfoxide-based solvents, and ester-based solvents, but is not limited thereto.

The aqueous solvent may be, for example, any one of water, an aqueous hydrochloric acid solution, and an aqueous sodium hydroxide solution, and the alcohol-based solvent may be, for example, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and 1-methoxy-2- It may be at least one selected from the group consisting of propanol, and the ketone-based solvent may be, for example, at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and the ether-based solvent is, for example, For example, it may be one or more selected from the group consisting of dimethyl ether, diethyl ether, and tetrahydrofuran, the sulfoxide-based solvent may be, for example, dimethyl sulfoxide, and the ester-based solvent may be, for example, an alkyl ester. It may be, but is not limited to this.

(S3) step

Step (S3) is a step performed to improve the yield of long-wavelength switching luminescent organic nanoparticles by removing excess surfactant from the dispersion.

The dialysis device used in step (S3) may be, for example, a dialysis tube made of cellulose acetate, but is not limited thereto.

Drying of the dialyzed dispersion in step (S3) may be, but is not limited to, concentrating the dispersion under vacuum for 10 to 12 hours.

Composition for color conversion film

Another aspect of the present invention provides a composition for a color conversion film, comprising the above-described long-wavelength conversion luminescent organic nanoparticles and a water-soluble polymer resin.

The water-soluble polymer resin may have a weight average molecular weight of 5,000 to 100,000 g/mol and a degree of hydration of 70 to 100%. In this case, the characteristics of the color conversion film may be further improved by exhibiting appropriate surface activity, but is limited to this. It doesn't work.

The water-soluble polymer resin may be one or more selected from the group consisting of nonionic water-soluble polymers, anionic water-soluble polymers, and cationic water-soluble polymers, but is not limited thereto.

Nonionic water-soluble polymers include, for example, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylamide (PAM), and polyvinylpyrrolidone (PVP). It may be one or more polymers or copolymers selected from, and the anionic water-soluble polymer is, for example, polyacrylic acid (PAA) and its derivatives, poly(styrene sulfonic acid) (PSSA), poly (Poly(silicic acid); PSiA), Poly(phosphoric acid); PPA), Poly(ethylenesulfinic acid); PESA), poly[3-(vinyloxy ) Propane-1-sulfonic acid](Poly[3-(vinyloxy)propane-1-sulfonic acid]), poly(4-vinylphenol), poly(4-vinylphenol sulfate) (4-vinylphenol sulfuric acid)), Poly(ethylenephosphoric acid), Poly(maleic acid), Poly(2-methacryloxyethane-1-sulfonic acid) (2-methacryloxyethane-1-sulfonic acid)), poly(3-methacryloyloxypropane-1-sulfonic acid)) and poly(4-vinylbenzoic acid) (Poly( It may be one or more polymers or copolymers selected from the group consisting of 4-vinylbenzoic acid), and the cationic water-soluble polymer is, for example, polyethyleneimine (PEI), polyamines, and polyamideamine (PAMAM). , Poly(diallyldimethyl ammonium chloride); PDADMAC), Poly(4-vinylbenzyltrimethylammonium salt), Poly[(dimethylimino)trimethylene(dimethylimino)hexamethylenedibromide](Poly[(dimethylimino) trimethylene(dimethylimino)hexamethylenedibromide]; Polybrene), Poly(2-vinylpiperidine salt), Poly(vinylamine salt) and poly(2-vinylpyridine) It may be one or more polymers or copolymers selected from the group consisting of (poly(2-vinylpyridine)) and its derivatives, but is not limited thereto.

The description of the long-wavelength switching luminescent organic nanoparticles is the same as described above.

The content of the long-wavelength conversion luminescent organic nanoparticles may be 1 to 20 parts by weight based on 100 parts by weight of the water-soluble polymer resin, but is not limited thereto. If the content of long-wavelength switching light-emitting organic nanoparticles is too small, the color conversion efficiency may decrease. Conversely, if the content of long-wavelength switching light-emitting organic nanoparticles is too high, the agglomeration between nanoparticles becomes stronger and the particle size increases. , extinction phenomenon may occur.

The composition for the color conversion film may further include a crosslinking agent in order to ensure high thermal stability of the color conversion film and prevent discoloration (reduction in transmittance) due to heat, but is not limited thereto.

Crosslinking agents include, for example, glutaraldehyde, glyoxal, maleic acid, citric acid, trisodium trimetaphosphate, and sodium hexametaphosphate. , dianhydrides, succinic acid, suberic acid, sulfosuccinic acid, and K ₂ S ₂ O ₈ , which is a radical cross-linking agent, but is limited thereto. That is not the case.

When the water-soluble polymer resin is PVA, it is preferable to use suberic acid or K ₂ S ₂ O ₈ , a radical cross-linking agent, as a cross-linking agent to improve thermal stability and maintain permeability, but is not limited thereto.

The content of the cross-linking agent may be 0.01 to 20 parts by weight based on 100 parts by weight of the water-soluble polymer resin, but is not limited thereto.

The composition for a color conversion film may further include a light scattering agent to generate a light scattering effect to increase light absorption efficiency, improve dispersibility, and secure high thermal stability and incombustibility, but is not limited thereto.

The light scattering agent is, for example, one or more inorganic oxide particles selected from the group consisting of TiO ₂ , ZnO, Fe ₃ O ₄ , CeO ₂ , MoO ₂ , Ag ₂ O, CuO and NiO, and has an average particle size of 200. It may be an inorganic oxide particle of ∼400 nm, but is not limited thereto.

The content of the light scattering agent may be 1 to 20 parts by weight based on 100 parts by weight of the water-soluble polymer resin, but is not limited thereto.

color conversion film

Another aspect of the present invention provides a color conversion film manufactured using the composition for a color conversion film described above.

The color conversion film can be manufactured into a color conversion film using the composition for the color conversion film described above using a bar coating method, a sol-gel method, an inkjet printing method, a roll coating method, a spin coating method, and a drop casting method. You can.

For example, when manufacturing a color conversion film using a bar coating method, the composition for the color conversion film described above is sprayed on a glass substrate, then a film is formed by bar coating, and placed in an oven at 50 to 70°C to remove the solvent. The color conversion film can be manufactured by annealing for a certain period of time, but is not limited to this.

The thickness of the color conversion film may be 200 μm or less, preferably 180 μm or less, and more preferably 150 μm, but is not limited thereto.

display device

Another aspect of the present invention provides a display device including the color conversion film described above.

The display device according to the present invention may include a liquid crystal display device, an organic light emitting display device, and a micro LED display device.

Organic phosphors used in display devices must have a narrow half width for high color purity. Accordingly, the second organic phosphor used in the display device may be the boron compound described above, but is not limited thereto.

Typically, a liquid crystal display device includes two substrates. Specifically, it includes a lower substrate having a switching element including a thin film transistor, an upper substrate facing the lower substrate and having a common electrode, and liquid crystal injected between the upper and lower substrates.

In contrast, organic light emitting devices and micro LEDs can be formed on a single substrate. A switching element including a thin film transistor may be formed on the lower part, and an organic light emitting element or micro LED that is turned on/off by the switching element may be formed on the upper part of the switching element. In the case of organic light emitting devices or micro LEDs, they can be formed using a single substrate, but they are generally used by providing an upper substrate and forming an anti-reflection film on the upper substrate.

The display device according to the present invention can typically be formed with an upper substrate including a base film, an anti-reflection film, and a color conversion film, and the color conversion film can be formed using the light-emitting organic nanoparticles according to the present invention.

In the case of a liquid crystal display device, the light source emitted from the backlight is converted into three primary colors using a color conversion film, and in the case of a display device using an organic light emitting device or micro LED, a single color organic light emitting device or micro LED is applied, which is used according to the present invention. Light is emitted in three primary colors using a color conversion film according to .

light emitting diode device

Another aspect of the present invention provides a light emitting diode device including the color conversion film described above.

A light emitting diode device is a light emitting device that emits light by applying voltage to a PN junction diode of a compound semiconductor. The energy generated when holes and electrons move between p and n and combine with each other emits light in the form of light. It corresponds to a device and should be understood as a concept that also includes organic light-emitting devices.

Organic phosphors used in light-emitting diode devices must have a wide full width at half maximum (FWHM) to implement a high color rendering index (CRI). Accordingly, the second organic phosphor used in the light emitting diode device may be the above-described delayed fluorescence material, but is not limited thereto.

In general, light emitting diode devices are divided into chip LEDs with high brightness, ultra-small size, and thinness, top LEDs, ultra-high brightness, high moisture resistance, and heat resistance lamp LEDs used in outdoor displays or electronic signboards, etc., depending on the purpose of use.

The light emitting diode device according to the present invention may include a substrate and an LED chip disposed on the substrate. The color conversion film according to the present invention can absorb light emitted from the LED chip (or LED backlight) using the luminescent organic nanoparticles according to the present invention and convert it into light of another long wavelength.

Hereinafter, embodiments of the present specification will be described in more detail. However, the following experimental results describe only representative experimental results among the above examples, and the scope and content of the present specification cannot be interpreted as being reduced or limited by the examples. Each effect of various implementations of the present specification that are not explicitly presented below will be described in detail in the corresponding section.

Preparation example: Preparation of organic phosphor

<Preparation Example 1: Preparation of Compound B-23>

Compound B-23 (hereinafter referred to as '4tBuMB') having the following formula was obtained from ACS Appl. Mater. It was synthesized with reference to Interfaces 13, pp 17882-17891 (2021).

<Preparation Example 2: Preparation of Compound B-33>

Compound B-33 (hereinafter referred to as 'tPhBODIPY') having the following formula was prepared by Adv. Optical Mater. 8, 2000483 (2020).

<Preparation Example 3: Preparation of Compound B-36>

Compound B-36 (hereinafter referred to as '4tBuPhBODIPY') having the following chemical formula was subjected to Luminescence. Synthesized with reference to 2021, 36, 1697-1705.

<Preparation Example 4: Preparation of compound BPer-4>

BPer-4 (hereinafter referred to as '4tBuPerylene'), a compound having the following chemical formula, was obtained from Chem. Synthesized with reference to Commun., 2022, 58, 8802-8805. The molar extinction coefficient (ε) of the 4tBuPerylene at a wavelength of 450 nm was 1.9×10 ⁴ L/mol·cm.

<Preparation Example 5: Preparation of compound BPyr-3>

The compound BPyr-3 (hereinafter referred to as 'T4tBuPhpyrene') with the following chemical formula was synthesized with reference to Chemistry Select, 2020, 5, 12465-12469. The molar extinction coefficient (ε) of the T4tBuPhpyrene at a wavelength of 450 nm was 1.7×10 ⁴ L/mol·cm.

<Preparation Example 6: Preparation of compound BM-2>

Compound BM-2 (hereinafter referred to as 'Mt-DAVNA') having the following chemical formula was prepared by Adv. Mater. Synthesized with reference to 2022, 34, 2100161-2100179. The molar extinction coefficient (ε) of the Mt-DAVNA at a wavelength of 450 nm was 1.9×10 ⁴ L/mol·cm.

<Preparation Example 7: Preparation of compound BD-4>

Compound BD-4 (hereinafter referred to as '4F-DAVNA') having the following chemical formula was synthesized with reference to Chemical Engineering Journal, 432, 2022, 134381. The molar extinction coefficient (ε) of the 4F-DAVNA at a wavelength of 450 nm was 8.3 × 10 ⁴ L/mol·cm.

<Preparation Example 8: Preparation of compound BB-1>

Compound BB-1 (hereinafter referred to as 'AzaBoron') having the following chemical formula was synthesized with reference to Dyes and Pigments 99, 2013, 240-249. The molar extinction coefficient (ε) of the AzaBoron at a wavelength of 450 nm was 5.6 × 10 ⁴ L/mol·cm.

Preparation Example 1: Preparation of luminescent organic nanoparticles (organic nano-dot; OND)

<Manufacturing Example 1-1>

A solution (0.5mM) was prepared by dissolving the organic phosphor 4tBuMB in tetrahydrofuran. A nonionic surfactant (Triton X-100) was also separately dissolved in tetrahydrofuran to prepare a solution (0.1M). The first mixture was prepared by adding the surfactant solution (0.36 mL) and tetrahydrofuran (0.14 mL) to the 4tBuMB solution (0.10 mL). A dispersion was prepared by mixing the first mixture and 5.40 mL of deionized water. The dispersion was dialyzed using a cellulose acetate tube for 12 hours to remove the remaining surfactant, and the solvent was concentrated in vacuum to prepare red organic nanoparticles (hereinafter referred to as '4tBuMB ROND').

<Manufacturing Example 1-2>

Green organic nanoparticles tPhBODIPY GOND were prepared in the same manner as Preparation Example 1-1, except that tPhBODIPY was used instead of 4tBuMB as the organic phosphor.

<Production Example 1-3>

Green organic nanoparticles 4tBuPhBODIPY GOND were prepared in the same manner as Preparation Example 1-1, except that 4tBuPhBODIPY was used instead of 4tBuMB as the organic phosphor.

<Production Example 1-4>

Red long-wavelength down conversion organic nanoparticles (Per-4tBuMB) were prepared in the same manner as Preparation Example 1-1, except that instead of using 4tBuMB alone as an organic phosphor, a mixture of blue phosphor 4tBuPerylene and 4tBuMB was used at a weight ratio of 9:1. DC-ROND) was prepared.

<Production Example 1-5>

Red long-wavelength conversion organic nanoparticles Per-4tBuMB DC-ROND were prepared in the same manner as in Preparation Example 1-4, except that the weight ratio of 4tBuPerylene and 4tBuMB was changed to 7:3.

<Production Example 1-6>

Red long-wavelength conversion organic nanoparticles Per-4tBuMB DC-ROND were prepared in the same manner as in Preparation Example 1-4, except that the weight ratio of 4tBuPerylene and 4tBuMB was changed to 6:4.

<Production Example 1-7>

Green long-wavelength conversion organic nanoparticles Per-tPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-2, except that instead of using tPhBODIPY alone as an organic phosphor, a mixture of blue phosphor 4tBuPerylene and tPhBODIPY was used at a weight ratio of 7:3. did.

<Production Example 1-8>

Green long-wavelength conversion organic nanoparticles Per-4tPhBODIPY DC-GOND were prepared in the same manner as in Preparation Example 1-7, except that the weight ratio of 4tBuPerylene and tPhBODIPY was changed to 5:5.

<Production Example 1-9>

Green long-wavelength conversion organic nanoparticles Per-4tBuPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-3, except that instead of using 4tBuPhBODIPY alone as an organic phosphor, a mixture of blue phosphor 4tBuPerylene and 4tBuPhBODIPY was used at a weight ratio of 7:3. did.

<Production Example 1-10>

Green long-wavelength conversion organic nanoparticles Pyr-tPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-7, except that T4tBuPhpyrene was used instead of 4tBuPerylene as the blue phosphor.

<Production Example 1-11>

Green long-wavelength conversion organic nanoparticles MtD-tPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-7, except that M-t-DAVNA was used instead of 4tBuPerylene as the blue phosphor.

<Production Example 1-12>

Green long-wavelength conversion organic nanoparticles FD-tPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-7, except that 4F-DAVNA was used instead of 4tBuPerylene as the blue phosphor.

<Production Example 1-13>

Green long-wavelength conversion organic nanoparticles AB-tPhBODIPY DC-GOND were prepared in the same manner as Preparation Example 1-7, except that AzaBoron was used instead of 4tBuPerylene as the blue phosphor.

<Production Example 1-14>

Mixed-color, long-wavelength conversion organic nanoparticles were prepared in the same manner as Preparation Example 1-1, except that instead of using 4tBuMB alone as an organic phosphor, blue phosphor 4tBuPerylene, green phosphor 4tBuPhBODIPY, and red phosphor 4tBuMB were used at a weight ratio of 7:2:1. Per-4tBuPhBODIPY-4tBuMB DC-GROND was prepared.

<Production Example 1-15>

Mixed-color, long-wavelength conversion organic nanoparticles were produced in the same manner as Preparation Example 1-1, except that instead of using 4tBuMB alone as the organic phosphor, the green phosphor 4tBuPhBODIPY and the red phosphor 4tBuMB were used in the blue phosphor 4tBuPerylene at a weight ratio of 7: 2.5: 0.5. Per-4tBuPhBODIPY-4tBuMB DC-GROND was prepared.

<Comparative Manufacturing Example 1>

Red organic nanoparticles were prepared in the same manner as Preparation Example 1-1, except that the surfactant solution was not mixed.

Experimental Example 1: Particle size of organic nanoparticles

The particle diameters were measured for the organic nanoparticles prepared according to Preparation Example 1 and Comparative Preparation Example 1, and the results are shown in Table 1 below.

Average (μm) Standard deviation (μm) Min (μm) Maximum (μm) Manufacturing Example 1-1 0.16 0.07 0.04 0.41 Comparative Manufacturing Example 1-1 17.38 4.25 10.70 32.34

From Table 1, when a surfactant is not used, the phosphor aggregates and the average particle size becomes approximately 100 times larger than when a surfactant is used, resulting in micro-unit organic particles, whereas when a surfactant is used, the organic particles are much more uniform and It can be seen that small nanoparticles are obtained.

Experimental Example 2: Evaluation of optical properties

4tBuMB was dissolved in a minimum amount of THF and dispersed in deionized water to obtain a 4tBuMB solution, and 4tBuMB ROND of Preparation Example 1-1 and Per-4tBuMB DC-ROND of Preparation Example 1-5 were each dispersed in deionized water to obtain a 4tBuMB ROND solution. and Per-4tBuMB DC-ROND solution was obtained. In addition, tPhBODIPY was dissolved in a minimum amount of THF and dispersed in deionized water to obtain a tPhBODIPY solution, and tPhBODIPY GOND of Preparation Example 1-2 and Per-tPhBODIPY DC-GOND of Preparation Example 1-7 were each dispersed in deionized water to obtain tPhBODIPY. GOND solution and Per-tPhBODIPY DC-GOND solution were obtained.

Afterwards, the optical properties of each solution were measured, and the results are shown in Table 2 and Figure 1. The room temperature photoluminescence spectrum was measured using the JASCO-FP 8500 equipment, and the absolute PLQY (Photoluminescence Quantum Yield) value was measured using the integrating sphere built into the JASCO-FP 8500 equipment for the prepared solution.

Figure 1a is a graph showing the normalized photoluminescence intensity spectra at room temperature for the 4tBuMB solution, the 4tBuMB ROND solution, and the Per-4tBuMB DC-ROND solution, and Figure 1b is a graph showing the normalized photoluminescence intensity spectra for the tPhBODIPY solution, the tPhBODIPY GOND solution, and the Per-tPhBODIPY DC-GOND solution. This is a graph showing the room temperature photoluminescence spectrum of a solution.

maximum luminescence
Spectrum (nm) FWHM (nm) PLQY (%) 4tBuMB solution 620 31.2 95 4tBuMB ROND solution 622 31.3 87 Per-4tBuMB DC-ROND solution 618 31.0 90 tPhBODIPY solution 522 24.0 95 tPhBODIPY GOND SOLUTION 523 25.0 84 Per-tPhBODIPY DC-GOND solution 520 23.0 86

Referring to Table 2 and Figure 1, it can be seen that the position of the emission spectrum peak varies depending on the particle size of the phosphor and whether it is mixed with the blue phosphor. Specifically, in the case of OND, as the particle size decreased, the emission spectrum shifted toward long wavelengths, and PLQY also decreased due to aggregation. In the case of DC-OND, the maximum emission spectrum shifted again to shorter wavelengths compared to OND, and since it contains blue phosphor, blue emission appears to have had a slight effect. In addition, the blue phosphor reduced the concentration of the green or red phosphor, thereby reducing aggregation, which resulted in a decrease in self-quenching, resulting in an increase in PLQY.

Preparation Example 2: Preparation of color conversion film (1)

<Production Example 2-1>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.80 ml of the PVA-SA aqueous solution with the 4tBuMB ROND solution (0.8 wt % aqueous dispersion, 0.53 ml) and TiO ₂ solution (6.0 wt % aqueous solution, 0.07 ml) of Preparation Example 1-1. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 2-2>

A color conversion film was prepared in the same manner as Preparation Example 2-1, except that the Per-4tBuMB DC-ROND solution of Preparation Example 1-5 was used instead of the 4tBuMB ROND solution.

<Production Example 2-3>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.80 ml of the PVA-SA aqueous solution with the tPhBODIPY GOND solution (1.0 wt % aqueous dispersion, 0.6 ml) and TiO ₂ solution (15.0 wt % aqueous solution, 0.04 ml) of Preparation Example 1-2. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 2-4>

A color conversion film was prepared in the same manner as Preparation Example 2-1, except that the Per-tPhBODIPY DC-GOND solution of Preparation Example 1-7 was used instead of the tPhBODIPY GOND solution.

Experimental Example 3: Evaluation of optical properties

The optical properties of the color conversion films according to Preparation Examples 2-1 to 2-4 were measured, and the results are shown in Table 3 and Figures 2 to 4 below.

Figure 2a is a graph showing the room temperature photoluminescence spectrum of the color conversion film according to Preparation Example 2-1 and Preparation Example 2-2, and Figure 2b is a graph showing the room temperature photoluminescence spectrum of the color conversion film according to Preparation Example 2-3 and Preparation Example 2-4. This is a graph showing the photoluminescence spectrum.

Figure 3a is a graph showing the absorption spectrum of the color conversion film according to Preparation Example 2-2, and Figure 3b is a graph showing the photoluminescence spectrum of the color conversion film according to Preparation Example 2-2.

Figure 4a is a graph showing the absorption spectrum of the color conversion film according to Preparation Example 2-4, and Figure 4b is a graph showing the photoluminescence spectrum of the color conversion film according to Preparation Example 2-4.

organic nanoparticles
(weight%) TiO ₂
(weight%) maximum luminescence
Spectrum (nm) FWHM
(nm) CCE
(%) Blue light reduction rate (%) Manufacturing Example 2-1 2.5 2.5 622 35.0 36.17 34.04 Manufacturing Example 2-2 2.5 2.5 620 35.0 63.80 47.92 Manufacturing Example 2-3 3.95 3.95 520 26.0 34.00 74.19 Manufacturing Example 2-4 3.95 3.95 519 25.0 90.00 42.43

Referring to Table 2 and Figures 2 to 4, it can be seen that the position of the emission spectrum peak of the DC-OND film is somewhat shifted toward a shorter wavelength compared to the OND film, which is due to the aggregation of the second organic phosphor ( This is because aggregation has decreased. In addition, the color conversion efficiency of the DC-OND film compared to the OND film increased 1.76 times for the DC-ROND film and 2.65 times for the DC-GOND film, which is due to the absorption of LED light due to the use of the first organic phosphor. Because it increased. In the case of DC-GOND film, the spectral overlap was greater than that of DC-ROND film, so it showed a higher increase rate.

Preparation Example 3: Preparation of color conversion film (1)

<Production Example 3-1>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.80 ml of the PVA-SA aqueous solution with the Per-4tBuMB DC-ROND solution (0.8 wt % aqueous dispersion, 0.37 ml) of Preparation Example 1-5 and TiO ₂ solution (6.0 wt % aqueous solution, 0.05 ml). was manufactured. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 3-2>

A color conversion film was prepared in the same manner as Preparation Example 3-1, except that the TiO ₂ solution was not used.

<Production Example 3-3>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.70 ml of the PVA-SA aqueous solution with the Per-tPhBODIPY DC-GOND solution (1.0 wt % aqueous dispersion, 0.3 ml) and TiO ₂ solution (15.0 wt % aqueous solution, 0.02 ml) of Preparation Example 1-7. was manufactured. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 3-4>

A color conversion film was prepared in the same manner as Preparation Example 3-3, except that the TiO ₂ solution was not used.

Experimental Example 4: Evaluation of optical properties

The optical properties of the color conversion films according to Preparation Example 3-1 to Preparation Example 3-4 were measured, and the results are shown in Table 4 and Figure 5 below.

Figure 5a is a graph showing the light intensity (radiant power) of the color conversion film according to Preparation Example 3-1 and Preparation Example 3-2, and Figure 5b is a color conversion film according to Preparation Example 3-3 and Preparation Example 3-4. This is a graph showing the light intensity (Radiant Power).

organic nanoparticles
(weight%) TiO ₂
(weight%) maximum luminescence
Spectrum (nm) CCE
(%) Blue light reduction rate (%) Manufacturing Example 3-1 1.73 1.92 620 63.50 26.22 Manufacturing Example 3-2 1.73 - 620 48.82 29.25 Manufacturing Example 3-3 2.00 1.54 519 84.81 58.00 Manufacturing Example 3-4 2.00 - 519 93.70 21.83

Referring to Table 4 and Figure 5, in the case of a color conversion film manufactured by mixing DC-ROND with TiO ₂ , the blue light reduction rate is almost the same as when TiO ₂ is not used, but the color conversion efficiency increases by 1.3 times. indicated. Meanwhile, in the case of a color conversion film manufactured by mixing TiO ₂ with DC-GOND, the blue light reduction rate was 2.7 times higher than when TiO ₂ was not used, and the color conversion efficiency was slightly reduced, but still showed a good result at 84.8%. It was.

Preparation Example 4: Preparation of color conversion film (3)

<Production Example 4-1>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.80 ml of the PVA-SA aqueous solution with the Per-4tBuMB DC-ROND solution (1.4 wt % aqueous dispersion, 0.19 ml) and TiO ₂ solution (15.0 wt % aqueous solution, 0.018 ml) of Preparation Example 1-5. was manufactured. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 4-2>

A color conversion film was prepared in the same manner as Preparation Example 4-1, except that the content of Per-4tBuMB DC-ROND solution (1.4% aqueous dispersion) was adjusted to 0.23 mL.

<Production Example 4-3>

A color conversion film was prepared in the same manner as Preparation Example 4-1, except that the content of TiO ₂ solution (15.0% aqueous solution) was adjusted to 0.044 mL.

<Production Example 4-4>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. A mixed solution was prepared by mixing 0.51 ml of the PVA-SA aqueous solution with the Per-tBuPhBODIPY DC-GOND solution (2.13 wt % aqueous solution dispersion, 0.10 ml) and TiO ₂ solution (15.0 wt % aqueous solution, 0.01 ml) of Preparation Example 1-9. was manufactured. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 4-5>

Preparation example _4-4 and A color conversion film was prepared in the same manner.

<Production Example 4-6>

A color conversion film was prepared in the same manner as Preparation Example 4-5, except that the content of TiO ₂ solution (15.0% aqueous solution) was adjusted to 0.06 mL.

Experimental Example 5: Evaluation of optical properties

The optical properties of the color conversion films according to Preparation Examples 4-1 to 4-6 were measured, and the results are shown in Table 5 below.

organic nanoparticles
(weight%) TiO ₂
(weight%) maximum luminescence
Spectrum (nm) CCE
(%) Blue light reduction rate (%) Manufacturing Example 4-1 2.50 2.50 620 63.80 47.92 Manufacturing Example 4-2 4.00 2.50 620 66.40 48.34 Manufacturing Example 4-3 2.50 6.00 620 54.02 62.17 Manufacturing Example 4-4 2.00 1.42 520 92.00 39.34 Manufacturing Example 4-5 3.08 4.48 520 78.00 59.67 Manufacturing Example 4-6 3.08 8.00 520 76.30 74.40

Referring to Table 5, when the content of DC-ROND is increased while the content of TiO ₂ is fixed, the color conversion efficiency and blue light reduction rate remain similar, whereas when the content of TiO ₂ is increased, the blue light reduction rate increases by 1.3 times. The results were shown. In the case of DC-GOND, the blue light reduction rate was high when the TiO ₂ content was increased. In addition, the color conversion efficiency and blue light reduction rate of DC-GOND, which overlaps more with the emission spectrum of the first organic phosphor, were better than those of DC-ROND. For reference, since OLED is a self-luminous device, the use of a color conversion film with higher blue light reduction is required.

Preparation Example 5: Preparation of color conversion film (4)

<Production Example 5-1>

A color conversion film was prepared in the same manner as Preparation Example 2-4, except that Pyr-tPhBODIPY DC-GOND of Preparation Example 1-10 was used instead of Per-tPhBODIPY DC-GOND of Preparation Example 1-7.

<Production Example 5-2>

A color conversion film was prepared in the same manner as Preparation Example 2-4, except that MtD-tPhBODIPY DC-GOND of Preparation Example 1-11 was used instead of Per-tPhBODIPY DC-GOND of Preparation Example 1-7.

<Production Example 5-3>

A color conversion film was prepared in the same manner as Preparation Example 2-4, except that FD-tPhBODIPY DC-GOND of Preparation Example 1-12 was used instead of Per-tPhBODIPY DC-GOND of Preparation Example 1-7.

<Production Example 5-4>

A color conversion film was prepared in the same manner as Preparation Example 2-4, except that AB-tPhBODIPY DC-GOND of Preparation Example 1-13 was used instead of Per-tPhBODIPY DC-GOND of Preparation Example 1-7.

Experimental Example 6: Evaluation of optical properties

The photoluminescence spectrum and light intensity of the color conversion films according to Preparation Example 2-4 and Preparation Examples 5-1 to 5-6 were measured, Ro was calculated, and shown in Table 6 below.

Ro(nm) calculated value DC-GONDs
(weight%) TiO ₂
(weight%) CCE
(%) Blue light reduction rate (%) Manufacturing Example 2-4 4.36 3.95 3.95 90.00 42.43 Manufacturing Example 5-1 4.17 3.95 3.95 73.45 40.10 Manufacturing Example 5-2 4.03 3.95 3.95 81.76 39.17 Manufacturing Example 5-3 3.80 3.95 3.95 61.87 35.19 Manufacturing Example 5-4 3.89 3.95 3.95 69.70 38.90

Referring to Table 6, it can be seen that even if the contents of DC-GOND and TiO ₂ are the same, the blue light reduction rate and color conversion efficiency are different depending on the type of the first organic phosphor. This is the molar extinction coefficient of each first organic phosphor, the degree of overlap between the LED light and the absorption spectrum of the first organic phosphor, PLQY, the degree of overlap between the emission spectrum of the first organic phosphor and the absorption spectrum of the second organic phosphor, the first organic phosphor This is because Ro, etc. between the and the second organic phosphor are different, and the dispersibility of the first organic phosphor in water is also different. As already explained in Experimental Example 5, the blue light reduction rate and color conversion efficiency may vary depending on the content of DC-GOND and TiO ₂ , so the content of DC-GOND and TiO ₂ and the type of the first organic phosphor are adjusted. By doing so, it is possible to manufacture and apply a color conversion film optimized according to the characteristics required for application fields such as LED, OLED, and micro LED.

Preparation Example 6: Preparation of color conversion film (5)

<Production Example 6-1>

0.49 g of polyvinyl alcohol (PVA, weight average molecular weight 13,000 to 23,000 g/mol, degree of hydration 87 to 89%) and 0.01 g of suberic acid (SA) were mixed in 5.0 ml of deionized water and heated at 80°C for 3 hours to 20 °C. % by weight PVA-SA aqueous solution was prepared. Per-4tBuPhBODIPY-4tBuMB DC-GROND solution (2.26% by weight aqueous dispersion, 0.29ml) and TiO ₂ solution (15.0% by weight aqueous solution, 0.043ml) of Preparation Example 1-14 were mixed with 0.80ml of the PVA-SA aqueous solution. A mixed solution was prepared. After spraying the mixed solution on a glass substrate, a film was formed by bar coating. To remove the solvent, it was stored in an oven at 60°C for 4 hours, and the crosslinking reaction was performed at 120°C for 2 hours to prepare a color conversion film.

<Production Example 6-2>

Preparation Example 6, except that Per-4tBuPhBODIPY-4tBuMB DC-GROND (2.26% aqueous solution dispersion, 0.29 ml) of Preparation Example 1-15 was used instead of Per-4tBuPhBODIPY-4tBuMB DC-GROND of Preparation Example 6-1. A color conversion film was manufactured in the same manner as -1.

<Production Example 6-3>

Preparation Example 6-, except that the content of Per-4tBuPhBODIPY-4tBuMB DC-GROND solution (2.26% aqueous solution dispersion) was adjusted to 0.4 ml and the content of TiO ₂ solution (15.0% aqueous solution) was adjusted to 0.11 ml. A color conversion film was manufactured in the same manner as in 1.

<Production Example 6-4>

Preparation Example 6-, except that the content of Per-4tBuPhBODIPY-4tBuMB DC-GROND solution (2.26% aqueous solution dispersion) was adjusted to 0.4 ml and the content of TiO ₂ solution (15.0% aqueous solution) was adjusted to 0.11 ml. A color conversion film was manufactured in the same manner as in 2.

Experimental Example 7: Evaluation of optical properties

The optical properties of the color conversion films according to Preparation Example 6-1 to Preparation Example 6-4 were measured, and the results are shown in Table 7 and Figure 6 below.

Figure 6a is a graph showing the light intensity (radiant power) of the color conversion film according to Preparation Example 6-1 and Preparation Example 6-2.

In addition, Figure 6b is a photograph observing the photoluminescence and DC-GROND color conversion film of the DC-GROND solution of Preparation Example 6-1 in a UV lamp.

organic nanoparticles
(weight%) TiO ₂
(weight%) CCE
(%) Blue light reduction rate (%) Production Example 6-1 3.07 3.03 83.90 64.27 Manufacturing Example 6-2 3.07 3.06 83.26 62.10 Manufacturing Example 6-3 4.00 7.31 75.50 75.74 Manufacturing Example 6-4 4.00 7.31 67.00 73.22

Referring to Table 7 and Figure 6, it can be seen that DC-GROND emits all red, green, and blue light, producing white light. The blue light reduction rate was all over 60%, and the color conversion efficiency was also high. In the case of using 70% of the first organic phosphor, the blue light reduction rate can be adjusted by the content of DC-GROND and TiO ₂ rather than the ratio of green phosphor and red phosphor. If the blue light reduction rate is high, the color conversion efficiency decreases. It appeared that there was a tendency. Since the intensity of green and red phosphors can be adjusted by changing the content of green and red phosphors, it is possible to manufacture DC-GROND with the content of blue/green/red phosphors adjusted according to required characteristics.

The description of the present specification described above is for illustrative purposes, and a person skilled in the art to which an aspect of the present specification pertains can easily transform it into another specific form without changing the technical idea or essential features described in the present specification. You will be able to understand it. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as single may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present specification is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present specification.

Claims (20)

Long-wavelength switching luminescent organic nanoparticles containing first and second organic phosphors,
The first organic phosphor has a molar extinction coefficient (ε) of 10,000 L/mol·cm or more at a wavelength of 450 nm,
Long-wavelength switching luminescent organic nanoparticles, wherein the emission spectrum of the first organic phosphor overlaps the absorption spectrum of the second organic phosphor. According to paragraph 1,
Foerster radius between the first and second organic phosphors ( ; Long-wavelength switching luminescent organic nanoparticles with R _O ) of 7.0 nm or less According to paragraph 1,
The weight ratio of the first and second organic phosphors is 5.0:5.0 to 9.5:0.5. Long-wavelength switching light-emitting organic nanoparticles. According to paragraph 1,
Long-wavelength switching luminescent organic nanoparticles having an average particle diameter of 100 to 170 nm and a standard deviation of the particle diameter of 500 nm or less. According to paragraph 1,
Long-wavelength switching light-emitting organic nanoparticles having a core-shell structure in which the first and second organic phosphors are surrounded by a surfactant. According to clause 5,
The surfactant is one or more types selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants. According to paragraph 1,
Long-wavelength switching luminescent organic nanoparticles, wherein the PLQY of the first organic phosphor is 50% or more. According to paragraph 1,
The first organic phosphor is composed of the following compounds BB-1 to BB-11, BD-1 to BD-9, BM-1 to BM-12, BPer-1 to BPer-20, and BPyr-1 to BPyr-11. One or more types of long-wavelength switching luminescent organic nanoparticles selected from the group:





. According to paragraph 1,
The second organic phosphor is a delayed fluorescence material, a long-wavelength switching light-emitting organic nanoparticle. According to clause 9,
The delayed fluorescent material is a long-wavelength switching light-emitting organic nanoparticle, which is a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
L is any one selected from the group consisting of an aryl group, an arylene group, and a carbon-nitrogen single bond,
When L is an aryl group, A is a cyano group substituted by 1 or 2 of the aryl group, D is a substituent of 4 or 5 substituted by the aryl group, and each of the substituents is independently a nitrogen substituted with a hydrocarbon group having 1 to 10 carbon atoms. It is a heteroaryl group containing an atom,
When L is an arylene group, A is a substituted or unsubstituted triazine group, and D is a substituted or unsubstituted heteroaryl group, which contains a nitrogen atom bonded to the arylene group. It contains a non-conjugated pentagonal or hexagonal ring, and is a multi-fused ring fused to the conjugated or non-conjugated pentagonal or hexagonal ring, with 1 to 9 rings within the multi-fused ring. Contains a nitrogen atom or one Group 16 element,
When L is a carbon-nitrogen single bond, D is a fused ring of 10 to 40 carbon atoms, and is a conjugated or non-conjugated pentagon containing the nitrogen atom of L or Contains a hexagonal ring, and includes a substituted or unsubstituted aryl group forming a conjugated ring with the conjugated or unconjugated pentagonal or hexagonal ring, and the conjugated or unconjugated pentagonal or hexagonal ring is substituted or unsubstituted. It is a ring that does not contain or contains a Group 16 element in the ring, contains 1 or 2 nitrogen atoms in the ring, and A is a heterocycle having 15 to 40 carbon atoms, containing the carbon atom bonded to L. A pentagon containing an aryl group, containing a ring structure containing a boron atom and an oxygen atom in the ring, forming a fused ring with the aryl group containing the carbon atom, or containing two nitrogen atoms conjugated. or a hexagonal ring structure. According to clause 10,
The compound represented by Formula 1 is one or more types selected from the group consisting of the following compounds T-1 to T-32, long-wavelength switching luminescent organic nanoparticles:



. According to paragraph 1,
The second organic phosphor is a long-wavelength switching luminescent organic nanoparticle, which is a boron compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R ₁ to R ₅ are each independently hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted At least one member selected from the group consisting of a substituted or unsubstituted heterocycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group; ,
X ₁ to X ₄ are each independently hydrogen, or are bonded to each other to form a ring. According to clause 12,
The boron compound represented by Formula 2 is a long-wavelength conversion luminescent organic nanoparticle that is at least one selected from the group consisting of the following compounds D-1 to D-30:



. According to paragraph 1,
The second organic phosphor is a long-wavelength switching luminescent organic nanoparticle, which is a boron compound represented by the following formula (3):
[Formula 3]

In Formula 3 above,
C ₁ to C ₃ each have a 5-membered or 6-membered ring structure
R ₁₁ and R ₁₂ may each independently be substituted with 1, 2, or 3, and the substituents include hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amidino, and hydrazino groups. , hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted thioether group, substituted or unsubstituted Cycloalkyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted heterocycloalkyl group, substituted or unsubstituted heterocycloalkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or It corresponds to any one selected from the group consisting of an unsubstituted heteroaryl group and a substituted or unsubstituted heteroaryloxy group, or two or more substituents combine with each other to form a ring,
R ₁₃ is hydrogen, deuterium, halogen group, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted Or an unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted thioether group, a substituted or unsubstituted heterocycloalkyl group, Any selected from the group consisting of a substituted or unsubstituted heterocycloalkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group. Corresponds to one,
Y ₁ and Y ₂ are each independently a fluorine group or an alkoxy group. According to clause 14,
The boron compound represented by Formula 3 is one or more types selected from the group consisting of the following compounds B-1 to B-51, long wavelength conversion luminescent organic nanoparticles:






. A composition for a color conversion film comprising the long-wavelength conversion luminescent organic nanoparticles according to any one of claims 1 to 15 and a water-soluble polymer resin. According to clause 16,
A composition for a color conversion film, comprising 1 to 20 parts by weight of the long-wavelength conversion luminescent organic nanoparticles, based on 100 parts by weight of the water-soluble polymer resin. A color conversion film manufactured using the composition for a color conversion film according to claim 16. A display device comprising the color conversion film according to claim 18. A light emitting diode device comprising the color conversion film according to claim 18.