KR101735168B1 - Color conversion film with improved oxygen barrier property and method for manufacturing the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color conversion film having improved oxygen barrier properties and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a color conversion film having improved oxygen barrier properties and a method for producing the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color conversion film having improved oxygen barrier properties and a method for producing the same.

Quantum dots are materials with a crystal structure of a few nanometers in size, consisting of hundreds to thousands of atoms. Since quantum dots are very small, quantum confinement effects appear. The quantum confinement effect refers to a phenomenon in which an energy band gap of an object becomes larger when an object becomes smaller than a nano-size. Accordingly, when light having a wavelength larger than the energy band gap is incident on the quantum dot, the quantum dot absorbs the energy of the light and is excited, and falls to the ground state while emitting light of a specific wavelength. The wavelength of the emitted light is determined by the energy corresponding to the band gap.

Generally, the smaller the size of the quantum dot, the shorter wavelength light is emitted. The larger the size, the longer wavelength light is emitted. This is a unique electrical and optical property different from conventional semiconductor materials. Therefore, the quantum dot can achieve desired luminescence characteristics by adjusting the size and composition thereof.

However, there is a problem that it is difficult to commercialize a film using a quantum dot because of the characteristics of the quantum dot susceptible to moisture and oxygen and the light leakage phenomenon during film formation.

Korean public disclosure: 10-2012-0095486

The present specification intends to provide a color conversion film having improved oxygen barrier properties and a manufacturing method thereof.

One embodiment of the present disclosure includes quantum dots; Radical unreactive oxygen scavenger; And a curable resin.

Another embodiment of the present disclosure relates to a method of manufacturing a curable resin composition, And mixing the curable resin composition with a quantum dot and an oxygen scavenger.

Another embodiment of the present invention relates to the above-mentioned color conversion film; A light source unit including a light source for generating light; And a light guide plate for guiding the light.

Conventional color conversion films have lowered the oxygen concentration in contact with the quantum dots by using a radical reaction material such as antioxidants or HALS (Hindered Amine Light Stabilizer). However, in such a case, the curing of the quantum dot color conversion film is affected. For this reason, instability of the color conversion film is caused, which affects the stability of the quantum dots and thus has a problem that the luminous efficiency is lowered.

The color conversion film produced according to one embodiment of the present disclosure can block oxygen that can penetrate into the film during the color conversion film formation process. Thus, lifetime and performance of the quantum dot can be improved.

Further, the color conversion film according to one embodiment of the present invention can secure the stability of a quantum dot, and can manufacture a color conversion film exhibiting a high luminescent effect.

FIG. 1 is a graph illustrating PL (Photo Luminescence) emission intensity according to the wavelength of a color conversion film according to Examples and Comparative Examples.
2 shows a color conversion film according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

In this specification, a quantum dot is a part of a substance in which excitons are localized in all three-dimensional spaces, and is a nanometer-sized particle having a zero-dimensional structure having unique optical and electronic properties. For example, semiconductor crystals of nanometer size.

One embodiment of the present disclosure includes quantum dots; Radical unreactive oxygen scavenger; And a curable resin.

In the present specification, radical unreactivity refers to a property of lowering the concentration of oxygen by quenching singlet oxygen without radical reaction.

The color conversion film may include one or more quantum dots.

In order to form a color conversion film on a quantum dot and apply it to a device, stability against stimulation received from an external environment (such as moisture or oxygen) and excellent luminescence characteristics should be secured.

The addition of an oxygen scavenger to lower the oxygen concentration in the color conversion film has the advantage of blocking oxygen that can penetrate the film during film formation.

The quantum dot may include semiconductors of group II-VI, group III-V, group IV-VI, group IV, and mixtures thereof. The semiconductor material is not particularly limited but may be any of Si, Ge, Sn, Se, Te, B, C, P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, ZnS, ZnTe, CdS, CdSe, CdxSeySz, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, InS, InS, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, , MgS, MgSe, GeS, GeSe , GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuInS 2, Cu 2 SnS 3, CuBr, CuI, Si 3 N 4, Ge 3 N 4 _{, Al 2 O 3, (Al} , Ga, In) 2 (S, Se, Te) 3, CIGS, CGS, (ZnS) y - a _{(Cu x Sn 1 x S 2} ) 1-y , and mixtures of these semiconductor .

According to one embodiment of the present disclosure, the quantum dot may be a core / shell structure or an alloy structure. Quantum dots having a core / shell structure or an alloy structure, CdSe / ZnS, CdSe / ZnSe / ZnS, CdSe / CdS x (Zn 1 - y Cd y) S / ZnS, CdSe / CdS / ZnCdS / ZnS, InP / ZnS, InP CdSe / CdS / ZnS, CdTe / CdS, CdTe / ZnS, CuInS ₂ , / ZnS or Cu ₂ SnS ₃ / ZnS. , But is not limited thereto.

The quantum dot may include quantum dots representing at least one color selected from the group consisting of red light, green light, blue light, and yellow light, but is not limited thereto. Preferably, the quantum dots are red or green or red and green quantum dots. . The quantum dots may absorb ultraviolet light having a wavelength between about 100 and about 400 nm and visible light having a wavelength between about 380 and 780 nm.

The blue light may have an emission peak in a wavelength range of from 410 nm to less than 500 nm, the green light may have an emission peak in a wavelength range of from 500 nm to less than 550 nm, and the yellow light may have a wavelength of from 550 nm to less than 600 nm Region, and the red light may have an emission peak in a wavelength region of 600 nm or more and less than 700 nm. In this specification, four colors of blue, green, yellow, and red are used for the sake of simplicity, but the wavelength range includes various colors such as orange, indigo, and violet in addition to these colors.

In one embodiment of the present disclosure, the oxygen scavenger may be an organic material. For example, the oxygen scavenger may include, but is not limited to, a heterocycle containing carbon and nitrogen as ring members. Specifically, the oxygen scavenger may be DABCO (1,4-1,4-diazabicyclo [2,2,2] octane).

According to another embodiment of the present invention, the oxygen scavenger may be 0.5 to 1.0 wt% based on 100 parts by weight of the entire color conversion film. When the oxygen scavenger is in the above-mentioned numerical range, there is an advantage that the penetration of oxygen into the film is prevented to improve the luminescence characteristics.

In one embodiment of the present disclosure, the curable resin may include a polymerizable compound containing an ethylenic unsaturated bond.

The curable resin may be an acrylate compound. Examples of the curable resin include acrylate compounds such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di But are not limited to, one or more compounds selected.

 According to one embodiment of the present disclosure, the color conversion film comprises a photoinitiator; Thermal initiators; And an antioxidant may be further included.

Wherein the photoinitiator is selected from the group consisting of a triazine-based compound, a nonimidazole compound, an acetophenone-based compound, an O-acyloxime compound, a thioxanthone compound, a phosphine oxide compound, a coumarin compound, and a benzophenone compound Species or two or more species.

Specifically, in one embodiment of the present disclosure, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4 -Methoxystyryl) -6-triazine, 2,4-trichloromethyl- (pupylonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl Yl) phenylthio} propanoic acid, 2,4-trichloromethyl- (4 ', 5'- -Ethylbiphenyl) -6-triazine or 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine; Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5'-tetraphenylbiimidazole and the like; 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-methylthiophenyl) -2-morpholinocyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 1-one (Irgacure-907) or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Nonnary compounds; O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy; Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone or 4,4'-bis (diethylamino) benzophenone; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, or diisopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide or bis (2,6-dichlorobenzoyl) propylphosphine oxide Phosphine oxide-based compounds; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin or 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- -Benzopyrano [6,7,8-ij] -quinolizine-11-one, or the like, or a mixture of two or more of them may be used, but the present invention is not limited thereto.

As the thermal initiator, those known in the art can be used.

In one embodiment of the present invention, the content of the quantum dot may be 0.5 to 2.0 wt% with respect to 100 parts by weight of the entire color conversion film.

When the content of the quantum dots is within the above-mentioned numerical range, there is an advantage that the color conversion film including the quantum dots can have a high luminous efficiency and luminance.

In another embodiment of the present invention, the content of the curable resin may be 95 to 98 wt% based on 100 parts by weight of the whole color conversion film, but is not limited thereto.

In some embodiments of the present invention, the content of each of the additives may be 1.0 to 2.0 wt% with respect to 100 parts by weight of the entire color conversion film, but is not limited thereto.

In one embodiment of the present disclosure, the quantum dots may be red or green or red and green quantum dots, but are not limited thereto.

According to one embodiment of the present invention, there is provided a method of manufacturing a curable resin composition, And mixing the curable resin composition with a quantum dot and an oxygen scavenger.

The curable resin composition may include the above-mentioned curable resin.

The curable resin, the quantum dot, and the oxygen scavenger are as described above.

In another embodiment of the present invention, the above-mentioned color conversion film; A light source unit including a light source for generating light; And a light guide plate for guiding the light.

In some embodiments of the present disclosure, there is provided a display device including the backlight unit. The display may include a display panel and a backlight unit, wherein the display panel is a liquid crystal display panel, an electrophoretic display panel, A wetting display panel, and the like.

The backlight unit may be disposed in a direction opposite to a direction in which the image is emitted from the display panel. The backlight unit may further include a light guide plate, a light source unit including a plurality of light sources, an optical member, and a reflective sheet.

Besides, the configuration of the display device may be applied to those known in the art.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

[ Example - Production of color conversion film]

3 g of TMPTA (trimethylolpropane triacrylate) and 0.03 g of IRG184 and D-1173 as photoinitiators were mixed to prepare a photocurable resin composition.

Then, a red or green quantum dot was mixed with the photocurable resin composition to prepare a quantum dot composition, and sonication was carried out for 30 minutes to homogeneously mix. The concentration of only the CdSe / ZnS quantum dot in the photocurable resin composition was 1 wt% with respect to the photocurable resin composition.

The quantum dot composition was coated on PET (polyethylene terephthalate) film through bar coating. To completely remove the toluene contained in the quantum dot composition, the film was heated in a 60 ° C oven for 5 minutes and then cured at about 400 mJ / cm ² in a UV curing machine (D-bulb) to produce an optical film. Then, improvement of PL (photo luminescence) emission intensity and quantum efficiency was observed with quantum efficiency measuring equipment. The PL emission intensity of the optical film according to the embodiment is shown in FIG. 1, and the measured absolute quantum efficiency and PL intensity are shown in Table 1 below.

QY  / Absorbance
( EXT  w / 450 nm ) PL intensity Comparative Example 0.384 / 0.222 487.2 Example 0.405 / 0.363 840.1

Referring to Table 1, it can be seen that the absolute quantum efficiency (QY) and the PL intensity of the embodiment are superior to those of the comparative example.

 [ Comparative Example ]

The color conversion film was produced in the same manner as described above except that the oxygen scavenger was not included in the above example, and quantum yield, absorbance, and PL luminescence intensity were measured using a quantum efficiency measuring apparatus Respectively. The PL emission intensity of the color conversion film according to the comparative example is shown in Fig.

FIG. 1 is a graph showing PL emission intensity according to light wavelengths of color conversion films according to Examples and Comparative Examples. As can be seen from the results of FIG. 1, it can be seen that the color conversion film of the embodiment to which the oxygen scavenger is added has a luminescence intensity superior to that of the color conversion film of the color comparison example to which no oxygen scavenger is added.

Claims (15)

Quantum dot;
Radical unreactive oxygen scavenger; And
And a curable resin,
Wherein the radical unreactive oxygen scavenger lowers the concentration of oxygen by quenching singlet oxygen without radical reaction and converts the organic substance including a heterocycle containing carbon and nitrogen as a ring source Color conversion film. delete delete The method according to claim 1,
Wherein the oxygen scavenger is 0.5 to 1.0 wt% based on 100 parts by weight of the whole color conversion film. The method according to claim 1,
Wherein the curable resin comprises a polymerizable compound containing an ethylenic unsaturated bond. The method according to claim 1,
Wherein the color conversion film comprises a photoinitiator; Thermal initiators; And at least one additive selected from the group consisting of an antioxidant. The method according to claim 1,
Wherein the content of the quantum dots is 0.5 to 2.0 wt% with respect to 100 parts by weight of the entire color conversion film. The method according to claim 1,
Wherein the content of the curable resin is 95 to 98 wt% with respect to 100 parts by weight of the whole color conversion film. The color conversion film according to claim 1, wherein the quantum dots are red, green, or red and green quantum dots. Preparing a curable resin composition; And
Mixing the curable resin composition with a quantum dot and an oxygen scavenger,
Wherein the radical unreactive oxygen scavenger lowers the concentration of oxygen by quenching singlet oxygen without radical reaction and converts the organic substance including a heterocycle containing carbon and nitrogen as a ring source Lt; RTI ID = 0.0 >%< / RTI > delete delete The method of claim 10,
Wherein the quantum dots are red, green, or red and green quantum dots. A color conversion film according to any one of claims 1 and 4 to 9;
A light source unit including a light source for generating light; And
And a light guide plate for guiding the light. A display device comprising a backlight unit according to claim 14.

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