KR102409453B1 - Display device - Google Patents

Abstract

a light source emitting light at a wavelength of 400 nm to 500 nm and having an intensity of light at a wavelength of 420 nm of 3% or more of the highest intensity; a quantum dot-containing layer positioned on the light source; a pressure-sensitive adhesive layer positioned on the quantum dot-containing layer; and a blue color filter layer positioned on the adhesive layer, wherein the light at a wavelength of 420 nm derived from the light source passes through the quantum dot-containing layer, the adhesive layer and the blue color filter layer, and then 1% or less of the highest intensity of light A display device having an intensity of

Description

display device {DISPLAY DEVICE}

The present disclosure relates to a display device including quantum dots.

In the case of quantum dot-containing display materials that are recently commercialized or under development, the emission of green quantum dots and red quantum dots through a blue light source or a white light source is used. The quantum dot-containing display device is intended to improve color gamut and luminance by using a quantum dot material, and development of a panel using quantum dot light emission using various types of light sources continues. In addition, it is possible to improve the viewing angle according to the application position of the quantum dot material in the panel configuration. The next-generation quantum dot display device is being developed in the direction of increasing the intensity of the light source or in the direction of developing the light source in which the blue region is extended in order to improve the luminous efficiency of quantum dots, which is technically very important.

In the quantum dot display device, the spectrum of the light source that reaches the quantum dot material has a very close influence on the efficiency of the quantum dot, and the characteristics of the current light source are different. Efforts are continuing in

One embodiment is to provide a display device having high color gamut and excellent luminance by increasing quantum dot efficiency.

One embodiment is a light source emitting light at a wavelength of 400 nm to 500 nm, the light intensity at a wavelength of 420 nm having a value of 3% or more of the highest intensity; a quantum dot-containing layer positioned on the light source; a pressure-sensitive adhesive layer positioned on the quantum dot-containing layer; and a blue color filter layer positioned on the adhesive layer, wherein the light at a wavelength of 420 nm derived from the light source passes through the quantum dot-containing layer, the adhesive layer and the blue color filter layer, and then 1% or less of the highest intensity of light To provide a display device having a strength of

Any one of the adhesive layer and the blue color filter layer may have an absorbance of less than 50% at a wavelength of 420 nm or less.

The adhesive layer may have an absorbance of 50% or more at a wavelength of 420 nm or less.

The blue color filter layer may have an absorbance of 50% or more at a wavelength of 420 nm or less.

The adhesive layer or the blue color filter layer may include at least one of an azo-based dye, an azomethine-based dye, and a porphyrin-based dye.

The azomethine-based dye may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

M is Zn, Co, Cu or V;

X ¹ to X ⁴ are each independently an oxygen atom or a sulfur atom,

R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a mercapto group, or a substituted or unsubstituted C1 to C20 alkylmercaptanyl group,

n1 to n4 are each independently an integer of 0 to 4.

The azomethine-based dye represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-7 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

The porphyrin-based dye may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

M is Zn, Co, Cu or V;

R ⁵ to R ¹² are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted a cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkylester group,

n5 to n12 are each independently an integer of 0 or 1, provided that 1 ≤ n5+n6 ≤ 2, 1 ≤ n7+n8 ≤ 2, 1 ≤ n9+n10 ≤ 2, and 1 ≤ n11+n12 ≤ 2.

The porphyrin-based dye represented by Formula 2 may be represented by any one of Formulas 2-1 to 2-20.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

In Formula 2-13,

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

m1 and m2 are each independently an integer from 0 to 20, provided that 4 ≤ m1+m2 ≤ 20;

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

[Formula 2-20]

The quantum dots may include green quantum dots, red quantum dots, or a combination thereof.

The display device may further include a liquid crystal layer between the adhesive layer and the blue color filter layer.

The display device may further include an overcoat layer between the liquid crystal layer and the blue color filter layer.

The quantum dot-containing layer may further include a diffusing agent.

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

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

It is possible to provide a display device capable of high color reproduction and excellent luminance by improving light conversion efficiency of quantum dots while preventing a decrease in blue color purity.

1 is a schematic diagram illustrating a display device according to an embodiment.
2 is a graph showing an absorption spectrum of a quantum dot and an absorption spectrum of a conventional (blue) light source used in a display device.
3 is a graph showing a spectral spectrum of a light source.
4 is a graph showing the spectral spectrum of the adhesive layer.
5 is a graph illustrating a spectral spectrum of a blue color filter layer.
6 is a graph showing spectral spectra (Example 1, Example 2, and Comparative Example 2) of light having a wavelength of 420 nm that has passed through a blue color filter layer.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, , "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, and "heteroarylene group" means a C3 to C20 hetero It means an arylene group, and "alkoxyylene group" means a C1 to C20 alkoxyylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof means substituted with a substituent.

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

In addition, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" is "acrylic acid" and "methacrylic acid" “It means that both are possible.

Unless otherwise specified herein, "combination" means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

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

A display device according to an exemplary embodiment includes: a light source emitting light at a wavelength of 400 nm to 500 nm and having an intensity of light at a wavelength of 420 nm of 3% or more of a maximum intensity; a quantum dot-containing layer positioned on the light source; a pressure-sensitive adhesive layer positioned on the quantum dot-containing layer; and a blue color filter layer positioned on the adhesive layer, wherein the light at a wavelength of 420 nm derived from the light source passes through the quantum dot-containing layer, the adhesive layer and the blue color filter layer, and then 1% or less of the highest intensity of light has the strength of

Green quantum dots and red quantum dots emit light by absorbing light from a blue light source (LED, OLED, etc.), respectively.

Most of the existing quantum dot-containing display devices use a blue LED of sharp spectrum having a max intensity (maximum light intensity) near 450 nm as a light source (see FIG. 2), and a sheet or chip containing quantum dots On the blue LED light source, some light of blue light is converted to green/red to become white including all of red/green/blue. The conversion efficiency (Quantum Yield, QY) of the quantum dots is very high, at a maximum of about 90%, but the problem is that the absorption of blue light in the vicinity of 450 nm used as an actual light source is very small, and the total amount actually converted to green/red is relatively small. Since the absorption spectrum of an actual quantum dot shows greater absorption in the violet or ultraviolet region than in blue (see FIG. 2), the quantum dot may emit brighter light when there is a light source in a shorter wavelength region. However, if there is spectroscopy in the shorter wavelength band, the color purity of blue is lowered and the color gamut is lowered, so the purpose of using the quantum dot-containing display (high color reproduction) is diluted. . However, when a light source of a shorter wavelength band is not used, the brightness (luminance) of the display containing quantum dots is reduced, which is a problem.

One embodiment contains quantum dots, and the light at a wavelength of 420 nm or less, for example, at a wavelength of 420 nm derived from a light source (backlight unit: BLU) for activating the quantum dots, has a value of 3% or more of the highest intensity, By providing a display device in which the intensity of light passing through the quantum dot-containing layer falls to 1% or less of the maximum intensity due to absorption of the color material included in the adhesive layer and the blue color filter layer, the light absorption area of the quantum dots is improved and the actual quantum dot conversion efficiency As this increases, the overall luminance of the panel can be improved, and at the same time, there is no need to sacrifice the color purity of blue. In addition, the display device having this structure is much more efficient than improving the transmittance of each of the color filters (a red color filter layer, a green color filter layer, and a blue color filter layer).

That is, the display device according to an embodiment emits light at a wavelength of 400 nm to 500 nm, unlike a light source used in a conventional display device, but the light intensity at a wavelength of 420 nm is 3% or more of the maximum light intensity. At the same time, the light derived from the 420 nm wavelength goes through the quantum dot-containing layer, the adhesive layer, and the blue color filter layer to cancel the light from the 420 nm wavelength, so that the light intensity is 1% or less of the highest light intensity. By designing the display device to fall apart, high color and high luminance can be realized at the same time.

More specifically, any one of the adhesive layer and the blue color filter layer may have an absorbance of less than 50% at a wavelength of 420 nm or less, for example, a wavelength at 420 nm. That is, any one of the adhesive layer and the blue color filter layer may have an absorbance of 50% or more at a wavelength of 420 nm or less, for example, 420 nm, and at the same time, the other one may have an absorbance of 50% or less at a wavelength of 420 nm or less, for example, 420 nm. % of absorbance. For example, when both the adhesive layer and the blue color filter layer have an absorbance of 50% or more at a wavelength of 420 nm or less, for example, a wavelength at 420 nm, the color purity of the final blue color decreases, which may decrease the color gamut of the entire display. not.

For example, the adhesive layer or the blue color filter layer may include an azo-based dye, an azomethine-based dye or a porphyrin-based dye, but is not necessarily limited thereto, and absorbance of 50% or more at a wavelength of 420 nm or less, for example, 420 nm. If it is a material having a, it may be included in the adhesive layer or the blue color filter layer.

For example, when the adhesive layer includes the azo-based dye, azomethine-based dye, or porphyrin-based dye, the blue color filter layer may not include the azo-based dye, azomethine-based dye, and porphyrin-based dye.

For example, when the blue color filter layer includes the azo-based dye, azomethine-based dye, or porphyrin-based dye, the adhesive layer may not include the azo-based dye, azomethine-based dye, and porphyrin-based dye.

For example, the azomethine-based dye may be represented by the following formula (1).

[Formula 1]

In Formula 1,

M is Zn, Co, Cu or V;

X ¹ to X ⁴ are each independently an oxygen atom or a sulfur atom,

R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a mercapto group, or a substituted or unsubstituted C1 to C20 alkylmercaptanyl group,

n1 to n4 are each independently an integer of 0 to 4.

For example, the azomethine-based dye represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-7, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

For example, the porphyrin-based dye may be represented by the following formula (2).

[Formula 2]

In Formula 2,

M is Zn, Co, Cu or V;

R ⁵ to R ¹² are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted a cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkylester group,

n5 to n12 are each independently an integer of 0 or 1, provided that 1 ≤ n5+n6 ≤ 2, 1 ≤ n7+n8 ≤ 2, 1 ≤ n9+n10 ≤ 2, and 1 ≤ n11+n12 ≤ 2.

For example, the porphyrin-based dye represented by Formula 2 may be represented by any one of Formulas 2-1 to 2-20, but is not necessarily limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

In Formula 2-13,

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

m1 and m2 are each independently an integer from 0 to 20, provided that 4 ≤ m1+m2 ≤ 20;

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

[Formula 2-20]

For example, the display device may further include a liquid crystal layer between the adhesive layer and the blue color filter layer. Furthermore, the display device may further include an overcoat layer between the liquid crystal layer and the blue color filter layer.

Referring to FIG. 1 , in the display device, a blue color filter layer 6 having a blue color filter and a quantum dot-containing layer 2 are positioned to face each other by a column spacer (not shown) with respect to the liquid crystal layer 3 , and liquid crystal An adhesive layer 12 is positioned between the layer 3 and the quantum dot-containing layer 2 . An overcoat layer 4 may be further included between the liquid crystal layer 3 and the blue color filter layer 6 . The quantum dot-containing layer 2 may further include a diffusion agent 11 in addition to the quantum dots 9 and 10 . In addition, a silica deposition layer (not shown) may be present on one surface of the quantum dot-containing layer 2 , and the silica deposition layer absorbs blue light from a light source through the light guide plate 1 . Glass 5 is positioned on the blue color filter layer 6 .

Since the display device further includes an adhesive layer between the quantum dot-containing layer and the blue color filter layer at the same time as the quantum dot-containing layer is composed of a separate layer from the blue color filter layer, it is possible to effectively prevent the decrease in quantum efficiency of the quantum dots. In addition, the light guide plate may be a glass light guide plate, not a PMMA light guide plate. By using the glass light guide plate instead of the PMMA light guide plate, the thickness of the panel can be reduced, and thus the luminance improvement effect can be expected.

The quantum dot-containing layer may further include a binder resin, a reactive unsaturated compound, a diffusing agent, and other additives in addition to the quantum dots, which will be described later.

The quantum dots may have a maximum absorption wavelength at 460 nm to 490 nm in a wavelength range of 440 nm to 550 nm.

The quantum dots may have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dot has a full width at half maximum in the above range, as the color purity is high, when used as a color material in a color filter, color gamut is increased.

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

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

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. , but is not necessarily limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

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

The structure of the quantum dot is not particularly limited, but in the case of the quantum dot having the core/shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example 5 nm to 15 nm.

For example, the quantum dots may include red quantum dots, green quantum dots, or a combination thereof. For example, the quantum dots may include both green quantum dots and red quantum dots. In this case, the green quantum dot may be included in an amount greater than that of the red quantum dot. The red quantum dots may have an average particle diameter of 10 nm to 15 nm. The green quantum dots may have an average particle diameter of 5 nm to 8 nm.

On the other hand, for the dispersion stability of the quantum dots, it may further include a dispersing agent. The dispersing agent helps to uniformly disperse a light conversion material such as quantum dots in the curable composition, and any nonionic, anionic or cationic dispersant may be used. Specifically, polyalkylene glycol or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide Adducts, alkyl amines, etc. may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1 wt% to 100 wt%, such as 10 wt% to 20 wt%, based on the solid content of the light conversion material such as quantum dots.

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

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene or vinylbenzylmethyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds, such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic resin include polybenzyl methacrylate, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2 -Hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. may be mentioned, but are not limited thereto, and these may be used alone or in two or more types. may be used in combination.

The weight average molecular weight of the acrylic resin may be 1,000 g/mol to 15,000 g/mol.　When the weight average molecular weight of the acrylic resin is within the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

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

As the epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, cyclic aliphatic epoxy resin, aliphatic polyglycidyl ether, and the like may be used, but is not necessarily limited thereto.

As a commercially available product of the epoxy resin, bisphenyl epoxy resins such as YX4000, YX4000H, YL6121H, YL6640, and YL6677 of Yuka Shell Epoxy Co., Ltd.; Cresol no-block type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 from Nippon Kayaku Co., Ltd. and Epicoat 180S75 from Yuka Shell Epoxy Co., Ltd. ; and the like, and in addition to this, the bisphenol A type epoxy resin includes Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 of Yuka Shell Epoxy Co., Ltd.; Examples of the bisphenol F-type epoxy resin include Epicoat 807 and 834 of Yuka Shell Epoxy Co., Ltd.; Examples of the phenol no-block type epoxy resin include Epicoat 152, 154, 157H65 of Yuka Shell Epoxy Co., Ltd. and EPPN 201, 202 of Nippon Kayaku Co., Ltd.; Other cyclic aliphatic epoxy resins include CIBA-GEIGY A.G's CY175, CY177 and CY179, U.C.C's ERL-4234, ERL-4299, ERL-4221 and ERL-4206, Showa Denko Co., Ltd.'s Shodyne 509 , CIBA-GEIGY A.G. Araldite CY-182, CY-192 and CY-184, Dainippon Ink Kogyo Co., Ltd. Epichron 200 and 400, Eucashell Epoxy Co., Ltd. Epicoat 871, 872 and EP1032H60, ED-5661 and ED-5662 of Celanese Coating Co., Ltd.; Examples of aliphatic polyglycidyl ethers include Epicoat 190P and 191P from Yuccal Epoxy Co., Ltd., Eporite 100MF from Kyoesha Yushi Chemical Co., Ltd., and Epiol TMP from Nippon Yushi Co., Ltd. can

The reactive unsaturated compound may be used by mixing monomers or oligomers generally used in conventional photocurable compositions and thermosetting compositions.

The reactive unsaturated compound may be an acrylate-based compound. For example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate , novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6 - One or more types of hexanediol dimethacrylate may be selected or mixed and used.

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

The quantum dot-containing layer may further include a diffusing agent.

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

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

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

In order to improve the stability and dispersibility of the quantum dots, the quantum dot-containing layer may further include a thiol-based additive.

The thiol-based additive may be substituted on the shell surface of the quantum dots to improve the dispersion stability of the quantum dots to a solvent, thereby stabilizing the quantum dots.

The thiol-based additive may have 2 to 10, for example, 2 to 4 thiol groups (-SH) at the terminal depending on the structure thereof.

For example, the thiol-based additive may include at least two or more functional groups represented by the following Chemical Formula 3 at the terminal thereof.

[Formula 3]

In Formula 3,

L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted It is a C2 to C20 heteroarylene group.

For example, the thiol-based additive may be represented by the following formula (4).

[Formula 4]

In Formula 4,

L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted is a C2 to C20 heteroarylene group,

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

For example, in Formulas 3 and 4, L ⁷ and L ⁸ may each independently represent a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

Specific examples of the thiol-based additive include pentaerythritol tetrakis (3-mercaptopropionate) represented by the following Chemical Formula 3a, and trimethylolpropane tris (3) represented by the following Chemical Formula 3b. -mercaptopropionate) (trimethylolpropane tris (3-mercaptopropionate)), pentaerythritol tetrakis (mercapto acetate) represented by the following formula 3c Pentaerythritol tetrakis (mercaptoacetate), trimethylolpropane tris ( Any selected from the group consisting of 2-mercaptoacetate) (trimethylolpropane tris(2-mercaptoacetate)), glycol di-3-mercaptopropionate represented by the following formula 3e, and combinations thereof can take one

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Formula 3d]

[Formula 3e]

The quantum dot-containing layer may further include a polymerization inhibitor including a hydroquinone-based compound, a catechol-based compound, or a combination thereof. As the quantum dot-containing layer further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, it is possible to prevent cross-linking at room temperature during exposure after printing (coating) the composition including quantum dots.

For example, the hydroquinone-based compound, the catechol-based compound, or a combination thereof is hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, pyroga Rol, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum (Tris(N-hydroxy-N) -nitrosophenylaminato-O,O')aluminium) or a combination thereof, but is not necessarily limited thereto.

The quantum dot-containing layer may include malonic acid in addition to the thiol-based additive and polymerization inhibitor; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactants; Or it may further include a combination thereof.

For example, the quantum dot-containing layer may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, and an epoxy group in order to improve adhesion to the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, γ glycidoxy propyl and trimethoxysilane and β-epoxycyclohexyl)ethyl trimethoxysilane, and these may be used alone or in combination of two or more.

In addition, the quantum dot-containing layer may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defect generation, if necessary.

As the fluorine-based surfactant, BM-1000 ^® of BM Chemie, BM-1100 ^® , etc.; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® and the like of Dai Nippon Inky Chemical High School Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , copper FC-170C ^® , copper FC-430 ^® , copper FC-431 ^® , etc.; Saffron S-112 ^® , Copper S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® from Asahi Grass Co., Ltd., etc.; SH-28PA ^® , Copper-190 ^® , Copper-193 ^® , SZ-6032 ^® , SF-8428 ^® , etc. of Toray Silicone Co., Ltd.; F-482, F-484, F-478, F-554 commercially available fluorine-based surfactants of DIC Co., Ltd. may be used.

In addition, in the quantum dot-containing layer, other additives such as antioxidants and stabilizers may be further added in a certain amount within a range that does not impair physical properties.

The manufacturing method of the quantum dot-containing layer includes the steps of forming a pattern by applying a curable composition including the above-described components on a substrate by an inkjet spraying method (S1); and curing the pattern (S2).

(S1) forming a pattern

The curable composition is preferably applied on the substrate in a thickness of 0.5 to 10 μm by an inkjet dispersion method. In the inkjet jetting, a pattern may be formed by jetting only a single color and repeatedly jetting according to the required number of colors, or a pattern may be formed by simultaneously jetting the required number of colors in order to reduce the process.

(S2) curing step

A cured resin film can be obtained by curing the obtained pattern. At this time, as a method of hardening, a thermosetting process is preferable. The thermosetting process may be a process of heating at a temperature of about 100° C. or higher for about 3 minutes to first remove the solvent in the curable composition, and then curing it by heating at a temperature of 160° C. to 300° C., more preferably 180 It may be a process of curing by heating at a temperature of ℃ to 250 ℃ for about 30 minutes.

In addition, the quantum dot-containing layer may be prepared without inkjetting. In this case, the manufacturing method is, for example, 0.5 µm to 10 µm, using an appropriate method such as spin coating, roller coating, spray coating, etc. is applied to a thickness of , and irradiated with light to form a pattern required for the color filter. As a light source used for irradiation, UV, electron beam, or X-ray may be used, for example, 190 nm to 450 nm, specifically, UV in the 200 nm to 400 nm region may be irradiated. In the step of irradiating, the photoresist mask may be further used. After performing the irradiating step in this way, the layer of the composition irradiated with the light source is treated with a developer. At this time, the unexposed portion of the composition layer is dissolved to form a pattern required for the color filter. A color filter having a desired pattern can be obtained by repeating this process according to the required number of colors. In addition, if the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, crack resistance, solvent resistance, and the like can be improved.

The curable composition may further include a solvent.

Examples of the solvent include alcohols such as methanol and ethanol; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, -n-butyl acetate, and isobutyl acetate; lactic acid alkyl esters such as methyl lactate and ethyl lactate; hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; or ketonic acid esters such as ethyl pyruvate, and also N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, dimethyl adipate, etc. may be used, but the present invention is not limited thereto.

For example, the solvent may include glycol ethers such as ethylene glycol monoethyl ether and ethylenediglycol methylethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; It is preferable to use alcohols, such as ethanol, or a combination thereof.

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

The solvent may be included in a balance based on the total amount of the curable composition.

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

(Check the spectral spectrum of the light source, the adhesive layer and the blue color filter layer)

As shown in FIG. 3, light is emitted at a wavelength of 400 nm to 500 nm, i) a light source having an intensity of light at a wavelength of 420 nm less than 3% of the maximum intensity of light as light source 1, ii) a light source of 420 nm A light source having an intensity of light at a wavelength of 3% or more of the maximum intensity of light was used as light source 2. Specifically, in light source 1, the intensity of light at a wavelength of 420 nm (intensity of about 0.01) has a value of about 1% of the highest intensity of light, and in light source 2, the intensity of light (intensity of about 0.05) at a wavelength of 420 nm is the intensity of light. It has a value of about 5% of the highest strength.

As shown in FIG. 4, i) the adhesive layer having an absorbance of less than 50% at a wavelength of 420 nm was used as the adhesive layer 1, and ii) the adhesive layer having an absorbance of 50% or more at a wavelength of 420 nm was used as the adhesive layer 2.

As shown in FIG. 5 , i) a blue color filter layer having an absorbance of less than 50% at a wavelength of 420 nm is referred to as a blue color filter layer 1, and ii) a blue color filter layer having an absorbance of 50% or more at a wavelength of 420 nm is a blue color filter layer. was set to 2.

(Manufacturing of display devices)

Example 1

A display device having a structure of a light source/quantum dot-containing layer/adhesive layer/blue color filter layer was manufactured using light source 2, InP/ZnSe/ZnS quantum dots, adhesive layer 2 and blue color filter layer 1.

Example 2

It was the same as in Example 1, except that the adhesive layer 1 was used instead of the adhesive layer 2, and the blue color filter layer 2 was used instead of the blue color filter layer 1.

Example 3

Except for using the blue color filter layer 2 instead of the blue color filter layer 1, it was carried out in the same manner as in Example 1.

Comparative Example 1

It was the same as Example 1, except that the light source 1 was used instead of the light source 2, and the adhesive layer 1 was used instead of the adhesive layer 2.

Comparative Example 2

Except that the adhesive layer 1 was used instead of the adhesive layer 2, it was the same as in Example 1.

(Measure the final intensity of light)

In the display devices of Examples 1, 2 and Comparative Example 2, the intensity of light finally exhibited by the light of a wavelength of 420 nm originating from the light source was measured by SR-3, and the results are shown in FIG. 6 below. . 6, the display devices of Examples 1 and 2 have a value of 1% or less of the maximum intensity of light after light at a wavelength of 420 nm derived from the light source passes through the quantum dot-containing layer, the adhesive layer and the blue color filter layer, In the display device of Comparative Example 2, it can be confirmed that light at a wavelength of 420 nm derived from a light source has a value of more than 1% of the maximum intensity of light after passing through the quantum dot-containing layer, the adhesive layer, and the blue color filter layer. Specifically, in each of the display devices of Examples 1 and 2, the intensity of light (intensity of 0.2) at a wavelength of 420 nm from the light source passed through the quantum dot-containing layer, the adhesive layer, and the blue color filter layer, and then the highest intensity of light (of 39) intensity) of about 0.51%, but in the display device of Comparative Example 2, the intensity of light (intensity of 0.42) at a wavelength of 420 nm from the light source passed through the quantum dot-containing layer, the adhesive layer and the blue color filter layer, and then the highest intensity of light (strength of 40.5) has a value of about 1.03%.

(Measurement of color purity and luminance)

Color purity and luminance of light emitted from the display devices of Examples 1 to 3, Comparative Examples 1 and 2 were measured. Specifically, color purity based on C light source was evaluated using a spectrophotometer (MCPD3000, Otsuka electronic), luminance (Y) was calculated based on CIE color coordinates, and the results are shown in Table 1 below.

CIE color coordinates (Bx) Luminance (%) Example 1 0.152 105 Example 2 0.152 105 Example 3 0.151 96 Comparative Example 1 0.152 100 Comparative Example 2 0.158 108

From Table 1, it can be seen that Comparative Example 1 is capable of realizing high color gamut compared to Examples 1 and 2, but a luminance degradation problem occurs, and Comparative Example 2 is compared with Examples 1 and 2 Therefore, it can be confirmed that although it is possible to improve the luminance, it is impossible to realize a high color gamut. Furthermore, from Example 3, when both the adhesive layer and the blue color filter layer have an absorbance of 50% or more at 420 nm or less, it can be confirmed that high color reproducibility can be realized, but the luminance degradation problem occurs seriously.

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

1 light guide plate
2 Quantum dot-containing layer
3 liquid crystal layer
4 overcoat layer
5 glass
6 Blue color filter layer
9 green quantum dots
10 red quantum dots
11 diffusion agent
12 adhesive layer

Claims (14)

a light source emitting light at a wavelength of 400 nm to 500 nm and having an intensity of light at a wavelength of 420 nm of 3% or more of the highest intensity;
a quantum dot-containing layer positioned on the light source;
a pressure-sensitive adhesive layer positioned on the quantum dot-containing layer; and
A blue color filter layer positioned on the adhesive layer
including,
The light at a wavelength of 420 nm derived from the light source has an intensity of 1% or less of the highest intensity of light after passing through the quantum dot-containing layer, the adhesive layer and the blue color filter layer,
Any one of the adhesive layer and the blue color filter layer has an absorbance of less than 50% at a wavelength of 420 nm or less.
delete According to claim 1,
The adhesive layer is a display device having an absorbance of 50% or more at a wavelength of 420 nm or less.
According to claim 1,
The blue color filter layer has an absorbance of 50% or more at a wavelength of 420 nm or less.
According to claim 1,
The adhesive layer or the blue color filter layer is a display device comprising at least one of an azo dye, an azomethine dye, and a porphyrin dye.
6. The method of claim 5,
The azomethine-based dye is a display device represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1,
M is Zn, Co, Cu or V;
X ¹ to X ⁴ are each independently an oxygen atom or a sulfur atom,
R ¹ to R ⁴ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a mercapto group, or a substituted or unsubstituted C1 to C20 alkylmercaptanyl group,
n1 to n4 are each independently an integer of 0 to 4.
7. The method of claim 6,
The azomethine-based dye represented by Formula 1 is a display device represented by any one of Formulas 1-1 to 1-7.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

6. The method of claim 5,
The porphyrin-based dye is a display device represented by the following Chemical Formula 2:
[Formula 2]

In Formula 2,
M is Zn, Co, Cu or V;
R ⁵ to R ¹² are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted a cyclic sulfonamide group or a substituted or unsubstituted C1 to C20 alkylester group,
n5 to n12 are each independently an integer of 0 or 1, provided that 1 ≤ n5+n6 ≤ 2, 1 ≤ n7+n8 ≤ 2, 1 ≤ n9+n10 ≤ 2, and 1 ≤ n11+n12 ≤ 2.
9. The method of claim 8,
The porphyrin-based dye represented by Formula 2 is a display device represented by any one of Formulas 2-1 to 2-20.
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

In Formula 2-13,
R is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m1 and m2 are each independently an integer from 0 to 20, provided that 4 ≤ m1+m2 ≤ 20;
[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

[Formula 2-20]

According to claim 1,
The quantum dot is a display device including a green quantum dot, a red quantum dot, or a combination thereof.
According to claim 1,
The display device further includes a liquid crystal layer between the adhesive layer and the blue color filter layer.
12. The method of claim 11,
The display device further includes an overcoat layer between the liquid crystal layer and the blue color filter layer.
According to claim 1,
The quantum dot-containing layer further comprises a diffusion agent.
14. The method of claim 13,
The dispersing agent includes barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

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