KR102521519B1 - Self emission type photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The self-luminous photosensitive resin composition according to the present invention is characterized in that it includes one or more quantum dots including one or more edges.

Description

Self-luminous photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a self-luminous photosensitive resin composition containing quantum dots of a specific type, a color filter and an image display device manufactured using the same.

A color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes it possible in minute pixel units, and the size of one pixel is about tens to hundreds of micrometers. This color filter is a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel and a plurality of colors (usually red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order have a sequentially stacked structure.

Recently, as one of the methods for implementing a color filter, a pigment dispersion method using a pigment-dispersive photosensitive resin has been applied. Efficiency is lowered, and color reproduction is lowered due to the characteristics of the pigments included in the color filter.

In particular, as color filters are used in various fields including various image display devices, performance such as excellent high luminance and high contrast ratio along with excellent pattern characteristics as well as high color gamut are required. In order to solve these problems, quantum dots are used. A method for manufacturing a color filter using a self-luminous photosensitive resin composition comprising the present invention has been proposed.

Republic of Korea Patent Publication No. 2013-0000506 relates to a display device, a light source; and a display panel into which light emitted from the light source is incident, wherein the display panel includes a plurality of color conversion units, wherein the color conversion units include a plurality of wavelength conversion particles that convert a wavelength of the light; and a display device including a plurality of color filter particles absorbing light of a predetermined wavelength range from the light.

However, in the case of manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots, the quantum dots are oxidized due to an out gas component generated in a hard bake process at 150° C. or higher, which is usually performed, resulting in luminous efficiency. This degradation problem arises.

Therefore, it is a situation in which development for maintaining the luminous efficiency of quantum dots is required.

Republic of Korea Patent Publication No. 2013-0000506 (2013.01.03.)

An object of the present invention is to provide a self-luminous photosensitive resin composition capable of producing a color filter having excellent luminous efficiency or heat resistance.

In addition, the present invention is to provide a color filter and an image display device manufactured using the above-described self-luminous photosensitive resin composition.

The self-luminous photosensitive resin composition according to the present invention for achieving the above object is characterized in that it includes one or more quantum dots including one or more corners.

In addition, the present invention provides a color filter including a cured product of the above-described self-luminous photosensitive resin composition and an image display device including the same.

Since the self-luminous photosensitive resin composition according to the present invention includes quantum dots of a specific type, there is an advantage in that a color filter having excellent initial emission luminance and excellent heat resistance can be manufactured.

In addition, the color filter manufactured using the self-luminous photosensitive resin composition of the present invention and the image display device including the same have an advantage of excellent luminous efficiency by suppressing a decrease in light efficiency or a defect in photosensitive characteristics occurring during the manufacturing process.

1 is a TEM image photograph of a quantum dot according to an embodiment of the present invention.
2 is a TEM image of a quantum dot according to a comparative example of the present invention.

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

In the present invention, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

In the present invention, when a part "includes" a certain component, it means that it may further include other components, not excluding other components unless otherwise stated.

< self-luminous Photosensitive Resin Composition>

One aspect of the present invention relates to a self-luminous photosensitive resin composition comprising at least one quantum dot including at least one corner.

quantum dot

Quantum dots according to the present invention may include one or more corners.

In the present invention, the "edge" may refer to a line segment formed when two faces of a polyhedron meet, but in the present invention, the "edge" may further include a line segment formed when a face and a curved surface meet. For example, in the present invention, the quantum dots may include the shape of a hemisphere formed when a sphere is cut into an arbitrary plane, and the "corner" is a boundary between the bottom of the hemisphere and a curved surface, in short, the hemisphere. It may be a concept including the circumference of a circle constituting the base of

The quantum dot may refer to a nano-sized semiconductor material. Atoms form molecules, and molecules form a collection of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots. When the quantum dot reaches an excited state by receiving energy from the outside, energy is emitted according to an energy bandgap corresponding to the quantum dot itself.

The color filter made of the self-luminous photosensitive resin composition according to the present invention may emit light (luminescence) by light irradiation by including the quantum dots, specifically, quantum dots having at least one edge.

In a typical image display device including a color filter, white light passes through the color filter to realize color. In this process, light efficiency is lowered because a part of the light is absorbed by the color filter. However, in the case of including a color filter made of the photosensitive resin composition according to the present invention, since the color filter emits itself by the light of the light source, it is possible to implement superior light efficiency and also emits colored light. Color reproducibility is better, and since light is emitted in all directions by photoluminescence, there are advantages in that a viewing angle can be improved.

In another embodiment of the present invention, the quantum dot may include one or more angled corners.

Further, in another embodiment of the present invention, the quantum dots may include 3 or more and 20 or less angular corners.

In the present invention, the "angular corner" may be interpreted as a conventional meaning.

The quantum dot is not particularly limited as long as it includes one or more edges and can emit light when stimulated by light. For example, II-VI group semiconductor compounds; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; Group IV elements or compounds containing them; And it may be selected from the group consisting of combinations thereof, which may be used alone or in combination of two or more.

Specifically, the II-VI group semiconductor compound is a binary element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a quaternary compound selected from the group consisting of mixtures thereof, but is not limited thereto.

The group III-V semiconductor compound is a binary element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and a quaternary compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

The group IV-VI semiconductor compound is a binary element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and may be at least one selected from the group consisting of quaternary compounds selected from the group consisting of mixtures thereof, but is not limited thereto either.

Although not limited thereto, the group IV element or a compound containing the same is an elemental compound selected from the group consisting of Si, Ge, and mixtures thereof; And it may be selected from the group consisting of a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The structure of the quantum dot is not limited in the present invention as long as it includes one or more corners, specifically, one or more angled corners. For example, the quantum dots may have a homogeneous unitary structure; dual structures such as core-shell and gradient structures; or a mixture thereof. In the present invention, the "uniform homogeneous structure" refers to that the component materials constituting the quantum dots are homogeneous, and is not interpreted as a term referring to a state in which the shape of the quantum dots is spherical.

Specifically, in the core-shell dual structure, materials constituting each core and shell may be made of different semiconductor compounds mentioned above. For example, the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

In the present invention, the quantum dot including one or more corners may mean that the outermost periphery of the quantum dot includes one or more corners. If the quantum dot has a core-shell double structure or a hollow structure, the corner may be included in the outermost outermost part of the shell or the outermost outermost part of the hollow shape, and the shape of the core or hollow itself is limited in the present invention. It is not. In short, the quantum dot including one or more edges according to the present invention may include a quantum dot composed of a spherical core and a shell part including one or more edges.

In another embodiment of the present invention, the quantum dots may have a particle diameter of 1 to 30 nm. In general, a quantum dot may have a specific composition, structure, and/or size selected so that light of a desired wavelength is emitted from the quantum dot.

Specifically, the quantum dots may be red quantum dots, green quantum dots, or blue quantum dots depending on the size of the particle size, and the quantum dots according to the present invention may include at least one selected from the group consisting of red quantum dots, green quantum dots, and blue quantum dots. can As the colored photosensitive resin composition used in the manufacture of conventional color filters includes red, green, and blue colorants for color implementation, photoluminescence quantum dots can also be classified into red quantum dots, green quantum dots, and blue quantum dots. In short, the quantum dots according to the present invention may be red quantum dots emitting red light, green quantum dots emitting green light, or blue quantum dots emitting blue light.

The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process, but are not limited thereto. .

The wet chemical process is a method of growing particles by putting a precursor material in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal, so it is easier and cheaper than vapor deposition methods such as organometallic chemical vapor deposition or molecular beam epitaxy to produce nano Since the growth of the particles can be controlled, it is preferred to use the wet chemical process to prepare the quantum dots according to the present invention.

In another embodiment of the present invention, the quantum dots are included in an amount of 3 to 80% by weight, specifically 10 to 70% by weight, and more specifically 15 to 35% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. can

When the quantum dot is included within the above range, it is preferable that the luminous efficiency can be maximized. When the quantum dots are included below the above range, the luminous efficiency may be insignificant, and when the quantum dots are included above the above range, the content of other components, such as alkali-soluble resins and photopolymerizable compounds, which will be described later, is relatively lowered. Formation of a pattern may be difficult, so it is preferably included within the above range.

Since the self-luminous photosensitive resin composition according to the present invention includes quantum dots including one or more edges, specifically, quantum dots including one or more angled edges, even if subjected to a hard bake process at 150° C. or higher, the binder resin during the hard bake process Since the degradation of luminous efficiency can be prevented by suppressing the phenomenon of oxidation by outgas components generated due to decomposition, the advantage of manufacturing a color filter having excellent luminous efficiency compared to the case of including conventional spherical quantum dots is an advantage. there is.

Although not wishing to be bound by theory, in the case of the quantum dot having an edge according to the present invention, since the crystal structure is formed without cracking, the stability of the quantum dot can be secured under external oxidizing conditions, thereby manufacturing a color filter with excellent luminous efficiency. There are possible advantages.

In another embodiment of the present invention, the self-luminous photosensitive composition may further include at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.

In addition, if the self-luminous photosensitive resin composition according to the present invention includes at least one quantum dot including at least one corner, it is okay to additionally include a conventional spherical quantum dot, that is, a quantum dot having no corner. .

In this case, the number of quantum dots including one or more corners may be 50% or more of the number of the spherical quantum dots. When the self-luminous photosensitive resin composition according to the present invention further includes the spherical quantum dots, and the number of quantum dots including at least one edge is 50% or more of the number of the spherical quantum dots, the initial luminous intensity increases and after hard baking There is an advantage that the emission intensity retention rate is improved.

In another embodiment of the present invention, the quantum dot including one or more corners may not be spherical. In the present invention, the sphere may include not only a perfect sphere, but also a slightly distorted sphere in the range of 0.6 to 1 when the sphere is normal, and specifically, may refer to a shape that does not include a corner.

alkali soluble resin

The self-luminous photosensitive resin composition according to the present invention may include an alkali-soluble resin.

The alkali-soluble resin may perform a role of making the non-exposed portion of the color filter manufactured with the self-luminescence photosensitive resin composition soluble in alkali so as to be removable and leaving the exposed area. In addition, when the self-luminous photosensitive resin composition includes the alkali-soluble resin, the quantum dots may be evenly dispersed in the composition, and may protect the quantum dots during a process to maintain luminance.

The alkali-soluble resin according to the present invention may be selected and used having an acid value of 50 to 200 (KOHmg / g). The above "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is related to solubility. If the acid value of the alkali-soluble resin is less than the above range, it may be difficult to secure a sufficient development rate, and if it exceeds the above range, adhesion with the substrate is reduced, and short circuit of the pattern is likely to occur, and storage stability of the entire composition is lowered, resulting in viscosity A rise problem may occur.

In addition, the alkali-soluble resin may be limited in molecular weight and molecular weight distribution (Mw/Mn) in order to improve surface hardness for use as a color filter. Preferably, the weight average molecular weight is 3,000 to 30,000, preferably 5,000 to 20,000, and the molecular weight distribution is directly polymerized or purchased to have a range of 1.5 to 6.0, preferably 1.8 to 4.0. The alkali-soluble resin having molecular weight and molecular weight distribution in the above range can have improved hardness, high film retention rate, excellent solubility in non-exposed areas in a developing solution, and improved resolution.

The alkali-soluble resin includes at least one selected from the group consisting of a polymer of a carboxyl group-containing unsaturated monomer, a copolymer of a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof.

In this case, the carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Specifically, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. As unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. An acid anhydride may be sufficient as an unsaturated polyhydric carboxylic acid, and maleic acid anhydride, itaconic acid anhydride, a citraconic acid anhydride, etc. are mentioned specifically. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-methacryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate ), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both terminals thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer is an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated In the group consisting of ether compounds, cyanide vinyl compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, macromonomers having monoacryloyl groups or monomethacryloyl groups at the ends of molecular chains, bulky monomers, and combinations thereof One selected paper is possible.

More specifically, the copolymerizable monomer is styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxy styrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Rate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. acid aminoalkyl ester compounds; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and polysiloxane have a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain. macromonomers having; A bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton capable of lowering the relative dielectric constant can be used.

The alkali-soluble resin may be included in an amount of 10 to 80% by weight, specifically 10 to 70% by weight, and more specifically 30 to 45% by weight based on the total solid weight of the self-luminous photosensitive resin composition.

When the alkali-soluble resin is contained within the above range, the solubility in the developing solution is sufficient to facilitate pattern formation, and it is preferable because the film reduction of the pixel portion of the exposed portion is prevented during development, resulting in good omission of the non-pixel portion. When the alkali-soluble resin is included in less than the above range, non-pixel parts may be slightly omitted, and when the alkali-soluble resin is included in excess of the above range, solubility in a developer solution is slightly lowered, and pattern formation may be somewhat difficult.

photopolymerization compound

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator to be described later, and includes monofunctional monomers, bifunctional monomers, and other multifunctional monomers.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl acrylate. rate, N-vinylpyrrolidone, etc. are mentioned.

The type of the bifunctional monomer is not particularly limited, and examples thereof include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene. Glycoldi(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc. are mentioned.

The type of the multifunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. )Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa (meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexaacrylate, etc. are mentioned. Among these, bifunctional or higher functional monomers are preferably used.

Commercially available examples of the photopolymerizable compound include Shin-Nakamura's A9550, but are not limited thereto.

The photopolymerizable compound may be included in an amount of 5 to 50% by weight, specifically 7 to 45% by weight, and more specifically 24 to 35% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included within the above range, there is a preferable advantage in terms of strength or smoothness of the pixel unit.

When the photopolymerizable compound is included in less than the above range, the intensity of the pixel portion may be slightly lowered, and when the photopolymerizable compound is included in excess of the above range, smoothness may be slightly lowered, so it is preferable that the photopolymerizable compound is included within the above range. .

light polymerization initiator

The self-luminous photosensitive resin composition according to the present invention may include a photopolymerization initiator. When the self-luminous photosensitive resin composition includes the photopolymerization initiator, as the self-luminous photosensitive resin composition becomes highly sensitive, the pixel pixel made of the self-luminous photosensitive resin composition has the advantage of having good strength or pattern property of its pixel portion. there is.

The photopolymerization initiator is not particularly limited, but may include at least one selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biidazole-based compounds, and oxime compounds.

Specifically, the triazine-based compound is 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine or 2,4-bis(trichloromethyl) )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, but is not limited thereto.

The acetophenone-based compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1- oligomers of one, and the like, and may also include a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, Or it may be a naphthyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms.

More specifically, specific examples of the compound represented by Formula 1 include 2-methyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-ethyl-2-amino(4-morpholino Phenyl) ethan-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino ( 4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) Propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one etc. can be mentioned.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichloro). Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5' position is carboalkoxy The imidazole compound etc. which are substituted by the group are mentioned. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole is preferably used.

The oxime compound may include compounds represented by Formulas 2 to 4 below, but are not limited thereto either.

[Formula 2]

[Formula 3]

[Formula 4]

The photopolymerization initiator may be additionally used in combination with other photopolymerization initiators commonly used in the art, as long as the effect of the present invention is not impaired. For example, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, or an anthracene-based compound may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

Specifically, the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based compounds include o-benzoyl methyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butylperoxy carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, and the like.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. can be heard

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. However, it is not limited thereto.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenyl cloxylic acid Methyl, a titanocene compound, etc. are mentioned as other photoinitiators.

The photopolymerization initiator may be included in an amount of 0.1 to 20% by weight, specifically 1 to 10% by weight, more specifically 5 to 7% by weight based on the total weight of the total solid content of the self-luminous photosensitive resin composition.

When the photopolymerization initiator is included within the above range, the self-luminous photosensitive resin composition may be highly sensitive, and thus strength of the pixel portion or smoothness of the surface of the pixel portion may be improved.

The self-luminous photosensitive resin composition according to the present invention may further include a photopolymerization initiation aid, and the photopolymerization initiation aid may be used in combination with the photopolymerization initiator. When the photopolymerization initiation aid is included together with the photopolymerization initiator, it is preferable because sensitivity efficiency can be further improved.

The photopolymerization initiation aid may include, for example, at least one selected from the group consisting of amine compounds and carboxylic acid compounds, but is not limited thereto.

Specifically, the amine compound is an aliphatic amine compound such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethyl) Aromatic amine compounds, such as amino) benzophenone, are mentioned. As the amine compound, the aromatic amine compound is preferably used.

The carboxylic acid compound is, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid, but are not limited thereto.

solvent

The solvent included in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and may include an organic solvent commonly used in the art.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

The above solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ among the above solvents in terms of coating and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid and esters such as ethyl and 3-methoxymethylpropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethylpropionate, and 3-methoxypropionate. methyl toxypropionate, etc. are mentioned. These solvents can be used individually or in mixture of two or more types, respectively.

The solvent may be included in 60 to 90% by weight, specifically 70 to 85% by weight based on the total weight of the self-luminous photosensitive resin composition, but is not limited thereto.

However, when the content of the solvent is within the above range, the coating property becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, or the like. It is desirable to be able to When the content of the solvent is less than the above range, the process may be somewhat difficult as the coating property is slightly lowered, and when the content exceeds the above range, the performance of the color filter formed of the self-luminous photosensitive resin composition may be slightly deteriorated. Problems can arise.

additive

The self-luminous photosensitive resin composition according to the present invention may further include additives such as an adhesion promoter and a surfactant in order to improve coating properties or adhesion.

The adhesion promoter may be added to increase adhesion with the substrate, and may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof, but It is not limited. For example, the silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy As long as propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, these can be used alone or in combination of two or more types.

When the self-luminescence photosensitive resin composition according to the present invention includes the surfactant, there is an advantage in that coating properties can be improved. For example, the surfactant is BM-1000, BM-1100 (BM Chemie Co.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Tore Siri Corn Co., Ltd.), but may use a fluorine-based surfactant, but is not limited thereto.

In addition, the self-luminous photosensitive resin composition according to the present invention may further include additives such as antioxidants, ultraviolet absorbers, and anti-aggregation agents within a range that does not impair the effects of the present invention, and the additives also inhibit the effects of the present invention. It is possible for those skilled in the art to use it by appropriately adding it to the extent that it is not. For example, the additive may be used in an amount of 0.05 to 10% by weight, specifically 0.1 to 10% by weight, and more specifically 0.1 to 5% by weight based on the total weight of the self-luminous photosensitive resin composition, but is not limited thereto.

<Color filter>

Another aspect of the present invention relates to a color filter prepared using the above-described self-luminous photosensitive resin composition.

In another embodiment of the present invention, the color filter may have an emission intensity retention rate of 80% or more after hard baking. The hard bake may be performed at a temperature of 150 °C or higher, specifically at 230 °C or higher, and more specifically at 230 °C for 60 minutes.

Since the color filter of the present invention includes quantum dots having at least one corner, when applied to an image display device, since it emits light from a light source of the display device, it is possible to implement superior light efficiency, and also light with color Since it is emitted, color reproducibility is more excellent, and since light is emitted in all directions by photoluminescence, there is an advantage in that a viewing angle can be improved. In particular, since it includes quantum dots having one or more edges rather than conventional spherical quantum dots, it is possible to suppress the phenomenon of oxidation of the quantum dots by outgas during the manufacturing process of the color filter, thereby suppressing the decrease in light efficiency. There is an advantage to being

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion where a color filter is positioned, such as a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer containing the self-luminescence photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminescence photosensitive resin composition and exposing, developing, and thermally curing the composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include barrier ribs formed between each pattern, and may further include a black matrix, but is not limited thereto.

In addition, a protective film formed on an upper portion of the pattern layer of the color filter may be further included.

In another embodiment of the present invention, the color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter comprises a red pattern layer including red quantum dots including one or more edges, a green pattern layer including green quantum dots including one or more edges, and blue quantum dots including one or more edges according to the present invention. It may include one or more selected from the group consisting of a blue pattern layer containing. The red pattern layer, the green pattern layer, and the blue pattern layer may emit red light, green light, and blue light when light is irradiated, respectively. At this time, the light emitted from the light source is not particularly limited, but blue light is emitted in terms of better color reproducibility. An emitting light source can be used.

The color filter may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer, but is not limited thereto. However, when the color filter includes only two color pattern layers, the pattern layer may further include a transparent pattern layer that does not contain the quantum dot particles.

When the color filter includes only the pattern layer of the two colors, a light source emitting light having a wavelength representing a color other than the two colors may be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, the red quantum dots emit red light and the green quantum dots emit green light. As the blue light from the light source is transmitted as it is, it may have a blue color.

<Image Display Device>

Further, another aspect of the present invention relates to an image display device including the color filter described above.

The color filter of the present invention can be applied to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device as well as a general liquid crystal display device.

Since the image display device according to the present invention includes one or more quantum dots including one or more corners, it has excellent light efficiency, high luminance, excellent color reproducibility, and a wide viewing angle.

In another embodiment of the present invention, the image display device may further include a light source emitting blue light and a transparent pattern layer, and the light source emitting blue light and the transparent pattern layer may apply the above information. there is.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, the embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art. In addition, "%" and "parts" indicating content below are based on weight unless otherwise specified.

manufacturing example One : CdSe (core)/ ZnS Synthesis of Photoluminescent Green Quantum Dot Particles with (Shell) Structure

CdO (0.4 mmol), zinc acetate (4 mmol), and oleic acid (5.5 mL) dmf 1-octadecene (1-Octadecene) (20 mL) were put into a reactor and heated to 150 ° C. reacted Thereafter, in order to remove acetic acid generated by replacing zinc with oleic acid, the reactant was left under a vacuum of 100 mTorr for 20 minutes. Then, heat was applied at 310 ° C to obtain a transparent mixture, which was maintained at 310 ° C for 20 minutes, and then 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. and S solutions were rapidly injected into the reactor containing Cd (oleic acid) ₂ and Zn (oleic acid) ₂ solutions. The mixture obtained therefrom was grown at 310° C. for 5 minutes and then growth was stopped using an ice bath. Thereafter, the quantum dots were separated using a centrifuge by precipitation with ethanol, and excess impurities were washed off using chloroform and ethanol to obtain quantum dot particles B stabilized with oleic acid.

manufacturing example 2: Synthesis of Alkali-Soluble Resin

In a four-neck flask equipped with a dropping funnel, thermometer, cooling tube, and stirrer, 23.3 g of methyl-2-(bromomethyl)-acrylate (made by Aldrich), 15.8 g of triethylamine (made by Aldrich) and propylene glycol methyl 115.0 g of ether (manufactured by TCI) was added and the inside of the four-necked flask was substituted with nitrogen. Next, the flask was heated to 90 ° C., and then 15.1 g of methyl-2- (hydroxymethyl) -acrylate (manufactured by Aldrich), 3.2 g of 2,2'-azobis isobutyronitrile (manufactured by Wako) and propylene A mixed solution of 110.0 g of glycol methyl ether (manufactured by TCI) was added dropwise over 1 hour and polymerization was performed for 0.5 hour to produce a pyran-containing polymer. Next, a mixed solution of 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol methyl ether, and 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako) was slowly added dropwise over 1 hour. After polymerization was performed for 8 hours, the mixture was allowed to cool to room temperature. After the inside of the four-necked flask was purged with nitrogen, 61.5 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Rayon), 3.6 g of tetra-n-butylammonium bromide (manufactured by TCI) and methoquinone (manufactured by Junsei) were added to the flask. 0.15 g was added and reacted at 80° C. for 12 hours to obtain an alkali-soluble resin by adding GMA to the carboxyl group of the copolymer. The weight average molecular weight of the alkali-soluble resin measured by GPC was 23,000.

Example 1 to 4 and comparative example 1 to 3: self-luminous Preparation of photosensitive resin composition

After mixing each component as shown in Table 1 below, the mixture was diluted with propylene glycol monomethyl ether acetate to a total solid content of 20% by weight, and then sufficiently stirred to obtain a self-luminous photosensitive resin composition.

Self-luminous photosensitive resin composition Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 quantum dot A1 ⁾ 30 15 25 8 - - 10 B2 ⁾ - - 5 7 30 15 20 alkali soluble resin ^{3 )} 30 30 30 30 30 30 30 photopolymerizable compound ^{4 )} 24 26 24 26 24 24 24 Photopolymerization initiator ^{5 )} 5 5 5 5 5 5 5 1) QDS-200 from Quantum Dot Technology, Korea
2) CdSe (core) / Zn (shell) structure quantum dots according to Preparation Example 1
3) Alkali-soluble resin according to Preparation Example 2
4) Dipentaerythritol hexaacrylate (A9550, manufactured by Shin Nakamura Co., Ltd.)
5) Irgacure-907 (BASF)

Manufacture of color filters

Color filters were prepared using the self-luminous photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 3. Each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a 20 mm x 20 mm square transmission pattern and a line/space pattern of 1 μm to 100 μm was placed on the thin film, and ultraviolet rays were irradiated at a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with light at an exposure amount (365 nm) of 200 mJ/cm ² in an air atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Electric Co., Ltd., and no special optical filter was used. Thereafter, the thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds and developed. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 10 minutes to prepare a color filter pattern. The film thickness of the self-luminous color pattern prepared above was 3.0 μm.

Experimental example

(1) Observation of quantum dots

Quantum dots (A) according to Examples and quantum dots (B) according to Comparative Example prepared in Preparation Example 1 were observed with a transmission electron microscope (TEM). The transmission electron microscope was observed at an accelerating voltage of 100 kV using JEOL's JEM-2100F model, and the results are shown in FIGS. 1 and 2, respectively.

Referring to FIGS. 1 and 2 , each quantum dot according to FIG. 1 was confirmed to have a size of 12 to 15 nm, and it was confirmed that the shape of the particle was triangular to heptagonal in a plane. On the other hand, it was confirmed that the quantum dot according to FIG. 2 had a circular shape on the plane.

(2) Measurement of luminous intensity (Intensity)

Among the color filters on which the self-emitting pixels manufactured according to Examples and Comparative Examples were formed, the pattern portion formed in a 20 mm × 20 mm square pattern was converted to light through a 365 nm tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT). The area was measured, and in Examples 1 to 4 and Comparative Examples 1 to 3, the emission intensity in the 550 nm area was measured using a spectrum meter (Optics Co.). It can be determined that the higher the measured emission intensity is, the better self-luminescence characteristics are exhibited, and the emission intensity measurement results are shown in Table 2 below. In addition, a hard bake was performed at 230° C. for 60 minutes to measure the luminescence intensity before and after the hard bake, and to confirm the level at which the luminous efficiency was maintained, the luminescence intensity retention rate was shown in Table 2 below.

initial luminous intensity Luminescence intensity retention rate after hard baking Example 1 43,234 86.5% Example 2 39,568 84.6% Example 3 41,325 84.3% Example 4 38,305 83.5% Comparative Example 1 32,698 63.5% Comparative Example 2 23,681 59.6% Comparative Example 3 33,912 65.7%

As can be seen from Table 2, in the case of Examples 1 to 4, the emission intensity is superior to that of Comparative Examples 1 to 3, and it can be confirmed that the emission intensity is maintained high even after the 230 ° C hard bake process. Examples 1 to 2 In the case of, it can be seen that the initial luminance is improved according to the shape of the quantum dots and the heat resistance is also excellent.

Claims (13)

A self-luminous photosensitive resin composition comprising one or more; quantum dots including 3 to 20 angled corners,
The quantum dots are self-luminous photosensitive resin composition having a particle diameter of 1 nm to 30 nm. delete delete delete According to claim 1,
The self-luminous photosensitive resin composition of the self-luminous photosensitive resin composition is included in 3 to 80% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. According to claim 1,
A self-luminous photosensitive resin composition further comprising at least one member selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. According to claim 1,
The quantum dot is a self-luminous photosensitive resin composition that is not spherical. According to claim 1,
Further comprising spherical quantum dots,
The quantum dots including 3 to 20 angular corners are included in a number of 50% or more compared to the number of spherical quantum dots. A color filter comprising a cured product of the self-luminous photosensitive resin composition according to any one of claims 1 and 5 to 8. According to claim 9,
Wherein the color filter has a luminous intensity retention rate of 80% or more after hard baking. According to claim 9,
The color filter comprising at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. An image display device comprising the color filter according to claim 9. According to claim 12,
An image display device further comprising a light source emitting blue light and a transparent pattern layer.

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