KR102512672B1 - Yellow curable resin composition, and color filter comprising thereof and display device comprising of the same - Google Patents

Abstract

The present invention relates to a yellow curable resin composition capable of producing a color filter and an image display device having improved color gamut and luminance by including a yellow colorant and a metal oxide, and a color filter and an image display device manufactured using the same.

Description

Yellow curable resin composition, color filter and image display device containing the same

The present invention relates to a yellow curable resin composition having improved color gamut and luminance, a color filter and an image display device including the same.

A color filter is a thin film type optical component that extracts three colors, red, green, and blue, from white light and enables them in microscopic pixel units.

The color filter includes 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 (typically, red (R), green (G)) to form each pixel. and blue (B)) have a structure in which pixel units in which three primary colors are arranged in a predetermined order are sequentially stacked.

In general, color filters can be produced by coating three or more colors on a transparent substrate by dyeing, electrodeposition, printing, pigment dispersion, etc. Recently, pigment dispersion using pigment dispersion type photosensitive resin is the mainstream. achieve

Among them, the pigment dispersion method coats a photosensitive resin composition including a colorant, an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives on a transparent substrate provided with a black matrix, and forms a pattern in the form to be formed. After exposure, it is a method of forming a colored thin film by repeating a series of processes of removing unexposed areas with a solvent and curing by heat, and is actively applied to manufacturing LCDs such as mobile phones, laptop computers, monitors, and TVs.

In recent years, even in the photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also improved performance such as high brightness and high contrast ratio along with high color reproduction is required.

However, color reproduction is implemented by passing light emitted from a light source through a color filter. In this process, some of the light is absorbed by the color filter, reducing light efficiency, and due to the characteristics of pigments as color filters, perfect color reproduction is not possible. There are fundamental limits to its impact.

As a way to solve this problem, a color filter using a quantum dot photosensitive resin composition has been proposed.

Korean Patent Publication No. 2013-0000506 discloses a display device with improved color reproducibility and luminance by including a plurality of wavelength conversion particles (quantum dots or phosphors) and a plurality of color filter particles (pigments or dyes). , there is a problem that the light emission luminance is not sufficient.

Patent Publication No. 2013-0000506 (2013.01.03)

In order to solve the above problems, an object of the present invention is to provide a yellow curable resin composition for providing a color filter and an image display device with improved color gamut and luminance.

In addition, an object of the present invention is to provide a color filter and an image display device having improved color reproducibility and luminance by including a cured product of the yellow curable resin composition.

The yellow curable resin composition of the present invention for achieving the above object includes a yellow colorant and a metal oxide.

In addition, the color filter of the present invention for achieving the above object is a yellow coating layer comprising a cured product of the yellow curable resin composition; and a self-emitting pixel layer formed on the yellow coating layer and containing quantum dots.

In addition, the image display device of the present invention for achieving the above object includes the color filter.

The yellow curable resin composition according to the present invention has the advantage of being able to manufacture a color filter and an image display device having excellent color reproducibility and luminance.

In addition, the color filter and the image display device including the cured product of the yellow curable resin composition according to the present invention have excellent color reproducibility and luminance.

1 is a cross-sectional view showing a color filter according to an embodiment of the present invention.
2 is a cross-sectional view showing the arrangement of a color filter for a light source according to 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.

<Yellow Curable Resin Composition>

The yellow curable resin composition according to one aspect of the present invention includes a yellow colorant and a metal oxide, thereby improving the color gamut and luminance of a color filter and image display device containing a yellow coating layer containing a cured product of the yellow curable resin composition. There are benefits to improving.

coloring agent

A yellow curable resin composition according to one aspect of the present invention includes a yellow colorant.

A color filter using quantum dots is a material that emits light by itself, unlike color filters containing pigments, and a self-emitting pixel layer is formed on a pixel area so as to self-emit red, green, and blue colors. The self-emitting pixel layer has a self-emitting characteristic of emitting red light, blue light, and green light by itself by absorbing irradiated light. That is, when light is irradiated on red quantum dots, blue quantum dots, and green quantum dots, red light emission occurs at 600 to 700 nm, green light emission at 490 to 590 nm, and blue light emission at 400 to 480 nm to realize full color. At this time, the light source of the image display device in which the color filter is mounted uses blue light. Due to this blue light, when looking at the emission spectrum of the red and green self-emitting pixel layers, the emission spectrum of blue light exists together in the range of 400 to 480 nm, resulting in self-emitting light. Color mixing of the pixel layers occurs, which seriously occurs in the red and green pixel layers.

In order to prevent the above problem, by placing a yellow coating layer, which is a cured product of a yellow curable resin composition containing a yellow colorant, on the red and green pixel layers, only green, red and blue colors are mixed in the green pixel layer. Only red is displayed in this mixed-color red pixel layer, and as a result, pure green and pure red light can be extracted, improving color purity and light efficiency of self-emitting light.

The yellow colorant is not particularly limited, and may be selected from among the following yellow colorants. At this time, as the yellow colorant, a commonly known yellow colorant may be used, and any of pigments, dyes, and pigments may be used. Specifically, those to which the following color index (C.I.; published by The Society of Dyers and Colourists) numbers are assigned are exemplified. However, it is preferable that the colorant does not contain a halogen in terms of reducing environmental load and affecting the human body.

Monoazo Pigments: Pigment Yellow 1, 2, 5, 8, 105, 120, 150, 168, 182, 183, 190;

Pyrazolone azo pigments: Pigment Yellow 10;

Diazo Pigments: Pigment Yellow 12, 16, 63, 83, 126, 127, 128, 152, 170, 188;

Azomethine pigments: Pigment Yellow 101, 129;

Anthraquinone pigments: Pigment Yellow 108, 147, 193, 197, 199, 202;

Isoindolinone pigments: Pigment Yellow 109, 110, 139, 173, 185;

Quinoline pigments: Pigment Yellow 115;

Quinophthalone pigments: Pigment Yellow 138, 231;

Polycyclic Pigments: Pigment Yellow 148;

Dioxime pigment: Pigment Yellow 153;

Benzimidazolone pigments: Pigment Yellow 154, 175, 180, 181;

Heterocyclic pigments: Pigment Yellow 192;

Perinone pigments: Pigment Yellow 196;

Inorganic Pigments: Pigment Yellow 30, 31, 32, 119, 157, 162, 184;

Cyanine-based pigment; Xanthene-based pigments; Merocyanine-based pigments; Dipyrrin-based pigment; Arylmethine-based pigment; Acridine-based pigment; Coumarin-based pigments; Oxazine-based pigment; Tetrapyrrole pigment.

These pigments are optionally treated with rosin, surface treatment using pigment derivatives into which acidic or basic groups are introduced, surface grafting treatment using polymer compounds, etc., fine particleization treatment using sulfuric acid, or washing using organic solvents or water. Processing or the like may have been performed.

In particular, the yellow curable resin composition according to one embodiment of the present invention is C.I. It may include one or more selected from the group consisting of Pigment Yellow 138, 185 and 231. The C.I. Pigment Yellow 138, 185, and 231 can be preferably used because they can satisfy the spectral wavelength and spectral characteristics to be described later.

Specifically, the yellow colorant preferably absorbs a low wavelength region (about 330 to 550 nm) in the visible region of a wavelength region of 380 to 780 nm as a spectral characteristic, and transmits or reflects light in other regions. do. Therefore, it is possible to use one whose transmittance satisfies a specific range in the transmittance spectrum of 470 to 510 nm, and transmittance in ±20 nm of the above range may also have a controlled characteristic.

In the case of red light, this does not matter, but in the case of the green light emitting layer, a phenomenon in which blue and green wavelengths overlap occurs in the 470 to 510 nm region. In this area, it is necessary to minimize the loss of the green emitted light and to block the blue light source as much as possible. It is desirable to make it clear.

Therefore, the yellow curable resin composition according to an embodiment of the present invention may include a yellow colorant that satisfies the transmission characteristics of Equation 1 below.

[Equation 1]

50 ≤ T(λ) ≤ 60%

T(λ-20nm) < 2%

T(λ+20nm) ≥ 80%

(In Equation 1, T is transmittance (%), and λ means a wavelength selected from 470 nm to 510 nm.)

In Equation 1, the yellow colorant in which the range of spectral wavelength (λ) that can be selected is less than the above range cannot sufficiently prevent the influence of blue light, and conversely, when the above range is exceeded, a yellow peak also appears on the color filter As a result, the transmittance of light emitted from the self-luminous layer is lowered, which may cause a problem in that color purity is lowered.

The yellow colorant may be included in an amount of 5 to 80 wt%, preferably 10 to 70 wt%, and more preferably 20 to 50 wt%, based on 100 wt% of the total solid content in the total yellow curable resin composition. If the content is less than the above range, it is difficult to expect the above-described color purity and light efficiency improvement effect due to blocking of blue light, and on the contrary, even if it exceeds the above range, there is no significant increase in effect, so it is uneconomical. appropriately used in

According to one embodiment of the present invention, the yellow curable resin composition may further include at least one selected from the group consisting of red and green colorants other than yellow colorants.

The red or green colorant is not particularly limited, and examples thereof include pigments and dyes.

Specifically as a red pigment, C.I. Pigment Red 177, 179, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; etc.,

As a green pigment, C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, 63; and the like, but is not limited thereto.

Also, as a red dye,

C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; can be backed up,

As a green dye,

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;

C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 65, 80, 104, 106, 109;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

C.I. Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; dyes such as, but are not limited thereto.

The above-mentioned pigment may be used together with a dispersing agent and a dispersing auxiliary agent, if necessary.

As the dispersant, suitable dispersants such as cationic, anionic, and nonionic dispersants can be used, but polymeric dispersants are preferable. Specifically, an acryl-type copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, etc. are mentioned. These dispersants are commercially available, for example, DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol) as acrylic copolymers. ), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, manufactured by Big Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol) ), Solsperse 24000 (manufactured by Lubrizol) as polyethyleneimine, and Ajisper PB821, Ajisper PB822, and Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as polyester.

Examples of the dispersing aid include pigment derivatives, and specific examples thereof include sulfonic acid derivatives of copper phthalocyanine, diketopyrrolopyrrole, and quinophthalone.

These dispersing agents can be used individually or in mixture of 2 or more types. The content of the dispersant is usually 1 part by weight or less, preferably 0.1 to 0.7 parts by weight, more preferably 0.05 to 0.5 parts by weight, based on 1 part by weight of the yellow colorant. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

metal oxide

By including a metal oxide, the yellow curable resin composition according to one aspect of the present invention has the advantage of improving the color gamut and luminance of a color filter and an image display device manufactured using the same.

Specifically, the metal oxide may include ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , SiON, Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, and the like. However, it is not limited thereto.

More specifically, it is preferable to use at least one selected from the group consisting of TiO ₂ , Al ₂ O ₃ , ZrO ₂ , ZnO and SiO ₂ in that the luminous intensity of light emitted from the self-emitting layer can be further increased. do.

The metal oxide may be included in an amount of 1 to 40 wt%, preferably 3 to 30 wt%, and more preferably 5 to 20 wt%, based on 100 wt% of the total solid content in the yellow curable resin composition. When the metal oxide is included within the above range, the effect of increasing the luminous intensity cannot be expected, and when the above range is exceeded, the content of the photosensitive component in the yellow curable resin composition is relatively reduced, so that it is difficult to implement a pixel pattern. .

The yellow curable resin composition according to an embodiment of the present invention 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.

alkali soluble resin

The colored photosensitive resin composition according to an embodiment of the present invention may further include an alkali-soluble resin.

The alkali-soluble resin has reactivity and alkali solubility by the action of heat, acts as a dispersion medium for solids including colorants, and functions as a binder resin, which is a binder soluble in an alkaline developer used in the development step of film production using a resin composition. Any resin can be used.

The alkali-soluble resin may have an acid value of 20 to 200 (KOH mg/g). At this time, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is involved in solubility. If the acid value of the alkali-soluble resin is less than the above range, it is difficult to secure a sufficient development rate. Conversely, if it exceeds the above range, adhesion with the substrate is reduced, and short circuits of the pattern are likely to occur, and storage stability of the entire composition is lowered, resulting in increased viscosity. A problem arises

In addition, the alkali-soluble resin may preferably have a weight average molecular weight of 3,000 to 200,000 Da, preferably 5,000 to 100,000 Da, and a molecular weight distribution of 1.5 to 6.0, preferably 1.8 to 4.0, for use as a color filter. It can be directly polymerized or purchased and used to have a range. The alkali-soluble resin having a molecular weight and molecular weight distribution within the above-mentioned range has advantages such as improved hardness, high film remaining rate, excellent solubility in non-exposed areas in a developing solution, and improved resolution.

The alkali-soluble resin may be an acrylic monomer having an unsaturated double bond. In the case of a dispersion resin having an acid value, it can be prepared by copolymerizing a monomer having an unsaturated bond with the following carboxyl group and a monomer having an unsaturated bond copolymerizable therewith.

Specific examples of the monomer having a carboxyl group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as omega-carboxypolycaprolactone mono(meth)acrylate.

More specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid or maleic acid alkyl esters may be used, wherein the maleic acid alkyl esters include monomethyl maleic acid, ethyl maleic acid, n-propyl maleic acid, isopropyl maleic acid, n-butyl maleic acid, n-hexyl maleic acid, n-octyl maleic acid, 2-ethylhexyl maleic acid, n-nonyl maleic acid, or n-dodecyl maleic acid; and the like.

The monomer having an unsaturated bond with the carboxyl group and the monomer copolymerizable therewith may be used alone or in combination of two or more.

The copolymerizable monomers include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, carboxylic acid vinyl ester compounds, unsaturated ether compounds, and vinyl cyanide. Compounds, unsaturated imides compounds, aliphatic conjugated diene compounds, macromonomers having a monoacryloyl group or monomethacryloyl group at the end of a molecular chain, bulky monomers, and one selected from the group consisting of combinations thereof is possible.

Specifically, the copolymerizable monomers include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m - Aromatic vinyl compounds such as vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate or t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0.2.6]decan-8-yl (meth)acrylate, 2-dicy alicyclic (meth)acrylates such as clofentanyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N'-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane or 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. The unsaturated oxetane compound of , etc. are mentioned.

The content of the alkali-soluble resin may be included in 2 to 80% by weight, preferably 5 to 75% by weight, more preferably 10 to 70% by weight, based on 100% by weight of the total solid content in the yellow curable resin composition. If the content of the alkali-soluble resin falls within the above range, it is easy to form a yellow coating layer, and in a process including a development process, film reduction of the pixel portion of the exposed portion is prevented during development, resulting in good omission of the non-pixel portion There is an advantage.

photopolymerization compound

The yellow curable resin composition according to an embodiment of the present invention may further include a photopolymerizable compound.

The photopolymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of a photopolymerization initiator, which will be described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher functional photopolymerizable compound. can be heard

Specific examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- vinylpyrrolidone, etc., and commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Biscott 158 (Osaka Yuki Kagaku Kogyo).

Specific examples of the bifunctional photopolymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. rate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Biscott 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co.) and the like.

Specific examples of the trifunctional or higher functional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylate Tide dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Commercial products include Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku) etc. are mentioned.

Among the photopolymerizable compounds exemplified above, trifunctional or higher functional (meth)acrylic acid esters and urethane (meth)acrylates are particularly preferred in that they are excellent in polymerizability and can improve strength.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound may be included in an amount of 5 to 70 wt%, preferably 10 to 60 wt%, and more preferably 15 to 50 wt%, based on 100 wt% of the total solid content in the yellow curable resin composition. When the photopolymerizable compound is included within the above range, there is an advantage in that the strength or smoothness of the pixel portion is good.

light polymerization initiator

The yellow curable resin composition according to an embodiment of the present invention may further include a photopolymerization initiator.

The photopolymerization initiator may be used without particular limitation as long as it can polymerize a photopolymerizable compound. Specifically, a group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime compounds and thioxanthone-based compounds from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability or price, etc. It is preferred to use at least one compound selected from

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Roxyethoxy) 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 -one or 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one; and the like.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone; and the like.

Specific examples of the triazine-based compound include 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; and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 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, 2,2-bis(2,6-dichlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; and the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole or 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred. can be used

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercial products include OXE01 and OXE02 from BASF.

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

Further, a photopolymerization initiator other than the above may be further used in combination within a range not impairing the effects of the present invention. Examples thereof include benzoin-based compounds and anthracene-based compounds, which may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. can be heard

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl-9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid A methyl or titanocene compound or the like can be further used in combination as a photopolymerization initiator.

The photopolymerization initiator may be included in an amount of 0.1 to 40 wt%, preferably 0.5 to 35 wt%, and more preferably 1 to 30 wt%, based on 100 wt% of the total solid content in the yellow curable resin composition. When the photopolymerization initiator is included within the above range, the yellow curable resin composition is highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution. In addition, there is an advantage in that the strength of the pixel portion formed using the composition under the above-mentioned conditions and the smoothness of the surface of the pixel portion are improved.

In addition, in order to improve the sensitivity of the yellow curable resin composition, a photopolymerization initiation auxiliary agent may be further included. By containing the said photopolymerization start adjuvant, sensitivity can further increase and productivity can be improved.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group may be preferably used.

As the amine compound, it is preferable to use an aromatic amine compound, specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 4-dimethylaminobenzoic acid-2-ethylhexyl, benzoic acid-2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone Healer's ketone) or 4,4'-bis(diethylamino)benzophenone may be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) or tetraethylene glycol bis (3-mercaptopropionate), etc. can

In addition, commercially available products such as Darocur 1173, Irgacure 184, Irgacure 907, and Irgacure 1700 (Ciba) may also be used. These can be used individually or in mixture of 2 or more types.

The photopolymerization initiation aid may be used in the same content range as the photopolymerization initiator, and when used in the above-described content, the sensitivity of the yellow curable resin composition containing the same is higher, and the productivity of a color filter formed using the composition is improved. provide effect.

solvent

The yellow curable resin composition according to an embodiment of the present invention may further include a solvent.

The solvent is not particularly limited and may be an organic solvent commonly used in the art. As long as the solvent is effective in dissolving other components, solvents used in conventional yellow curable resin compositions may be used without particular limitation, specifically ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides. More specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 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 γ-butyrolactone; etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

Since the viscosity of the solvent may vary depending on the coating method or device, the content is appropriately adjusted so that the concentration of the yellow curable resin composition having the above-mentioned composition is 5 to 90% by weight, preferably 15 to 80% by weight. This content is a range selected in consideration of the dispersion stability of the composition and the ease of processing (eg, coatability) in the manufacturing process.

additive

The colored photosensitive resin composition according to an embodiment of the present invention may contain fillers, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, and curing agents according to the needs of those skilled in the art within the scope of not impairing the object of the present invention. Additives such as may be further included.

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters and polyurethanes. can

The surfactant is a component that improves the film formation of the yellow curable resin composition, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acids There are modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Supple ( Surflon) (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As said adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole and alkoxybenzophenone. Specifically as an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

The curing agent is a component for enhancing core curing and mechanical strength, and its type is not particularly limited, and examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

The epoxy compound is not particularly limited, and examples thereof include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, noblock-type epoxy resins, other aromatic epoxy resins, and alicyclics. family type epoxy resins, glycidyl ester type resins, glycidyl amine type resins, or brominated derivatives of these epoxy resins; aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives; butadiene (co)polymer epoxides; isoprene (co)polymer epoxides; glycidyl(meth)acrylate (co)polymers; Triglycidyl isocyanurate etc. are mentioned.

The oxetane compound is not particularly limited, and examples thereof include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. there is.

In addition, in order to further increase the degree of curing, the yellow curable resin composition according to the present invention may further include a curing aid. Curing aids that can be used are not particularly limited in the present invention, and any curing aid known in the art may be used.

Representatively, tertiary amines such as benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, and tri(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole and 2-phenylimidazole; organic phosphines such as triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and the like.

Preparation of the yellow curable composition as described above is not particularly limited in the present invention, and follows a known method for preparing a curable composition.

For example, a yellow colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant is about 0.2 μm or less. At this time, a pigment dispersant is used as needed, and some or all of the alkali-soluble resin may be blended. The remainder of the alkali-soluble resin, the photopolymerizable compound and the photopolymerization initiator, other components used as necessary, and additional solvents as necessary are further added to the obtained dispersion (hereinafter sometimes referred to as mill base) to a predetermined concentration. Thus, the desired yellow curable resin composition is obtained.

The yellow curable resin composition prepared in this way can be used to prepare a color filter by wet coating. At this time, a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, etc. of application devices may be used.

<Color filter>

Another aspect of the present invention is a yellow coating layer comprising a cured product of the yellow curable resin composition described above; and a self-emitting pixel layer formed on the yellow coating layer and containing quantum dots.

The pixel layer of the color filter is a self-emitting pixel layer including quantum dots. In this case, in order to absorb the blue light emission spectrum, the yellow colorant is not mixed and used with the quantum dots in the self-emitting pixel layer, but a separate layer is formed to be in contact therewith. do. That is, the light emitted by the quantum dots emits light of a specific wavelength. At this time, when a yellow colorant is used in the self-luminous pixel layer, the self-luminous red, blue, and green colors are not emitted outside the pixel layer. In addition, since the yellow colorant aims to quench blue light in the red and green colors that have already been emitted, it is desirable to be located in a place opposite to the light source, and the effect cannot be secured when located between the light source and the self-luminous pixel layer. may occur.

1 is a cross-sectional view of a color filter according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view showing the arrangement of color filters for a light source according to the present invention.

Referring to Figures 1 and 2, the color filter, as an example, the substrate 11; a yellow coating layer 13 formed on the substrate 11; and a self-emitting pixel layer 15 formed on the yellow coating layer 13 .

At this time, the yellow coating layer 13 is made of the yellow curable resin composition as described above, more preferably, as shown in FIG. 2, the red and green pixel layers 15a and 15b defined by the barrier ribs 51a, 51b and 51c It is formed only on, but is located on the opposite side to the light source 101 (see FIG. 2).

The yellow coating layer 13 shows only green in the green pixel layer 15b in which green and blue are mixed, and only red in the red pixel layer 15a in which red and blue are mixed, resulting in extraction of pure green and pure red light. This makes it possible to improve overall color purity and light efficiency.

The above effect may be affected by the content of the yellow colorant in the yellow coating layer 13 and the thickness of the yellow coating layer. For example, the yellow coating layer 13 may be formed to a thickness of 1 μm to 5 μm. If the thickness is less than the above range, the above effect cannot be secured, and even if the thickness exceeds the above range, a great effect cannot be secured.

In the color filter of the present invention, the substrate 11 may be a substrate of the color filter itself, or may be a portion where the color filter is positioned, such as a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ) or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The self-luminous pixel layer 15 is a layer containing quantum dots, and is formed by preparing a self-luminous photosensitive resin composition containing photoluminescence quantum dots, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. At this time, the type and content of the alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, and solvent follow those mentioned in the yellow curable resin composition.

The quantum dot is a nano-sized semiconductor material. Atoms make up molecules, and molecules make up aggregates of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots. When the quantum dot receives energy from the outside and reaches an excited state, it emits energy according to the corresponding energy bandgap.

The color filter includes such photoluminescence quantum dot particles, and the color filter manufactured therefrom can emit light (photoluminescence) by light irradiation.

The quantum dot is not particularly limited as long as it can emit light when stimulated by light, and examples thereof include a II-VI group semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; group elements or compounds containing them; And it may be selected from the group consisting of combinations thereof. These can be used individually or in mixture of 2 or more types.

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 a quaternary compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, and the group III-V semiconductor compound is GaN , GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and binary element compounds selected from the group consisting of 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 it may be selected from the group consisting of quaternary compounds selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof, , The 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 a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof, and the group IV element or compound containing the same is a group consisting of Si, Ge, and mixtures thereof. An elemental compound selected from; and a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

In addition, the quantum dot has a homogeneous unitary structure; dual structures such as core-shell and gradient structures; or a mixture thereof.

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.

Just as the colored photosensitive resin composition used in the manufacture of conventional color filters includes red, green, and blue colorants to realize color, the color filter of the present invention also has quantum dots representing red, quantum dots representing green, and quantum dots representing blue. Including, it may be one selected from the above-described red, green, blue, and combinations thereof.

The quantum dots may be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process.

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. The growth of nanoparticles can be controlled through a process that is easier and cheaper than vapor deposition methods such as beam epitaxy.

The self-luminous photosensitive resin composition including these quantum dots includes 3 to 80% by weight of quantum dots, 5 to 80% by weight of alkali-soluble resin, 5 to 70% by weight of photopolymerizable compound, and 0.1 to 20% by weight of photopolymerization initiator, in 100% by weight of the total composition. % may be included. In addition, the additives described above may be further included.

The color filter may be manufactured in the following method as an example, but is not limited thereto, and the order of each step described below may be changed according to the designer's needs.

S1) forming a yellow coating layer 13 on a substrate 11;

S2) forming barrier ribs 51a, 51b, and 51c defining red, blue, and green pixel regions on the yellow coating layer 13; and

S3) It is manufactured through a step of forming self-emitting pixel layers 15, 15a, and 15b in the pixel region (see FIGS. 1 and 2).

At this time, the yellow coating layer is formed only on the red (15a) and green (15b) pixel areas.

Formation of the barrier rib, the self-emitting pixel layer, and the yellow coating layer may be layers formed by applying each composition, exposing, developing, and curing in a predetermined pattern.

If necessary, the color filter may further include a black matrix.

<Image display device>

Further, another aspect of the present invention is an image display device including the color filter.

The color filter 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.

The image display device may include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In such a case, when applied to an image display device, the emitted light of the light source is not particularly limited, but a light source emitting blue light may be preferably used in terms of better color reproducibility.

According to another embodiment of the present invention, the image display device of the present invention may include a color filter including only pattern layers of two colors among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles.

In the case of having only two color pattern layers, a light source emitting light of a wavelength representing the colors other than those not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, showing a blue color.

The image display device has excellent light efficiency, high luminance, and excellent color reproducibility.

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 / ZnS core shell structural Luminescence green quantum dot synthesis of particles

0.4 mmol of CdO, 4 mmol of zinc acetate, and 5.5 mL of oleic acid were put into a reactor together with 20 mL of 1-octadecene and reacted by heating to 150°C. 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, and after maintaining 310 ° C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine, and Se and The S solution was rapidly injected into the reactor containing the Cd(OA) ₂ and Zn(OA) ₂ solutions.

The mixture obtained therefrom was grown at 310° C. for 5 minutes, and then growth was stopped using an ice water bath.

Then, ethanol was added to the mixture to precipitate it, and the quantum dots were separated using a centrifuge, and excess impurities were washed away using chloroform and ethanol, so that the sum of the core particle diameter and the shell thickness stabilized with oleic acid was 3 to 5 nm. Green quantum dot particles having a CdSe (core)/ZnS (shell) structure in which phosphorus particles are distributed were obtained.

manufacturing example 2: synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe was prepared, and 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, t - butyl 4 parts by weight of peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were added, stirred and mixed to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanediol, propylene glycol monomethyl ether acetate 24 Part by weight was added and stirred and mixed to prepare a chain transfer agent dropping lot.

Thereafter, 395 parts by weight of propylene glycol monomethyl ether acetate was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Subsequently, loading of the monomer and chain transfer agent from the loading lot was started. Dropping proceeded for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Then, a gas inlet pipe was introduced to bubble the oxygen / nitrogen = 5/95 (v / v) mixed gas. ring started.

Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-t - butylphenol), and 0.8 parts by weight of triethylamine were put into a flask and kept at 110°C for 8 hours. The reaction was continued, and an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH/g was obtained while cooling to room temperature after that.

manufacturing example 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.

Composition (unit: % by weight) Preparation Example 3 quantum dot ^{1 )} 30 photopolymerizable compound ^{2 )} 30 Photopolymerization initiator ^{3 )} 5 alkali soluble resin ^{4 )} 35 1) Quantum dot: Green quantum dot of Preparation Example 1
2) Photopolymerizable compound: dipentaerythritol pentaacrylate (DPHA, Donga Synthesis)
3) Photopolymerization initiator: Irgacure-907 (manufactured by Ciba)
4) alkali-soluble resin: alkali-soluble resin of Preparation Example 2

Example 1 to 8 and comparative example 1 to 4: Preparation of yellow curable resin composition

As shown in Table 2 below, each component was mixed according to the indicated amount, diluted with propylene glycol monomethyl ether acetate so that the total solid content was 20% by weight, and then sufficiently stirred to obtain a yellow curable resin composition.

Composition (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 yellow colorant A-1 ¹⁾ 30 30 30 30 30 - - - 35 - - - A-2 ²⁾ - - - - - 30 - - - 35 - - A-3 ³⁾ - - - - - - 30 - - - 35 - A-4 ⁴⁾ - - - - - - - 30 - - - 35 metal oxide S-1 ⁵⁾ 5 - - - - - - - - - - - S-2 ⁶⁾ - 5 - - - 5 5 5 - - - - S-3 ⁷⁾ - - 5 - - - - - - - - - S-4 ⁸⁾ - - - 5 - - - - - - - - S-5 ⁹⁾ - - - - 5 - - - - - - - photopolymerization
compound ^{10 )} 30 30 30 30 30 30 30 30 30 30 30 30 light polymerization
Initiator ^{11 )} 5 5 5 5 5 5 5 5 5 5 5 5 alkali
soluble resin ^{12 )} 30 30 30 30 30 30 30 30 30 30 30 30 1) CI Pigment Yellow 231 (manufactured by Toyo Ink Co.)
2) CI Pigment Yellow 138 (manufactured by BASF)
3) CI Pigment Yellow 185 (manufactured by BASF)
4) CI Pigment Yellow 129 (manufactured by BASF)
5) TiO ₂ (manufactured by Ishihara Co., Ltd.)
6) ZnO (manufactured by Aldrich)
7) ZrO ₂ (manufactured by Aldrich)
8) SiO ₂ (manufactured by Degussa)
9) Al ₂ O ₃ (made by Allied Co.)
10) Dipentaerythritol pentaacrylate (DPHA, manufactured by Dong-A Synthetic Co., Ltd.)
11) Irgacure-907 (manufactured by Ciba)
12) Alkali-soluble resin of Preparation Example 2

Experimental example 1: Permeation Characteristic Analysis of Yellow Curable Resin Composition

The transmittance characteristics of the yellow curable resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4 were confirmed as follows.

First, the yellow curable resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 4 was applied on a 5 × 5 cm glass substrate (Eagle 2000 Glass, manufactured by Samsung Corning) by spin coating, and then placed on a heating plate. A thin film was formed by holding at a temperature of 100° C. for 3 minutes.

Subsequently, light was irradiated with an exposure amount of 200 mJ/cm2 (365 nm) 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. Then, it was heated in a heating oven at 150° C. for 10 minutes to prepare a yellow coating layer with a thickness of 2 μm.

The transmittance of the yellow coating layer was measured using an Olympus Spectrometer OPS-200, and the obtained results are shown in Table 3 below. In this case, the smaller the transmittance, the better the wavelength absorption effect of the yellow coating layer.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 λ(nm) 505 505 505 505 505 490 500 505 505 490 500 505 T _λ 51.1 52.3 50.4 52.6 51.1 53.5 48.2 49.7 53.1 54.7 51.5 52.1 T _{λ -20 nm} 0.1 0.1 0.1 0.1 0.1 0.1 0.6 4.9 0.3 0.5 0.8 5.3 T _{λ +20 nm} 84.1 88.6 84.6 89.2 86.3 89.0 86.1 72.3 92.2 93.2 88.6 74.1

Referring to Table 3, when the same type of yellow colorant was used, that is, Examples 1 to 5 and Comparative Example 1, Example 6 and Comparative Example 2, Example 7 and Comparative Example 3, and Example 8 and Comparative Example. When comparing 4 to each other, it can be seen that the transmittance decreases when the metal oxide of the present invention is included together (Examples 1 to 8), than when the metal oxide of the present invention is not included (Comparative Examples 1 to 4). there is.

manufacturing example 4: Manufacturing of color filters

A color filter was prepared as follows using the self-luminous photosensitive resin composition prepared in Preparation Example 3 and the yellow curable resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 4.

(1) Formation of yellow curable resin layer

First, the yellow curable resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 4 was applied on a 5 × 5 cm glass substrate (Eagle 2000 Glass, manufactured by Samsung Corning) by spin coating, and then placed on a heating plate. It was maintained at a temperature of 100° C. for 3 minutes to form a thin film.

Subsequently, light was irradiated with an exposure amount of 100 mJ/cm 2 (365 nm) 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.

The thin film irradiated with ultraviolet light was developed by immersing it in a KOH aqueous solution of pH 10.5 for 80 seconds. 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 230° C. for 20 minutes to form a 2 μm thick yellow curable resin layer.

(2) Formation of self-emitting pixel layer

Using the self-luminous photosensitive resin composition prepared in Preparation Example 3, each of Examples 1 to 8 and Comparative Examples 1 to 4 prepared in (1) in the same manner as in (1) above, 5 A self-emitting pixel layer having a thickness of ㎛ was formed.

Experimental example 2: Analysis of light source transmission spectrum and luminous intensity of color filter

The light source transmission spectrum (transmission intensity) and the luminous intensity of the self-emitting layer of the color filter including the yellow coating layer made of the yellow curable resin composition of Examples 1 to 8 and Comparative Examples 1 to 4 were measured with an Ocean Optics spectrometer. , The results are shown in Table 4 below. At this time, as a light source, XLamp® XRE-Roy (Royal blue) manufactured by Cree, which has a central wavelength of 450 nm as a blue light source, was used.

At this time, the measured 450nm transmission intensity of the light source region is small, and the higher the emission intensity of 520nm, which is the emission region, means that the color purity is excellent and the emission characteristics are excellent.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 450nm transmittance 8 8 8 8 7 8 16 134 11 14 20 167 520nm emission intensity 54,160 54,578 52,114 54,947 53,161 54,824 53,038 42,134 51,632 52,192 49,616 40,096

Referring to Table 4, when the same type of yellow colorant was used, that is, Examples 1 to 5 and Comparative Example 1, Example 6 and Comparative Example 2, Example 7 and Comparative Example 3, and Example 8 and Comparative Example. When 4 was compared with each other, when the metal oxide of the present invention was included together (Examples 1 to 8), the transmittance at a wavelength of 450 nm was reduced compared to the case where the metal oxide of the present invention was not included (Comparative Examples 1 to 4). And, it can be seen that the emission intensity at the wavelength of 520 nm increases.

11: registration
13: yellow coating layer
15: self-luminous pixel layer
15a: red pixel area
15b: green pixel area
51a, 51b, 51c: bulkhead
101: light source

Claims (10)

Contains a yellow colorant and metal oxides,
The metal oxide is at least one yellow curable resin composition selected from the group consisting of TiO ₂ , Al ₂ O ₃ , ZrO ₂ , ZnO and SiO ₂ ,
The resin layer formed using the yellow curable resin composition has a transmittance of 10 or less, the yellow curable resin composition measured at a thickness of 2 μm and a wavelength of 450 nm. According to claim 1,
The yellow curable resin composition further comprises at least one selected from the group consisting of a red or green colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. According to claim 1,
The yellow colorant is a yellow curable resin composition that satisfies the transmission characteristics of Equation 1 below:
[Equation 1]
50 ≤ T(λ) ≤ 60%
T(λ-20nm) < 2%
T(λ+20nm) ≥ 80%
(In Equation 1, T is transmittance (%), and λ means a wavelength selected from 470 nm to 510 nm.) According to claim 1,
The yellow colorant is a yellow curable resin composition comprising at least one selected from the group consisting of CI Pigment Yellow 138, 185 and 231. According to claim 1,
A yellow curable resin composition comprising a yellow colorant in an amount of 5 to 80% by weight based on 100% by weight of the total solid content in the total yellow curable resin composition. delete A yellow coating layer comprising a cured product of the yellow curable resin composition of any one of claims 1 to 5; and a self-emitting pixel layer formed on the yellow coating layer and containing quantum dots. According to claim 7,
The yellow coating layer is a color filter formed on a red pixel layer and a green pixel layer. An image display device comprising the color filter of claim 7 . According to claim 9,
The color filter is an image display device in which the yellow coating layer is disposed in a direction opposite to the light source.

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