TWI791476B - Blue photosensitive resin composition and color filter and image display device manufactured using the same - Google Patents

Abstract

This invention relates to a blue photosensitive resin composition and to a color filter and an image display device manufactured using the same, the blue photosensitive resin composition including scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerization initiator, a photopolymerizable compound, a UV absorber, and a solvent, the UV absorber including at least one of benzotriazole-, triazine- and benzophenone-based UV absorbers.

Description

Blue photosensitive resin composition and color filter and image display device manufactured therefrom

The invention relates to a blue photosensitive resin composition and a color filter and an image display device manufactured by using the blue photosensitive resin composition.

A color filter is a thin-film optical part in which three colors, red, green, and blue, are extracted from white light so that the three colors can be used pixel by pixel, and the size of a single pixel is approximately tens to hundreds of microns . Such a color filter is configured to include sequentially stacked black matrix layers and pixel parts, the black matrix layer is formed on a transparent substrate in a predetermined pattern, and is intended to shield the boundaries between pixels, and the pixel parts It is composed of three colors (ie, red (R), green (G), and blue (B)) arranged in a predetermined order to form each pixel.

Recently, color filters are manufactured by a pigment dispersion process using a pigment dispersion type photosensitive resin. However, in the process of the light emitted from the light source passing through the color filter, part of the light is absorbed by the color filter, thereby reducing the light efficiency, and due to the nature of the pigment contained in the color filter, the accuracy of color reproduction likely to fall.

In order to solve these problems, a method of manufacturing a color filter using a self-luminous photosensitive resin composition including quantum dots has been proposed.

Specifically, Korean Patent Application Publication No. 2007-0094679 discloses a color filter layer formed of quantum dots for the purpose of increasing color reproducibility, and Korean Patent Application Publication No. 2009-0036373 discloses that by The light-emitting layer containing the quantum dot phosphor is used to replace the existing color filter to improve the light efficiency and achieve the improvement of the display quality.

However, photosensitive resin compositions for producing color filters developed so far cannot sufficiently satisfy requirements such as excellent pattern characteristics, heat resistance, and the like.

[citation list]

[Patent Document]

(Patent Document 1) Korean Patent Application Publication No. 2007-0094679

(Patent Document 2) Korean Patent Application Publication No. 2009-0036373

Therefore, the present invention aims to provide a blue photosensitive resin composition and a color filter and an image display device manufactured using the blue photosensitive resin composition, the blue photosensitive resin composition can realize color filter Sheets, especially self-luminous color filters, which have excellent developing speed and thus high processability, can prevent yellowing at high temperature due to high heat resistance when forming a cured film, and can present Uniform light intensity, and since it has good pattern characteristics by forming a fine pattern at a predetermined value, the problem of fine pixel defects can be alleviated.

Therefore, the present invention provides a blue photosensitive resin composition comprising scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable A compound, a photopolymerization initiator, an ultraviolet absorber, and a solvent. The ultraviolet absorber includes at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber.

In addition, the present invention provides a color filter, which includes a blue pattern layer formed from the above blue photosensitive resin composition.

In addition, the present invention provides an image display device, which includes the above-mentioned color filter and a light source for emitting blue light.

According to the present invention, the blue photosensitive resin composition includes an ultraviolet absorber containing at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber, and thus can be Realization of color filters, especially self-illuminating color filters, which exhibit uniform light intensity due to high heat resistance against yellowing at high temperatures, and by forming fine patterns at predetermined values, due to excellent pattern characteristics The problem of fine pixel defects is alleviated. In addition, self-illuminating color filters with high-quality images and excellent viewing angles are available.

According to the present invention, the blue photosensitive resin composition may include scattering particles, a blue colorant, an arbor resin as a binder resin, a photopolymerization initiator, a photopolymerizable compound, a thermosetting agent, and a solvent. . Specifically, the blue photosensitive resin composition of the present invention includes at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber, thereby including such The color filter of the blue pattern layer formed by the blue photosensitive resin composition, especially the self-luminous color filter, can exhibit uniform light intensity by preventing yellowing at high temperature due to high heat resistance, and The problem of fine pixel defects can be alleviated by forming fine patterns at predetermined values. In addition, a color filter having a high-quality image and an excellent viewing angle, especially a self-luminous color filter, and an image display device including the color filter can be provided.

Hereinafter, the constitution of the present invention will be described in detail.

scattering particles

In the present invention, the scattering particles may be metal oxides with an average particle diameter of 10 nm to 1000 nm, and preferably 30 nm to 300 nm. If the average particle diameter of the scattering particles is smaller than the above-mentioned lower limit, sufficient scattering of incident light cannot be achieved. On the other hand, if the average particle size exceeds the above upper limit, the scattering particles may precipitate in the composition, or the surface of the self-luminous layer with uniform quality cannot be obtained.

The metal oxide may be an oxide comprising any metal selected from the following groups: Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu , Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er , Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and combinations thereof. More specifically, the metal oxide may be at least one selected from the following group: Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO , Nb ₂ O ₃ , SnO, MgO and combinations thereof. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

The average particle size of the scattering particles and the amount in the composition can be properly adjusted as required to fully improve the light intensity of the color filter.

Based on the total weight of the solid content of the blue photosensitive resin, the content of the scattering particles may be 0.1% to 50% by weight, preferably 5% to 30% by weight. When the amount of scattering particles falls within the above range, light intensity can be increased and stability of the composition can be ensured.

blue colorant

In the blue colorant of the present invention, the blue pigment may include a compound classified as a pigment according to the Color Index (Published by the Society of Dyers and Colourists), and may specifically be The terms include, but are not limited to, pigments with the following Color Index (C.I.) numbers. Specific examples of blue pigments may include C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 21, C.I. It is preferable to use at least one selected from the following groups: C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6 and C.I. Pigment Blue 16.

The blue coloring agent of the present invention may further include a blue dye, and the blue dye may include a compound classified as a dye according to the colorimetric index (published by the British Association of Dyestuffs and Colorists) or dyeing notes (Dyeing Note, by Color Dyeing A conventional dye disclosed in Shikisensha Co. Ltd. (published by Shikisensha Co. Ltd.).

Specific examples of dyes that may be additionally used may include C.I. solvent dyes, C.I. acid dyes, C.I. direct dyes, and C.I. mordant dyes.

Solvent Blue 5, C.I. Solvent Blue 35, C.I. Solvent Blue 36, C.I. Solvent Blue 37, C.I. Solvent Blue 44, C.I. Solvent Blue 45, C.I. Solvent Blue 59, C.I. Solvent Blue 67, and C.I. Solvent Blue 70, and it is preferable to use at least one of C.I. Solvent Blue 35, C.I. Solvent Blue 36, C.I. Solvent Blue 44, C.I. Solvent Blue 45 and C.I. Solvent Blue 70.

And, examples of C.I. acid dyes may include C.I. acid blue 1, C.I. acid blue 7, C.I. acid blue 9, C.I. acid blue 15, C.I. acid blue 18, C.I. acid blue 23, C.I. acid blue 25, C.I. acid blue 27, C.I. Acid Blue 29, C.I. Acid Blue 40, C.I. Acid Blue 42, C.I. Acid Blue 45, C.I. Acid Blue 51, C.I. Acid Blue 62, C.I. Acid Blue 70, C.I. Acid Blue 74, C.I. Acid Blue 80, C.I. Acid Blue 83, C.I. Acid blue 86, C.I. acid blue 87, C.I. acid blue 90, C.I. acid blue 92, C.I. acid blue 96, C.I. acid blue 103, C.I. acid blue 112, C.I. acid blue 113, C.I. acid blue 120, C.I. acid blue 129, C.I. Acid blue 138, C.I. acid blue 147, C.I. acid blue 150, C.I. acid blue 158, C.I. acid blue 171, C.I. acid blue 182, C.I. acid blue 192, C.I. acid blue 210, C.I. acid blue 242, C.I. acid blue 243, C.I. Acid Blue 256, C.I. Acid Blue 259, C.I. Acid Blue 267, C.I. Acid Blue 278, C.I. Acid Blue 280, C.I. Acid Blue 285, C.I. Acid Blue 290, C.I. Acid Blue 296, C.I. Acid Blue 315, C.I. Acid Blue 324:1 , C.I. Acid Blue 335 and C.I. Acid Blue 340. Among them, at least one of C.I. Acid Blue 80 and C.I. Acid Blue 90 is preferably used.

Direct Blue 38, C.I. Direct Blue 44, C.I. Direct Blue 57, C.I. Direct Blue 70, C.I. Direct Blue 77, C.I. Direct Blue 80, C.I. Direct Blue 81, C.I. Direct Blue 84, C.I. Direct Blue 85, C.I. Direct Blue 86, C.I. Direct Blue 90, C.I. Direct Blue 93, C.I. Direct Blue 94, C.I. Direct Blue 95, C.I. Direct Blue 97, C.I. Direct Blue 98, C.I. Direct Blue 99, C.I. Direct Blue 100, C.I. Direct Blue 101, C.I. Direct Blue 106, C.I. Direct Blue 107, C.I. Direct Blue 108, C.I. Direct Blue 109, C.I. Direct Blue 113, C.I. Direct Blue 114, C.I. Direct Blue 115, C.I. Direct Blue 117, C.I. Direct Blue 137, C.I. Direct Blue 149, C.I. Direct Blue 150, C.I. Direct Blue 153, C.I. Direct Blue 155, C.I. Direct Blue 156, C.I. Direct Blue 158, C.I. Direct Blue 159, C.I. Direct Blue 160, C.I. Direct Blue 162, C.I. Direct Blue 163, C.I. Direct Blue 164, C.I. Direct Blue 166, C.I. Direct Blue 167, C.I. Direct Blue 170, C.I. Direct Blue 171, C.I. Direct Blue 172, C.I. Direct Blue 173, C.I. Direct Blue 189, C.I. Direct Blue 190, C.I. Direct Blue 192, C.I. Direct Blue 193, C.I. Direct Blue 194, C.I. Direct Blue 196, C.I. Direct Blue 198, C.I. Direct Blue 199, C.I. Direct Blue 200, C.I. Direct Blue 209, C.I. Direct Blue 210, C.I. Direct Blue 212, C.I. Direct Blue 213, C.I. Direct Blue 214, C.I. Direct Blue 222, C.I. Direct Blue 228, C.I. Direct Blue 229, C.I. Direct Blue 237, C.I. Direct Blue 242, C.I. Direct Blue 243, C.I. Direct Blue 244, C.I. Direct Blue 245, C.I. Direct Blue 247, C.I. Direct Blue 248, C.I. Direct Blue 250, C.I. Direct Blue 251, C.I. Direct Blue 252, C.I. Direct Blue 257, C.I. Direct Blue 259, C.I. Direct Blue 260, C.I. Direct Blue 268, C.I. Direct Blue 274, C.I. Direct Blue 275 and C.I. Direct Blue 293.

Mordant blue 1, C.I. Mordant blue 2, C.I. Mordant blue 3, C.I. Mordant blue 7, C.I. Mordant blue 8, C.I. Mordant blue 9, C.I. Mordant blue 12, C.I. Mordant Blue 15, C.I. Mordant Blue 16, C.I. Mordant Blue 19, C.I. Mordant Blue 20, C.I. Mordant Blue 21, C.I. Mordant Blue 22, C.I. Mordant Blue 23, C.I. Mordant Blue 24, C.I. Mordant Blue 26, C.I. Mordant Blue 31, C.I. Mordant Blue 32, C.I. Mordant Blue 39, C.I. Mordant Blue 40, C.I. Mordant Blue 41, C.I. Mordant Blue 43, C.I. Mordant Blue 44, C.I. Mordant Blue 48, C.I. Mordant Blue 49, C.I. Mordant Blue 61, C.I. Mordant Blue 74, C.I. Mordant Blue 77, C.I. Mordant Blue 83 and C.I. Mordant Blue 84.

These blue dyes may be used alone or in combination of two or more.

The blue colorant of the present invention may further include other colorants, such as purple colorant. The purple colorant may include at least one of a purple pigment and a purple dye, and specific examples of the purple pigment may include C.I. Pigment Violet 1, C.I. Pigment Violet 14, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 32, C.I. Pigment Violet 33, C.I. Pigment Violet 36, C.I. Pigment Violet 37, and C.I. Pigment Violet 38. Among them, C.I. Pigment Violet 23 is preferably used.

Specific examples of violet dyes may include, but are not limited to, C.I. Solvent Violet, C.I. Acid Violet, C.I. Direct Violet, and C.I. Mordant Violet.

Specifically, examples of C.I. solvent violet may include C.I. solvent violet 8, C.I. solvent violet 9, C.I. solvent violet 13, C.I. solvent violet 14, C.I. solvent violet 36, C.I. solvent violet 37, C.I. solvent violet 47, and C.I. solvent violet 49 , and preferably C.I. Solvent Violet 13. Acid Violet 6B, C.I. Acid Violet 7, C.I. Acid Violet 9, C.I. Acid Violet 17, C.I. Acid Violet 19, and C.I. Acid Violet 66, and preferably C.I. Direct Violet 47, C.I. Direct Violet 52, C.I. Direct Violet 54, C.I. Direct Violet 59, C.I. Direct Violet 60, C.I. Direct Violet 65, C.I. Direct Violet 66, C.I. Direct Violet 81, C.I. Direct Violet 82, C.I. Direct Violet 84, C.I. Direct Violet 89, C.I. Direct Violet 90, C.I. Direct Violet 93, C.I. Direct Violet 95, C.I. Direct Violet 96, C.I. Direct Violet 103 and C.I. 104.

And, C.I. Mordant Violet 1, C.I. Mordant Violet 2, C.I. Mordant Violet 4, C.I. Mordant Violet 5, C.I. Mordant Violet 7, C.I. Mordant Violet 14, C.I. Mordant Violet 22, C.I. Mordant Violet 31, C.I. Mordant Violet 32, C.I. Mordant Violet 37, C.I. Mordant Violet 40, C.I. Mordant Violet 41, C.I. Mordant Violet 44, C.I. Mordant Violet 45, C.I. Mordant Violet 47, C.I. Mordant Violet 58.

Based on the total weight of the solid content of the blue photosensitive resin, the blue colorant can be used in an amount of 0.1% to 50% by weight, preferably 0.5% to 30% by weight. When the amount of the blue colorant falls within the above range, the desired effect of suppressing external light reflection can be achieved, the color with good light intensity can be effectively displayed, and the viscosity stability of the composition can be ensured.

In the case of a self-luminous photosensitive resin including quantum dots, quantum efficiency may decrease and desired properties may not be obtained. In particular, blue quantum dots are expensive, resulting in high manufacturing costs, and their process applications are limited due to potentially damaging high-temperature processing. However, in the present invention, instead of including blue quantum dots, blue colorants and scattering particles are included, thereby preventing the efficiency of blue pixels of color filters, especially self-luminous color filters from being reduced.

binder resin

The binder resin of the present invention includes a hub-based binder resin. The arbor system binder resin has alkali solubility and reactivity under the action of light or heat, and is used as a dispersion medium for coloring materials. The nodular binder resin contained in the blue photosensitive resin composition of the present invention functions as a binder resin for scattering particles, and is not limited as long as it can be dissolved in the development process during the production of the color filter The resin in the alkaline developer used can be used.

The hubbub binder resin of the present invention may include at least one of the compounds represented by the following Chemical Formula 1-1 and Chemical Formula 1-2.

，其中X為氫原子、C1-C5烷基、或羥基，且R₅為氫原子或C1-C5烷基。 In Chemical Formula 1-1 or Chemical Formula 1-2, R ₁ , R ₂ , R ₃ and R ₄ are independently

, wherein X is a hydrogen atom, a C1-C5 alkyl group, or a hydroxyl group, and R ₅ is a hydrogen atom or a C1-C5 alkyl group.

In the present invention, the compound of Chemical Formula 1-1 may be synthesized from the compound represented by the following Chemical Formula 2-1, and the compound of Chemical Formula 1-2 may be synthesized from the compound represented by the following Chemical Formula 2-2.

[chemical formula 2-2]

Specifically, the compound of Chemical Formula 1-1 may be at least one of the compounds represented by the following Chemical Formula 1-1-1 and Chemical Formula 1-1-2, and the compound of Chemical Formula 1-2 may be represented by the following Chemical Formula 1-1- At least one of the compounds represented by 2-1 and Chemical Formula 1-2-2.

The arbor system binder resin can be selected from 9,9-bis(3-cinnamic acid diester) fluorine, 9,9-bis(3-cinnamyl-4-hydroxyphenyl) fluorine, 9,9 - Bis(glycidyl methacrylate ether) fennel, 9,9-bis(3,4-dihydroxyphenyl) terrene dicinnamate, 3,6-diglycidyl methacrylate ether spiro( Perylene-9,9-dibenzopyran (xanthene)), 9,9-bis(3-allyl-4-hydroxyphenyl) fluorine, 9,9-bis(4-allyloxyphenyl ) and at least one of the group consisting of 9,9-bis(3,4-methacrylic acid diester) fluorene is prepared by reacting at least one of the following: from maleic anhydride, succinic anhydride, Icon Acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride Acid anhydride group composed of phthalic anhydride; or aromatic polycarboxylic acid anhydride such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and biphenyl An acid dianhydride group composed of ether tetracarboxylic dianhydride, but the present invention is not limited thereto.

The binder resin of the present invention may further include an acrylic alkali-soluble resin. Acrylic alkali-soluble resins can be exemplified by copolymers of carboxyl group-containing monomers and other comonomers polymerizable therewith. Carboxyl group-containing monomers may include, for example, unsaturated carboxylic acids having at least one carboxyl group in their molecules, including unsaturated monocarboxylic acids or unsaturated polycarboxylic acids, such as unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and the like. Here, examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of unsaturated dicarboxylic acids may include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof may include maleic anhydride, itaconic anhydride, and citraconic anhydride. Also, the unsaturated polycarboxylic acid may be its mono(2-methacryloxyalkyl)ester, for example, mono(2-acryloxyethyl)succinate, mono(2-methacryl oxyethyl)succinate, mono(2-acryloxyethyl)phthalate, or mono(2-methacryloxyethyl)phthalate. The unsaturated polycarboxylic acid may be a mono(meth)acrylate having a dicarboxylic acid polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate Esters etc. These carboxyl group-containing monomers may be used alone or in combination of two or more thereof. Examples of other comonomers that can be copolymerized with carboxyl-containing monomers may include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate , ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, methyl Isobutyl acrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-methacrylic acid -Hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, vinyl methacrylate Propyl, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methacrylate -Methoxyethyl ester, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate , Methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxy Dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantane (meth)acrylate Esters, norbornyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; unsaturated carboxylic acid aminoalkyl esters, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate , 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, methacrylic acid -2-Dimethylaminopropyl acrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethacrylate Methylaminopropyl esters; glycidyl esters of unsaturated carboxylic acids, e.g. acrylates Glyceryl water and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanides such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -Chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide Amines, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and Macromonomers with monoacryl or monomethacryl groups at the end of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polyn-butyl acrylate, polymethyl n-butyl acrylate, and polysiloxane. These monomers may be used alone or in combination of two or more thereof. As other comonomers polymerizable with carboxyl-containing monomers, particularly useful are bulky monomers, such as monomers with a norbornyl backbone, monomers with an adamantane backbone, monomers with a rosin backbone, Monomers, etc., because such monomers will reduce the relative dielectric constant. In the present invention, the pitch-based binder resin and/or the acrylic alkali-soluble resin may have an acid value of 20 to 200 (mg KOH/g). Within the range of the above acid value, the solubility in the developer can be improved, and thus the unexposed part can be easily dissolved and the sensitivity can be increased, whereby the pattern of the exposed part can be retained at the time of development, thereby improving the residual film ratio . Here, the acid value is the amount (mg) of potassium hydroxide required to neutralize 1 gram of the acrylic polymer, and is generally determined by performing a titration process using an aqueous potassium hydroxide solution. In addition, the arbor system binder resin or acrylic alkali-soluble resin may have a polystyrene standard by gel permeation chromatography (GPC, using tetrahydrofuran as an eluting solvent) of 2,000 to 200,000, and preferably 3,000 to 100,000. The measured weight average molecular weight (hereinafter referred to as "weight average molecular weight"). Within the above molecular weight range, the hardness of the coating film may be increased, thereby obtaining a high film residue rate, and the solubility of the unexposed portion in the developer is high, and its resolution is improved.

The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of the nodose-based binder resin and/or acrylic alkali-soluble resin preferably falls within the range of 1.0 to 6.0, and more preferably 1.5 to 6.0 . When the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0, high developability can be produced.

Based on the total weight of the solid content of the blue photosensitive resin, the amount of the binder resin of the present invention is 5% to 85% by weight, and preferably 5% to 60% by weight. When the amount of the binder resin falls within the above-mentioned range, the solubility in a developing solution becomes sufficiently large, so that it is difficult to generate a developing residue of a non-pixel portion on the substrate. In addition, film reduction in the pixel portion of the exposed portion is difficult to occur during development, so the non-pixel portion can be treated as needed.

photopolymerizable compound

In the blue photosensitive resin composition of the present invention, the photopolymerizable compound is a compound that can be polymerized under the action of light and a photopolymerization initiator described later, and may include monofunctional monomers, bifunctional mono Body and other multifunctional monomers. Specific examples of monofunctional monomers may include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone. Specific examples of difunctional monomers may include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Alcohol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether, and 3-methylpentanediol di(meth)acrylate. Specific examples of other polyfunctional monomers may include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, and Dipentaerythritol hexa(meth)acrylate. Among them, it is preferable to use a bifunctional monomer or a higher functional polyfunctional monomer. Based on the total weight of the solid content of the blue photosensitive resin composition, the amount of the photopolymerizable compound is 5% to 50% by weight, and preferably 5% to 45% by weight. When the amount of the photopolymerizable compound falls within the above range, the photosensitivity may not be lowered, and thus sufficient film strength may be obtained, and there may be no pattern loss at the time of development, whereby a pattern may be efficiently formed in a fine pattern portion , and can improve resist smoothness.

Photopolymerization initiator

In the present invention, the photopolymerization initiator may include at least one selected from the compounds represented by Chemical Formula 3 to Chemical Formula 5 below. When the compounds of Chemical Formula 3 to Chemical Formula 5 are included in this manner, radical reaction of the photosensitive resin composition is initiated, thereby causing curing and increasing sensitivity.

In chemical formula 3, R ₈ can be a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or C1-C12 alkyl substituted phenyl group, an unsubstituted or C1-C12 alkyl substituted benzyl group, an unsubstituted Or naphthyl substituted by C1-C12 alkyl, or -SR ^a , R ^a is hydrogen, C1-C12 alkyl or benzyl; and R ₉ to R ₁₂ are independently hydrogen atom, halogen atom, hydroxyl, un Substituted or C1-C12 alkyl substituted phenyl, unsubstituted or C1-C12 alkyl substituted benzyl, or unsubstituted or C1-C12 alkyl substituted naphthyl, R ₁₁ and R ₁₂ able to form a ring together.

Examples of compounds of chemical formula 3 may include 2-methyl-2-amino (4-morpholinophenyl) ethyl-1-ketone, 2-ethyl-2-amino (4-morpholinophenyl) ethyl -1-one, 2-propyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-butyl-2-amino(4-morpholinophenyl)ethan-1 -ketone, 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- Ketone and 2-methyl-2-diethylamino(4-morpholinophenyl)propan-1-one.

[chemical formula 4]

，n為1至4的整數且m為1至6的整數；R₁₅為C1-C8烷基、苯基、經取代的苯基、苄基、或經取代的苄基；且R₁₃為二苯基硫醚基、經取代的二苯基硫醚基、咔唑基(carbazole group)、經取代的咔唑基、茀基、或經取代的茀基。 In chemical formula 4, R ₁₄ is hydrogen, C1-C20 alkyl, C3-C8 cycloalkyl, unsubstituted or substituted phenyl or

, n is an integer from 1 to 4 and m is an integer from 1 to 6; R ₁₅ is C1-C8 alkyl, phenyl, substituted phenyl, benzyl, or substituted benzyl; and R ₁₃ is two A phenylsulfide group, a substituted diphenylsulfide group, a carbazole group, a substituted carbazole group, a fenene group, or a substituted carbazole group.

In Chemical Formula 5, R ₁₆ , R ₁₇ and R ₁₈ are independently R, OR, COR, SR, CONRR', ROR' or CN, wherein R and R' represent C1-C20 alkyl, C6-C30 aryl , C7-C30 aralkyl group or C2-C20 heterocyclic group, each of which may be substituted by a halogen atom and/or a C2-C20 heterocyclic group and wherein the alkyl group and the alkylene part of the aralkyl group may be replaced by an unsaturated bond , ether bond, thioether bond or ester bond are interrupted, R and R' can form a ring together; Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom, m is an integer from 0 to 4, and r is an integer from 0 to 5; s is 0 or 1; R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ independently represent a hydrogen atom, a halogen atom or a C1-C8 alkyl group; X ₁ and X ₂ represent a C1-C20 alkyl group or a C6-C30 aryl group , C7-C30 aralkyl group or C2-C20 heterocyclic group, each of which may be substituted by a halogen atom and/or a C2-C20 heterocyclic group and wherein the alkyl group and the alkylene part of the aralkyl group may be replaced by an unsaturated bond , ether bond, thioether bond or ester bond are interrupted; X ₂ can form a ring together with carbon atoms of adjacent rings, and more specifically can form a C6-C30 aromatic ring; and Y ₂ and Y ₃ represent independently Oxygen atom, sulfur atom or selenium atom.

唑-2'-基)乙烯基等。其中，較佳使用C1-C8烷基。 Preferred examples of alkyl groups represented by R and R' include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl , third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butyl Alkenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethyl Oxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzo

Azol-2'-yl) vinyl, etc. Among them, a C1-C8 alkyl group is preferably used.

唑-2-基、四氫哌喃基、吡咯啶基、咪唑啶基、吡唑啶基、四氫噻唑基、異四氫噻唑基、

唑啶基、異

唑啶基、哌啶基、哌嗪基或嗎啉基等C5-C7雜環基取代。 In addition, examples of the aryl group represented by R and R' include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthracenyl, phenanthrenyl and the like. Among them, a C6-C12 aryl group is preferably used. In addition, the aralkyl group represented by R and R' may include, for example, C7-C13 aralkyl groups such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenethyl , Styrene, etc. The heterocyclic groups represented by R and R' may include, for example, C5-C7 heterocyclic groups such as pyridyl, pyrimidinyl, furyl, thienyl and the like. In addition, the ring formed by both R and R' may include, for example, a C5-C7 ring, such as a piperidine ring, a morpholine ring, and the like. In addition, R and R' can be replaced by halogen elements such as fluorine, chlorine, bromine, iodine, etc., or can be replaced by pyridyl, pyrimidyl, furyl, benzo

Azol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidine, tetrahydrothiazolyl, isotetrahydrothiazolyl,

Azolidinyl, iso

Substituted by a C5-C7 heterocyclic group such as azolidinyl, piperidinyl, piperazinyl or morpholinyl.

唑-2'-基)乙烯基等。其中，較佳使用C1-C8烷基。 Preferred examples of alkyl groups represented by _X1 and _X2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl Base, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, Butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxy Ethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzo

Azol-2'-yl) vinyl, etc. Among them, a C1-C8 alkyl group is preferably used.

唑-2-基、四氫哌喃基、吡咯啶基、咪唑啶基、吡唑啶基、四氫噻唑基、異四氫噻唑基、

唑啶基、異

唑啶基、哌啶基、哌嗪基、嗎啉基、噻吩 基等。 In addition, examples of the aryl group represented by _X1 and _X2 include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthracenyl, phenanthrenyl and the like. Among them, a C6-C12 aryl group is preferably used. In addition, the aralkyl groups represented by _X1 and _X2 may include, for example, C7-C13 aralkyl groups such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl base, styrene base, etc. The heterocyclic groups represented by _X1 and _X2 may include, for example, C5-C7 heterocyclic groups, such as pyridyl, pyrimidyl, furyl, benzo

Azol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidine, tetrahydrothiazolyl, isotetrahydrothiazolyl,

Azolidinyl, iso

Azolidinyl, piperidinyl, piperazinyl, morpholinyl, thienyl, etc.

In addition, examples of the halogen atom represented by _X1 and _X2 may include fluorine, chlorine, bromine and iodine.

Examples of alkyl groups _represented by X _and X may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl , a third pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group and a third octyl group, each of which is substituted by a halogen atom.

X ₂ may form a ring together with carbon atoms of adjacent rings, and specifically, may form a C6-C30 aromatic ring or a C5-C10 cyclic compound.

Examples of the halogen atom represented by R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ may include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group represented by R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, Pentyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl and tertiary octyl.

The compound of Chemical Formula 5 may include the following compounds.

Moreover, it is preferable that a photoinitiator contains an acetophenone compound. Examples of acetophenone-based compounds may include oligomers such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2 -Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylthio phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-hydroxy -2-methyl[4-(1-methylvinyl)phenyl]propan-1-one oligomer, and preferably includes 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)butan-1-one.

In addition, the photopolymerization initiators of Chemical Formula 3 to Chemical Formula 5 may include structures represented by the following Chemical Formula 5-1 to Chemical Formula 5-8.

[chemical formula 5-2]

[chemical formula 5-8]

In addition, an acetophenone-based compound can be used in combination with other photopolymerization initiators.

Other photopolymerization initiators other than the acetophenone-based compound may include active radical generators for generating active radicals by light irradiation, sensitizers, acid generators, and the like. Examples of active radical generators may include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of benzophenone-based compounds may include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide Ether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Examples of thioxanthone-based compounds may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of triazine compounds may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane Base)-6-(4-methoxynaphthyl)-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)vinyl]-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, 2,4-bis(trichloromethyl)-6-[2-( 3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

Examples of active free radical generators may include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5' -Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylethyl Alkyd esters, titanocene compounds, etc. Examples of acid generators may include onium salts such as 4-hydroxyphenyldimethylconium p-toluenesulfonate, 4-hydroxyphenyldimethylconium hexafluoroantimonate, 4-acetyloxyphenyl di Methyl percited p-toluenesulfonate, 4-acetyloxyphenylmethyl benzyl percited hexafluoroantimonate, triphenyl percited p-toluenesulfonate, triphenyl percited hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

In addition, active radical generators may include compounds capable of simultaneously generating active radicals and acids, and for example, triazine-based photopolymerization initiators may also be used as acid generators.

Based on the total weight of the solid content of the blue photosensitive resin, the amount of the photopolymerization initiator is 0.1% to 20% by weight, and preferably 0.3% to 15% by weight. Within the above amount range, the blue photosensitive resin composition is highly sensitized, and thus the strength of a pixel portion formed using the above composition or the surface smoothness of a pixel portion can be improved.

Also, in the present invention, a photopolymerization initiator adjuvant may be used. The photopolymerization initiator auxiliary agent can be used in combination with a photopolymerization initiator, and is a compound for promoting polymerization of a photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator reaction.

Examples of photopolymerization initiator auxiliary agents may include amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone-based compounds.

Examples of amine compounds may include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (ie Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4' - bis(ethylmethylamino)benzophenone. Particularly useful is 4,4'-bis(diethylamino)benzophenone.

Examples of alkoxyanthracene compounds may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl- 9,10-diethoxyanthracene.

Examples of thioxanthone-based compounds may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1 -Chloro-4-propoxythioxanthone.

These photopolymerization initiators may be used alone or in combination of two or more thereof. In addition, commercially available photopolymerization initiator auxiliary agents can be used, and an exemplary commercially available photopolymerization initiator auxiliary agent is "EAB-F" (manufactured by Hodogaya Chemical Co. Ltd.).

When the photopolymerization initiator auxiliary agent is used in this way, the amount of the photopolymerization initiator auxiliary agent is 10 mol or less, and preferably 0.01 mol for 1 mol of the photopolymerization initiator to 5 moles. Within the range of the above amount, the sensitivity of the blue photosensitive resin composition is further improved, and the productivity of the color filter formed using the above composition can be improved.

UV absorber

It was confirmed in the present invention that the ultraviolet absorber is effective in adjusting the pattern size and is also effective in preventing yellowing during high temperature treatment, thereby improving quantum efficiency.

Generally, when a fine pattern cannot be formed due to an increase in CD bias of a photosensitive resin composition, it is known that an ultraviolet absorber is useful. Here, "CD" refers to the embossed portion of the pattern, and "CD deviation" indicates the extent to which the formed pattern is larger in size than the mask pattern to be realized. When an ultraviolet absorber is added, the ultraviolet absorber can absorb a part of ultraviolet light, thereby reducing CD deviation caused by diffraction, thereby obtaining a desired pattern.

Furthermore, the use of quantum dots with low heat resistance makes it difficult to maintain high light intensity during the manufacture of color filters. Here, when a UV absorber is added, high light intensity can be maintained even through multiple post-baking treatments.

According to the present invention, the ultraviolet absorber basically contains at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber.

Benzotriazole-based ultraviolet absorbers may include known compounds, specific examples of which may include 3-[3-tert-butyl-4-hydroxyl-5-(5-chloro-2H-benzotriazole-2- Base) phenyl] octyl propionate, (3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl) phenyl) propionate-2-ethylhexyl Esters, [3-[3-(2H-benzotriazol-2-yl)-5-(1,1-methylethyl)-4-hydroxyphenyl]-1-oxypropyl]-w- [3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxypropoxy]poly(oxy -1,2-ethylenediyl), (3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl)- 1-oxypropyl)-hydroxypoly(oxy-1,2-ethylenediyl), 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzene Triazole, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 3-(2H-benzotriazolyl)-5-(1,1-di Methylethyl)-4-hydroxy-octylphenylpropionate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc. .

Triazine-based ultraviolet absorbers may include known compounds, and specific examples thereof may include 2-(4,6-dimethyl-1,3,5-triazin-2-yl)-5-((hexyl)oxy ) phenol, 2-(4-(2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(4-(2-hydroxy-3-didecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-(3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy)phenyl)-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,2'-[6-(2,4-dibutoxyphenyl)-1,3, 5-triazine-2,4-diyl]bis(5-butoxyphenol), 2-{4-[4,6-bis(4-biphenyl)-1,3,5-triazine- 2-yl]-3-hydroxyphenoxy}propanoic acid 6-methylheptyl ester, etc.

The benzophenone-based ultraviolet absorber may include known compounds, and specific examples thereof may include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like.

Based on the total weight of the solid content of the blue photosensitive resin, the amount of the ultraviolet absorber is 0.001% by weight to 10% by weight, and preferably 0.025% by weight to 7% by weight. When the amount of the ultraviolet absorber falls within the above range, the effect of the absorber can be improved, and a pattern can be efficiently formed without hindering the action of the photopolymerization initiator.

solvent

In the blue photosensitive resin composition according to the present invention, the solvent is not particularly limited, and may include various organic solvents used in the field of blue photosensitive resin compositions. Specific examples thereof may include 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, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; glycol alkyl ether acetates, such as acetic acid-2-methoxy Methylcellosolve acetate and ethyl cellosolve acetate; 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 glycerol; esters, such as 3-ethoxypropionic acid ethyl ester and methyl 3-methoxypropionate; and cyclic esters such as gamma-butyrolactone. The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coating and drying, and more preferably includes alkylene glycol alkyl ether acetates, ketones and esters, such as 3-ethoxypropane ethyl acetate and methyl 3-methoxypropionate. Specific examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. These solvents may be used alone or in combination of two or more thereof.

In the blue photosensitive resin composition according to the present invention, based on the total weight of the blue photosensitive resin composition, the amount of the solvent is 60 mass % to 90 mass %, and preferably 60 mass % to 85 mass % . When the amount of the solvent falls within the above range, it can be applied using a coating device such as a roll coater, spin coater, slit spin coater, slit coater (or die coater) or inkjet coater. composition, thereby improving coatability.

additive

The blue photosensitive resin composition according to the present invention for forming the blue pattern layer may further include additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, Anti-coagulation agent, etc.

Examples of other polymer compounds may include curable resins such as epoxy resins or maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, acrylic polyfluoroalkyl ester, polyester or polyurethane.

The pigment dispersant may include commercially available surfactants, examples of which include silicone-based surfactants, fluorine-based surfactants, ester-based surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, and Amphoteric surfactants, which may be used alone or in combination of two or more thereof.

Examples of surfactants may include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine, and commercially available products such as KP (manufactured by Shin-Etsu Chemical Industry Co.), POLYFLOW (manufactured by Kyoeisha Chemical Co.) , EFTOP (manufactured by Tochem Products Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink & Chemical Industry Co.), Flourad (manufactured by Sumitomo 3M Ltd.), Asahi guard and Surflon (manufactured by Asahi Glass Co.), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA Chemicals), and PB 821 (manufactured by Ajinomoto Co. .) system)

Examples of adhesion promoters may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidol Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethylsilane Dimethoxysilane, 3-Chloropropyltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane and 3-Mercaptopropyltrimethoxysilane. Specific examples of antioxidants may include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

The anti-agglomeration agent can be exemplified by sodium polyacrylate.

Those skilled in the art can appropriately add additives within the range that does not interfere with the effect of the present invention. For example, based on a total of 100 parts by weight of the blue photosensitive resin composition, the additive is used in an amount of 0.05 parts by weight to 10 parts by weight, preferably 0.1 parts by weight to 10 parts by weight, and more preferably 0.1 parts by weight to 5 parts by weight , but not limited to this.

The blue photosensitive resin composition according to the present invention can be prepared by the following method. Specifically, the scattering particles are pre-mixed with a solvent, and dispersed to an average particle diameter of 30 nm to 300 nm using a bead mill or the like. As such, a dispersant may be further used if desired, and some or all of the binder resin may be mixed therewith. The remaining binder resin, photopolymerizable compound and photopolymerization initiator, and other components and additional solvent as needed are added to the obtained dispersion solution (may also be referred to as "grind base") so that the composition has a predetermined concentration, so as to obtain the desired blue photosensitive resin composition.

<Color filter and image display device>

In addition, the present invention provides a color filter, which includes a blue pattern layer comprising a cured product of the above blue photosensitive resin composition.

The color filter of the present invention is manufactured by using a blue photosensitive resin composition for forming a blue pattern layer instead of blue quantum dots, thereby reducing manufacturing costs and ensuring excellent viewing angles.

In addition, the blue photosensitive resin composition of the present invention includes an ultraviolet absorber containing at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber, thereby The color filter (especially the self-luminous color filter) including the blue pattern layer formed by the blue photosensitive resin composition of the present invention has high heat resistance, so it can prevent high-temperature yellowing, thereby being able to display uniform light intensity, and the problem of fine pixel defects can be alleviated by forming a fine pattern at a predetermined value.

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

The substrate itself may be a color filter, or may be a position where the color filter is located on the display device, and is not particularly limited. The substrate can be glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the polymer substrate can be polyethersulfone (PES) or polycarbonate (PC).

The blue pattern layer is a layer comprising the blue photosensitive resin composition of the present invention, and can be formed by applying the blue photosensitive resin composition for forming the blue pattern layer, exposing in a predetermined pattern, developing and heat cured. The patterned layer can be formed by implementing any method generally known in the art.

In another embodiment of the present invention, the color filter may further include at least one member selected from the group consisting of a red pattern layer and a green pattern layer.

In yet another embodiment of the present invention, the red pattern layer or the green pattern layer may include quantum dots and/or scattering particles. Specifically, the color filter of the present invention may include a red pattern layer containing red quantum dots or a green pattern layer containing green quantum dots, and the red pattern layer or the green pattern layer may include scattering particles. The red pattern layer or the green pattern layer can emit red light or green light by a light source for emitting blue light, which will be described later.

In yet another embodiment of the present invention, the scattering particles included in the red pattern layer or the green pattern layer may include metal oxides with an average particle diameter of 30 nm to 500 nm, and in order to describe the scattering particles and the metal oxide For the matter, reference will be made to the description of the scattering particles and the metal oxide included in the blue photosensitive resin composition according to the present invention.

In the present invention, the shape, configuration, and amount of quantum dots of the red pattern layer or the green pattern layer are not limited, and quantum dots generally used in this technology can be applied.

The color filter including the substrate and the pattern layer may further include barrier ribs formed between the patterns, and may also include a black matrix, but the invention is not limited thereto.

In the present invention, the color filter may be a self-illuminating color filter.

In addition, the present invention proposes an image display device comprising the above-mentioned color filter and a light source for emitting blue light. The image display device of the present invention includes a color filter and a light source emitting blue light, and the color filter includes a blue pattern layer containing a cured product of a blue photosensitive resin composition.

The color filter of the present invention can be applied not only to typical liquid crystal display devices, but also to various image display devices, such as electroluminescent displays, plasma displays, field emission displays, and the like.

When the image display device includes the color filter containing the blue pattern layer of the present invention and a light source, it can exhibit excellent light intensity or excellent viewing angle. In addition, the blue pattern layer included in the color filter of the present invention does not include blue quantum dots, so it is expected that it is possible to manufacture an image display device at low cost.

The present invention can be better understood through the following examples, which are given for the purpose of illustration and should not be construed as limiting the scope of the invention. The embodiments of the present invention are provided to more fully explain the description to those skilled in the art to which the present invention pertains. Unless otherwise mentioned, "%" and "parts" representing amounts in the following examples are given on a weight basis.

Synthesis example: Synthesis of binder resin

Preparation Example 1: Acrylic Alkali-soluble Resin

Prepare a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube. Add 74.8 g (0.20 mol) benzylmaleimide, 43.2 g (0.30 mol) acrylic acid, 118.0 g (0.50 mol) vinyltoluene, 4 g tert-butylperoxy-2-ethyl hexanoate and 40 grams of propylene glycol monomethyl ether acetate (PGMEA) and mixed under stirring to prepare a monomer dropping funnel in this way, and add 6 grams of n-dodecanethiol and 24 grams of PGMEA and mix under stirring to In this way, the chain transfer agent dropping funnel is prepared. After that, 395 g of PGMEA was put into the flask, and the air in the flask was replaced with nitrogen, and then the temperature of the flask was raised to 90° C. with stirring. Subsequently, monomers and chain transfer agents were dropped from respective dropping funnels. Each was dripped for 2 hours while the temperature was kept at 90°C. After 1 hour, the temperature was raised to 110° C. and maintained for 3 hours, and then a gas mixture of oxygen/nitrogen=5/95 (vol/vol) was blown through the gas inlet tube. Next, 28.4 grams of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid in this reaction)], 0.4 gram of 2,2'-methylene Bis(4-methyl-6-tert-butylphenol) and 0.8 g of triethylamine were reacted at 110° C. for 8 hours to obtain a resin A with a solid acid value of 70 mg KOH/g. As measured by GPC against polystyrene standards, its weight average molecular weight was 16000, and its molecular weight distribution (Mw/Mn) was 2.3.

Preparation Example 2: Synthesis of Compounds of Chemical Formula 1-1-1

In a 3000 ml three-neck round bottom flask, mix 364.4 g of 3',6'-dihydroxyspiro(fluorene-9,9-dibenzopyran) and 0.4159 g of tertiary butylammonium bromide, and mix 2359 g Epichlorohydrin was added thereto, and the resulting mixture was heated to 90°C and reacted. When the 3',6'-dihydroxyspiro(terpine-9,9-dibenzopyran) was completely consumed by liquid chromatography analysis, it was cooled to 30°C, and 50% NaOH aqueous solution (3 equivalent). When epichlorohydrin was completely consumed by liquid chromatography analysis, it was extracted with dichloromethane, then washed with water three times, after which the organic layer was dried over magnesium sulfate, and then the dichloromethane was distilled off under reduced pressure, followed by mixing dichloromethane with methanol A 50:50 mixture was recrystallized.

1 equivalent of the thus synthesized epoxy compound, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed, and then 24.89 grams of propylene glycol monomethyl ether acetate solvent. The resulting reaction solution was blown with air at 25 ml/min, and heated to 90°C to 100°C. The reaction solution in a turbid state was heated to 120° C. to completely dissolve. When the solution became clear and its viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mg KOH/gram. It took 11 hours to reach the desired acid number (0.8). After the reaction, the temperature of the reactor was lowered to room temperature, thereby obtaining a colorless and transparent compound of the following chemical formula 1-1-1.

Preparation Example 3: Synthesis of Compounds of Chemical Formula 1-1-2

In a 3000 milliliter three-necked round bottom flask, 364.4 grams of 3',6'-dihydroxyspiro(fennel-9,9-dibenzopyran) of chemical formula 2-1 and 0.4159 grams of tert-butylammonium bromide After mixing, 2359 g of epichlorohydrin was added thereto, and the resulting mixture was heated to 90° C. and reacted. When the 3',6'-dihydroxyspiro(terpine-9,9-dibenzopyran) was completely consumed by liquid chromatography analysis, it was cooled to 30°C, and 50% NaOH aqueous solution (3 equivalent). When epichlorohydrin was completely consumed by liquid chromatography analysis, it was extracted with dichloromethane, then washed with water three times, after which the organic layer was dried over magnesium sulfate, and then the dichloromethane was distilled off under reduced pressure, followed by mixing dichloromethane with methanol A 50:50 mixture was recrystallized.

Mix 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid, and then add 24.89 grams of propylene glycol monomethyl ether Acetate solvent. The resulting reaction solution was blown with air at 25 ml/min, and heated to 90°C to 100°C. The reaction solution in a turbid state was heated to 120° C. to completely dissolve. When the solution became clear and its viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mg KOH/gram. It took 11 hours to reach the desired acid number (0.8). After the reaction, the temperature of the reactor was lowered to room temperature, thereby obtaining a colorless and transparent compound of the following chemical formula 1-1-2.

Preparation Example 4: Synthesis of Compounds of Chemical Formula 1-2-1

In a 3000 ml three-neck round bottom flask, 364.4 grams of 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol and 0.4159 grams of tertiary butylammonium bromide were mixed, and 2359 1 g of epichlorohydrin was added thereto, and the resulting mixture was heated to 90° C. and reacted. When 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol was completely consumed by liquid chromatography analysis, it was cooled to 30 °C, and 50% NaOH aqueous solution ( 3 equivalents). When epichlorohydrin was completely consumed by liquid chromatography analysis, it was extracted with dichloromethane, then washed with water three times, after which the organic layer was dried over magnesium sulfate, and then the dichloromethane was distilled off under reduced pressure, followed by mixing dichloromethane with methanol A 50:50 mixture was recrystallized. Mix 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid, and then add 24.89 grams of propylene glycol monomethyl ether acetic acid ester solvent. The resulting reaction solution was blown with air at 25 ml/min, and heated to 90°C to 100°C. The reaction solution in a turbid state was heated to 120° C. to completely dissolve. When the solution became clear and its viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mg KOH/gram. It took 11 hours to reach the desired acid number (0.8). After the reaction, the temperature of the reactor was lowered to room temperature, thereby obtaining a colorless and transparent compound of the following chemical formula 1-2-1.

Preparation Example 5: Synthesis of Compounds of Chemical Formula 1-2-2

In a 3000 ml three-neck round bottom flask, mix 364.4 grams of 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol and 0.4159 grams of tertiary butylammonium bromide, and mix 2359 grams of Epichlorohydrin was added thereto, and the resulting mixture was heated to 90°C and reacted. When 4,4'-(9H-dibenzopyran-9,9-diyl)diphenol was completely consumed by liquid chromatography analysis, it was cooled to 30 °C, and 50% NaOH aqueous solution ( 3 equivalents). When epichlorohydrin was completely consumed by liquid chromatography analysis, it was extracted with dichloromethane, then washed with water three times, after which the organic layer was dried over magnesium sulfate, and then the dichloromethane was distilled off under reduced pressure, followed by mixing dichloromethane with methanol A 50:50 mixture was recrystallized. Mix 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid, and then add 24.89 grams of propylene glycol monomethyl ether Acetate solvent. The resulting reaction solution was blown with air at 25 ml/min, and heated to 90°C to 100°C. The reaction solution in a turbid state was heated to 120° C. to completely dissolve. When the solution became clear and its viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mg KOH/gram. It took 11 hours to reach the desired acid number (0.8). After the reaction, the temperature of the reactor was lowered to room temperature, thereby obtaining a colorless and transparent compound of the following chemical formula 1-2-2.

Preparation Example 6: Synthesis of Hubbing Adhesive Resin (A-1)

The compound of the chemical formula 1-1-1 of 307.0 gram preparation example 2 is added in 600 gram propylene glycol monomethyl ether acetates, dissolves, and with 78 gram biphenyltetracarboxylic dianhydride and 1 gram tetraethylammonium bromide Mix, heat gradually, and react at 110°C to 115°C for 4 hours. After confirming the loss of the anhydride group, the reaction solution was mixed with 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, and reacted at 90°C for 6 hours, thereby polymerizing into an arbor system binder resin. The loss of anhydride was confirmed by infrared spectroscopic analysis. Weight average molecular weight: 3500.

Preparation Example 7: Synthesis of Arbor Adhesive Resin (A-2)

The compound of the chemical formula 1-1-2 of 307.0 gram preparation examples 3 is added in 600 gram propylene glycol monomethyl ether acetates, dissolves, and with 78 gram biphenyltetracarboxylic dianhydride and 1 gram tetraethylammonium bromide Mix, gradually heat and react at 110°C to 115°C for 4 hours. After confirming the loss of the anhydride group, the reaction solution was mixed with 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, and reacted at 90°C for 6 hours, thereby polymerizing into an arbor system binder resin. The loss of anhydride was confirmed by infrared spectroscopic analysis. Weight average molecular weight: 3800.

Preparation Example 8: Synthesis of Hubbing Adhesive Resin (A-3)

The compound of chemical formula 1-2-1 of 307.0 grams of Preparation Example 4 is added in 600 grams of propylene glycol monomethyl ether acetate, dissolves, and mixes with 78 grams of phenyltetracarboxylic dianhydride and 1 gram of tetraethylammonium bromide , heated gradually, and reacted at 110°C to 115°C for 4 hours. After confirming the loss of the anhydride group, the reaction solution was mixed with 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, and reacted at 90°C for 6 hours, thereby polymerizing into an arbor system binder resin. The loss of anhydride was confirmed by infrared spectroscopic analysis. Weight average molecular weight: 4500.

Preparation Example 9: Synthesis of Arbor System Binder Resin (A-4)

The compound of the chemical formula 1-2-2 of 307.0 grams of Preparation Example 5 is added in 600 grams of propylene glycol monomethyl ether acetate, dissolved, and mixed with 78 grams of phenyltetracarboxylic dianhydride and 1 gram of tetraethylammonium bromide , heated gradually, and reacted at 110°C to 115°C for 4 hours. After confirming the loss of the anhydride group, the reaction solution was mixed with 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride, and reacted at 90°C for 6 hours, thereby polymerizing into an arbor system binder resin. The loss of anhydride was confirmed by infrared spectroscopic analysis. Weight average molecular weight: 4900.

Device: HLC-8120 GPC (manufactured by Tosoh Corp.)

Column: TSK-GELG4000HXL+TSK-GELG2000HXL (tandem)

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Introduced volume: 50 microliters

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard calibration material: TSK polystyrene standard F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight to the number average molecular weight obtained above is defined as molecular weight distribution (Mw/Mn).

Example 1 to Example 9 and Comparative Example 1 to Comparative Example 4: Preparation of Blue Photosensitive Resin Composition

The corresponding blue photosensitive resin compositions of Example 1 to Example 9 and Comparative Example 1 to Comparative Example 4 were prepared using the respective components in the amounts shown in Table 1 to Table 3 below. (Table 1 shows the scattering particles, Table 2 shows the components and amounts of the compositions of each example, and Table 3 shows the components and amounts of the compositions of each comparative example).

⁰⁾ Blue colorant: CI Pigment Blue 15:6

¹⁾ Binder resin:

A-1: Preparation Example A-1

A-2: Preparation Example A-2

A-3: Preparation Example A-3

A-4: Preparation Example A-4

A-5: Mono(2-methacryloxyalkyl) ester

²⁾ Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku)

³⁾ Photopolymerization initiator:

D-1: Irgacure-907 (manufactured by BASF)

D-2: OXE-01 (made by BASF)

D-3: OXE-02 (made by BASF)

D-4: PBG-327 (chemical formula 5-3) (manufactured by Tronly)

⁴⁾ UV absorber:

F-1: TINUVIN 109 (manufactured by BASF) - benzotriazole type

F-2: TINUVIN 328 (manufactured by BASF) - benzotriazole type

F-3: TINUVIN 1577 (manufactured by BASF) - triazine type

F-4: TINUVIN 400 (manufactured by BASF) - triazine type

F-5: Chimassorb 81 (manufactured by BASF) - benzophenone type

⁵⁾ Solvent: propylene glycol monomethyl ether acetate

⁰⁾ Blue colorant: CI Pigment Blue 15:6

¹⁾ Binder resin:

A-1: Preparation Example A-1

A-2: Preparation Example A-2

A-3: Preparation Example A-3

A-4: Preparation Example A-4

A-5: Mono(2-methacryloxyalkyl) ester

²⁾ Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku)

³⁾ Photopolymerization initiator:

D-1: Irgacure-907 (manufactured by BASF)

D-2: OXE-01 (made by BASF)

D-3: OXE-02 (made by BASF)

D-4: PBG-327 (chemical formula 5-3) (manufactured by strong company)

⁴⁾ UV absorber:

F-1: TINUVIN 109 (manufactured by BASF) - benzotriazole type

F-2: TINUVIN 328 (manufactured by BASF) - benzotriazole type

F-3: TINUVIN 1577 (manufactured by BASF) - triazine type

F-4: TINUVIN 400 (manufactured by BASF) - triazine type

F-5: Chimassorb 81 (manufactured by BASF) - benzophenone type

⁵⁾ Solvent: propylene glycol monomethyl ether acetate

Manufacture of color filters

Color filters were produced using the blue photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4. Specifically, each photosensitive resin composition was applied on a glass substrate by spin coating, and the glass substrate was placed on a hot plate and kept at 100° C. for 3 minutes to form a thin film.

Subsequently, a test photomask having a square transmission pattern with a size of 20 mm (width) × 20 mm (length) and a line/space pattern of 1 μm to 100 μm was placed on the film, and then irradiated with ultraviolet light at a distance of 100 μm According to.

Here, an ultra-high pressure mercury lamp (USH-250D) manufactured by Ushio Electric Co. was used as an ultraviolet light source to apply ultraviolet light in an atmospheric atmosphere at an exposure amount of 200 mJ/cm2 (365 nm). Light. No special filters are used.

The film to which ultraviolet light was applied was immersed in a KOH developing aqueous solution having a pH of 10.5 for 80 seconds, thereby performing development. The film-coated glass substrate was washed with distilled water, dried with nitrogen, and heated in an oven at 150° C. for 10 minutes, thereby fabricating a color filter pattern. The film thickness of the color pattern thus produced was 5.0 micrometers.

Test Example 1: Developing speed, sensitivity, pattern stability, and heat resistance of color filters

As shown in Table 4 below, the color filters produced using the respective blue photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated. The evaluation criteria for each test are described below.

Development rate: the time (seconds) required to first dissolve the unexposed part in the developing solution during development <spray developer HPMJ method>

Sensitivity: Sensitivity mask for fine patterns (1 to 60) degree of film formation without wrinkling (sensitivity is considered excellent as the value decreases)

Pattern Stability: The degree of pattern error after exposing the pattern mask at low exposure doses (20 to 100 millijoules (mJ)).

Excellent: No pattern errors

Good: One or two pattern errors

Reasonable: three pattern errors

Poor: Four or more pattern errors

Evaluation is performed by observation using an optical microscope for three-dimensional surface shape measurement.

Evaluation of heat resistance and brightness change: The color filter manufactured as above was heated in an oven at 230° C. for 2 hours.

The change in its color was determined using the mathematical formula (1), and the change in luminance (ΔY) before and after heat resistance evaluation was measured, thereby evaluating whether the luminance was lowered due to thermal yellowing.

△Y (brightness change):

O: -0.04 to 0.00

X: less than -0.04

As can be seen from Table 4, Examples 1 to 9 show excellent processing effects, including a developing rate of 15 or less than 15, excellent sensitivity of 50 or less, no pattern error after pattern mask exposure, Therefore, it has excellent pattern stability and high heat resistance.

However, in Comparative Example 2 containing only an acrylic alkali-soluble resin without a nodular binder resin, peeling tended to occur due to difficulty in curing, and therefore such values could not be measured. In Comparative Example 3, the content of the photopolymerizable compound fell out of an appropriate range, and thus curing was difficult and resulted in peeling of the entire pattern. In addition, in Comparative Example 4 which did not contain an ultraviolet absorber, since it was difficult to control the generation of radicals, desired heat resistance could not be obtained.

Test Example 2: Measurement of Fine Patterns

Among the color filters manufactured using the blue photosensitive resins of Examples 1 to 9 and Comparative Examples 1 to 4, one of the patterns formed using a mask having a line/space pattern of 100 μm The dimensions are measured using an OM device (ECLIPSE LV100POL, manufactured by Nikon).

When the difference between the designed value of the line/space pattern of the mask and the measured value of the obtained fine pattern is 20 μm or more, it is difficult to achieve fine pixels, and the pattern linearity and flattening may become degraded Gotta be a problem. Also, it is difficult to achieve the desired taper.

As can be seen from Table 5, in Examples 1 to 9, the difference between the design value of the mask pattern and the measured value of the obtained fine pattern is 20 micrometers or less, thus making it possible to form a fine pattern. pixels and exhibited excellent pattern properties.

However, in Comparative Example 2 containing only acrylic resin, film wrinkling occurred due to difficulty in curing, and in Comparative Example 3, the content of the photopolymerizable compound was lower than the appropriate range, disadvantageously causing difficulty in curing and Membrane wrinkled. In addition, in Comparative Example 4 which did not contain an ultraviolet absorber, it was difficult to form a fine pattern.

Test Example 3: Measurement of Light Intensity

In the color filter that uses embodiment 1 to embodiment 9 and comparative example 1 to the color filter that comparative example 4 makes respectively blue photosensitive resin, use 365 nanometer tube type 4 watts ultraviolet lamps (VL-4LC, VILBER LOURMAT) irradiates a square pattern portion with a size of 20 mm x 20 mm with light to measure the light conversion area. In Example 1 to Example 9 and Comparative Example 1 to Comparative Example 4, the light intensity at 450 nm was measured using a spectrometer (manufactured by Ocean Optics).

Light efficiency is considered higher when the measured light intensity increases.

In Example 1 to Example 9, the light intensity was as high as 2 or more, indicating high light efficiency. However, in Comparative Example 2 containing only an acrylic resin, film wrinkling occurred due to difficulty in curing, and in Comparative Example 4 containing no ultraviolet absorber, light efficiency decreased.

Test Example 4: Measurement of Angle of View

In the color filters manufactured using the blue photosensitive resins of Examples 1 to 9 and Comparative Example 1 to Comparative Example 4, a goniophotometer (GC-5000L, Nippon Denshoku )) The light intensity depending on the viewing angle under the light transmission condition was measured for a square pattern portion having a size of 20 mm×20 mm, and the diffusivity was calculated using Equation 1 below.

[Equation 1] Expansion rate = (B ₇₀ +B ₂₀ )/2×B ₅ ×100

(B _θ =I _θ /cosθ)

Here, I represents the light intensity measured at each angle, and B ₇₀ , B ₂₀ and B ₅ are the corresponding values measured at 70°, 20° and 5°.

Viewing angles are considered excellent as the measured diffusivity increases. It can be seen from Table 7 that the viewing angles of Embodiment 1 to Embodiment 9 have been improved. However, in Comparative Example 4 which did not contain an ultraviolet absorber, the diffusivity decreased.

Although preferred embodiments of the present invention have been disclosed for purposes of illustration, those skilled in the art will appreciate that, without departing from the scope and spirit of the present invention as disclosed in the appended claims, Various modifications, additions, and substitutions are possible.

Claims (12)

A blue photosensitive resin composition comprising scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photopolymerization initiator, an ultraviolet absorber, and A solvent, wherein based on the total weight of the solid content of the blue photosensitive resin, the blue photosensitive resin composition includes 0.1% to 50% by weight of the scattering particles, 0.1% to 50% by weight of the blue Colorant, the binder resin of 5% to 85% by weight, the photopolymerizable compound of 5% to 50% by weight, the photopolymerization initiator of 0.1% to 20% by weight, and 0.001% by weight % to 10% by weight of the ultraviolet absorber, and based on the total weight of the blue photosensitive resin composition comprising 60% by weight to 90% by weight of the solvent, wherein the scattering particles include 10 nm to 1000 nm The average particle size of the metal oxide, wherein the ultraviolet absorber includes at least one of benzotriazole ultraviolet absorber, triazine ultraviolet absorber and benzophenone ultraviolet absorber, wherein the photopolymerization The initiator includes at least one selected from the group consisting of the following chemical formulas:

[chemical formula 5-2]

, and wherein a 365-nm tube-type 4-watt ultraviolet lamp is used to irradiate the coating film manufactured with the blue photosensitive resin composition to measure the light conversion area, and the light intensity at 450 nm is 2.78 to 3.98 mW/cm2. The blue photosensitive resin composition according to Claim 1, wherein the scattering particles include at least one selected from the following groups: Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Nb ₂ O ₃ , SnO, and MgO. The blue photosensitive resin composition as described in claim 1 further includes a purple colorant. The blue photosensitive resin composition according to claim 1, wherein the blue colorant includes at least one of a blue pigment and a blue dye. The blue photosensitive resin composition according to claim 1, wherein the arbor system binder resin includes at least one of the compounds represented by the following chemical formula 1-1 and chemical formula 1-2:

[chemical formula 1-2]

(In chemical formula 1-1 and chemical formula 1-2, R ₁ , R ₂ , R ₃ and R ₄ are independently

, wherein X is a hydrogen atom, a C1-C5 alkyl group, or a hydroxyl group, and R ₅ is a hydrogen atom or a C1-C5 alkyl group). The blue photosensitive resin composition as described in Claim 1, wherein the arbor system binder resin includes at least one member selected from the following groups: 9,9-bis(3-cinnamic acid diester) fluorine, 9 ,9-bis(3-cinnamoyl-4-hydroxyphenyl) terrene, 9,9-bis(glycidyl methacrylate ether) terrene, 9,9-bis(3,4-dihydroxyphenyl) ) fennel dicinnamate, 3,6-diglycidyl methacrylate ether spiro (xanthene-9,9-dibenzopyran (xanthene)), 9,9-bis(3-allyl 4 -Hydroxyphenyl) terpine, 9,9-bis(4-allyloxyphenyl) terpine, and 9,9-bis(3,4-methacrylic acid diester) terpine. The blue photosensitive resin composition according to claim 1, wherein the binder resin further includes an acrylic alkali-soluble resin. A color filter, comprising a blue pattern layer formed of the blue photosensitive resin composition as claimed in any one of Claims 1 to 7. The color filter according to Claim 8 further includes at least one selected from the group consisting of a red pattern layer and a green pattern layer. The color filter as described in Claim 9, wherein the red pattern layer or the green pattern The case layer includes quantum dots. The color filter according to claim 10, wherein the color filter is a self-luminous color filter. An image display device, comprising: the color filter according to Claim 8; and a light source for emitting blue light.