TWI636325B - Colored photosensitive resin composition, color filter and display device including the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and a color filter and a display device including the same, and more particularly, to a photo or thermal polymerizable compound including a colorant, an alkali-soluble resin, an isocyanurate compound, and photopolymerization. A coloring photosensitive resin composition containing a basic monomer, a photopolymerization initiator, and a solvent, which has excellent adhesion, brightness, and sensitivity, and a color filter and a display device including the colored photosensitive resin composition.

Description

Colored photosensitive resin composition, color filter and display device including the same Field of invention

The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same, and more particularly, to a photo or thermal polymerizable compound containing a colorant, an alkali-soluble resin, an isocyanurate compound, and a photopolymerizable property. A colored photosensitive resin composition of a monomer, a photopolymerization initiator and a solvent, which has excellent adhesion, brightness, and sensitivity, and a color filter and a display device including the colored photosensitive resin composition.

Background of the invention

Color filters are widely used in imaging devices, liquid crystal display devices (LCD), and the like, and the application range is rapidly increasing. A color filter used in a liquid crystal display device, an imaging device, and the like is generally manufactured as follows: A substrate containing a black matrix pattern formed thereon by spin coating is uniformly coated with a pigment containing pigments corresponding to various colors of red, green, and blue. The photosensitive resin composition is colored, a film formed by heating and drying (hereinafter sometimes referred to as 'pre-baking') a product is exposed and developed, and a thermal curing operation is further repeated for each color as necessary (hereinafter sometimes referred to as 'Post-baking') forming pixels of each color. here, The black matrix having a pattern formed thereon is conventionally formed with a black photosensitive resin composition.

In addition, the liquid crystal display device has a structure in which a liquid crystal material and a plurality of pixels are provided between two polarizing plates. In a liquid crystal display device, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the transmitted light transmitted through the second polarizing plate is controlled for image display by changing the degree of polarization of the light transmitted through the first polarizing plate.

By installing a color filter between these two polarizing plates in a liquid crystal display device, a color display becomes possible, and the liquid crystal display device has been used in a television, a personal computer, and a monitor.

The color filter has a black matrix (hereinafter referred to as BM), i.e., a grid-shaped light-shielding film mounted on a transparent substrate such as a glass plate to prevent transmitted light colors from mixing and enhance display contrast, and a multi-color (normally arranged) corresponding to pixels Red, green, and color). The filter sections are tiny, ranging from several to several hundred μm. The filter section arrangement may include two or more types of thin-strip arrangement (strip arrangement), regular arrangement of length and width (δ arrangement), and the like arranged in different colors. The filter node and the BM are formed by applying a coloring composition and drying the resultant at a high temperature of usually 180 ° C or higher and preferably 230 ° C or higher.

In a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed thereon. These transparent electrodes and alignment films need to be formed at a high temperature of 180 ° C or higher and preferably 230 ° C or higher in order to fully achieve their quality. Therefore, as a current method of manufacturing a color filter, the main A method called a pigment dispersion method is used, which uses a pigment having excellent light resistance and heat resistance as a colorant.

The qualities required for a liquid crystal display device may include high definition, low power consumption, and the like, and in order to achieve these goals, color filters with high brightness, high contrast, and high resolution are required.

In particular, in terms of recent power consumption, high-brightness color filters have become a trend. When a high-brightness color filter is used, the light transmittance is high, and therefore, the number of backlights as a light source can be reduced, and thus power consumption can be suppressed.

In the existing color filters, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, and the like have been incorporated in the red filter section. Copper or zinc phthalocyanine pigments, nickel azo complex-based pigments, etc. have been incorporated in the green filter section. Copper phthalocyanine pigments, dioxazine-based pigments, etc. have been incorporated in the blue filter section. Therefore, it has been possible to realize a high-brightness and wide-color display area. However, as described above, the color filter needs to further increase the brightness.

As the demand for further improvement in brightness has increased, dye-based coloring materials have received attention. Japanese Patent Application Publication No. 2009-265641 and Japanese Patent Application Publication No. 2010-32999 disclose rhodamine colorants, xanthene-based colorants such as eosin pigments, and triarylmethane colorants such as triphenylmethane because these The colorant has advantages in color properties and is expected to be a material for improving brightness.

However, when a pixel containing these color materials is manufactured and the chromaticity is measured, when the pixel is formed, after drying at a high temperature of 230 ° C., the brightness is reduced as compared with that before drying at a high temperature. Dye-based materials are in phase with pigments that have been routinely used Specific heat resistance is poor, and therefore, sufficient brightness cannot be obtained due to heat treatment.

In addition, Korean Patent Application Publication No. 10-2013-0082469 discloses a colored photosensitive resin composition having improved heat resistance, however, problems such as a decrease in dispersion stability and a decrease in brightness due to heat treatment occur.

Therefore, there is a need for research that can further improve the brightness by suppressing the decrease in brightness caused by the heat treatment.

[Existing technical literature] [Patent Literature]

Japanese Patent Application Publication No. 2009-265641

Japanese Patent Application Publication No. 2010-32999

Korean Patent Application Publication No. 10-2013-0082469

Summary of invention

An object of the present invention is to provide a colored photosensitive resin composition which, by including a light or thermally polymerizable compound including an isocyanurate compound, can form a pattern even with an exposure amount of 40 mJ / m ² or less and has excellent properties. Substrate adhesion, brightness, sensitivity and reliability.

Another object of the present invention is to provide a color filter having excellent chemical resistance and flatness without the presence of surface defects in a pixel unit by using the colored photosensitive resin composition in color filter manufacturing, and including The liquid crystal display device of the color filter is described.

In view of the foregoing, one aspect of the present invention provides a colored photosensitive resin composition including a colorant, an alkali-soluble resin, a photo or thermally polymerizable compound including an isocyanurate compound of the following Chemical Formula 1, and a photopolymerizable monomer. A photopolymerization initiator and a solvent, wherein the photo or thermal polymerizable compound including the isocyanurate compound of the following Chemical Formula 1 accounts for 10% by weight to the total solid weight in the colored photosensitive resin composition 30% by weight.

R1, R2, and R3 are the same or different from each other, and are one selected from the following Formulae 2 to 4, and at least one of R1, R2, and R3 includes the following Chemical Formula 2.

[Chemical Formula 2] -CH ₂ OH

Another aspect of the present invention provides a color filter including the colored photosensitive resin composition.

Another aspect of the present invention provides a display device including the color filter.

detailed description

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

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photo or thermally polymerizable compound including an isocyanurate compound of the following Chemical Formula 1, a photopolymerizable monomer, a photopolymerization initiator, and The solvent, wherein the light or thermal polymerizable compound including the isocyanurate compound of the following Chemical Formula 1 accounts for 10% to 30% by weight with respect to the total solid weight in the colored photosensitive resin composition.

R1, R2, and R3 are the same or different from each other, and are one selected from the following Formulae 2 to 4, and at least one of R1, R2, and R3 includes the following Chemical Formula 2.

[Chemical Formula 2] -CH ₂ OH

By including the photo or thermally polymerizable compound including the isocyanurate compound of Chemical Formula 1 with respect to the total solid weight in the colored photosensitive resin composition, it is possible to provide A colored photosensitive resin composition capable of forming a pattern at an exposure amount of 40 mJ / m ² or less and having excellent substrate adhesion, brightness, sensitivity, and reliability.

Herein, the colored photosensitive resin composition of the present invention will be described in detail by each component.

(A) Colorant

In the present invention, the colorant includes one or more pigments, one or more dyes, or a mixture thereof, and preferably includes one or more pigments.

(a1) Pigment

As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used. In addition, according to need, the pigment may be treated with resin Surface treatment using pigment derivatives that introduce acidic or basic groups, grafting treatment on the pigment surface with polymers, etc., atomization treatment using sulfuric acid atomization, washing treatment with organic solvents or water, etc. The impurities are removed, or a process such as an ion exchange method is used to remove the ionic impurities.

As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isocyanate Indolinone pigment, isoindolinol pigment, osmium pigment, fluorenone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinone-based pigment, anthracene pigment, anthracene dione pigment, indoanthraquinone pigment, Flavanone pigments, dermatanthone pigments, diketopyrrolopyrrole pigments, and the like.

In addition, as the inorganic pigment, a metal compound such as a metal oxide or a metal complex salt may be included, and specific examples thereof may include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Oxides, carbon black, organic black pigments, pigments that look black by mixing titanium black and red and green and blue, or composite metal oxides, etc.

In particular, as the organic pigment and the inorganic pigment, a compound classified as a pigment in a color index (published by the Society of Dyers and Colourists) may be included, and more specifically, the following color index (CI) numbers However, the pigment is not limited thereto.

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147 , 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264, and 265; CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; CI Pigment Blue 15 ( 15: 3, 15: 4, 15: 6, etc.) and 60; CI Pigment Green 7, 36, and 58; CI Pigment Brown 23 and 25; CI Pigment Black 1 and 7; and so on.

The pigment may be used alone or as a combination of two or more.

The pigment accounts for 15 to 45% by weight and preferably 20 to 40% by weight with respect to the total solid weight in the colorant. When the pigment accounts for less than 20% by weight, it is difficult to obtain color reproducibility, and when the pigment accounts for more than 40% by weight, the solubility to the developing solution decreases, making pattern formation difficult.

The solubility to the developing solution can be excellent, and a pattern can be accurately formed during development.

The pigment is preferably a pigment dispersion liquid in which pigment particles are uniformly dispersed. Examples of a method of uniformly dispersing pigment particles may include a dispersion method containing a pigment dispersant (a2) and the like, and using this method, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.

(a2) Pigment dispersant

The pigment dispersant is added to dissolve and maintain stability of the pigment. Specific examples of the pigment dispersant may include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and the like, and These may be used alone or as a combination of two or more.

Specific examples of the cationic surfactant may include an amine salt or a quaternary ammonium salt, such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant may include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylaryl sulfonates Acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the non-ionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, ethylene oxide / propylene oxide blocks Copolymer, fatty acid sorbitan ester, fatty acid polyoxyethylene sorbitan ester, fatty acid polyoxyethylene sorbitol ester, fatty acid glyceride, fatty acid polyoxyethylene ester and polyoxyethylene alkane And so on.

In addition to these, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modification Polyurethane, polyethyleneimine and so on.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant including butyl methacrylate (BMA) or N, N-dimethyl methacrylate Aminoethyl ester (DMAEMA) (hereinafter, referred to as an acrylate-based dispersant). The commercially available acrylate-based dispersant may include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like, and the acrylate-based dispersant may be separately or as a kind thereof. Or more in combination.

In addition to the above-mentioned acrylate-based dispersant, the pigment dispersant may use other resin-based pigment dispersants. Examples of the other resin-based pigment dispersants may include known resin-based pigment dispersants, particularly oily dispersants such as polyurethane, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamines, polycarboxylic acids, (Partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, polycarboxylic acid esters containing hydroxyl groups, and modifications thereof Or a salt thereof; a water-soluble resin or a water-soluble polymer compound such as a (meth) acrylic acid-styrene copolymer Polymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylate; ethylene oxide / cyclo Oxypropane adducts; phosphate esters, etc.

As a commercial product of the other resin-based dispersant, examples of the cationic resin dispersant may include trade names of BYK Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade names of BASF Corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA- 4510 and EFKA-4800; trade names of Lubrizol Corporation: SOLSPERS-24000, SOLSPERS-32550, and NBZ-4204 / 10; trade names of Kawaken Fine Chemicals Co., Ltd .: HINOACT T-6000, HINOACT T-7000, and HINOACT T -8000; Trade names of Ajinomoto Fine-Techno Co., Inc .: AJISPER PB-821, AJISPER PB-822, and AJISPER PB-823; Trade names of Kyoeisha Chemical Co., ltd .: FLORENE DOPA-17HF, FLORENE DOPA- 15BHF, FLORENE DOPA-33 and FLORENE DOPA-44, etc.

The resin-based pigment dispersant other than the acrylate-based dispersant may be used alone or as a combination of two or more types, or may be used together with the acrylate-based dispersant.

The pigment dispersant accounts for more than 0 parts by weight and less than or equal to 1 part by weight, and preferably 0.05 to 0.5 parts by weight, with respect to 1 part by weight of the colorant. Since a uniformly dispersed pigment can be obtained, the pigment dispersant occupying more than 0 parts by weight and less than or equal to 1 part by weight is preferable.

(a3) Dye

The dye may be used without limitation as long as it has organic solvent solubility. Preferably, a dye capable of ensuring reliability such as solubility in an alkali developing solution, heat resistance, and solvent resistance while having solubility in an organic solvent can be used.

As the dye, one selected from those having an acidic group such as Acid dyes of sulfonic acid or carboxylic acid, salts of the acid dyes and nitrogen-containing compounds, sulfonamide of the acid dyes, and the like, and derivatives thereof, and in addition, azo and oxa groups may be selected Anthracene and phthalocyanine-based acid dyes, and their derivatives. The dye preferably includes a compound classified as a dye in a color index (published by the Society of Dyers and Colourists) or a known dye described in Dye Note (published by Shikisensha).

As CI solvent dyes, specific examples of the dyes include, for example, the following dyes, CI Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179; CI Solvent Blue 5, 35, 36, 37, 44, 59, 67, and 70; CI Solvent Violet 8, 9, 13, 13, 14, 36, 37, 47, and 49; CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162; CI Solvent Orange 2, 7, 11, 15, 26, and 56; and CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 And 35.

Among the CI solvent dyes, CI solvent red 8, 49, 89, 111, 122, 132, 146, and 179 are preferred; CI solvent blue 35, 36, 44, 45, and 70; CI solvent violet 13, and more preferred CI Solvent Red 8, 122 and 132.

In addition, as the CI acid dye, for example, the following dyes may be included, such as CI 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, and 426; CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42 , 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157 , 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228 , 230, 232, 235, 238, 240, 242, 243, and 251; CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173; CI Acid Blue 1, 7, 9, 15, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83 , 86, 87 , 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290 , 296, 315, 324: 1, 335, and 340; CI Acid Violet 6B, 7, 9, 17, 19, and 66; and CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58 ,, 63, 65, 80, 104, 105, 106, and 109.

Among the C.I. acid dyes, it is preferable to have an organic solvent C.I. Acid Red 92; C.I. Acid Blue 80 and 90; and C.I. Acid Violet 60 with excellent solubility.

In addition, as the CI direct dye, for example, the following dyes CI 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, and 250; CI Direct Yellow 2, 33, 34, 35, 38 , 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84 , 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155 , 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207 , 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 25 6, 257, 259, 260, 268, 274, 275, and 293; CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95 , 96, 103 and 104; and C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

In addition, the CI mordant dye may include, for example, the following dyes CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; CI mordant 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, and 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23 , 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48; CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; CI mordant purple 1, 2 , 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58; and CI Mordant Green 1, 3, 4, 5, 10 , 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The dye may be used alone or as a combination of two or more.

The content of the dye in the colorant is 0.5% to 80% by weight, preferably 0.5% to 60% by weight, and more preferably 1% to 50% by weight with respect to the total solid weight in the colorant. When the content of the dye in the colorant is 0.5% to 80% by weight, it is possible to prevent organic Solvent-induced problems with reduced reliability of dye elution and increased sensitivity.

The content of the colorant is 3 to 60% by weight and preferably 5 to 55% by weight with respect to the total solid weight in the colored photosensitive resin composition. When the colorant accounts for 3 to 60% by weight, the color density when the color filter is manufactured is sufficient, and a pattern having sufficient mechanical strength can be formed.

(B) Alkali-soluble resin

The alkali-soluble resin is generally reactive and alkali-soluble by the action of light or heat, and functions as a dispersion medium of the colorant.

The alkali-soluble resin contained in the colored photosensitive resin composition functions as a binder resin of the colorant (A), and its type is not particularly limited as long as it is soluble in the developing step for manufacturing the color filter The binder resin in the alkaline developing solution used may be sufficient.

Examples of the alkali-soluble resin may include a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the carboxyl group-containing monomer.

Specific examples of the carboxyl group-containing monomer may include an unsaturated carboxylic acid such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated polyvalent carboxylic acid having one or more carboxyl groups in the molecule such as an unsaturated tricarboxylic acid. carboxylic acid.

Specific examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like.

Specific examples of the unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like.

The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof may be To include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

In addition, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and specific examples thereof may include mono (2-propenyloxyethyl) succinate, mono (2-Methacryloxyethyl) succinate, mono (2-acryloxyethyl) phthalate, mono (2-methacryloxyethyl) phthalate Formate and so on.

In addition, both ends of the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer, and specific examples thereof may include ω-carboxy polycaprolactone monoacrylate, ω-carboxy polycaproate Lactone monomethacrylate and the like.

The carboxyl group-containing monomer may be used alone or as a mixture of two or more.

Specific examples of the other monomer copolymerizable with the carboxyl group-containing monomer 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-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl Ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl 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 Ester, isobutyl methacrylate Ester, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methyl acrylate 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, formazan Cyclohexyl acrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-methacrylate Phenoxyethyl ester, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol Acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol propylene Acid ester, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, adamantane (meth) acrylate Esters, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate ; Unsaturated amino carboxylic acid alkyl esters, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, acrylic acid 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminomethacrylate Propyl ester, propyl ester 3-dimethylaminopropyl enoate and 3-dimethylaminopropyl methacrylate; unsaturated glycidyl carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylic acids such as acetic acid Vinyl esters, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds, such as Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated fluorenes, such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxy Ethacrylamidine and N-2-hydroxyethyl methacrylamidine; unsaturated hydrazone imines such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated diene such as 1,3-butadiene, isoprene and chloroprene; in polystyrene, polymethyl acrylate, polymethacrylic acid Polymers of methyl ester, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane have a monopropenyl group at the molecular chain end or Bing Xixi macromonomer methyl group; and the like.

These monomers may be used alone or as a mixture of two or more.

In addition, specific examples of the alkali-soluble resin, that is, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer may include (meth) acrylic acid / (meth) acrylate Copolymer, (methyl) Acrylic acid / (meth) acrylic acid copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylic acid / benzyl (meth) acrylic acid copolymer, (meth) acrylic acid / (meth) acrylic acid Methyl ester / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / (formaldehyde) Base) benzyl acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / (methyl) ) Benzyl acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, ( (Meth) acrylic acid / mono (2-propenyloxy) succinate / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2 -Acryloxy) succinate / styrene / (formaldehyde) ) Allyl acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (methyl) ) Acrylate copolymers and the like.

Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, and (meth) acrylic acid / (formaldehyde) can be preferably used. Methyl acrylate copolymer and (meth) acrylic acid / methyl (meth) acrylate / styrene copolymer.

When the alkali-soluble resin is a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the carboxyl group-containing monomer, the carboxyl group-containing monomer is relative to the total weight of the alkali-soluble resin. 10% to 50% by weight, preferably 15% to 40% by weight and more preferably 25% by weight to 40% by weight. When the carboxyl group-containing monomer accounts for 10 to 50% by weight, the solubility to the developing solution may be excellent, and a pattern may be accurately formed during development.

In addition, the alkali-soluble resin preferably has an acid value of 20 mgKOH / g to 200 mgKOH / g. Within the above range of acid values, the solubility in the developing solution is improved, the unexposed units are easily dissolved, and the sensitivity can be increased. Therefore, because the pattern in the exposed units is retained during development, the film residual rate can be improved.

The acid value is a value measured as an amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

In addition, the polystyrene-equivalent weight average molecular weight of the alkali-soluble resin (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 3,000 to 200,000 and It is preferably 5,000 to 100,000. When the weight-average molecular weight of the alkali-soluble resin is 3,000 to 200,000, the hardness of the coating film is increased, resulting in a high film residual rate, the solubility of the unexposed unit to the developing solution is excellent, and the resolution is also improved.

In the present invention, the alkali-soluble resin accounts for 10 to 80% by weight and preferably 20 to 70% by weight with respect to the total solid weight in the colored photosensitive resin composition.

When the content of the alkali-soluble resin is 10% by weight to 80% by weight, a pattern can be formed, and the resolution and the film residual ratio can be improved.

(C) Photo or thermally polymerizable compound including an isocyanurate compound

The colored photosensitive resin composition of the present invention contains a light or thermally polymerizable compound including an isocyanurate compound of the following Chemical Formula 1.

R1, R2, and R3 are the same or different from each other, and are one selected from the following Formulae 2 to 4, and at least one of R1, R2, and R3 includes the following Chemical Formula 2.

[Chemical Formula 2] -CH ₂ OH

The photo or thermally polymerizable compound including the isocyanurate compound of Chemical Formula 1 can control the number of functional groups through the functional groups of R1, R2, and R3, and all of thermal curing or photocuring can be performed. Reactivity and adhesion of the colored photosensitive resin composition.

In addition, since the brightness reduction due to heat treatment is small, the sensitivity and reliability are excellent, no surface defects in the pixel unit occur, and excellent heat resistance, chemical resistance, and flatness effects can be obtained.

The light or thermally polymerizable compound including the isocyanurate compound of Chemical Formula 1 accounts for 10% by weight to 30% by weight and preferably 10% by weight to the total solid weight in the colored photosensitive resin composition. 20% by weight.

When the light or thermally polymerizable compound including the isocyanurate compound of Chemical Formula 1 accounts for less than 10% by weight, a decrease in brightness due to heat treatment occurs, and sensitivity and adhesion are not improved. When it is more than 30% by weight, the viscosity of the colored photosensitive resin composition increases, resulting in poor coatability, dispersion stability may decrease due to reactivity, and yellowing may occur.

(D) Photopolymerizable monomer

The photopolymerizable compound, which is one of the colored photosensitive resin compositions of the present invention, needs to be polymerized by the action of a photopolymerization initiator (E) described later.

As the photopolymerizable compound, a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer may be used, and preferably a difunctional or higher polyfunctional monomer may be used, and a pentafunctional or higher polyfunctional may be more preferably used. A monomer, however, the photopolymerizable compound is not limited thereto.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethyl acrylate Hexylcarbitol, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, but are not limited thereto.

Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol Alcohol di (meth) acrylate, bis (propylene ethoxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propane Oxidized dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are not limited thereto.

The photopolymerizable monomer accounts for 5 to 50% by weight and preferably 7 to 45% by weight with respect to the total solid weight in the colored photosensitive resin composition of the present invention. Within the above 5 to 50% by weight, the photopolymerizable compound allows the pixel unit to have favorable flatness intensity.

(E) Photopolymerization initiator

The photopolymerization initiator preferably includes an acetophenone-based compound.

Specific examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy -1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) but-1-one, 2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propan-1-one oligomer and the like, and may preferably include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) but-1 -Ketones, etc.

In addition, the photopolymerization initiator may use a mixture of an acetophenone-based compound and other types of photopolymerization initiators.

The other type of photopolymerization initiator may include an active group generator that generates an active group by light irradiation, a sensitizer, an acid generator, and the like.

Specific examples of the reactive group generating agent may include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, a triazine-based compound, and the like.

Specific examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Specific examples of the benzophenone-based compound may include benzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, 4-benzophenyl-4'-methyldione Phenyl sulfide, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, etc.

Specific examples of the triazinyl compound may 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- (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) vinyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (4-diethylamino-2-tolyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Specific examples of the sensitizer may include 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) -4,4 ', 5,5 '-Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylic acid Esters, titanocene compounds, etc.

Specific examples of the acid generator may include an onium salt such as 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, 4-ethylfluorenyloxybenzene Dimethyl sulfonium p-toluenesulfonate, 4-ethoxyfluorenylmethylbenzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, Diphenyliodonium p-toluenesulfonate, diphenyliodonium and hexafluoroantimonate, nitrobenzyltoluenesulfonate, benzointoluenesulfonate, and the like.

In addition, the reactive group generator further includes a compound that generates an acid and a reactive group among the above compounds. For example, the triazine-based photopolymerization initiator can also be used as an acid generator.

The photopolymerization initiator may be used alone or as a combination of two or more.

In the present invention, the photopolymerization initiator accounts for 0.1 to 20% by weight and preferably 1 to 10% by weight with respect to the total solid weight in the colored photosensitive resin composition.

Within the range of 0.1% by weight to 20% by weight, the colored photosensitive resin composition becomes highly sensitized, reducing the exposure time, and therefore, an increase in production and a high resolution can be expected.

In addition, in the present invention, a photopolymerization initiation aid may be used in addition to the photopolymerization initiator.

The photopolymerization initiation aid is a compound for promoting polymerization of the photopolymerizable compound initiated by the photopolymerization initiator, and the photopolymerization initiation aid may include an amine compound, an alkoxyanthracene group, and the like. Compounds etc.

Specific examples of the amine-based compound may include triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'- Bis (dimethylamino) benzophenone (collectively referred to as stilbone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) bis Benzophenone and the like, and among these, 4,4′-bis (diethylamino) benzophenone is preferred.

Specific examples of the alkoxyanthracene compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2- Ethyl-9,10-diethoxyanthracene and the like.

In addition, a commercially available compound as the photopolymerization initiation aid may be used, and the commercially available photopolymerization initiation aid may include a trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.) and the like.

When the photopolymerization initiator and the photopolymerization initiator are mixed When the agent is used, specific examples of the preferred combination may include the following combinations: diethoxyacetophenone and 4,4'-bis (diethylamino) benzophenone; 2-methyl-2-morpholine 1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1-phenylpropane -1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1 -Ketones and 4,4'-bis (diethylamino) benzophenone; 1-hydroxycyclohexylphenyl ketone and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer and 4,4'-bis (diethylamino) benzophenone; 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) but-1-one and 4,4'-bis (diethylamino) benzophenone and the like, and 2-methyl is preferred Of 2-methylmorpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone.

The photopolymerization initiation aid is usually preferably used in an amount of 0.01 mole to 5 moles relative to 1 mole of the photopolymerization initiator. When the photopolymerization initiation aid is used in a range of 0.01 mol to 5 mol, the sensitivity of the colored photosensitive resin composition is further improved, and the productivity of a color filter formed using the colored photosensitive resin composition can be improved. .

(F) Solvent

The solvent may be a solvent generally used in the colored photosensitive resin composition, and there is no limitation as long as it effectively dissolves other components contained in the colored photosensitive resin composition, and particularly, ether, acetate, etc. are preferable , Aromatic hydrocarbons, ketones, alcohols, esters, amidines, etc.

Examples of the ether 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. Ethers; and diethylene glycol dialkyl ethers such as diglyme, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

Examples of the acetate may include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate , 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, Methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

Examples of the aromatic hydrocarbon may include benzene, toluene, xylene, mesitylene, and the like.

Examples of the ketone may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.

Examples of the alcohol may include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, 4-hydroxy-4-methyl-2-pentanone, and the like.

Examples of the ester may include ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, γ-butyrolactone, and the like.

Examples of the amidine may include dimethylformamide (DMF) And N-methyl-2-pyrrolidone (NMP).

The solvents may be used alone or as a mixture of two or more.

According to coatability and drying property, the solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C, and more preferably may include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy Ethyl propionate, methyl 3-methoxypropionate, and the like.

The solvent accounts for 60 to 90% by weight and preferably 70 to 85% by weight with respect to the total weight of the colored photosensitive resin composition. When the solvent accounts for 60 to 90% by weight, when using coating equipment such as a roll coater, a spin coater, a slit spin coater, a slit coater (sometimes referred to as a die coater) In the case of inkjet coating, the coatability becomes favorable.

(G) Additives

The additive may be optionally added as required, and examples thereof may include one or more selected from other polymers, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and deagglomeration agents.

Specific examples of the other polymers may include cured resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylic acid Ester, polyester and polyurethane.

The curing agent is used for deep curing and improving mechanical strength, and specific examples of the curing agent may include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.

Specific examples of the epoxy compound in the curing agent may include Including bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac-type epoxy resin, other aromatic-based epoxy resins, Alicyclic epoxy resin, glycidyl ester-based resin, glycidylamine-based resin, or brominated derivative of said epoxy resin, aliphatic, cycloaliphatic or aromatic epoxy compound other than epoxy resin, and Its brominated derivatives, butadiene (co) polymer epoxide, isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, isocyanuric acid Glycidyl esters and more.

Specific examples of the oxetane compound in the curing agent may include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalic acid Ester dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

As the curing agent, a curing assistant compound capable of ring-opening polymerization of an epoxy group of the epoxy compound and an oxetane skeleton of the oxetane compound together with the curing agent can be used.

Examples of the curing auxiliary compound include a polyvalent carboxylic acid, a polyvalent carboxylic anhydride, an acid generator, and the like. As the polyvalent carboxylic acid anhydride, a compound commercially available as an epoxy resin curing agent can be used. Specific examples of the epoxy resin curing agent may include Adeka primer EH-700 (manufactured by Adeka Corporation), Rikacid HH (manufactured by New Japan Chemical Co., Ltd.), and MH-700 (manufactured by New Japan Chemical Co., Ltd.) )Wait. The curing agents exemplified above may be used alone or as a mixture of two or more.

The surfactant can be used to further improve the coloring The film-forming property of the photosensitive resin composition is preferably a silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, amphoteric surfactant, or the like.

As a commercial product, examples of the silicone-based surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF- manufactured by GE Toshiba Silicone Co., Ltd. 4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc.

As a commercial product, examples of the fluorine-based surfactant include Megafac F-470, F-471, F-475, F-482, F-489, and the like manufactured by DIC Corporation.

In addition, other usable products may include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), MEGAFAC (DIC Corporation), Flourad (Sumitomo 3M Ltd. .), Asahi guard, Surflon (above, AGC Seimi Chemical Co., Ltd.), SOLSPERSE (Lubrisol), EFKA (EFKA Chemicals), PB 821 (Ajinomoto Fine-Techno Co., Inc.), Disperbyk series (BYK- Chemi) and so on.

The surfactants exemplified above may be used alone or as a combination of two or more.

The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethyl) (Oxy) Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethyl Oxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc.

The adhesion promoters exemplified above may be used alone or as a combination of two or more. The adhesion promoter may generally account for 0.01 to 10% by weight and preferably 0.05 to 2% by weight with respect to the total solid weight in the colored photosensitive resin composition.

The type of the antioxidant is not particularly limited, and examples thereof may include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methyl Phenol, etc.

The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used may include 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxy Benzophenone and the like.

The type of the deagglomeration agent is not particularly limited, and specific examples thereof that can be used may include sodium polyacrylate and the like.

The method for preparing the colored photosensitive resin composition of the present invention is as follows.

First, the colorant (A) is mixed with the solvent (F) and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. Here, if necessary, the pigment dispersant (a2), and a Part or all of the alkali-soluble resin (B) may be mixed with the solvent (F) and dissolved or dispersed therein.

To the mixed coloring material, the remaining alkali-soluble resin (B), the photo or thermally polymerizable compound (C) including the isocyanurate compound of Chemical Formula 1, and the photo-polymerizable monomer (D) are further added. ), A photopolymerization initiator (E), an additive (G) as necessary, and a solvent (F) is further added so as to have a specific concentration, and the colored photosensitive resin composition of the present invention can be prepared.

In addition, the present invention provides a color filter manufactured using the colored photosensitive resin composition, and a display device provided therewith.

First, the colored photosensitive resin composition is coated on a substrate (usually glass) or a layer formed in advance from a solid of the colored photosensitive resin composition, and then the resultant is thermally dried to remove volatile components such as a solvent And thus get a flat film.

The coating can be performed by, for example, spin coating, flexible coating method, roll coating method, slit and spin coating, slit coating method, and the like. After coating, volatile components such as solvents are evaporated by heating after heat drying (pre-baking) or vacuum drying. Here, the heating temperature is usually from 70 ° C to 200 ° C and preferably from 80 ° C to 130 ° C. The thickness of the film after heat drying is usually from about 1 μm to 8 μm. On the film obtained as described above, ultraviolet rays were irradiated through a mask to form a target pattern. Here, it is preferable to use a device such as a mask aligner or a stepper so that the parallel light is uniformly irradiated on the entire exposure unit, and the mask and the substrate are accurately positioned. When the ultraviolet rays are irradiated, the portions irradiated with the ultraviolet rays are cured.

As ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), and the like can be used. The ultraviolet dose can be appropriately determined as needed, and is not limited in the present invention. The cured film is brought into contact with a developing solution and developed by dissolving an unexposed unit, and a spacer having a target pattern can be obtained.

The developing method is not particularly limited to a liquid addition method, a dipping method, a spray method, and the like. In addition, the substrate may be inclined at any angle during development. The developing solution is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound is not particularly limited to an inorganic or organic basic compound. Examples of the inorganic basic compound may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate , Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc.

Examples of the organic basic compound may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethyl Amine, monoisopropylamine, diisopropylamine, ethanolamine, etc.

The inorganic or organic basic compound may be used alone or as a mixture of two or more. The concentration of the basic compound in the developing solution is 0.01 to 10% by weight and preferably 0.03 to 5% by weight with respect to the total weight of the developing solution.

The surfactant in the developing solution may be selected from the group consisting of a nonionic surfactant, an anionic surfactant and a cationic surface. One or more of the active agents. The concentration of the surfactant in the developing solution is 0.01% to 10% by weight, preferably 0.05% to 8% by weight and more preferably 0.1% to 5% by weight with respect to the total weight of the developing solution. After development, the product is washed, and post-baking can be performed at 150 ° C to 230 ° C for 10 minutes to 60 minutes, if necessary.

By using the colored photosensitive resin composition of the present invention and through the respective steps as described above, a specific pattern can be formed on a substrate.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those skilled in the art.

<Synthesis of isocyanurate compound>

Synthesis Example 1.

43.4 parts by weight of isocyanuric acid and 500 parts by weight of toluene were put into a 4-necked round bottom flask including a cooling tube and a stirrer, and 0.4 parts by weight of hydroxide was introduced thereto while stirring the mixture. Barium, 27.5 parts by weight of formaldehyde and 29.1 parts by weight of acrylic acid.

The reflux reaction continued for 12 hours and was monitored by TLC to identify the completion of the reaction.

After the temperature of the reactor was reduced to room temperature, the organic solution was washed three times with water and ethyl acetate, and the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum to obtain 83.2 parts by weight (yield: 83%) of the compound of the following Chemical Formula 5 as a white solid.

Synthesis Example 2.

35.9 parts by weight of isocyanuric acid and 500 parts by weight of toluene were put into a 4-necked round bottom flask including a cooling tube and a stirrer, and 0.4 parts by weight of hydroxide was introduced thereto while stirring the mixture. Barium, 10.1 parts by weight of formaldehyde and 54.0 parts by weight of acrylic acid.

The reflux reaction continued for 12 hours and was monitored by TLC to identify the completion of the reaction.

After the temperature of the reactor was reduced to room temperature, the organic solution was washed three times with water and ethyl acetate, and the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum to obtain 85.1 parts by weight (yield: 85%) of the compound of the following Chemical Formula 6 as a white solid.

Synthesis Example 3.

42.1 parts by weight of isocyanuric acid and 500 parts by weight of toluene were put into a 4-necked round bottom flask including a cooling tube and a stirrer, and 0.4 parts by weight of hydroxide was introduced thereto while stirring the mixture. Barium, 25.0 parts by weight of formaldehyde and 32.9 parts by weight of vinyl chloride.

The reflux reaction continued for 12 hours and was monitored by TLC to identify the completion of the reaction.

After the temperature of the reactor was reduced to room temperature, the organic solution was washed three times with water and ethyl acetate, and the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum to obtain 84 parts by weight (yield: 84.3%) of the compound of the following Chemical Formula 7 as a white solid.

<Preparation of colored photosensitive resin composition>

Examples 1 to 6 and Comparative Examples 1 to 8.

The colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8 were prepared according to the compositions of Table 1 below.

Colorant A-1: C.I. Pigment Blue 15: 6

Colorant A-2: C.I. Pigment Violet 23

Alkali-soluble resin (B): a copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid units and benzyl methacrylic acid units is 31:69, the acid value is 100 mgKOH / g, polystyrene conversion (Weight average molecular weight is 20,000)

Isocyanurate compound C-1: Chemical formula 5 prepared in Synthesis Example 1

Isocyanurate compound C-2: Chemical formula 6 prepared in Synthesis Example 2

Isocyanurate compound C-3: Chemical formula 7 prepared in Synthesis Example 3

Isocyanurate compound C-4: Epoxy acrylate containing isocyanurate (DA-MGIC SHIKOKU Chemicals Corporation)

Photopolymerizable monomer (D): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (E): 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals Corporation)

Solvent (F): propylene glycol monomethyl ether acetate

Additive G-1: Surfactant (SH-8400, manufactured by Toray Silicone Co., Ltd.)

Additive G-2: epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Company Ltd.)

Additive G-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

Test example 1. Manufacturing of color filters and evaluation of physical properties

Each of the colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8 was applied on a 2-inch-angle glass substrate (# 1797, manufactured by Corning Incorporated) by a spin coating method, and the resultant was placed on a hot plate It was kept at 100 ° C for 3 minutes to form a thin film. After that, a pattern in which the transmittance was changed in a stepwise manner in a range of 1% to 100% was arranged on the film, and an ultra-high pressure mercury lamp (USH-250D, manufactured by USHIO Inc.) was used in the ionization test in an atmospheric atmosphere. The photomask was irradiated with light at an exposure amount (365 nm) of 40 mJ / cm ² at a distance of 1000 μm. Using a spray developer, the UV-irradiated film was developed in a KOH developing aqueous solution having a pH of 12.5 for 80 seconds. The film-coated glass plate was washed with distilled water, then dried by blowing nitrogen gas, and heated at 220 ° C. for 20 minutes in a heating oven to manufacture each color filter. The thickness of the manufactured color filter is from 1.9 μm to 2.1 μm.

Sensitivity evaluation

Measure the sensitivity, that is, the minimum exposure (mJ / cm ² ) required to form a film without pattern tearing after development during color filter manufacturing.

The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Evaluation criteria for sensitivity>

○ (Excellent): more than 40mJ / cm ²

△ (Good): more than 30mJ / cm ² and less than or equal to 40mJ / cm ²

× (poor): 30mJ / cm ² or lower

2. Evaluation of adhesion

After the manufactured substrate was cut into 100 matrix structures with an area of 10 mm × 10 mm, an adhesive tape was adhered thereon, and the number of matrices that fell off when the adhesive tape was vertically removed was measured.

The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Evaluation Criteria for Adhesion>

○ (excellent): less than 5

△ (Good): 5 or more and less than 15

× (Poor): 15 or more

3. Evaluation of heat resistance

After the pattern was finally formed, the discoloration (heat resistance) of about 230 ° C / 2hr was compared and evaluated. The formula used here is calculated by the following mathematical formula 1, which expresses discoloration in a 3-dimensional colorimeter defined by L *, a *, and b *, and can be manufactured because the discoloration value is small. Highly reliable color filter.

[Mathematical formula 1] △ Eab * = (△ L *) 2+ (△ a *) 2+ (△ b *) 2] ^1/2

The heat resistance results are shown in Table 2 below.

4. Evaluation of NMP solvent resistance

The manufactured substrate was cut into 3 cm x 3 cm, and then immersed in 14.6 mL of NMP solution at 80 ° C for 40 minutes. After that, the absorbance of the solution was evaluated using an ultraviolet-visible spectrometer.

The results are shown in Table 2 below.

Based on the results of Table 2, the colored photosensitive resin compositions of Examples 1 to 6 of the present invention include an isocyanurate compound of Chemical Formula 1. The light or thermal polymerizable compounds, color filters manufactured using them all show excellent and good results in terms of sensitivity, adhesion, heat resistance and solvent resistance, even with low exposure (40mJ / cm2).

Meanwhile, the colored photosensitive resin compositions of Comparative Examples 1 to 6 include a light or thermally polymerizable compound including an isocyanurate compound of Chemical Formula 1, but relative to the total solid weight in the colored photosensitive resin composition, Including the compound in a range of 10% to 30% by weight, a color filter manufactured using the colored photosensitive resin composition exhibits one or more of sensitivity, adhesion, heat resistance, and solvent resistance. the result of.

In addition, the colored photosensitive resin compositions of Comparative Examples 7 and 8 do not contain a light or thermally polymerizable compound including an isocyanurate compound of Chemical Formula 1. The color filters manufactured using them have sensitivity, adhesion, and heat resistance. Poor results in terms of both solvent resistance and solvent resistance.

Therefore, by using the light-sensitive or thermally polymerizable compound including the isocyanurate compound of Chemical Formula 1 and the colored photosensitive resin of the present invention in an amount of 10% to 30% by weight relative to the total solid weight of the colored photosensitive resin composition, The resin composition can manufacture a color filter having excellent sensitivity, adhesion, heat resistance and solvent resistance, and excellent reliability, and a display device including the color filter.

The colored photosensitive resin composition of the present invention contains a light or thermally polymerizable compound including an isocyanurate compound, and therefore can form a pattern even at an exposure amount of 40 mJ / m ² or less, and exhibits excellent Substrate adhesion, brightness, sensitivity and reliability.

In addition, by using the colored photosensitive resin composition of the present invention, A color filter and a liquid crystal display device including the same having excellent heat resistance, chemical resistance, and flatness without surface defects such as developing spots or water spots can be manufactured.

Claims (5)

A colored photosensitive resin composition comprising: a colorant; an alkali-soluble resin; a light or thermally polymerizable compound, which is an isocyanurate compound of the following Chemical Formula 1; a photopolymerizable monomer; a photopolymerization initiator; and a solvent Wherein the light or thermal polymerizable compound including the isocyanurate compound of the following Chemical Formula 1 accounts for 10% to 30% by weight with respect to the total solid weight in the colored photosensitive resin composition: Wherein R1, R2, and R3 are the same or different from each other, and are one selected from the following Formulae 2 to 4; and at least one of R1, R2, and R3 is represented by the following Chemical Formula 2: [Chemical Formula 2] -CH ₂ OH [ Chemical formula 3] The colored photosensitive resin composition according to claim 1, comprising: 3% to 60% by weight of the colorant with respect to the total solid weight of the colored photosensitive resin composition; and 10% to 80% by weight of the colorant. Said alkali-soluble resin; 5 to 50% by weight of said photopolymerizable monomer; 0.1 to 20% by weight of said photopolymerization initiator; and relative to the total weight of said colored photosensitive resin composition, 60% to 90% by weight of solvent. The colored photosensitive resin composition as claimed in claim 1, further comprising an additive. A color filter comprising the coloring photosensitive resin composition of claim 1. A display device includes a color filter of claim 4.